Abstract

The effect of activation environment (N2, H2 and H2S/H2) on the hydrocracking performance of a NiMo/Al catalyst was studied at 380 °C and 3.5 MPa using octacosane (C28). The catalyst physical structure and acidity were characterized by BET, XRD, SEM-EDX and FTIR techniques. The N2 activation generated more active nonsulfided NiMo/Al catalyst relative to the H2 or H2S activation (XC28, 70–80% versus 6–10%). For a comparison, a NiMo/Si-Al catalyst was also tested after normal H2 activation and showed higher activity at the same process conditions (XC28, 81–99%). The high activity of the NiMo/Al (N2 activation) and NiMo/Si-Al catalysts was mainly ascribed to a higher number of Brønsted acid sites (BAS) on the catalysts. The hydrocracking of cobalt wax using Pt/Si-Al and Pt/Al catalysts confirmed the superior activity of the Si-Al support. A double-peak product distribution occurred at C4–C6 and C10–C16 on all catalysts, which illustrates secondary hydrocracking and faster hydrocracking at the middle of the chain. The nonsulfided NiMo/Al and Pt/Al catalysts, and NiMo/Si-Al catalyst produced predominantly diesel (sel. 50–70%) and gasoline range (sel. > 50%) hydrocarbons, respectively, accompanied by some CH4 and light hydrocarbons C2–C4. On the other hand, the hydrocarbon distribution of the Pt/Si-Al varied with conditions (i.e., diesel sel. 87–90% below 290 °C or gasoline sel. 60–70% above 290 °C accompanied by little CH4) The dependence of the isomer/paraffin ratio on chain length was studied as well. The peak iso/paraffin value was observed at C10–C13 for the SiAl catalyst.

Highlights

  • Hydrocracking is a key process in petroleum refining for the conversion of heavy hydrocarbons into a variety of high-value fuels such as gasoline (C5–C11), jet fuel (C8–C16), and middle distillates (C10–C20)

  • For the hydroconversion of hydrocarbons, the reaction mechanism occurring on metal/acid catalysts is the subject of debate, even though numerous related studies have been performed

  • The actual surface areas of the NiMo and Pt catalysts are lower than the estimated values (310–390 m2/g or 148 m2/g) assuming that the support was the only contributor to the surface area

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Summary

Introduction

Hydrocracking is a key process in petroleum refining for the conversion of heavy hydrocarbons into a variety of high-value fuels such as gasoline (C5–C11), jet fuel (C8–C16), and middle distillates (C10–C20). For the hydroconversion of hydrocarbons, the reaction mechanism occurring on metal/acid catalysts is the subject of debate, even though numerous related studies have been performed. For the purpose of comparison, the NiMo/Al catalyst showing poor activity under H2 and H2S activation, a different NiMo/Si-Al catalyst showing very high activity under normal H2 activation are investigated; (2) to establish the relationship between iso-paraffin content versus chain length on the Al2O3 and Si-Al supported NiMo and Pt catalysts; and (3) to shed light on the reaction mechanism occurring on various Pt and NiMo catalysts

Material and Catalyst Preparation
BET Measurement
FTIR Pyridine Adsorption
Results
40 H2 38040
Isoparaffin Content versus Carbon Number
Mechanistic Considerations
Full Text
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