Hydrocracking Kinetics of a Heavy Crude Oil on a Liquid Catalyst

Abstract

Heavy crude oil hydrocracking was carried out in a continuous reactor using a liquid acid catalyst. Experiments were conducted at 100 kg/cm2 pressure, a low to moderate reaction temperature (350 and 370 °C), and a hydrogen/hydrocarbon ratio of 10 m3/barrel for 180 h. The reaction temperature was below typical industrial hydrocracking reactors to avoid coke or sediment formation. Experimental results demonstrated that heavy oil was importantly upgraded, hydrocracked oil was less viscous, lighter, and with a higher content of valuable distillates than the original heavy crude oil. Kinetics of the process based on a five lump reaction scheme was determined using a modified Marquard–Levenberg optimization technique. The experimental and calculated yield comparison for each of the lumps is in close agreement.

Using Separate Kinetic Models to Predict Liquid, Gas, and Coke Yields in Heavy Oil Hydrocracking

“…This liquid composition can be used to generate kinetic models based on lumping approach. The literature reports some lumping kinetic models for heavy oil hydrocracking that have been reviewed elsewhere. − All of the literature kinetic models were obtained with experimental data at severe operating conditions using nonmineral catalyst, which include various liquid lumps and gases and coke produced by several reaction pathways from the liquid fractions.…”

A Review of Thermal Cracking, Hydrocracking, and Slurry Phase Hydroconversion Kinetic Parameters in Lumped Models for Upgrading Heavy Oils

“…Specific gravity is a good measure of how heavy a petroleum liquid is, with a value of >1 defining an extra heavy oil. Figure concerns the residue feedstocks used in the kinetic models considered here. ,,− It gives the frequency distribution for feedstock specific gravity for the three types of process studied. The widest range of feedstocks has been used to research thermal cracking while the heaviest liquids were used in studies into slurry phase hydroconversion.…”

“…Above 430 °C, cracking reaction rates become faster than hydrogenation, leading to more coke deposition on the catalyst, fouling in the reactor and sintering of the active phase of the catalyst. Slurry-phase hydrotreatment tests ,,,− ,,, have used conditions very similar to those for hydrocracking with slightly wider temperature (320–460 °C) and lower pressure (2.8–16 MPa) ranges.…”

“…In contrast to hydrocracking kinetic studies, batch systems were preferred for investigation of slurry phase hydroconversion. However, Loria et al used an upflow tubular continuous reactor and some authors used semibatch reactors ,, or, more recently, CSTRs. ,, Studies with AR and VR feedstocks ,,,,,,,, were performed under severe operating conditions with a temperature range of 380–460 °C and hydrogen pressures of 7–16 MPa. Kinetic experiments were performed with an oil-soluble Mo precursor, such as octoate or naphthenate, and Song et al used an ammonium phosphomolybdate (APM) catalyst.…”

“…Kinetic experiments were performed with an oil-soluble Mo precursor, such as octoate or naphthenate, and Song et al used an ammonium phosphomolybdate (APM) catalyst. Other kinetic studies were directed toward application of dispersed catalysts to reservoir fluids, i.e., crude or bitumen feedstocks. ,− ,, These were performed under more moderate operating conditions with a temperature range of 310–400 °C and hydrogen pressure of 2.7–10 MPa and were performed with an aqueous solution of Ni, W, and Mo. The work of Huang et al is the exception, where the conditions usually used for upgrading residues were applied to an Iranian heavy crude.…”