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Petroleum Processing

Hydrotreatment

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Hydrotreatment

As a natural substance, crude oil contains heteroatom (S, N, and O) compounds as well as metals (mainly Ni and V) in addition to hydrocarbons. The sulfur content of crude oils normally ranges from 0.05 to 6 wt %, nitrogen content varies from 0.1 to 1 wt %, oxygen from 0.1 to 2.0 wt %, and metals from 10 to 1000 ppm. Once crude is fractionated by distillation, the heteroatoms (particularly S, N, and metal compounds) are distributed in the products. Heteroatom compounds are mainly associated with the higher boiling fractions and the residues that are rich in aromatic compounds. The presence of heteroatom compounds in petroleum products is undesirable because they reduce fuel stability, contribute to the emission of pollutants, and damage engines. Heteroatom compounds in refinery streams (e.g., basic nitrogen compounds, sulfur compounds, and metals) can deactivate catalysts and promote coke formation [2].

Hydrogenation of unsaturated hydrocarbons for stabilization. reaction shows a double bond becoming a single bond
Figure 9.1. Hydrogenation of unsaturated hydrocarbons for stabilization.
Source: Dr. Semih Eser

The light products such as LPG and naphthas have low concentrations of sulfur and require minimal treatment, such as absorption in alkaline solvents (e.g., H2S or mercaptan sulfur) or conversion of mercaptans to sulfides to eliminate odor. For example, the UOP MeroxTM process is widely used to remove H2S and mercaptan sulfur (Merox extraction) or to convert mercaptan sulfur to less-objectionable disulfides (Merox sweetening) [2]. The Merox process can be used to treat liquids such as LPG, naphtha, and kerosene. Removing sulfur from higher molecular weight and more complex molecules requires hydrotreatment processes that use hydrogen.


[2] S. Eser and M. R. Riazi, “Crude Oil Refining Processes” In Petroleum Refining and Natural Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, ASTM International, West Conshohocken, PA, 2013, p. 119.