Sulfur Promotion in Conjugated Isomerization of Safflower Oil over Bifunctional Structured Rh/SBA‐15 Catalysts

Abstract

The sulfur effect on conjugated linoleic acid isomer (CLA) formation during the combined hydrogenation/directed isomerization of safflower oil over a bifunctional (hydrogenation and isomerization) highly structured rhodium‐based catalyst (Rh/SBA‐15) was investigated either by direct addition of increased concentrations of 3‐mercapto‐1,2‐propanediol to the reaction medium or by doping Rh/SBA‐15 with the same sulfur‐based compound yielding the sulfur‐doped Rh‐catalyst (S–Rh/SBA‐15). These catalysts exhibited interesting activity, stability, and recyclability. The maximum CLA contents obtained during the combined reactions with 0, 0.2, 1, 2, 5, and 10 ppm sulfur additions were 73, 99, 131, 110, 105, and 68 mgCLA goil−1, respectively, whereas the amount of harmful trans monoenes remained below 8 %. The safflower oil after partially hydrogenation under the same conditions over S–Rh/SBA‐15 catalyst contained up to 110 mgCLA goil−1. These results showed clear evidence of the sulfur promotion effect on CLA formation during the dual hydrogenation/directed isomerization of safflower oil. A mechanism for the sulfur promotion of the heterogeneous catalyst Rh/SBA‐15 for the conjugated isomerization activity during hydrogenation/directed isomerization of safflower oil was determined by solid‐state 1H NMR analysis of the fresh and spent catalysts. This was also confirmed by liquid‐state 2H NMR analysis of deuterium‐labeled product aliquots withdrawn throughout the reaction. The sulfur promotion towards the double bond conjugation of linoleic acid to form CLA isomers could be explained mechanistically through the preferable formation of the more nucleophilic rhodium sulfide (RhSH) over that of the hydride (RhH). However, both types of Rh clusters constituted distinct catalytic sites leading to the formation of hydrogenation as well as conjugated and geometric isomerization products. The lumped kinetics model described the experimental data well and complied simply with the proposed mechanism.

Hydroprocessing Catalysts Containing Noble Metals: Deactivation, Regeneration, Metals Reclamation, and Environment and Safety

“…Effect of trace amounts of sulfur (less than 10 ppm) on HPR reactions have been rarely investigated. In this regard, the study published by Chorfa et al is one of its kind. Thus, in the range of 0–10 ppm, sulfur promoted the isomerization of linoleic acid to conjugated isomer.…”

Supercritical CO2‐assisted Ru‐Pd/USY synchronised isomerisation to produce rice bran oil rich in conjugated linoleic acid

“…The metal‐catalysed isomerisation of LA was actually a competition between conjugation and hydrogenation. The difference between the two was that conjugation was a reversible reaction, while hydrogenation was an irreversible continuous reaction (Chorfa et al ., 2013). The content of CLA in the refined oil produced by the conjugation reaction under supercritical conditions was 30.22%, of which the content of c9, t11‐CLA was 12.76%, and the content of 10t, 12c‐CLA was 18.35%.…”

Catalytic Hydrogenation of Derived Vegetable Oils Using Ion-Exchange Resin-Supported Ruthenium Nanoparticles: Scope and Limitations

“…10−12 For non-noble-metal-based hydrogenation catalysts, nickel and copper appear to be good candidates. 13−17 Supported catalysts containing noble metals, for example, rhodium, 18 palladium, 19−21 ruthenium, 22−24 and platinum 25,26 have also been investigated. According to our literature survey, the reaction conditions with supported metal catalysts are generally harsh in terms of temperature.…”

“…Vegetable oil-derived compounds such as castor oil-based ricinoleic acid (12-hydroxy-9-octadecenoic acid) have been considered to be an important alternative to diesel fuel. − Methyl undecenoate, which comes from methyl ricinoleate pyrolysis, is also an interesting substrate because its carbon chain length is suitable for jet fuels . The CC hydrogenation of oleochemicals, one of the most encountered chemical transformations for these compounds, involves metal heterogeneous catalysts in most of the cases. − For non-noble-metal-based hydrogenation catalysts, nickel and copper appear to be good candidates. − Supported catalysts containing noble metals, for example, rhodium, palladium, − ruthenium, − and platinum , have also been investigated. According to our literature survey, the reaction conditions with supported metal catalysts are generally harsh in terms of temperature.…”