KINETIC REGULARITIES OF CATALYTIC OXIDATION OF SULPHIDES CONTAINED IN OIL BY HYDROGEN PEROXIDE
Rubrics: 2. CHEMICAL TECHNOLOGY
Authors:
1.
Kazan National Research Technological University (KNRTU),
2.
Kazan National Research Technological University (KNRTU)
(Department of General Chemical Technology)
Russian Federation
Russian Federation
3.
KNITU
4.
Kazanskiy nacional'nyy issledovatel'skiy tehnologicheskiy universitet
5.
Kazan National Research Technological University
Russian Federation
Russian Federation
Type:
Article
Pages:
from 89
to 95
Status:
In work
Language:
Russian
Keywords:
SULFIDES, SULFOXIDES, PEROXIDE OXIDATION, KINETICS, PROPYLENE EPOXIDATION, ALKALINE WASTE, MOLYBDENUM TRISULFIDE, MOLYBDENUM (VI) OXIDE
Abstract (English):
The kinetic patterns of oxidation of sulfides contained in oil to sulfoxides by hydrogen peroxide in a heterophase system (liquid-liquid) in the presence of glacial acetic acid and molybdenum (VI) peroxo complexes have been studied. The straight-run diesel fraction (220-350°C) of high-viscosity bituminous oil with a total sulfur and sulfide sulfur content of 2,75 and 1,14 wt. %, respectively was used as raw material. Molybdenum catalysts were synthesized based on molybdenum trisulfide MoS3 and molybdenum oxide MoO3. The original molybdenum compounds were substances of reagent A.C.S. purity and compounds obtained by processing molybdenum-containing residues of the propylene oxide and styrene joint production process by PSC «Nizhnekamskneftekhim». It has been determined that the catalytic oxidation rate of sulfides in the presence of molybdenum compounds significantly exceeds the oxidation rate in the presence of glacial acetic acid (5-6 times at a temperature of 60°C). Observed activation energies calculated from the initial rates of consumption of sulfide sulfur (23 kJ/mol) and accumulation of sulfoxide sulfur (25 kJ/mol) are comparable with the value calculated from the temperature dependence of the effective accumulation rate constant of sulfoxides (19 kJ/mol), what was shown by using the example of sulfide oxidation in the presence of glacial acetic acid. The ratio of the initial rates of sulfide consumption and sulfoxide sulfur accumulation in the presence of molybdenum catalysts correlates with the target product yield at the end of the experiment (reagent conversion ~ 80 %), what has been established. The most effective catalyst, providing high speed and selectivity for the oxidation of sulfide sulfur to sulfoxide sulfur with hydrogen peroxide, is a molybdenum peroxo complex obtained on the basis of molybdenum sulfide, which was separated from propylene oxide and styrene joint production waste.
The kinetic patterns of oxidation of sulfides contained in oil to sulfoxides by hydrogen peroxide in a heterophase system (liquid-liquid) in the presence of glacial acetic acid and molybdenum (VI) peroxo complexes have been studied. The straight-run diesel fraction (220-350°C) of high-viscosity bituminous oil with a total sulfur and sulfide sulfur content of 2,75 and 1,14 wt. %, respectively was used as raw material. Molybdenum catalysts were synthesized based on molybdenum trisulfide MoS3 and molybdenum oxide MoO3. The original molybdenum compounds were substances of reagent A.C.S. purity and compounds obtained by processing molybdenum-containing residues of the propylene oxide and styrene joint production process by PSC «Nizhnekamskneftekhim». It has been determined that the catalytic oxidation rate of sulfides in the presence of molybdenum compounds significantly exceeds the oxidation rate in the presence of glacial acetic acid (5-6 times at a temperature of 60°C). Observed activation energies calculated from the initial rates of consumption of sulfide sulfur (23 kJ/mol) and accumulation of sulfoxide sulfur (25 kJ/mol) are comparable with the value calculated from the temperature dependence of the effective accumulation rate constant of sulfoxides (19 kJ/mol), what was shown by using the example of sulfide oxidation in the presence of glacial acetic acid. The ratio of the initial rates of sulfide consumption and sulfoxide sulfur accumulation in the presence of molybdenum catalysts correlates with the target product yield at the end of the experiment (reagent conversion ~ 80 %), what has been established. The most effective catalyst, providing high speed and selectivity for the oxidation of sulfide sulfur to sulfoxide sulfur with hydrogen peroxide, is a molybdenum peroxo complex obtained on the basis of molybdenum sulfide, which was separated from propylene oxide and styrene joint production waste.
Keywords:
SULFIDES, SULFOXIDES, PEROXIDE OXIDATION, KINETICS, PROPYLENE EPOXIDATION, ALKALINE WASTE, MOLYBDENUM TRISULFIDE, MOLYBDENUM (VI) OXIDE
SULFIDES, SULFOXIDES, PEROXIDE OXIDATION, KINETICS, PROPYLENE EPOXIDATION, ALKALINE WASTE, MOLYBDENUM TRISULFIDE, MOLYBDENUM (VI) OXIDE
