Desulphurisation of dibenzothiophene and 4,6 – dimethyl dibenzothio-phene via enhanced hydrogenation reaction route using RePd–TiO2/SiO2 aerogel catalysts: Kinetic parameters estimation and modelling
Desulfurizacija dibenzotiofena i 4,6 – dimetildibenzotiofena procesom hidrogenovanja uz korišćenje RePd–TiO2/SiO2 aerogel katalizatora: proračun kinetičkih parametara i simulacijaprocesa
Članak u časopisu (Objavljena verzija)
Metapodaci
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Re/Pd-TiO2/SiO2 aerogel catalysts were synthesized by using a sol-gel method and supercritical drying in excess solvent and investigated in the reaction of hydrodesulphurisation (HDS) of dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). Both Re/Pd catalysts, obtained with and without the use of mesitylene in the synthesis step, have shown increased conversions of up to 70 % in the desulphurization of 4,6-DMDBT, when compared to conventional Co/Mo hydroprocessing catalysts. This observation is of importance for conversion of highly refractory 4,6-DMDBT and hydroprocessing to produce ultra-low sulphur diesel fuels, ULSD. In order to quantify the extent of desulphurisation, which proceeds via a hydrogenation route, conversions of DBT and 4,6-DMDBT along with evolution of reaction products characteristic for the direct desulphurisation route and the hydrogenation route were monitored by using a gas chromatography–mass spectrometry (GC-MS) analytical technique. The react...ion was performed at 630 K and 6 MPa in a batch catalytic reactor. The experimental results were used in the Hougen-Watson kinetic model describing DBT and 4,6-DMDBT desulphurisation on σ and τ active sites. Kinetic parameters of this complex catalytic kinetics were determined by using a Genetic Algorithm method and minimum deviation function. Values of calculated kinetic parameters and values of the ratio of 3-methylcyclohexyltoluene (MCHT and dimethyl biphenyl (DMBPH) expressed as the MCHT/(MCHT+DMBPH) ratio ranging between 0.66 and 0.94, have confirmed that the hydrogenation route is the dominant route for desulphurisation of 4,6-DMDBT.
Ključne reči:
4,6-DMDBT / Aerogel hydrodesulphurisation catalysts / Hougen-Watson kinetic model / hydrodesulphurisation / kinetic and adsorption parametersIzvor:
Hemijska industrija, 2022, 76, 3, 135-145Izdavač:
- Association of the Chemical Engineers of Serbia
Finansiranje / projekti:
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200135 (Univerzitet u Beogradu, Tehnološko-metalurški fakultet) (RS-MESTD-inst-2020-200135)
Institucija/grupa
Tehnološko-metalurški fakultetTY - JOUR AU - Prokić-Vidojević, Dragana AU - Glišić, Sandra B. AU - Pešić, Radojica AU - Orlović, Aleksandar M. PY - 2022 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/5184 AB - Re/Pd-TiO2/SiO2 aerogel catalysts were synthesized by using a sol-gel method and supercritical drying in excess solvent and investigated in the reaction of hydrodesulphurisation (HDS) of dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). Both Re/Pd catalysts, obtained with and without the use of mesitylene in the synthesis step, have shown increased conversions of up to 70 % in the desulphurization of 4,6-DMDBT, when compared to conventional Co/Mo hydroprocessing catalysts. This observation is of importance for conversion of highly refractory 4,6-DMDBT and hydroprocessing to produce ultra-low sulphur diesel fuels, ULSD. In order to quantify the extent of desulphurisation, which proceeds via a hydrogenation route, conversions of DBT and 4,6-DMDBT along with evolution of reaction products characteristic for the direct desulphurisation route and the hydrogenation route were monitored by using a gas chromatography–mass spectrometry (GC-MS) analytical technique. The reaction was performed at 630 K and 6 MPa in a batch catalytic reactor. The experimental results were used in the Hougen-Watson kinetic model describing DBT and 4,6-DMDBT desulphurisation on σ and τ active sites. Kinetic parameters of this complex catalytic kinetics were determined by using a Genetic Algorithm method and minimum deviation function. Values of calculated kinetic parameters and values of the ratio of 3-methylcyclohexyltoluene (MCHT and dimethyl biphenyl (DMBPH) expressed as the MCHT/(MCHT+DMBPH) ratio ranging between 0.66 and 0.94, have confirmed that the hydrogenation route is the dominant route for desulphurisation of 4,6-DMDBT. PB - Association of the Chemical Engineers of Serbia T2 - Hemijska industrija T1 - Desulphurisation of dibenzothiophene and 4,6 – dimethyl dibenzothio-phene via enhanced hydrogenation reaction route using RePd–TiO2/SiO2 aerogel catalysts: Kinetic parameters estimation and modelling T1 - Desulfurizacija dibenzotiofena i 4,6 – dimetildibenzotiofena procesom hidrogenovanja uz korišćenje RePd–TiO2/SiO2 aerogel katalizatora: proračun kinetičkih parametara i simulacijaprocesa EP - 145 IS - 3 SP - 135 VL - 76 DO - 10.2298/HEMIND220114008P ER -
@article{ author = "Prokić-Vidojević, Dragana and Glišić, Sandra B. and Pešić, Radojica and Orlović, Aleksandar M.", year = "2022", abstract = "Re/Pd-TiO2/SiO2 aerogel catalysts were synthesized by using a sol-gel method and supercritical drying in excess solvent and investigated in the reaction of hydrodesulphurisation (HDS) of dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). Both Re/Pd catalysts, obtained with and without the use of mesitylene in the synthesis step, have shown increased conversions of up to 70 % in the desulphurization of 4,6-DMDBT, when compared to conventional Co/Mo hydroprocessing catalysts. This observation is of importance for conversion of highly refractory 4,6-DMDBT and hydroprocessing to produce ultra-low sulphur diesel fuels, ULSD. In order to quantify the extent of desulphurisation, which proceeds via a hydrogenation route, conversions of DBT and 4,6-DMDBT along with evolution of reaction products characteristic for the direct desulphurisation route and the hydrogenation route were monitored by using a gas chromatography–mass spectrometry (GC-MS) analytical technique. The reaction was performed at 630 K and 6 MPa in a batch catalytic reactor. The experimental results were used in the Hougen-Watson kinetic model describing DBT and 4,6-DMDBT desulphurisation on σ and τ active sites. Kinetic parameters of this complex catalytic kinetics were determined by using a Genetic Algorithm method and minimum deviation function. Values of calculated kinetic parameters and values of the ratio of 3-methylcyclohexyltoluene (MCHT and dimethyl biphenyl (DMBPH) expressed as the MCHT/(MCHT+DMBPH) ratio ranging between 0.66 and 0.94, have confirmed that the hydrogenation route is the dominant route for desulphurisation of 4,6-DMDBT.", publisher = "Association of the Chemical Engineers of Serbia", journal = "Hemijska industrija", title = "Desulphurisation of dibenzothiophene and 4,6 – dimethyl dibenzothio-phene via enhanced hydrogenation reaction route using RePd–TiO2/SiO2 aerogel catalysts: Kinetic parameters estimation and modelling, Desulfurizacija dibenzotiofena i 4,6 – dimetildibenzotiofena procesom hidrogenovanja uz korišćenje RePd–TiO2/SiO2 aerogel katalizatora: proračun kinetičkih parametara i simulacijaprocesa", pages = "145-135", number = "3", volume = "76", doi = "10.2298/HEMIND220114008P" }
Prokić-Vidojević, D., Glišić, S. B., Pešić, R.,& Orlović, A. M.. (2022). Desulphurisation of dibenzothiophene and 4,6 – dimethyl dibenzothio-phene via enhanced hydrogenation reaction route using RePd–TiO2/SiO2 aerogel catalysts: Kinetic parameters estimation and modelling. in Hemijska industrija Association of the Chemical Engineers of Serbia., 76(3), 135-145. https://doi.org/10.2298/HEMIND220114008P
Prokić-Vidojević D, Glišić SB, Pešić R, Orlović AM. Desulphurisation of dibenzothiophene and 4,6 – dimethyl dibenzothio-phene via enhanced hydrogenation reaction route using RePd–TiO2/SiO2 aerogel catalysts: Kinetic parameters estimation and modelling. in Hemijska industrija. 2022;76(3):135-145. doi:10.2298/HEMIND220114008P .
Prokić-Vidojević, Dragana, Glišić, Sandra B., Pešić, Radojica, Orlović, Aleksandar M., "Desulphurisation of dibenzothiophene and 4,6 – dimethyl dibenzothio-phene via enhanced hydrogenation reaction route using RePd–TiO2/SiO2 aerogel catalysts: Kinetic parameters estimation and modelling" in Hemijska industrija, 76, no. 3 (2022):135-145, https://doi.org/10.2298/HEMIND220114008P . .