Vanadium-based catalysts for oxidation of organosulfur compounds: synthesis, catalysis and mechanistic studies
- Dembaremba, Tendai, Ogunlaja, Adeniyi
- Authors: Dembaremba, Tendai , Ogunlaja, Adeniyi
- Date: 2018
- Subjects: Organosulfur compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/30248 , vital:30909
- Description: A series of oxidovanadium(IV) complexes based on the ligand, 2-(2’-hydroxyphenyl)imidazole, with substituent groups of different electronegativities on the phenolic para position, were successfully synthesized, characterized and investigated for their catalytic activities in the oxidation of dibenzothiophene (DBT), a typical refractory sulfur compound found in fuel. It was observed from catalytic oxidation studies that the presence of an electron withdrawing group on the phenolic para position of the ligand results in higher catalytic activity. SC-XRD data and DFT studies were used to explain the trends in activity observed. The highest activity was observed with 6.5 nmol of the nitro derivative catalyst [VO(PIMNO2)2] when 100% of 100 mg (0.543 mmol) of DBT was converted to its sulfone derivative dibenzothiophene sulfoxide (DBTO2) using 2.0 mL (1.05 mmol) of t-BuOOH. Potential to immobilize the complex catalysts was demonstrated through the synthesis of oxidovanadium(IV) copolymer nanofibers. The oxidovanadium nanofibers were successfully employed in the oxidation of sulfur compounds in a real fuel sample (diesel 500) which were then removed through solvent extraction using acetonitrile to give clean fuel. SC-XRD, EPR and UV-Vis spectroscopy were instrumental in providing insight into the mechanism of the catalyzed reaction. Vanadium oxides were also investigated as a cheaper alternative for the catalytic oxidation reaction. Phases of different vanadium oxides were synthesized by calcining NH4VO3 in air at different temperatures with an intention to investigate them for their catalytic activities. The catalyst obtained from calcination at 600⁰C was predominantly the orthorhombic phase of V2O5. Potential to immobilize the vanadium oxides was demonstrated using a silica support where NH4VO3 was impregnated onto silica and calcined in air at 600⁰C. The catalyst showed good potential in the oxidation of DBT to DBTO2, with 10 mg (43.9 μmol) of catalyst successfully converting 100% of 100 mg (0.543 mmol) DBT to DBTO2 using 2.0 mL (1.05 mmol) of t-BuOOH. The catalyst was also employed for a real fuel sample (diesel 500) with good results. The mechanistic aspects of vanadium oxides were also investigated in this study.
- Full Text:
- Date Issued: 2018
- Authors: Dembaremba, Tendai , Ogunlaja, Adeniyi
- Date: 2018
- Subjects: Organosulfur compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/30248 , vital:30909
- Description: A series of oxidovanadium(IV) complexes based on the ligand, 2-(2’-hydroxyphenyl)imidazole, with substituent groups of different electronegativities on the phenolic para position, were successfully synthesized, characterized and investigated for their catalytic activities in the oxidation of dibenzothiophene (DBT), a typical refractory sulfur compound found in fuel. It was observed from catalytic oxidation studies that the presence of an electron withdrawing group on the phenolic para position of the ligand results in higher catalytic activity. SC-XRD data and DFT studies were used to explain the trends in activity observed. The highest activity was observed with 6.5 nmol of the nitro derivative catalyst [VO(PIMNO2)2] when 100% of 100 mg (0.543 mmol) of DBT was converted to its sulfone derivative dibenzothiophene sulfoxide (DBTO2) using 2.0 mL (1.05 mmol) of t-BuOOH. Potential to immobilize the complex catalysts was demonstrated through the synthesis of oxidovanadium(IV) copolymer nanofibers. The oxidovanadium nanofibers were successfully employed in the oxidation of sulfur compounds in a real fuel sample (diesel 500) which were then removed through solvent extraction using acetonitrile to give clean fuel. SC-XRD, EPR and UV-Vis spectroscopy were instrumental in providing insight into the mechanism of the catalyzed reaction. Vanadium oxides were also investigated as a cheaper alternative for the catalytic oxidation reaction. Phases of different vanadium oxides were synthesized by calcining NH4VO3 in air at different temperatures with an intention to investigate them for their catalytic activities. The catalyst obtained from calcination at 600⁰C was predominantly the orthorhombic phase of V2O5. Potential to immobilize the vanadium oxides was demonstrated using a silica support where NH4VO3 was impregnated onto silica and calcined in air at 600⁰C. The catalyst showed good potential in the oxidation of DBT to DBTO2, with 10 mg (43.9 μmol) of catalyst successfully converting 100% of 100 mg (0.543 mmol) DBT to DBTO2 using 2.0 mL (1.05 mmol) of t-BuOOH. The catalyst was also employed for a real fuel sample (diesel 500) with good results. The mechanistic aspects of vanadium oxides were also investigated in this study.
- Full Text:
- Date Issued: 2018
Oxidative desulfurization of fuel oils-catalytic oxidation and adsorptive removal of organosulfur compounds
- Authors: Ogunlaja, Adeniyi Sunday
- Date: 2014
- Subjects: Organosulfur compounds , Organosulfur compounds -- Oxidation , Organosulfur compounds -- Absorption and adsorption , Petroleum as fuel , Catalysis , Imprinted polymers , Molecular imprinting , Nanofibers , Electrospinning
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4498 , http://hdl.handle.net/10962/d1013152
- Description: The syntheses and evaluation of oxidovanadium(IV) complexes as catalysts for the oxidation of refractory organosulfur compounds in fuels is presented. The sulfones produced from the oxidation reaction were removed from fuel oils by employing molecularly imprinted polymers (MIPs). The oxidovanadium(IV) homogeneous catalyst, [V ͥ ͮ O(sal-HBPD)], as well as its heterogeneous polymer supported derivatives, poly[V ͥ ͮ O(sal-AHBPD)] and poly[V ͥ ͮ O(allylSB-co-EGDMA)], were synthesized and fully characterized by elemental analysis, FTIR, UV-Vis, XPS, AFM, SEM, BET and single crystal XRD for [V ͥ ͮ O(sal-HBPD)]. The MIPs were also characterized by elemental analysis, FTIR, SEM, EDX and BET. The catalyzed oxidation of fuel oil model sulfur compounds, thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), was conducted under batch and continuous flow processes at 40°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant. The continuous flow oxidation process presented the highest overall conversions and very high selectivity for sulfones. Maximum oxidation conversions of 71%, 89%, 99% and 88% was achieved for TH, BT, DBT and 4,6-DMDBT respectively when poly[V ͥ ͮ O(allylSB-co-EGDMA)] was employed at a flow-rate of 1 mL/h with over 90% sulfone selectivity. The process was further applied to the oxidation of hydro-treated diesel containing 385 ± 4.6 ppm of sulfur (mainly dibenzothiophene and dibenzothiophene derivatives), and this resulted to a high sulfur oxidation yield (> 99%), thus producing polar sulfones which are extractible by polar solid phase extractants. Adsorption of the polar sulfone compounds was carried-out by employing MIPs which were fabricated through the formation of recognition sites complementary to oxidized sulfur-containing compounds (sulfones) on electrospun polybenzimidazole (PBI) nanofibers, cross-linked chitosan microspheres and electrospun chitosan nanofibers. Adsorption of benzothiophene sulfone (BTO₂), dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) on the various molecularly imprinted adsorbents presented a Freundlich (multi-layered) adsorption isotherm which indicated interaction of adsorbed organosulfur compounds. Maximum adsorption observed for BTO₂, DBTO₂ and 4,6-DMDBTO₂ respectively was 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g when imprinted chitosan nanofibers were employed, 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g on molecularly imprinted chitosan microspheres, and 28.5 ± 0.4 mg/g, 29.8 ± 2.2 mg/g and 20.1 ± 1.4 mg/g on molecularly imprinted PBI nanofibers. Application of electrospun chitosan nanofibers on oxidized hydro-treated diesel presented a sulfur removal capacity of 84%, leaving 62 ± 3.2 ppm S in the fuel, while imprinted PBI electrospun nanofibers displayed excellent sulfur removal, keeping sulfur in the fuel after the oxidation/adsorption below the determined limit of detection (LOD), which is 2.4 ppm S. The high level of sulfur removal displayed by imprinted PBI nanofibers was ascribed to hydrogen bonding effects, and π-π stacking between aromatic sulfone compounds and the benzimidazole ring which were confirmed by chemical modelling with density functional theory (DFT) as well as the imprinting effect. The home-made pressurized hot water extraction (PHWE) system was applied for extraction/desorption of sulfone compounds adsorbed on the PBI nanofibers at a flow rate of 1 mL/min and at 150°C with an applied pressure of 30 bars. Application of molecularly imprinted PBI nanofibers for the desulfurization of oxidized hydro-treated fuel showed potential for use in refining industries to reach ultra-low sulfur fuel level, which falls below the 10 ppm sulfur limit which is mandated by the environmental protection agency (EPA) from 2015.
- Full Text:
- Date Issued: 2014
- Authors: Ogunlaja, Adeniyi Sunday
- Date: 2014
- Subjects: Organosulfur compounds , Organosulfur compounds -- Oxidation , Organosulfur compounds -- Absorption and adsorption , Petroleum as fuel , Catalysis , Imprinted polymers , Molecular imprinting , Nanofibers , Electrospinning
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4498 , http://hdl.handle.net/10962/d1013152
- Description: The syntheses and evaluation of oxidovanadium(IV) complexes as catalysts for the oxidation of refractory organosulfur compounds in fuels is presented. The sulfones produced from the oxidation reaction were removed from fuel oils by employing molecularly imprinted polymers (MIPs). The oxidovanadium(IV) homogeneous catalyst, [V ͥ ͮ O(sal-HBPD)], as well as its heterogeneous polymer supported derivatives, poly[V ͥ ͮ O(sal-AHBPD)] and poly[V ͥ ͮ O(allylSB-co-EGDMA)], were synthesized and fully characterized by elemental analysis, FTIR, UV-Vis, XPS, AFM, SEM, BET and single crystal XRD for [V ͥ ͮ O(sal-HBPD)]. The MIPs were also characterized by elemental analysis, FTIR, SEM, EDX and BET. The catalyzed oxidation of fuel oil model sulfur compounds, thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), was conducted under batch and continuous flow processes at 40°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant. The continuous flow oxidation process presented the highest overall conversions and very high selectivity for sulfones. Maximum oxidation conversions of 71%, 89%, 99% and 88% was achieved for TH, BT, DBT and 4,6-DMDBT respectively when poly[V ͥ ͮ O(allylSB-co-EGDMA)] was employed at a flow-rate of 1 mL/h with over 90% sulfone selectivity. The process was further applied to the oxidation of hydro-treated diesel containing 385 ± 4.6 ppm of sulfur (mainly dibenzothiophene and dibenzothiophene derivatives), and this resulted to a high sulfur oxidation yield (> 99%), thus producing polar sulfones which are extractible by polar solid phase extractants. Adsorption of the polar sulfone compounds was carried-out by employing MIPs which were fabricated through the formation of recognition sites complementary to oxidized sulfur-containing compounds (sulfones) on electrospun polybenzimidazole (PBI) nanofibers, cross-linked chitosan microspheres and electrospun chitosan nanofibers. Adsorption of benzothiophene sulfone (BTO₂), dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) on the various molecularly imprinted adsorbents presented a Freundlich (multi-layered) adsorption isotherm which indicated interaction of adsorbed organosulfur compounds. Maximum adsorption observed for BTO₂, DBTO₂ and 4,6-DMDBTO₂ respectively was 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g when imprinted chitosan nanofibers were employed, 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g on molecularly imprinted chitosan microspheres, and 28.5 ± 0.4 mg/g, 29.8 ± 2.2 mg/g and 20.1 ± 1.4 mg/g on molecularly imprinted PBI nanofibers. Application of electrospun chitosan nanofibers on oxidized hydro-treated diesel presented a sulfur removal capacity of 84%, leaving 62 ± 3.2 ppm S in the fuel, while imprinted PBI electrospun nanofibers displayed excellent sulfur removal, keeping sulfur in the fuel after the oxidation/adsorption below the determined limit of detection (LOD), which is 2.4 ppm S. The high level of sulfur removal displayed by imprinted PBI nanofibers was ascribed to hydrogen bonding effects, and π-π stacking between aromatic sulfone compounds and the benzimidazole ring which were confirmed by chemical modelling with density functional theory (DFT) as well as the imprinting effect. The home-made pressurized hot water extraction (PHWE) system was applied for extraction/desorption of sulfone compounds adsorbed on the PBI nanofibers at a flow rate of 1 mL/min and at 150°C with an applied pressure of 30 bars. Application of molecularly imprinted PBI nanofibers for the desulfurization of oxidized hydro-treated fuel showed potential for use in refining industries to reach ultra-low sulfur fuel level, which falls below the 10 ppm sulfur limit which is mandated by the environmental protection agency (EPA) from 2015.
- Full Text:
- Date Issued: 2014
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