- Title
- Molecularly imprinted polymeric materials for adsorptive removal of nitrogen compounds from fuel oils
- Creator
- Abdul-Quadir, Muhammad Sabiu
- Subject
- Polymerization
- Subject
- Organonitrogen compounds Nitrogen compounds
- Date Issued
- 2018
- Date
- 2018
- Type
- Thesis
- Type
- Doctoral
- Type
- DPhil
- Identifier
- http://hdl.handle.net/10948/23426
- Identifier
- vital:30542
- Description
- The deleterious effects of refractory polyaromatic hydrocarbons found in fuels such as organonitrogen compounds (quinoline, carbazole and its alkylated derivatives) are such that they emit NOx to the environment when combusted, thereby reducing air quality. These compounds also deactivate the catalyst used during fuel refinement and in catalytic converters of cars. Hydro-denitrogenation (HDN), a process currently being employed in petroleum refineries to eliminate organonitrogen compounds in fuels, is limited in treating these refractory compounds. Hence, this thesis describes the use of two separate complimentary approaches for the removal of organonitrogen compounds in fuel such as oxidative denitrogenation and adsorptive denitrogenation. The catalyzed oxidation of fuel oil model nitrogen containing compound, quinoline to quinoline N-oxide, was conducted under batch and continuous flow microreactor at 70°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant and silica supported V2O5 as catalyst, followed by the selective adsorption of the quinoline N-oxide. An overall conversion of 62% quinoline N-oxide was observed. Quinoline-N-oxide in model fuel was absorbed by employing synthesized molecularly imprinted 2,6-pyridine-polybenzimidazole (2,6-PyPBI) nanofibers, 86% of quinoline-N-oxide was removed to give an adsorption capacity (qe) of 4.8 mg/g. DFT calculations to study the interactions of quinoline-N-oxide vs 2,6-PyPBI indicated that: (i) hydrogen bonding (through amino group of 2,6-PyPBI and oxygen atoms of the quinoline-N-oxide), (ii) pi-pi stacking and (iii) extensive number of van der Waals interactions took place. Several oxygenates from N-compounds were produced, thus, complicating the fuel matrix. Therefore, there is a need to move towards adsorptive denitrogenation. Poly-2-(1H-imidazol-2-yl)-4-phenol (PIMH) imprinted microspheres was prepared by suspension polymerization using 2-(2’-hydroxy-4-ethenylphenyl) imidazole as a functional monomer and ethylene glycol dimethacrylate as a crosslinker in the presence of various organonitrogen compounds (templates) to produce 2-(2’-hydroxy-4-ethenylphenyl) imidazole (PIMH). Imprinted microspheres show selectivity for various target model nitrogen-containing compounds with adsorption capacities of 6.8 ± 0.2 mg/g, 6.3 ± 0.3 mg/g and 5.8 ± 0.3 mg/g for quinoline, pyrimidine and carbazole, respectively. Adsorption selectivity increased in the order of quinoline (αi-r = 136.9) ˃ pyrimidine (αi-r = 126.2) ˃carbazole (αi-r = 86.3), when naphthalene was selected as a reference compound. Though, imprinted microspheres displayed excellent nitrogen compound removal both in model and real fuel, there was a need to improve the adsorbent adsorption capacity for N-compounds in fuel through the fabrication of imprinted nanofibers. Molecularly imprinted poly-2-(1H-imidazol-2-yl)-4-phenol nanofibers was prepared by electrospinning of 2-(2’-hydroxy-4-ethenylphenyl) imidazole (PIMH) in the presence of various organonitrogen compounds. These imprinted nanofibers show selectivity for various target model nitrogen-containing compounds with adsorption capacities of 11.7 ± 0.9 mg/g, 11.9 ± 0.8 mg/g and 11.3 ± 1.1 mg/g for quinoline, pyrimidine and carbazole, respectively. Adsorption selectivity increased in the order of pyrimidine (αi-r = 258.8) ˃ quinoline (αi-r = 235.5) ˃ carbazole (αi-r = 168.2). It further displayed excellent nitrogen removal in real fuel. The use of polybenzimidazole (PBI) nanofibers showed selective adsorption of organonitrogen compounds as imprinted sorbent also displayed high selectivity for their target model nitrogen-containing compounds with adsorption capacities of 11.4 ± 0.4 mg/g, 11.9 ± 0.2 mg/g and 10.9 ± 0.7 mg/g for quinoline, pyrimidine and carbazole respectively. Adsorption selectivity increased in the order of pyrimidine (αi-r = 241.5) ˃ quinoline (αi-r = 237.6) ˃ carbazole (αi-r = 170). Thermodynamic parameters obtained from isothermal titration calorimetry (ITC) revealed that quinoline-PIMH/PBI and pyrimidine-PIMH/PBI interactions are exothermic in nature, while carbazole-PIMH/PBI is endothermic in nature. DFT calculations indicated that π-π interactions/stacking and hydrogen bond interactions took place between N-compounds (carbazole, quinoline and pyrimidine) and adsorbent (PIMH and PBI). A significant reduction in the quantity of nitrogen containing compounds in hydrotreated fuel was observed (peak area reduction) when adsorbents (PIMH and PBI) was employed, however, the complex nature of organonitrogen compounds in fuel complicate the structure/function approach on MIPs for targeting these unwanted compounds.
- Format
- xxiii, 239 leaves
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
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