Immobilization of catalyst in a wall-coated micro-structured reactor for gas/liquid oxidation of p-cymene
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
The oxidative coupling of phenols using stoichiometric metal oxidants
- Authors: Hoffmann, Eric
- Date: 2005
- Subjects: Phenols , Oxidation , Stoichiometry
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10977 , http://hdl.handle.net/10948/180 , Phenols , Oxidation , Stoichiometry
- Description: The oxidative coupling of 2,6-di-t-butylphenol under mild reaction conditions is well documented and the subject of many patents. However, the coupling of other monoand di- substituted phenols is not as well documented and thus there is scope for further investigation for providing a convenient, environmentally friendly and economically viable method for the oxidative coupling of these phenols. In this study, the oxidative coupling of a variety of alkylated phenolic substrates, 2-tbutylphenol, 2,6-di-t-butylphenol, 2,4 -di-t-butylphenol and ,4-dimethylphenol, using a range of different oxidizing agents, were investigated by means of experimental and/or theoretical means. The dibutylated aromatics provided the highest selectivities to their respective coupled products, with results obtained with the dimethyl analogue being only satisfactory, and that for 2 -t-butylphenol being totally inefficient. PM3 Molecular orbital (MO) calculations were used to predict the possible modes of coupling for the substrates 2,6 -di-t-butylphenol and 2,4-di-t-butylphenol, and these results were then compared with those obtained experimentally in the laboratory. Preliminarily, the coupling of unsubstituted phenolics was also assessed by means of MO calculations. Much emphasis was placed on Ce(IV) as the oxidant, and the reaction conditions under which it was used and the results that were obtained have not been reported before and are therefore novel. The oxidation of 2,4-di-t-butylphenol using Ce(IV) in the presence of methanesulphonic acid was optimized to afford high yields and selectivities to the desired ortho C-ortho C coupled product under mild reaction conditions. Various reaction parameters were also investigated in this case, such as varying the MeSO3H concentration, the solvent, the reaction temperature, the reaction time, the substrate loading, the rate of oxidant addition and the substrate to oxidant ratio. Ce(IV) also gave a high selectivity to the para C-para C coupled product when IX using 2,6-di-t-butylphenol as the substrate. However, it was not as effective with 2,4- dimethylphenol, and even less so with 2-t-butylphenol. The oxidation reactions of 2-t-butylphenol and 2,4-dimethylphenol with various coupling agents were also investigated with the intention of obtaining high selectivities to the respective desired coupled products. In these studies, 2-t-butylphenol afforded a large number of products, irrespective of the oxidant used. The dimethyl analogue was more selective, but results were not optimal. It was clear that the number of substituents on the phenol ring, their nature and their position with regards to the hydroxyl moiety was of great importance and made a significant impact on the preferred coupling mode of the substrate. It was observed that steric effects also played a major role in the outcome of these reactions: 2,6-di-t-butylphenol never afforded any C-O coupled products whereas 2-t-butylphenol, 2,4-di-t-butylphenol and 2,4-dimethylphenol all appeared to undergo some C-O coupling. Finally, reaction mechanisms were provided for both the K3Fe(CN)6 and Ce(IV) work, these reacting in basic and acidic media, respectively. It was proposed that both of these mechanisms operate through the initial formation of the phenoxyl radical.
- Full Text:
- Date Issued: 2005
- Authors: Hoffmann, Eric
- Date: 2005
- Subjects: Phenols , Oxidation , Stoichiometry
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10977 , http://hdl.handle.net/10948/180 , Phenols , Oxidation , Stoichiometry
- Description: The oxidative coupling of 2,6-di-t-butylphenol under mild reaction conditions is well documented and the subject of many patents. However, the coupling of other monoand di- substituted phenols is not as well documented and thus there is scope for further investigation for providing a convenient, environmentally friendly and economically viable method for the oxidative coupling of these phenols. In this study, the oxidative coupling of a variety of alkylated phenolic substrates, 2-tbutylphenol, 2,6-di-t-butylphenol, 2,4 -di-t-butylphenol and ,4-dimethylphenol, using a range of different oxidizing agents, were investigated by means of experimental and/or theoretical means. The dibutylated aromatics provided the highest selectivities to their respective coupled products, with results obtained with the dimethyl analogue being only satisfactory, and that for 2 -t-butylphenol being totally inefficient. PM3 Molecular orbital (MO) calculations were used to predict the possible modes of coupling for the substrates 2,6 -di-t-butylphenol and 2,4-di-t-butylphenol, and these results were then compared with those obtained experimentally in the laboratory. Preliminarily, the coupling of unsubstituted phenolics was also assessed by means of MO calculations. Much emphasis was placed on Ce(IV) as the oxidant, and the reaction conditions under which it was used and the results that were obtained have not been reported before and are therefore novel. The oxidation of 2,4-di-t-butylphenol using Ce(IV) in the presence of methanesulphonic acid was optimized to afford high yields and selectivities to the desired ortho C-ortho C coupled product under mild reaction conditions. Various reaction parameters were also investigated in this case, such as varying the MeSO3H concentration, the solvent, the reaction temperature, the reaction time, the substrate loading, the rate of oxidant addition and the substrate to oxidant ratio. Ce(IV) also gave a high selectivity to the para C-para C coupled product when IX using 2,6-di-t-butylphenol as the substrate. However, it was not as effective with 2,4- dimethylphenol, and even less so with 2-t-butylphenol. The oxidation reactions of 2-t-butylphenol and 2,4-dimethylphenol with various coupling agents were also investigated with the intention of obtaining high selectivities to the respective desired coupled products. In these studies, 2-t-butylphenol afforded a large number of products, irrespective of the oxidant used. The dimethyl analogue was more selective, but results were not optimal. It was clear that the number of substituents on the phenol ring, their nature and their position with regards to the hydroxyl moiety was of great importance and made a significant impact on the preferred coupling mode of the substrate. It was observed that steric effects also played a major role in the outcome of these reactions: 2,6-di-t-butylphenol never afforded any C-O coupled products whereas 2-t-butylphenol, 2,4-di-t-butylphenol and 2,4-dimethylphenol all appeared to undergo some C-O coupling. Finally, reaction mechanisms were provided for both the K3Fe(CN)6 and Ce(IV) work, these reacting in basic and acidic media, respectively. It was proposed that both of these mechanisms operate through the initial formation of the phenoxyl radical.
- Full Text:
- Date Issued: 2005
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