Vapour phase dehydrogenation of cyclohexane on microstructured reactors
- Authors: Mpuhlu, Batsho
- Date: 2012
- Subjects: Dehydrogenation , Cyclohexane
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: http://hdl.handle.net/10948/8661 , vital:26418
- Description: The work that is described in this thesis forms part of the research and development projects at InnoVenton: NMMU Institute of Chemical Technology in collaboration with Sasol Technologies. The broader view of the project was testing on the so-called “Small Production Platforms” (SPP’s). In particular the main aim of this study was to investigate the effect of micro-structuring on the heterogeneous catalysed, vapour-phase oxidative dehydrogenation of cyclohexane in the presence of air. Ground work studies were done to provide a proper comparison of the micro-structured reactor with a traditional fixed-bed reactor. These included evaluation of a proper vanadium pyrophosphate catalyst for the reaction, testing of reaction parameters for the oxidative dehydrogenation reaction on a fixed-bed reactor and lastly comparing the performance of the micro-structured reactor to that of the fixed-bed reactor Various vanadium pyrophosphate catalysts that were tested for activity included: bulk (VO)2P2O7, bulk (VO)2P2O7 promoted with Fe, (VO)2P2O7 supported on -Al2O3 and Fe promoted (VO)2P2O7 supported on -Al2O3. These catalysts showed significant differences in TOF, however it was not conclusive from the results whether these differences may be traced to increased activity for dehydrogenation for different catalysts since all reactions were run under conditions of oxygen deficiency. It is, however, clear that Fe promotion significantly increase activity, irrespective of the relative degrees of oxidative dehydrogenation and normal dehydrogenation. The Fe promoted catalyst was further tested for long term stability in-view of using it as the catalyst in the micro-structured reactor. These studies showed the catalyst to have a high degree of stability with minimal structural changes under the reaction conditions used. Various response surface models describing the variation in each of the cyclohexane conversion, cyclohexene selectivity, and benzene selectivity, respectively when changing reaction condition, were derived by means of multiple regression. To obtain some idea of the degree and nature of the normal dehydrogenation reaction, the amount of deficit oxygen was estimated from the measured results for cyclohexane conversion and cyclohexene and benzene selectivities. These estimated values were also modelled as described above. The regression models were used to interpret specific trends in the responses for the oxidative dehydrogenation of cyclohexane and account for the oxygen deficit in the system. The performance of a fixed bed tubular reactor (FBR) and micro-structured sandwich reactor (MSSR) were compared over an Fe promoted vanadium pyrophosphate. Reactor performance was evaluated by varying specific reaction conditions (temperature and space velocity). Subsequently the turn-over frequencies, conversion and selectivities from the two reactors were compared. The conversion achieved in the micro-structured reactor was observed to be significantly higher than that achieved in the fixed-bed reactor at all reaction parameters. This is despite the fact that the total amount of catalyst in the micro-structured reactor is approximately 5 times less than that used in the fixed bed reactor. In addition, the contact time (1/MHSV) in the micro-structured reactor is also significantly shorter than in the fixed-bed reactor.
- Full Text:
- Date Issued: 2012
- Authors: Mpuhlu, Batsho
- Date: 2012
- Subjects: Dehydrogenation , Cyclohexane
- Language: English
- Type: Thesis , Doctoral , DTech (Chemistry)
- Identifier: http://hdl.handle.net/10948/8661 , vital:26418
- Description: The work that is described in this thesis forms part of the research and development projects at InnoVenton: NMMU Institute of Chemical Technology in collaboration with Sasol Technologies. The broader view of the project was testing on the so-called “Small Production Platforms” (SPP’s). In particular the main aim of this study was to investigate the effect of micro-structuring on the heterogeneous catalysed, vapour-phase oxidative dehydrogenation of cyclohexane in the presence of air. Ground work studies were done to provide a proper comparison of the micro-structured reactor with a traditional fixed-bed reactor. These included evaluation of a proper vanadium pyrophosphate catalyst for the reaction, testing of reaction parameters for the oxidative dehydrogenation reaction on a fixed-bed reactor and lastly comparing the performance of the micro-structured reactor to that of the fixed-bed reactor Various vanadium pyrophosphate catalysts that were tested for activity included: bulk (VO)2P2O7, bulk (VO)2P2O7 promoted with Fe, (VO)2P2O7 supported on -Al2O3 and Fe promoted (VO)2P2O7 supported on -Al2O3. These catalysts showed significant differences in TOF, however it was not conclusive from the results whether these differences may be traced to increased activity for dehydrogenation for different catalysts since all reactions were run under conditions of oxygen deficiency. It is, however, clear that Fe promotion significantly increase activity, irrespective of the relative degrees of oxidative dehydrogenation and normal dehydrogenation. The Fe promoted catalyst was further tested for long term stability in-view of using it as the catalyst in the micro-structured reactor. These studies showed the catalyst to have a high degree of stability with minimal structural changes under the reaction conditions used. Various response surface models describing the variation in each of the cyclohexane conversion, cyclohexene selectivity, and benzene selectivity, respectively when changing reaction condition, were derived by means of multiple regression. To obtain some idea of the degree and nature of the normal dehydrogenation reaction, the amount of deficit oxygen was estimated from the measured results for cyclohexane conversion and cyclohexene and benzene selectivities. These estimated values were also modelled as described above. The regression models were used to interpret specific trends in the responses for the oxidative dehydrogenation of cyclohexane and account for the oxygen deficit in the system. The performance of a fixed bed tubular reactor (FBR) and micro-structured sandwich reactor (MSSR) were compared over an Fe promoted vanadium pyrophosphate. Reactor performance was evaluated by varying specific reaction conditions (temperature and space velocity). Subsequently the turn-over frequencies, conversion and selectivities from the two reactors were compared. The conversion achieved in the micro-structured reactor was observed to be significantly higher than that achieved in the fixed-bed reactor at all reaction parameters. This is despite the fact that the total amount of catalyst in the micro-structured reactor is approximately 5 times less than that used in the fixed bed reactor. In addition, the contact time (1/MHSV) in the micro-structured reactor is also significantly shorter than in the fixed-bed reactor.
- Full Text:
- Date Issued: 2012
Synthesis of P-Methane-3,8-Diol
- Authors: Mpuhlu, Batsho
- Date: 2007
- Subjects: Insect baits and repellents
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10411 , http://hdl.handle.net/10948/570 , http://hdl.handle.net/10948/d1011717 , Insect baits and repellents
- Description: The synthesis of para-menthane-3,8-diol in a batch reactor was investigated in some detail with the view to evaluate the potential of producing said p-menthane- 3,8-diol in a continuous-flow reactor from the results obtained from the batch process. The methodology used as base for this investigation was a published procedure by Takasago of Japan. The Takasago-method produced 92.3 percent Yield for the product para-menthane-3,8-diol, and 2.7 percent Yield of the by-product, acetal. The objective for this investigation was to produce a minimum p-menthane-3,8- diol content of 97.0 percent and a maximum content of 3.0 percent for the by-product acetal. The batch production process was evaluated in detail using statistical experimental design methodologies. Three process variables, namely catalyst loading, organic/aqueous phase ratio and reaction temperature were selected for the study. The experimental method was based on the Takasago procedure, however the substrate was added as a single slug as opposed to gradual addition method and the reaction period was reduced to 30 minutes. Apart from statistical analysis, mechanistic aspects were also used to interpret the following results. Using a central composite design, three response models (one for the conversion of citronellal, p-menthane-3,8-diol and acetal formation) were determined. An analysis of the response surfaces indicated that, to increase the citronellal conversion all three variables should be increased. To increase the amount of pmenthane- 3,8-diol, the reaction temperature and acid concentration should be increased, but the Aq/org ratio should be decreased as the acid catalyst concentration is increased. To minimize the amount of acetals formed during the reaction, the Aq/org ratio should be decreased; temperature and acid concentration can be decreased or increased. The reaction mechanism suggested that p-menthane-3,8-diol may be formed along two pathways: One pathway directly forms p-menthane-3,8-diol, whilst the second pathway forms the isopulegol first, then proceeds to form product by hydrolysis. The acetal is formed as result of the reaction between unreacted citronellal and p-menthane-3,8-diol. From the design experiments it was suggested that reaction time can be reduced to 8 minutes at reaction temperatures between, 80-85 0C The product and acetal were isolated by simple vacuum evaporation of the low boiling citronellal and isopulegol. Results from recycling the catalyst phase were similar to those of the initial process. The results of this investigation has clearly shown that with a proper understanding of the effect of process variables on the performance of the batch synthesis route, the conversion of this traditionally batch (actually semi-batch) process into a continuous process is quite feasible provided that suitable equipment is available. The most important features required for such equipment would be: Intense mixing throughout the reaction zone so as to maximise the surface area between the two immiscible phases, hence the rate of mass transfer between the two phases; and the ability to run reactions above the boiling point of water. Plans for the further study of the process are already well underway and sections of static mixing tubes have been acquired to build a continuous lab scale tubular reactor that would be capable of providing the level of mixing required.
- Full Text:
- Date Issued: 2007
- Authors: Mpuhlu, Batsho
- Date: 2007
- Subjects: Insect baits and repellents
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10411 , http://hdl.handle.net/10948/570 , http://hdl.handle.net/10948/d1011717 , Insect baits and repellents
- Description: The synthesis of para-menthane-3,8-diol in a batch reactor was investigated in some detail with the view to evaluate the potential of producing said p-menthane- 3,8-diol in a continuous-flow reactor from the results obtained from the batch process. The methodology used as base for this investigation was a published procedure by Takasago of Japan. The Takasago-method produced 92.3 percent Yield for the product para-menthane-3,8-diol, and 2.7 percent Yield of the by-product, acetal. The objective for this investigation was to produce a minimum p-menthane-3,8- diol content of 97.0 percent and a maximum content of 3.0 percent for the by-product acetal. The batch production process was evaluated in detail using statistical experimental design methodologies. Three process variables, namely catalyst loading, organic/aqueous phase ratio and reaction temperature were selected for the study. The experimental method was based on the Takasago procedure, however the substrate was added as a single slug as opposed to gradual addition method and the reaction period was reduced to 30 minutes. Apart from statistical analysis, mechanistic aspects were also used to interpret the following results. Using a central composite design, three response models (one for the conversion of citronellal, p-menthane-3,8-diol and acetal formation) were determined. An analysis of the response surfaces indicated that, to increase the citronellal conversion all three variables should be increased. To increase the amount of pmenthane- 3,8-diol, the reaction temperature and acid concentration should be increased, but the Aq/org ratio should be decreased as the acid catalyst concentration is increased. To minimize the amount of acetals formed during the reaction, the Aq/org ratio should be decreased; temperature and acid concentration can be decreased or increased. The reaction mechanism suggested that p-menthane-3,8-diol may be formed along two pathways: One pathway directly forms p-menthane-3,8-diol, whilst the second pathway forms the isopulegol first, then proceeds to form product by hydrolysis. The acetal is formed as result of the reaction between unreacted citronellal and p-menthane-3,8-diol. From the design experiments it was suggested that reaction time can be reduced to 8 minutes at reaction temperatures between, 80-85 0C The product and acetal were isolated by simple vacuum evaporation of the low boiling citronellal and isopulegol. Results from recycling the catalyst phase were similar to those of the initial process. The results of this investigation has clearly shown that with a proper understanding of the effect of process variables on the performance of the batch synthesis route, the conversion of this traditionally batch (actually semi-batch) process into a continuous process is quite feasible provided that suitable equipment is available. The most important features required for such equipment would be: Intense mixing throughout the reaction zone so as to maximise the surface area between the two immiscible phases, hence the rate of mass transfer between the two phases; and the ability to run reactions above the boiling point of water. Plans for the further study of the process are already well underway and sections of static mixing tubes have been acquired to build a continuous lab scale tubular reactor that would be capable of providing the level of mixing required.
- Full Text:
- Date Issued: 2007
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