Vapour phase dehydrogenation of cyclohexane on microstructured reactors

• Main Author: Mpuhlu, Batsho
• Format: Others
• Language: English
• Published: Nelson Mandela Metropolitan University 2012
• Subjects: Dehydrogenation; Cyclohexane
• Online Access: http://hdl.handle.net/10948/8661

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.