The development of a commercial production process for p-menthane-3,8-diol
- Authors: Rust, Nico
- Date: 2009
- Subjects: Insect pests -- Control , Repellents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10427 , http://hdl.handle.net/10948/d1018273
- Description: The synthesis of p-menthane-3,8-diol via the acid-catalyzed cyclization of citronellal in a dilute aqueous sulphuric acid medium was investigated using conventional batch and continuous systems in order to develop a commercial production process for said p-menthane-3,8-diol (PMD). The batch studies conducted during the first part of this study showed that the formation of PMD from citronellal occurs via an intra-molecular Prins reaction that results in the formation of both the desired PMD product, as well as the partially hydrated isopulegol. It was shown that the formationof the by- product, PMD-acetal, results from the reaction between an intermediate, 5-methyl-2- isopropylcyclohexanol, and the citronellal starting material, and not from the reaction between PMD and citronellal as previously reported. Kinetic studies confirmed the existence of a complicated kinetic model. The formation of PMD from citronellal displayed typical pseudo first order kinetics up to conversions of 70 after which the kinetic model becomes complicated as the result of the establishment of quasi equilibrium reactions between PMD and isopulegol (dehydration of PMD and hydration of isopulegol) and between PMD the PMD-acetal, both systems being acid catalysed. The PMD-acetal formation reaction appears to be second order with respect to PMD. Scale-up studies of the batch process to 30L and 50L scales showed that it would be extremely difficult to limit the level of PMD-acetal formation below the desired level of 1 percent, even if citronellal conversions are restricted to about 50 percent. During studies conducted on a commercially availablemicro-structured organic synthesis plant (OSP) it was shown that it is possible to perform the PMD reaction as a continuous process. The results obtained showed that the use of a micro-mixer such as the caterpillar micro-mixer did not provide enough residence time in order for desirable conversions (- 40 percent) to be obtained. By combining themicro-mixer with delay-loops of different thicknesses and lengths, and using increasing reaction temperatures, it was shown that the conversion of citronellal could be improved to some extent, but compared poorly to the expected conversions for a well-stirred batch reactor. By packing selected delay loops with inert SiC particles, improved mass transfer was observed between the organic and aqueous phases as reflected in the increased conversion of citronellal. Using the observations that were made during the use of the OSP, a continuous-flow, tubular reactor system was designed and constructed. Advanced statistical techniques were used to investigate the effect of variables such as temperature, acid concentration, reactor length, flow rate and the organic to aqueous ratio on the rate and selectivity of the reaction. Mathematical models were derived for citronellal conversion, yield of PMD and yield of PMD- acetals, and used to predict the concentrations of citronellal, PMD and PMD-acetals at set experimental conditions. The results obtained showed that it was possible to obtain a product which approached desired specifications.Downstream processing of the PMD reaction mixture as it exits the reactor requires phase separation and neutralization of the acid catalyst solution, followed by further work-up to recover unreacted starting material and intermediates for recycle back to the synthesis reactor, followed by purification of crude PMD to the desired specification. The study showed that neutralization, prior or after phase separation, does not affect the selectivity of the PMD to such a great extent, but does influence the relative conversion due to extended contact of the catalyst with the organic phase after the reaction is terminated. Recovery of unreacted citronellal and isopulegol could be achieved by a simple vacuum evaporation step, which may either be carried out in a batch manner using traditional distillation equipment, or in a continuous process using wiped-film (short path) techniques. It was also shown that selective crystallization of PMD from the crude product mixture by addition of a solvent, such as heptanes or hexane proved to be the best way of achieving the desired product specification.
- Full Text:
- Date Issued: 2009
- Authors: Rust, Nico
- Date: 2009
- Subjects: Insect pests -- Control , Repellents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10427 , http://hdl.handle.net/10948/d1018273
- Description: The synthesis of p-menthane-3,8-diol via the acid-catalyzed cyclization of citronellal in a dilute aqueous sulphuric acid medium was investigated using conventional batch and continuous systems in order to develop a commercial production process for said p-menthane-3,8-diol (PMD). The batch studies conducted during the first part of this study showed that the formation of PMD from citronellal occurs via an intra-molecular Prins reaction that results in the formation of both the desired PMD product, as well as the partially hydrated isopulegol. It was shown that the formationof the by- product, PMD-acetal, results from the reaction between an intermediate, 5-methyl-2- isopropylcyclohexanol, and the citronellal starting material, and not from the reaction between PMD and citronellal as previously reported. Kinetic studies confirmed the existence of a complicated kinetic model. The formation of PMD from citronellal displayed typical pseudo first order kinetics up to conversions of 70 after which the kinetic model becomes complicated as the result of the establishment of quasi equilibrium reactions between PMD and isopulegol (dehydration of PMD and hydration of isopulegol) and between PMD the PMD-acetal, both systems being acid catalysed. The PMD-acetal formation reaction appears to be second order with respect to PMD. Scale-up studies of the batch process to 30L and 50L scales showed that it would be extremely difficult to limit the level of PMD-acetal formation below the desired level of 1 percent, even if citronellal conversions are restricted to about 50 percent. During studies conducted on a commercially availablemicro-structured organic synthesis plant (OSP) it was shown that it is possible to perform the PMD reaction as a continuous process. The results obtained showed that the use of a micro-mixer such as the caterpillar micro-mixer did not provide enough residence time in order for desirable conversions (- 40 percent) to be obtained. By combining themicro-mixer with delay-loops of different thicknesses and lengths, and using increasing reaction temperatures, it was shown that the conversion of citronellal could be improved to some extent, but compared poorly to the expected conversions for a well-stirred batch reactor. By packing selected delay loops with inert SiC particles, improved mass transfer was observed between the organic and aqueous phases as reflected in the increased conversion of citronellal. Using the observations that were made during the use of the OSP, a continuous-flow, tubular reactor system was designed and constructed. Advanced statistical techniques were used to investigate the effect of variables such as temperature, acid concentration, reactor length, flow rate and the organic to aqueous ratio on the rate and selectivity of the reaction. Mathematical models were derived for citronellal conversion, yield of PMD and yield of PMD- acetals, and used to predict the concentrations of citronellal, PMD and PMD-acetals at set experimental conditions. The results obtained showed that it was possible to obtain a product which approached desired specifications.Downstream processing of the PMD reaction mixture as it exits the reactor requires phase separation and neutralization of the acid catalyst solution, followed by further work-up to recover unreacted starting material and intermediates for recycle back to the synthesis reactor, followed by purification of crude PMD to the desired specification. The study showed that neutralization, prior or after phase separation, does not affect the selectivity of the PMD to such a great extent, but does influence the relative conversion due to extended contact of the catalyst with the organic phase after the reaction is terminated. Recovery of unreacted citronellal and isopulegol could be achieved by a simple vacuum evaporation step, which may either be carried out in a batch manner using traditional distillation equipment, or in a continuous process using wiped-film (short path) techniques. It was also shown that selective crystallization of PMD from the crude product mixture by addition of a solvent, such as heptanes or hexane proved to be the best way of achieving the desired product specification.
- Full Text:
- Date Issued: 2009
The use and performance of recycling polypropylene in lead-acid battery cases
- Authors: Rust, Nico
- Date: 2004
- Subjects: Polypropylene , Lead-acid batteries
- Language: English
- Type: Thesis , Masters , MTech (Chemistry)
- Identifier: vital:10978 , http://hdl.handle.net/10948/269 , Polypropylene , Lead-acid batteries
- Description: Polypropylene has proven to be the ideal material for the outer shell of the lead acid batteries. Due to its mold-ability and inert properties the material provides a capsule for the functioning components of the lead acid battery and can withstand a variety conditions encountered during its application, such as impact shock resistance, high and low temperatures and acid resistance. Polypropylene has however become of great concern with regards to environmental pollution since it is generally resistant to normal conditions of degradation and can only be properly disposed of by incineration. This factor has encouraged the industry to find ways to regenerate spent polypropylene. A good example of such a process is the recycling of lead acid batteries. This allows not only for the regeneration of lead, but also for the recycling of polypropylene in the manufacturing of battery cases. There are some cost advantages in using recycled polypropylene. However it does have its disadvantages in that the material does start to deteriorate after multiple processes. A common practice amongst battery manufacturers is to add virgin polypropylene to the recycled material in order to ensure performance consistency. The comparative study investigated the use of various ratios of virgin and recycled PP in the manufacturing of lead acid battery cases and their influence on the physical properties and performance of the final material. The degradation of PP was also investigated as the material was subjected to multiple manufacturing processes where the influence of stabilizers was further considered. A common technique of PP analysis such as MFI was shown to be an effective technique to maintain good quality control. The study further showed that it is important that the material grade of PP used in the manufacturing of the battery case and lid is compatible in order to allow for effective heating sealing of the two components. Polypropylene has a waxy surface finish and it is generally difficult to label or write on. Labels tend to fall off in application and make it difficult to maintain a track record of the manufactured batteries with time. This study showed successfully that a laser activated dye can be added to the PP without influencing its color or its performance. This allows for successful labeling of battery cases by various bar coding writers that can trace the battery through its manufacturing process. Lead acid batteries are often operated outside the specified temperature range that is determined by battery manufacturers resulting in premature failure. These failures can occur within the warranty period of the battery and result in illicit claims since the monitoring of the batteries in its application was not possible. A suitable temperature monitoring device was designed that would be incorporated into the vent cap or lid of the battery case. The device contained temperature sensitive indicators that would undergo a permanent color change at specified temperatures thereby giving the battery manufacturer an indication as to the maximum temperature the battery was exposed to.
- Full Text:
- Date Issued: 2004
- Authors: Rust, Nico
- Date: 2004
- Subjects: Polypropylene , Lead-acid batteries
- Language: English
- Type: Thesis , Masters , MTech (Chemistry)
- Identifier: vital:10978 , http://hdl.handle.net/10948/269 , Polypropylene , Lead-acid batteries
- Description: Polypropylene has proven to be the ideal material for the outer shell of the lead acid batteries. Due to its mold-ability and inert properties the material provides a capsule for the functioning components of the lead acid battery and can withstand a variety conditions encountered during its application, such as impact shock resistance, high and low temperatures and acid resistance. Polypropylene has however become of great concern with regards to environmental pollution since it is generally resistant to normal conditions of degradation and can only be properly disposed of by incineration. This factor has encouraged the industry to find ways to regenerate spent polypropylene. A good example of such a process is the recycling of lead acid batteries. This allows not only for the regeneration of lead, but also for the recycling of polypropylene in the manufacturing of battery cases. There are some cost advantages in using recycled polypropylene. However it does have its disadvantages in that the material does start to deteriorate after multiple processes. A common practice amongst battery manufacturers is to add virgin polypropylene to the recycled material in order to ensure performance consistency. The comparative study investigated the use of various ratios of virgin and recycled PP in the manufacturing of lead acid battery cases and their influence on the physical properties and performance of the final material. The degradation of PP was also investigated as the material was subjected to multiple manufacturing processes where the influence of stabilizers was further considered. A common technique of PP analysis such as MFI was shown to be an effective technique to maintain good quality control. The study further showed that it is important that the material grade of PP used in the manufacturing of the battery case and lid is compatible in order to allow for effective heating sealing of the two components. Polypropylene has a waxy surface finish and it is generally difficult to label or write on. Labels tend to fall off in application and make it difficult to maintain a track record of the manufactured batteries with time. This study showed successfully that a laser activated dye can be added to the PP without influencing its color or its performance. This allows for successful labeling of battery cases by various bar coding writers that can trace the battery through its manufacturing process. Lead acid batteries are often operated outside the specified temperature range that is determined by battery manufacturers resulting in premature failure. These failures can occur within the warranty period of the battery and result in illicit claims since the monitoring of the batteries in its application was not possible. A suitable temperature monitoring device was designed that would be incorporated into the vent cap or lid of the battery case. The device contained temperature sensitive indicators that would undergo a permanent color change at specified temperatures thereby giving the battery manufacturer an indication as to the maximum temperature the battery was exposed to.
- Full Text:
- Date Issued: 2004
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