Iron polychlorophthalocyanine (FePc(Cl)₁₆) and tetrasulfophthalocyanine ([M¹¹TSPc]⁴) complexes of iron, cobalt and manganese are employed as catalysts for the oxidation of cyclohexane using tert-butyl hydroperoxide (TBHP), chloroperoxybenzoic acid (CPBA) and hydrogen peroxide as oxidants. Catalysis using the FePc(Cl)₁₆ was performed in a dimethylformamide:dichloromethane (3 :7) solvent mixture. For the [Fe¹¹TSPc]⁴⁻, [Co¹¹TSPc]⁻ and [Mn¹¹TSPc]⁴⁻catalysts, a water:methanol (1:9) mixture was employed. The products of the catalysis are cyclohexanone, cyclohexanol and cyclohexanediol. The relative percentage yields, percentage selectivity and overall percentage conversion of the products depended on types of oxidant, or catalyst, concentrations of substrate or catalysts and temperature. TBHP was found to be the best oxidant since minimal destruction of the catalyst and higher selectivity in the products were observed when this oxidant was employed. Of the four catalysts investigated [Fe¹¹TSPc]⁴⁻ yielded the highest overall percentage conversion of 20%.The mechanism of the oxidation of cyclohexane in the presence of the FePc(Cl)₁₆ and [M¹¹TSPc]⁴⁻ involves the oxidation of these catalysts, forming an Fe(IlI) phthalocyanine species as an intermediate. Electrocatalysis using [Co¹¹TSPc]⁴⁻ as catalyst, employed an aqueous pH 7 buffer medium for electro-oxidation of 4-pentenoic acid. An enone is suggested as the only oxidation product of 4-pentenoic acid. No degradation of [Co¹¹TSPc]⁴⁻ was observed during the electrocatalytic process. In this process water was used as a source of oxygen therefore eliminating the production of by products from oxidant as in the case of TBHP and CPBA. This system was studied In an attempt to set up conditions for alkane electrocatalytic oxidation.

M.Sc. (Chemistry) / This study was directed towards the investigation of oxidations by dimethyldioxirane, a new and versatile oxidant. To begin, the oxidation of various simple saturated hydrocarbons was examined. These oxidations gave alcohols in yields that varied considerably. This investigation showed that dimethyldioxirane reacts chemoselectively and that a preference is shown for tertiary C-H bonds and even more so for tertiary cis C-H bonds in bicyclic six-membered ring compounds and tertiary benzylic C-H bonds. A kinetic study of the oxidations of benzylic C-H bonds of various cumene derivatives by dimethyldioxirane confirmed the electrophilic nature of this reagent. In order to investigate the chemoselectivity of oxidations by dimethyldioxirane, the oxidation of eight steroids was examined. These oxidations were very selective and rarely gave more than two products. In all but one case, the oxidations selectively produced alcohols in good yields. The preference of dimethyldioxirane for tertiary cis C-H bonds in cyclic compounds and tertiary benzylic C-H bonds was confirmed by the oxidation' of an estrone derivative and two 5,8-5teroids. In all three cases the anticipated compounds were obtained as the major products. This oxidative method for the synthesis of 5,B-hydroxy steroids may provide a novel route for the synthesis of cardioactive steroids. The oxidation of a furo[2,3-b]benzofurane derivative was investigated to conclude this study of oxidations by dimethyldioxirane. The succesful oxidation of this compound at C-3a would furnish a synthon for aflatoxin M1 in a single step. Unfortunately, no product was obtained for the oxidation of the furo[2,3-b]benzofurane derivative by dimethyldioxirane. Futher studies into the source of this lack of reactivity are currently being undertaken.

The oxidation of cymene with dioxygen has been investigated in some detail with the view of establishing the feasibility of improving the efficiency of the oxidation process. Of particular interest were the rate of cymene oxidation and the selectivity of the oxidation process for the tertiary cymene hydroperoxide, especially at conversions above 15%. In order to be able to evaluate the selectivity of oxidation processes, a reliable method for analysis of the individual hydroperoxides had to be established. Two methods were investigated, namely reduction of the hydroperoxides to alcohols using ferrous sulphate and reduction using triphenylphosphine, and analysing the reduction products by gas chromatography. Of these two methods, the triphenylphosphine method proved to be superior to the ferrous sulphate method and was used as the method of choice for this investigation. A number of oxidation systems were evaluated in an initial screening experiment for the oxidation of p-cymene. The results of this screening experiment showed that three-phase oxidation systems, i.e. systems containing an organic phase, an aqueous phase and gas, gave significantly lower activities than two-phase oxidation systems. In addition, the use of a base in the aqueous layer does not improve the overall selectivity of the oxidation process, but improves the selectivity towards the tertiary hydroperoxide to some extent due to the decomposition and extraction of primary hydroperoxide into the basic aqueous phase. Oxidation systems using a non-autoxidation catalyst, i.e. a catalyst that does not catalyse the conventional autoxidation of organic compounds, gave by far the most promising results. These systems gave both a high selectivity as well as high reaction rate. From the initial screening experiment, and using multi-factorial statistical techniques, two catalyst systems were selected for investigation, namely vanadium phosphate and boron phosphate. The results of these investigations showed that these two catalysts are remarkably active and selective for the oxidation of p-cymene, giving the cymene tertiary hydroperoxide in selectivities exceeding 85% and at substrate conversions as high as 25%. These results are a considerable improvement over currently known oxidation systems and may offer opportunities for further commercial exploitation.

Municipal wastewater treatment using biological nutrient removal generates large amounts of waste sludge. An effort is made to solubilize nutrients from sludge and reuse them in subsequent processes. The microwave-enhanced advanced oxidation (MW/H₂O₂-AOP) process using hydrogen peroxide as the oxidant was applied to the treatment of different organic slurries including wasted sludge, blood meal, and fish silage. The factors controlling phosphates, ammonia, and COD release into solution included inorganic acid addition, hydrogen peroxide dosage, treatment times and temperatures. Higher dosages and treatment temperatures yielded better solubilization of phosphates and ammonia. It was found that approximately all of the COD was solubilized at a treatment temperature of 80°C. Volatile fatty acid (VFA) concentrations were also found to have increased with the amount of inorganic acid added into treatment. Up to 25% of soluble COD was composed of acetic acid. Higher irradiation levels tended to be more effective in the solubilization of nutrients. In terms of trends of particle size distribution, detectable particles increased in size in acidic conditions, with the largest fraction of larger particles in a given sample being the treatment with highest irradiation power. In neutral condition treatments, the higher the irradiation power provided to the samples, the more spread out the particle sizes range. In alkaline condition treatments, an increase in smaller particles were found after treatment; higher power irradiation yielded significantly higher numbers of smaller particles. This study provided an insight into the athermal effects of theMW/H₂O₂-AOP. Blood meal solubilization for the purpose of its application as an organic feritilizer was investigated using theMW/H₂O₂-AOP. It was found that over the treatment temperature range of 60 to l20C, solids particle reduction, ammonia and orthophosphate production were achieved. Maximum solubility of chemical oxygen demand (COD) occurred at 80°C. Without the addition of acid, soluble COD decreased due to protein denaturation and coagulation out of the solution. Fish silage is also a valuable fertilizer for organic greenhouse hydroponics operations, but a pretreatment step is required. It was found that up to 26% of total Kjeldahl nitrogen could be released as ammonia with 6% hydrogen peroxide dosage at 170°C. An increase of nitrate/nitrite concentration was observed with higher hydrogen peroxide dosage and higher microwave temperature. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate

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The subject of this thesis was chosen originally as a result of a suggestion made by a manufacturer of lactic acid. Lactic acid is made by a fermentation process from molasses and the acid is extracted from the fermentation liquors as calcium lactate. The conversion of the calcium lactate back to lactic acid is a tedious process from an industrial point of view. It was therefore suggested that the conversion may be more easily accomplished by electrolysis. The first experimental work was conducted with this object in view, but it soon became apparent that it was unlikely that lactic acid could be produced in suitable quantities for industrial purposes by this means. There was no reference in the literature to the electrolysis of calcium lactate, and little reference to the electrolysis of lactates in general, and what there was appeared to be conflicting, so it was decided to continue the investigation into the subject in order to determine what are the products of the anodic oxidation of calcium lactate. Intro., p.1.

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.

[No abstract available] / Science, Faculty of / Chemistry, Department of / Graduate