Catalytic intermediate pyrolysis of Brunei rice husk for bio-oil production

Rice husks from Brunei were subjected via intermediate pyrolysis for bio-oil production. Two main objectives were set out for this study. The application of intermediate pyrolysis on Brunei rice husk for the production of bio-oil is the main objective of this experiment. Characterisation of the rice husks was inclusive as a pre-requisite step to assess the suitability as feedstock for production of liquid fuels. Following on from the characterisation results, a temperature of 450°C was established as the optimum temperature for the production of bio-oil. A homogenous bio-oil was obtained from the pyrolysis of dry rice husk, and the physicochemical properties and chemical compositions were analysed. The second objective is the introduction of catalysts into the pyrolysis process which aims to improve the bio-oil quality, and maximise the desired liquid bio-oil properties. The incorporation of the catalysts was done via a fixed tube reactor into the pyrolysis system. Ceramic monoliths were used as the catalyst support, with montmorillonite clay as a binder to attach the catalysts onto the catalyst support. ZSM-5, Al-MCM-41, Al-MSU-F and Brunei rice husk ash (BRHA) together with its combination were adopted as catalysts. Proposed criterions dictated the selection of the best catalysts, subsequently leading to the optimisation process for bio-oil production. ZSM-5/Al-MCM-41 proved the most desirable catalyst, which increases the production of aromatics and phenols, decreased the organic acids and improved the physicochemical properties such as the pH, viscosity, density and H:C molar ratios. Variation in the ratio and positioning of both catalysts were the significant key factor for the catalyst optimisation study.

Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors

Two simple, reproducible methods of preparing evenly distributed Au nanoparticle containing mesoporous silica monoliths are investigated. These Au nanoparticle containing monoliths are subsequently investigated as flow reactors for the selective oxidation of cyclohexene. In the first strategy, the silica monolith was directly impregnated with Au nanoparticles during the formation of the monolith. The second approach was to pre-functionalize the monolith with thiol groups tethered within the silica mesostructure. These can act as evenly distributed anchors for the Au nanoparticles to be incorporated by flowing a Au nanoparticle solution through the thiol functionalized monolith. Both methods led to successfully achieving even distribution of Au nanoparticles along the length of the monolith as demonstrated by ICP-OES. However, the impregnation method led to strong agglomeration of the Au nanoparticles during subsequent heating steps while the thiol anchoring procedure maintained the nanoparticles in the range of 6.8 ± 1.4 nm. Both Au nanoparticle containing monoliths as well as samples with no Au incorporated were tested for the selective oxidation of cyclohexene under constant flow at 30 °C. The Au free materials were found to be catalytically inactive with Au being the minimum necessary requirement for the reaction to proceed. The impregnated Au-containing monolith was found to be less active than the thiol functionalized Au-containing material, attributable to the low metal surface area of the Au nanoparticles. The reaction on the thiol functionalized Au-containing monolith was found to depend strongly on the type of oxidant used: tert-butyl hydroperoxide (TBHP) was more active than H2O2, likely due to the thiol induced hydrophobicity in the monolith.