O presente trabalho estudou o aumento de capacidade de tratamento de um reator UASB (Upflow Anaerobic Sludge Blanket) por meio da adição de material suporte para adesão celular (Biobob®), avaliando-se as eficiências de remoção de matéria orgânica (expressa como DQO demanda química de oxigênio) e sólidos em suspensão (expressos como SST sólidos em suspensão totais). O reator híbrido, no qual a biomassa está presente em suspensão e imobilizada no material suporte, foi submetido a baixos tempos de detenção hidráulica (TDH) e altas velocidades ascensionais (vs). A operação do reator anaeróbio, de volume útil igual a 12,5 m³, foi conduzida em duas etapas. Na primeira o sistema foi operado como um reator de manta de lodo e escoamento ascendente (UASB), com TDH de 8,8 h e velocidade ascensional de 0,63 m.h-1. Na segunda etapa, introduziu-se 5,0 m³ de material suporte Biobob® no leito reacional do reator, transformando-o em reator anaeróbio híbrido (HAnR). Nessa condição, variou-se a vazão de alimentação, tendo o TDH variado entre 7,4 h (vs de 0,66 m.h-1) a 3,9 h (vs de 1,25 m.h-1). Para ambas as etapas o sistema foi alimentado com esgoto sanitário à temperatura ambiente, após tratamento preliminar (gradeamento e caixa de areia). Para condições de operação similares, o reator anaeróbio híbrido (HAnR) apresentou melhor desempenho na remoção de DQO e SST que o reator UASB, acrescendo em até 18% e 30% a eficiência de remoção, respectivamente. Para a velocidade ascensional de 1,25±0,02 m.h-1 e TDH de 3,9±0,1 h, o HAnR apresentou concentrações médias no efluente tratado de 205±46 mg DQOt.L-1 e 73±30 mg SST.L-1 e eficiências de remoção de 55±9% DQOt e 63±14% SST. / The increase of the treatability capacity of a UASB (Upflow Anaerobic Sludge Blanket) reactor by introducing an innovative packing material (Biobob®) in its reaction zone was evaluated. The hybrid anaerobic reactor (HAnR) containing suspended and immobilized biomass was evaluated regarding its efficiency of removing organic matter (expressed as COD chemical oxygen demand) and suspended solids (expressed as TSS total suspended solids) under lower hydraulic detention time (HDT) and higher upflow velocities (v s). The anaerobic reactor operation, with 12.5 m³ of working volume, was conducted in two phases. In the first phase, the system was operated as a conventional UASB reactor with HRT of 8.8 h and vs of 0.63 m.h -1 . In the second phase, 5.0 m³ of packing material Biobob® was introduced inside the reaction bed, changing the reactor configuration from suspended growth to hybrid growth. In this condition, the hybrid anaerobic reactor (HAnR) was subjected to decreasing flowrates with HDT ranging from 7.4 h (vs of 0.66 m.h-1) to 3.9 h (vs of 1.25 m.h-1). For both phases, the feed was domestic wastewater (after screens and grit chambers) at ambient temperature. Under similar operation conditions, the HAnR performed better than the UASB reactor increasing at 18% and 30% the COD and TSS removal efficiencies, respectively. For vs of 1.25±0.02 m.h-1 and HDT of 3.9±1.0 h, the HAnR produced a very high quality effluent, with average COD and TSS concentration of 205±46 mg DQOt.L-1 and 73±30 mg SST.L-1 and removal efficiencies of 55±9% and 63±14% for CODt and SST, respectively.

No / Oxidative coupling of methane (OCM) is suggested to be a promising process for the conversion of the abundant natural gas into useful chemicals. However, this reaction faces many drawbacks such as low yields for higher hydrocarbons, fast catalyst deactivation, and huge heat effects of the reaction. Only a well-designed fluidized bed reactor is able to overcome effectively those disadvantages and to provide a satisfactory continuous operation. However, design approaches for fluidized bed reactors are still based on models developed during 70s and 80s, which cannot take into account various hydrodynamic effects on the reactor performance. Thus, a reactor designer has usually to rely on extensive experiments in order to improve the classical fluidized bed reactor design. In this work, the relevance of hydrodynamics, reactor geometry, and feeding policy on the performance of a fluidized bed reactor for the OCM is shown. For this purpose, several case studies of fluidized bed reactors are simulated in full 3D geometry under the same reaction conditions, but with different reactor geometries and feeding policy. These studies show the significance of hydrodynamic parameters for the reactor performance, and moreover, how fluidized bed reactor performance can be improved by a careful study of coupled momentum-mass transport-reaction phenomena. Furthermore, it can be demonstrated that a suitable distributed feeding policy of oxygen provides an improved yield while a traditional fluidized bed reactor design results in an inferior performance among all investigated cases.

published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Sensitivity analysis was performed on a soot model using a partially stirred reactor (PaSR) in order to determine the effects of mixing model parameters on soot scalar values. The sensitivities of the mixture fraction zeta and progress variable C to the mixing model constant C_phi were calculated; these values were used to compute the sensitivity of water mass fraction Y_H2O to C_phi and several soot quantities to soot moments. Results were validated by evaluating the mean mixture fraction sensitivity and a long simulation time case. From the baseline case, it was noted that soot moment sensitivities tended to peak on the rich side of the stoichiometric mixture fraction zeta_st. Timestep, number of notional particles, mixing timescale tau_mix, and residence time tau_res were varied independently. Choices for timestep and notional particle count were shown to be sufficient to capture relevant scalar profiles, and did not greatly affect sensitivity calculations. Altering tau_mix or tau_res was shown to affect sensitivity to mixing, and it was concluded that the soot model is more heavily influenced by the chemistry than mixing. / text

This research forms part of a programme of work at the University of Canterbury investigating the production of liquid fuels from biomass. The drivers for this research are the plentiful supply of woody biomass in New Zealand as well as the necessity for a reduction in the use of fossil fuels. Fischer-Tropsch synthesis has been chosen as the base conversion method for syngas to liquid fuels. While Fischer-Tropsch plants are traditionally very large, the low geographical density of the biomass feedstock necessitates a shift from a traditional economies of scale approach. In this research a sawmill integrated polygeneration scenario is proposed that recognises the synergy between the heat and electrical requirements of a mill and the Fischer-Tropsch process that can supply both as well as liquid fuels. Techno-economic modelling of variations to this polygeneration arrangement were performed using a traditional Fischer-Tropsch slurry reactor as the basis. The breakeven price of syncrude produced in the process based on a 30 year plant life and 10% discount factor was as low as $US 167 per barrel. This arrangement is coupled with development of and experimentation with a microchannel reactor in a further attempt to overcome economies of scale disadvantages. The lab scale microchannel reactor consisted of a shim with 50 channels of 37mm length with 0.2mm height and 0.3mm width. The microchannel reactor was tested with shorter run periods to compare different catalyst washcoats consisting of neat cobalt, cobalt on titania and a combustion synthesis method over a temperature range of 210-240°C at 20 bar. Comparison was also made to a lab scale fixed bed reactor with a powdered cobalt on titania catalyst. The neat cobalt washcoat proved to have the best performance per unit mass of catalyst of the three washcoats. The performance of the microchannel reactor was 32-40 times better per unit catalyst mass than the fixed bed reactor. From data based on the shorter runs the neat cobalt washcoat and the cobalt on titania washcoat were selected for further analysis over longer runs at a range of pressures from 2-20 bar and temperatures from 210-240°C. These runs were each approximately 70 hours long and provided a better analysis of the narrowed catalyst choice. The productivity results of the catalysts were fitted to established kinetic equations from literature with an excellent correlation. More accurate Anderson-Schultz-Flory selectivity values were also obtained ranging between 0.72 to 0.82. This is certainly an area that would warrant further attention as a higher selectivity has a very positive affect on plant economics. Establishment of the kinetic equations for the catalyst performance allowed modelling of reactors with greater volume along with investigation of mass transfer limitations to assist in scale up of the technology. It was found that under 4-5mm hydraulic diameter channel dimensions the mass transfer limitation from the bulk gas phase to the catalyst interface is negligible. A scaled up microchannel reactor concept design is proposed utilising stainless steel mesh folded into 2mm channels to increase catalyst surface area compared to straight shim. A costing correlation was produced per unit of reactor volume to allow a full scale cost of the microchannel reactor to be estimated for inclusion into the techno-economic model. The revised techno-economic model was optimised through pressure variation to give a breakeven syncrude value of $US118 per barrel at Fischer-Tropsch reaction conditions of 10 bar and 240°C. This brings the value well within historical crude price trends.

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