Thesis (M.S.)--University of Tennessee, Knoxville, 2003. / Title from title page screen (viewed Mar., 19, 2004). Thesis advisor: Robert T. Burns. Document formatted into pages (xiv, 148 p. : ill. (some col.)). Vita. Includes bibliographical references.

Optimization of the performance of absorption systems during transient operations such as start-up and shut-down is particularly important for small-capacity chillers and heat pumps to minimize lifecycle costs. Dynamic models in the literature have been used to study responses to step changes in a single parameter, but more complex processes such as system start-up have not been studied in detail. A robust system-level model for simulating the transient behavior of an absorption chiller is developed here. Individual heat and mass exchangers are modeled using detailed segmental models. The UA-values and thermal masses of heat exchangers used in the model are representative of a practical operational chiller. Thermal masses of the heat exchangers and energy storage in the heat exchanging fluids are accounted for to achieve realistic transient simulation of the heat transfer processes in the chiller. The pressure drop due to fluid flow across the heat exchangers is considered negligible in comparison to the pressure difference between the high- and low-side components (~ 1.5 MPa). In components with significant mass transfer effects, reduced-order models are employed to decrease computational costs while also maintaining accurate system response. Mass and species storage in the cycle are modeled using storage devices. The storage devices account for expansion and contraction of the refrigerant and solution in the cycle as the system goes through start-up, shut-down, and other transient events. A counterflow falling film desorber model is employed to account for the heat and mass transfer interactions between the liquid and vapor phases, inside the desorber. The liquid film flows down counter to the rising vapor, thereby exchanging heat with the counterflowing heated coupling fluid. A segmented model is used to account for these processes, and a solver is developed for performing rapid iteration and quick estimation of unknown vapor and liquid states at the outlet of each segment of the desorber. Other components such as the rectifier, expansion valves and solution pump are modeled as quasi-steady devices. System start-up is simulated from ambient conditions, and the coupling fluid temperatures are assumed to start up to their steady-state values within the first 90 s of simulation. It is observed that the system attains steady-state in approximately 550 s. The evaporator cooling duty and COP of the chiller during steady-state are observed to be 3.41 kW and 0.60, respectively. Steady-state parameters such as flow rates, heat transfer rates and concentrations are found to match closely with results from simulations using corresponding steady-state models. Several control responses are investigated using this dynamic simulation model. System responses to step changes in the desorber coupling fluid temperature and flow rate, solution pumping rate, and valve setting are used to study the effects of several control strategies on system behavior. Results from this analysis can be used to optimize start-up and steady state performances. The model can also be used for devising and testing control strategies in commercial applications.

Energy shortages around the world necessitated research into alternative energy sources especially for domestic applications to reduce the load on conventional energy sources. This resulted in research done on the possibility of integrating solar energy with an aqua-ammonia diffusion absorption cycle specifically for domestic applications. The bubble pump can be seen as the heart of the diffusion absorption cycle, since it is responsible, in the absence of a mechanical pump, to circulate the fluid and to desorb the refrigerant (ammonia) from the mixture. It is thus of paramount importance to ensure that the bubble pump is designed efficiently. Various bubble pump simulation models have been developed over the years, but it was found that none of the existing models served as a good basis for application-specific design. Most of the models constrained too many parameters from the outset which made the investigation of the effects of certain parameters on the bubble pump’s performance impossible. According to the research, no bubble pump model investigated the effect of such a wide variety of factors including tube diameter, heat flux, mass flux, generator heat input and system pressure on the bubble pump’s lift height. A simulation model for a bubble pump for integration with a solar-driven aqua-ammonia diffusion absorption cycle was developed. It serves as a versatile design model to optimise the bubble pump for a large variety of conditions as well as changes in parameters. It was achieved by constraining the bubble pump dimensions and parameters as little as possible. A unique feature of this model was the fact that the bubble pump tube was divided into segments of known quality which made the length of the pipe completely dependent on the flow inside the pipe. It also made the demarcation of the flow development inside the tube easier. The model attempted to incorporate the most appropriate correlations for pressurised two-phase aqua-ammonia flow. The most appropriate void fraction correlation was found to be Abstract The design and optimisation of a bubble pump for an aqua-ammonia diffusion absorption heat pump the Rouhani-Axelsson (Rouhani I) correlation. It was mainly due to its exclusive use of thermophysical properties and the vapour quality. The most appropriate heat transfer coefficient that predicted the most realistic wall temperature, was the correlation from Riviera and Best (1999) which was the only correlation found in the literature developed with aqua-ammonia in mind. It was found that the published correlation could not reproduce their experimental results, and a modification of their correlation was made after which the simulation model’s results correlated well with the experimental values of Riviera and Best (1999). The main goal of the simulation model was to determine the height that the bubble pump was capable of lifting at the slug to churn flow transition under various conditions. The effect of varying a variety of parameters on the bubble pump lift height was also investigated. The results from Shelton & White Stewart (2002) were compared to the outputs of the simulation model, and it was found that their constraining of the submergence ratio limited their outputs, and that their heat inputs under different conditions was a bit optimistic. The simulation model’s outputs correlated well at higher tube diameters with the results from Shelton & White Stewart (2002), but at the lower diameters which was used in their study it was impossible to compare data, since their diameters was already in mini flow and micro flow regions. The temperatures also correlated well, all within 2% of the results from Shelton & White Stewart (2002). It was found that there couldn’t be just one set of optimised conditions and values for the bubble pump, but that each cycle with differing specifications and operating conditions would yield a unique set of optimised parameters. It was for that reason very important not to constrain parameters beforehand without investigating its effect on the bubble pump first. / Thesis (MIng (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2013.

Energy shortages around the world necessitated research into alternative energy sources especially for domestic applications to reduce the load on conventional energy sources. This resulted in research done on the possibility of integrating solar energy with an aqua-ammonia diffusion absorption cycle specifically for domestic applications. The bubble pump can be seen as the heart of the diffusion absorption cycle, since it is responsible, in the absence of a mechanical pump, to circulate the fluid and to desorb the refrigerant (ammonia) from the mixture. It is thus of paramount importance to ensure that the bubble pump is designed efficiently. Various bubble pump simulation models have been developed over the years, but it was found that none of the existing models served as a good basis for application-specific design. Most of the models constrained too many parameters from the outset which made the investigation of the effects of certain parameters on the bubble pump’s performance impossible. According to the research, no bubble pump model investigated the effect of such a wide variety of factors including tube diameter, heat flux, mass flux, generator heat input and system pressure on the bubble pump’s lift height. A simulation model for a bubble pump for integration with a solar-driven aqua-ammonia diffusion absorption cycle was developed. It serves as a versatile design model to optimise the bubble pump for a large variety of conditions as well as changes in parameters. It was achieved by constraining the bubble pump dimensions and parameters as little as possible. A unique feature of this model was the fact that the bubble pump tube was divided into segments of known quality which made the length of the pipe completely dependent on the flow inside the pipe. It also made the demarcation of the flow development inside the tube easier. The model attempted to incorporate the most appropriate correlations for pressurised two-phase aqua-ammonia flow. The most appropriate void fraction correlation was found to be Abstract The design and optimisation of a bubble pump for an aqua-ammonia diffusion absorption heat pump the Rouhani-Axelsson (Rouhani I) correlation. It was mainly due to its exclusive use of thermophysical properties and the vapour quality. The most appropriate heat transfer coefficient that predicted the most realistic wall temperature, was the correlation from Riviera and Best (1999) which was the only correlation found in the literature developed with aqua-ammonia in mind. It was found that the published correlation could not reproduce their experimental results, and a modification of their correlation was made after which the simulation model’s results correlated well with the experimental values of Riviera and Best (1999). The main goal of the simulation model was to determine the height that the bubble pump was capable of lifting at the slug to churn flow transition under various conditions. The effect of varying a variety of parameters on the bubble pump lift height was also investigated. The results from Shelton & White Stewart (2002) were compared to the outputs of the simulation model, and it was found that their constraining of the submergence ratio limited their outputs, and that their heat inputs under different conditions was a bit optimistic. The simulation model’s outputs correlated well at higher tube diameters with the results from Shelton & White Stewart (2002), but at the lower diameters which was used in their study it was impossible to compare data, since their diameters was already in mini flow and micro flow regions. The temperatures also correlated well, all within 2% of the results from Shelton & White Stewart (2002). It was found that there couldn’t be just one set of optimised conditions and values for the bubble pump, but that each cycle with differing specifications and operating conditions would yield a unique set of optimised parameters. It was for that reason very important not to constrain parameters beforehand without investigating its effect on the bubble pump first. / Thesis (MIng (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2013.

The purpose of this thesis was to carry out the experimental study of direct ammonia fuel cells. The use of hydrogen in fuel cells poses a lot of problems. There is a lot of safety, technical and economic issues to be overcome to make its use as a fuel widespread. Ammonia is being considered as a very promising source of hydrogen for fuel cells. However, until now its use in fuel cells has received very little attention. Ammonia presents many advantages over hydrogen and other potential sources of hydrogen such as an easy storage and a world-wide distribution network. Ammonia is a suitable hydrogen carrier and can be easily cracked at high temperatures such as those used in solid oxide fuel cells. The present study was conducting using ammonia as fuel and argon as carrier gas in different solid oxide fuel cell systems: an annular design, a planar design and a micro laminated reactor. The electrolyte materials were calcia stabilized zirconia and yttria stabilized zirconia. As far as the electrodes are concerned, silver, platinum and nickel cermet were used as anode/materials and silver was employed as cathode material. The cell yoltage was measured as function of reactor configuration, space time, ammonia flow rate and ammonia concentration. The results demonstrate the high potential of ammonia over hydrogen when nickel is used as anode material. Solid proton conducting fuel cells operating on ammonia fuel were also studied. The electrolyte materials were fabricated from neodymium and gadolinium doped barium and strontium cerates. The dopant fraction ranged from 1 to 20 wt%. Silver was employed as cathode and anode material and was spray deposited. The application of proton conducting electrolytes results in higher current densities for a given voltage than the using typical oxide ion conductors such as 8mol % yttria stabilized zirconia. The potential of the proton conducting materials for application in ammonia synthesis at atmospheric pressure was also studied. They demonstrated promising results and could prove to be an alternative to the common ammonia synthesis processes.

The effect of ammonia on anaerobic digestion of the organic fraction of municipal solid wastes (OFMSW) was investigated in this study. This study involved two sets of experiments. First set involved the investigation of ammonia toxicity on AD of synthetic OFMSW only (SW), at three different phases and pH 7.5, 8.0 and 8.5. Phase 1 was the Batch Methane Potential (BMP) phase. BMP tests were conducted under ammonia concentration of 2500 mg/L, 5000 mg/L, 7500 mg/L and 10,000 mg/L and at pH 7.5, 8.0, and 8.5, using 500 mL Kimax® glass bottles. The total working volume of the mixture was 300 mL comprising 120 mL of mesophilic anaerobically digested inoculums, 30 g of OFMSW, various TAN concentrations ranging from 2,500, 5,000, 7,500 to 10,000 mg/L, and equal portions of buffer in form of NaHCO3 and KHCO3. The second phase of the experiment examined whether the tolerance of the bacteria to high ammonia concentration would improve by acclimating the microbes to high ammonia concentrations, through gradual TAN loading. TAN concentration was increased gradually at pH 7.5, 8.0 and 8.5 weekly. The third phase of the experiment was Semi-continuous batch phase. This phase examined the possibility of reducing the inhibitory effect of ammonia on AD, batch reactors at pH values of 8.0 and 8.5 containing initial TAN concentrations of 7500 mg/L and 10,000 mg/L. 3 g of the digestate containing high ammonia concentration(s) was replaced with fresh substrate at every 4 days, 7 days and 15 days. The second set of experiment involved study of the effects of ammonia on anaerobic digestion of OFMSW with real landfill leachate (SW+L). Phase 1 was BMP in which the effect of ammonia was examined at TAN concentrations of 7,500 and 10,000 mg/L. The phase 2 of the (SW+L) gradual TAN TAN loading. The possibility of adapting mesophilic bacteria to high ammonia concentration was examined. The results of the study confirmed that ammonia is toxic to AD, at high concentrations. Biogas production reduced with increase in TAN concentration. Reduction in Cumulative Biogas Production (CBP) compared with control reactors was as much as 43 %, 64 % and 77 % in reactors containing 7500 mg/L TAN at pH 7.5, pH 8.0 and pH 8.5. CBP reduced to 80-85 % in reactors containing 10,000 mg/L TAN across the pH examined. Also, replacing 3g of digestate containing high TAN concentrations of 7500 mg/L and 10,000 mg/L with 3 g fresh substrate improved the activity of the mesophilic bacteria as seen in the surges in biogas production when fresh substrate was injected into the reactors. Similar results were obtained on effect of ammonia on AD of OFMSW mixed with real landfill leachate to simulate an anaerobic bioreactor landfill. CBP reduced as the TAN concentration increased. Compared with control reactors, reactors containing 7500 mg/L TAN at pH 8.0 and pH 8.5 had 61 % and 80 % reduction in CBP. Likewise, reactors containing 10,000 mg/L TAN at pH 8.0 and pH 8.5 had 68 % and 85 % reduction in CBP, compared with control reactors. Study confirmed that pH influenced the toxicity and composition of Total Ammonia Nitrogen (TAN). At high pH (i.e. 8.5), FAN component of TAN was about 26 % and was inhibitory to the methanogens. Results also showed that mesophilic bacteria could be adapted to a TAN concentration of about 5000 mg/L at pH 7.5 through gradual TAN loading. Similar results were obtained on effect of ammonia on AD of OFMSW mixed with real landfill leachate to simulate an anaerobic bioreactor landfill. CBP reduced as the TAN concentration increased. Compared with control reactors, reactors containing 7500 mg/L TAN at pH 8.0 and pH 8.5 had 61 % and 80 % reduction in CBP. Likewise, reactors containing 10,000 mg/L TAN at pH 8.0 and pH 8.5 had 68 % and 85 % reduction in CBP, compared with control reactors. Study confirmed that pH influenced the toxicity and composition of Total Ammonia Nitrogen (TAN). At high pH (i.e. 8.5), FAN component of TAN was about 26 % and was inhibitory to the methanogens. Results also showed that mesophilic bacteria could be adapted to a TAN concentration of about 5000 mg/L at pH 7.5 through gradual TAN loading.

Ammonia-oxidizing bacteria (AOB) are chemolithotrophs that oxidize ammonia/ammonium to nitrite in a two-step process to obtain energy for survival. AOB are difficult to isolate from the environment and iso lated strains may not represent the diversity in soil. A genetic database and molecular tools were developed based on the ammonia monooxygenase (AMO) encoding genes that can be used to assess the diversity of AOB that exist in soil and aquatic environments without the isolation of pure cultures. The amo genes have excellent potential as molecular markers; since AMO is only found in the AOB and is essential for their metabolism, AOB must carry at least one functional copy of the amo operon. The operon is composed of at least three genes, amoC, amoA. and amoB (encoding for the subunits AmoC, AmoA, and AmoB). The amoC gene was first discovered and its sequence was obtained from Nitrosospira sp. NpA V. The amooperon is found in several copies within AOB genomes in the β-subdivision but as a single copy in y-subdivision genomes. In Southern analysis, cross-hybridization was only observed between amo genes within a subdivision. They-subdivision amo sequences have higher identity values to the genes encoding the related particulate methane monooxygenase than to the β-subdivision amo sequences. Since amoA encodes the subunit containing the active site, it was sequenced entirely for all the strains studied (16 amoA sequences total). The amoC and amoB genes were also sequenced for several strains. The amo genes allow for better discrimination between closely related strains than the 16S rRNA genes. In all cases, the amo operon consists of amoC, followed by a variable length intergenic region, and then by amoAB. The variability in length of the intergenic region is strain specific, and is therefore potentially useful for profiling AOB communities. The amo-gene database was the basis for the design of conserved oligonucleotide primers for the polymerase chain reaction (PCR). These primers were used to amplify amo sequences from a mixed template of DNA extracted directly from soil. Results indicate that the amo genes are excellent molecular markers for the assessment of AOB communities in the environment.

No description available.

Anaerobic digestion (AD) is a sustainable waste management technology that primarily generates two products: biogas and digestate. The technology relies on the microorganisms' activity, which depends on several operational factors, such as pH, temperature, solid contents, and ammonia levels. Ammonia is an inorganic form of nitrogen resulting from the biodegradation of organic nitrogen. It is considered one of the major concerns for AD operations due to its inhibitory effects on some microorganisms, particularly methanogens. A common feedstock characterized by high nitrogen content is poultry manure (PM). PM is often avoided in anaerobic digesters due to the anticipated inhibition resulting from its high ammonia levels. However, since poultry manure is one of the most widely available organic wastes, researchers have extensively investigated ways to include PM as a primary feedstock for AD. One possible way to treat high ammonia levels in digestate is ammonia stripping, the physio-chemical separation of ammonia from a solution by introducing a stripping (carrier) gas. There are a few approaches to performing ammonia stripping in AD applications; the most commonly discussed in the literature are pre-hydrolysis and side-stream ammonia stripping. Pre-hydrolysis ammonia stripping is performed on raw feedstock after increasing pH and temperature and is usually not restricted in selecting the gas carrier. On the other hand, side-stream ammonia stripping is when a portion of the digester's working volume is filtered, and the filtrate is sent to a unit where pH and temperature are increased. The carrier gas in these systems is often limited to anaerobic gases such as biogas or steam. The third and most novel approach is post-hydrolysis ammonia stripping, conducted at an intermediate stage between hydrolysis and methanogenesis in a two-stage AD process. This configuration would address the shortcomings of the other two systems. However, there is minimal information on the feasibility and potential of this approach in the literature. This study aims to comprehensively investigate the post-hydrolysis ammonia stripping approach through the following four phases: Phase I) Proof of Concept; Phase II) Optimization; Phase III) Assessment of Alternative Carrier Gases; and Phase IV: Comparison of Different Ammonia Stripping Configurations. Phase I provided the proof of concept under the batch mode and compared the performance of post-hydrolysis ammonia stripping with two-stage AD and co-digestion to improve poultry manure's methane potential as the primary substrate. It was observed that ammonia stripping successfully improved methane potential by up to 150%, whereas improvements due to two-stage AD and co-digestion were limited to 41 and 9%, respectively. Phase II provided more insight into optimizing the ammonia stripping process. Different stripping conditions were tested (pH 7.8 (unadjusted), 9 and 10, temperature 25 (unadjusted), 40 and 55 °C, and flow rate 300 L/L/hour). The results showed that higher pH and temperature lead to higher removal efficiency. However, it was concluded that optimal conditions ultimately depend on the initial and target ammonia levels. Moreover, Analysis of Variance showed that pH and temperature were significant factors affecting the ammonia removal efficiency. In addition, it was observed that higher stripping temperatures (55 °C) enhanced the digestibility of PM and increased its methane potential more than stripping at 40 °C. It was concluded that the optimum stripping conditions were pH 9.5, temperature 40 or 55 °C, and flowrate of 100 L/L/hour to collectively increase ammonia removal while reducing the associated costs and material handling. In Phase III, renewable natural gas (RNG) was evaluated as a stripping medium in batch testing as a potential replacement for biogas and air. Ammonia stripping with RNG yielded promising results comparable to the application of air in terms of ammonia removal and enhancing biogas production from PM (60 and 69% ammonia removal for RNG and air, respectively). In addition, a metagenomic shotgun analysis showed that most biogas production was conducted through hydrogenotrophic methanogens instead of acetoclastic methanogens, which are more susceptible to high ammonia levels. Phase IV assessed the semi-continuous flow two-stage operation of mesophilic AD reactors coupled with different ammonia stripping configurations. Post-hydrolysis ammonia stripping successfully achieved a stable operation of PM mono-digestion at ammonia levels of 1700 and 2400 mg NH₃-N/L in the cases of stripping with air and RNG, respectively. In addition, post-hydrolysis ammonia stripping in semi-continuous flow mode may have promoted acetoclastic methanogens growth since volatile fatty acid concentrations were reduced in the digesters. Phase IV also proved that the performance of post-hydrolysis ammonia stripping is superior over pre-hydrolysis and side-stream ammonia stripping. In the semi-continuous flow reactors, post-hydrolysis ammonia stripping with air achieved on average 831 L biogas/ kg VS at an organic loading rate (OLR) of 2.6 g VS/L/day, whereas side-stream ammonia stripping resulted in average of 700 L biogas/ kg VS at OLR of 1.8 g VS/L/day and higher ammonia stripping requirements. Having said that, the base scenario (no ammonia stripping) was inhibited, indicating that both ammonia stripping configurations were considered successful in alleviating inhibitory effects of ammonia from poultry manure. Phase IV results also proved that air stripping repeatedly outperformed RNG as stripping mediums by having higher ammonia removal efficiencies resulting in higher methane production. However, stripping with RNG is believed to have more practical advantages than air due to avoiding the risk of oxygen infiltration into the reactor. Moreover, renewable natural gas has proven to be an efficient stripping medium that is available on-site. The final stage of Phase IV tested pre-hydrolysis ammonia stripping using air in batch mode and compared it with post-hydrolysis ammonia stripping. Pre-hydrolysis ammonia stripping provided little to no improvement to the methane potential of PM in batch mode and therefore was excluded from the semi-continuous flow experiment. The four phases of this study demonstrated the flexibility and the superiority of post-hydrolysis ammonia stripping over the other pre-hydrolysis and side-stream ammonia stripping. In addition, post-hydrolysis ammonia stripping was proven efficient and feasible for ammonia removal and enabling the mono- or co-digestion of poultry manure. The study also showed that using RNG instead of biogas can significantly reduce the operational costs of the treatment.

Ammonia excretion from the freshwater fish gill is thought to occur mainly via passive diffusion of NH3 aided by a favourable plasma-to-water ammonia gradient sustained by a pH gradient formed by an acidified gill boundary layer. Rhesus (Rh) proteins are the newest members of the ammonia transporter superfamily. In this thesis research, ten rainbow trout Rh cDNA sequences were cloned and characterized. Rhcg2 mRNA and H+-ATPase mRNA and activity levels were upregulated in the trout gill pavement cells in response to experimentally elevated plasma ammonia, concurrent with enhanced ammonia excretion. Controversially, Rh proteins are thought to transport C02. However, Rh mRNA levels in most tissues of hypercapnia-exposed trout remained stable suggesting that trout Rh proteins likely do not conduct C02. Xenopus oocytes expressing trout Rh proteins facilitated the bi-directional transport of methylamine, an ammonia analogue. Methylamine transport was inhibited by ammonia and sensitive to a pH gradient and the concentration of the protonated species. Use of the scanning ion electrode technique (SIET) indicated that trout Rh proteins have an ammonia affinity within the physiological range, which is greater than that for methylamine, and they transport ammonia more rapidly than methylamine. A model of ammonia excretion in the trout gill pavement cell is proposed wherein ammonia enters via basolateral Rhbg and exits via apical Rhcg2, binding to these channels as NH4+ but transiting as NH3. In the gill boundary layer, NH3 combines with an H+ ion released from H+-ATPase and/or Na+/H+ exchange, forming NH4+. As low-affinity, high-capacity ammonia transporters, Rh proteins in the trout gill would exploit the favourable pH gradient formed by the acidic boundary layer to facilitate rapid ammonia efflux when plasma ammonia levels are elevated. Basal plasma ammonia levels are likely maintained by simple passive NH3 diffusion with a smaller role for Rh proteins under these conditions. / Thesis / Doctor of Philosophy (PhD)