Arsenic and selenium distributions in coal-fired plant samples are studied. This research includes arsenic and selenium concentrations in samples of coal, fly ash, bottom ash, economizer ash, Flue Gas Desulfurization (FGD) slurry and flue gas taken from four power plants with the goal being to examine the distribution of these metals in these materials and calculate a materials balance for the system. All samples were analyzed using ICP-ES. This research shows that 60-80% of the arsenic in coal-fired plant samples will be associated with the fly ash. Approximately 35-55% of the selenium will be associated with the fly ash and approximately 30-40% will be associated with the FGD slurry materials. The amount of arsenic and selenium present in the flue gases escaping the stack is very little, 6-7% or less. Hopefully, research in this area will be helpful when setting emissions limits, identifying and disposing of hazardous wastes and improving air pollution control devices for maximum metal removal.

A 20 kg/hr ritual-money combustion chamber and a 20 Am3/min (@35oC) wet scrubber were setup for performance tests on the removal of TSP (total solid particulates) from the combustion flue gas. Test results indicate that (1) TSP in the flue gas ranged from 93-157 (avg. 126) and 127-182 (avg. 157) mg/m3 (@35oC) at gas drawing rates (QG) of 13.1 and 26.3 m3/min (@35oC), respectively, and ritual-money combustion rates of 14.2-16.3 (avg. 15.3) kg/hr. The lower gas drawing rate gave lower TSP concentrations in the flue gas. TSP removal efficacy varied linearly with the liquid scrubbing rate (QL) and a 70% TSP removal was achieved at a QL of 60 L/min which is equivalent to a scrubbing-liquid intensity of 4.0 L/m2.s over the scrubber cross section. (2) Visual smoke intensity in the exit of the scrubber chimney was not apparent with a combustion rate of 16 kg/hr, scrubbing intensity of 4.0 L/m2.s, and gas drawing rates of 13.1 and 26.3 m3/min. (3) Scrubbing water consumptions of 1.2-2.4 L were estimated for a combustion of 1 kg ritual money. (4) Pertinent design parameters of a scrubber for 70% TSP removal from the flue gas are (a) liquid/gas ratio (QL/QG) = 3-6 L liquid/(m3 gas @30oC); (b) superficial gas velocity over the scrubber cross section (UG) = 0.6-1.2 m/s; (c) superficial liquid velocity over the scrubber cross section (UL) = 0.004 m/s; and (d) a gas-liquid contacting length of 0.70 m. Results also show that the combustion exit gas odor concentration (D/T, dilution times to threshold) could be removed from 309 to 232 by the scrubber at operation conditions of QG = 13.1 and 26.3 m3/min, and QL = 60 L/min. Results also show that parts of CO2, CO, and NO could be removed by the scrubbing liquor, and there was no significant removal for NO2 and SO2 by the scrubber. By spraying KClO3 on a homemade wood pulp ritual money at a dosage of 3 wt.%, it shows that it burned more rapidly and with more smoke emission than a non-sprayed sample. Experiments also show that FeCl3 (15mg/L) was a satisfactory coagulant for enhancing the coagulation and sedimentation of the suspended solids (SS) in the wasted scrubbing liquor (known as Gray water). By the coagulant, SS in the Gray water with a pH of 7.0 could be removed from 100 to < 10 mg/L. XRD (X-Ray Diffraction) examination of a bottom ash sample indicates that the ash has an elemental composition of O, Na, Al, and Si of 49.9, 11.8, 23.8, and 15.1%, respectively. SEM (Scanning Electron Microscope) analysis indicates that the collected fly ash and the bottom one have particle sizes of 20-110 (mostly 45-60 nm) and 50-300 (average 250) nm, respectively.

The objective of this study was to remove mercury vapor from municipal waste incinerator (MWI) by the adsorption of powder activated carbon (PAC) prepared from the pyrolysis of waste tire. The study focused on the measurement of mercury concentration in flue gas emitted from municipal waste incinerator, the preparation of PAC from the pyrolysis of the waste tire and impregnated with sulfur, and the adsorption capacity of mercury by the self-made PAC. The measurement of heavy metals in flue gas emitted from four typical MWIs was conducted in this study. Experimental results obtained from the measurement of mercury from flue gas indicated that the removal efficiency of mercury ranged from 83.71%~96.22%for the tested MWIs. This study revealed that the injection of PAC in flue gas would enhance the removal efficiency of mercury. Besides, oxided mercury (Hg2+) can be removed much more easily than elemental mercury (Hg0). Experimental results obtained from the pyrolysis of waste tires indicated that the pyrolysis temperature of waste tire was approximately 400~500¢J, and the percentage of carbon residue is 35~37%. With higher temperature and water feed rate and longer activation time, the specific surface area and total pore volume of PAC increased while the average pore radius decreased. The highest specific surface area of PAC obtained in this study was 996 m2/g. In addition, experimental results obtained from sulfur impregnation process indicated that the specific surface area of PAC decreased dramatically as sulfur was added to PAC. Experiment results obtained from the adsorption capacity of HgCl2 on PAC by column test indicated that PAC with higher specific surface area could adsorb more HgCl2 at room temperature (25¢J). The adsorption capacity of sulfur impregnated PAC decreased at 25¢J was due to the decrease of specific surface area of PAC. However, results from the comparison of two PAC with similar specific surface area indicated that the PAC with higher sulfur content had higher adsorption capacity. It suggested that the addition of sulfur to PAC could enhance the adsorption of HgCl2 at 25¢J. Experimental results obtained from column tests at 150¢J showed that the adsorption capacity of PAC increased as sulfur content of PAC increased. These results suggested that the adsorption mechanism of HgCl2 by PAC was mainly physical adsorption at lower temperature and it was chemisorption at higher temperature. Besides, the self-made PAC demonstrated the similar adsorption capacity of HgCl2 with commercial PAC used in MWIs.

In the selection of candidates for CO2 absorption, solvent thermal degradation has become a general concern due to the significant impact on operational cost and the intention to use thermal compression from high temperature stripping to minimize the overall process energy. In this research, the impact of flue gas contaminants on Monoethanolamine (MEA) thermal degradation was investigated at elevated temperatures consistent with those in the CO2 stripper. Nitrite, fly ash, sulfate and thiosulfate were each added to 5.0 M MEA and the contaminant-containing MEA solutions were degraded at 125 °C, 135 °C and 145 °C. MEA degrades significantly more in the presence of nitrite (5000 ppm) than MEA alone at the same amine molar concentration for all three temperatures. MEA degradation activation energy of MEA-nitrite solution is approximately one-seventh of that of MEA solution without nitrite. Fly ash was observed to inhibit nitrite-induced MEA degradation and greatly increase the MEA degradation activation energy of MEA-nitrite solution. Fly ash, sodium sulfate and sodium thiosulfate by themselves were not shown to impact MEA thermal degradation rate. Sodium salts of glycine, sarcosine, alanine and ß-alanine were thermally degraded at 125 °C, 135 °C and 145 °C, respectively, to discover the structural reasons for their thermal stability. These four amino acids have enhanced thermal degradation rates compared to MEA. The stability order for amino acid salts tested to date is: sarcosinate > alaninate > ß-alaninate. Calculated activation energies for the degradation processes are lower than that of MEA. ß-Alaninate (ß-Ala) thermal degradation generates ß-Ala dimer (major degradation product), ß-Ala dimer carbamate and tetrahydro-1,3-oxazin-6-one. Functional groups, amine orders and steric effect were investigated for their impact on amine thermal degradation. Primary amines with chain structures showed a thermal stability trend as diamine > alkanolamine > amino acid salt. For alknolamine and diamine structural isomers, the primary amines are more stable than the secondary amines. Steric hindrance around the amine group plays a global positive role in protecting amines against thermal degradation.

Post-combustion carbon capture, wherein the CO2 produced as a result of coal combustion is trapped at the power plant exhaust, is seen as a bridging technology to reduce CO2 emissions and combat climate change. This capture process will however impose a parasitic load on the power plant and technologies need to be developed to minimize this energy penalty. This research focuses on a technology which uses solid sorbents fashioned into a hollow fiber form that allows water-moderated thermal cycling as a means of trapping CO2 from flue gas. While hollow fiber technology has intrinsic advantages over competing liquid amine and packed bed technologies, the materials used to fabricate hollow fibers and the fabrication process itself need to be optimized in order to result in competitive, robust hollow fiber sorbents. This dissertation focuses on the material selection process for each component of the hollow fiber platform and discusses ways to optimize the fiber and barrier layer formation. Different materials were evaluated to function as the solid sorbent, the matrix polymer and the barrier layer; and eventually their performance was measured against past work in this area.

Amine degradation in aqueous amine scrubbing systems for capturing CO₂ from coal fired power plants is a major problem. Oxygen in the flue gas is the major cause of solvent deterioration, which increases the cost of CO₂ capture due to reduced capacity, reduced rates, increased corrosion, solvent makeup, foaming, and reclaiming. Degradation also produces environmentally hazardous materials: ammonia, amides, aldehydes, nitramines, and nitrosamines. Thus it is important to understand and mitigate amine oxidation in industrial CO₂ capture systems. A series of lab-scale experiments was conducted to better understand the causes of and solutions to amine oxidation. This work included determination of rates, products, catalysts, and inhibitors for various amines at various conditions. Special attention was paid to understanding monoethanolamine (MEA) oxidation, whereas oxidation of piperazine (PZ) and other amines was less thorough. The most important scientific contribution of this work has been to show that amine oxidation in real CO₂ capture systems is much more complex than previously believed, and cannot be explained by mass transfer or reaction kinetics in the absorber by itself, or by dissolved oxygen kinetics in the cross exchanger. An accurate representation of MEA oxidation in real systems must take into account catalysts present (especially Mn and Fe), enhanced oxygen mass transfer in the absorber as a function of various process conditions, and possibly oxygen carriers other than dissolved oxygen in the cross exchanger and stripper. Strategies for mitigating oxidative degradation at low temperature, proposed in this and previous work are less effective or ineffective with high temperature cycling, which is more representative of real systems. In order of effectiveness, these strategies are: selecting an amine resistant to oxidation, reduction of dissolved metals in the system, reduction of the stripper temperature, reduction of the absorber temperature, and addition of a chemical inhibitor to the system. Intercooling in the absorber can reduce amine oxidation and improve energy efficiency, whereas amine oxidation should be considered in choosing the optimal stripper temperature. In real systems, 2-amino-2-methyl-1-propanol (AMP) is expected to be the most resistant to oxidation, followed by PZ and PZ derivatives, then methyldiethanolamine (MDEA), and then MEA. MEA oxidation with high temperature cycling is increased 70% by raising the cycling temperature from 100 to 120 °C, the proposed operational temperature range of the stripper. PZ oxidation is increased 100% by cycling to 150 °C as opposed to 120 °C. Metals are expected to increase oxidation in MEA and PZ with high temperature cycling by 40 - 80%. Inhibitor A is not expected to be effective in real systems with MEA or with PZ. MDEA is also not effective as an inhibitor in MEA, and chelating agents diethylenetriamine penta (acetic acid) (DTPA) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) are only mildly effective in MEA. Although MEA oxidation in real systems cannot be significantly reduced by any known additives, it can be accurately monitored on a continuous basis by measuring ammonia production from the absorber. Ammonia production was shown to account for two-thirds of nitrogen in degraded MEA at low temperature and with high temperature cycling, suggesting that it is a reliable indicator of MEA oxidation under a variety of process conditions. A proposed system, which minimizes amine oxidation while maintaining excellent rate and thermodynamic properties for CO₂ capture would involve use of 4 m AMP + 2 m PZ as a capture solvent with the stripper at 135 °C, intercooling in the absorber, and use of a corrosion inhibitor or continuous metals removal system. Reducing (anaerobic) conditions should be avoided to prevent excessive corrosion from occurring and minimize the amount of dissolved metals. This system is expected to reduce amine oxidation by 90-95% compared with the base case 7 m MEA with the stripper at 120 °C. / text

A range of porous solid adsorbents were synthesised and their ability to separate and capture carbon dioxide (CO2) from gas mixtures was examined. CO2 separation from flue gas – a type of exhaust gas from fossil fuel combustion that consists of CO2 mixed with mainly nitrogen and biogas (consists of CO2 mixed with mainly methane) were explicitly considered. The selected adsorbents were chosen partly due to their narrow pore sizes. Narrow pores can differentiate gas molecules of different sizes via a kinetic separation mechanism: a large gas molecule should find it more difficult to enter a narrow pore. CO2 has the smallest kinetic diameter in zeolites when compared with the other two gases in this study. Narrow pore adsorbents can therefore, show enhanced kinetic selectivity to adsorb CO2 from a gas mixture. The adsorbents tested in this study included mixed cation zeolite A, zeolite ZK-4, a range of aluminophosphates and silicoaluminophosphates, as well as two types of titanium silicates (ETS-4, CTS-1). These adsorbents were compared with one another from different aspects such as CO2 capacity, CO2 selectivity, cyclic performance, working capacity, cost of synthesis, etc. Each of the tested adsorbents has its advantages and disadvantages. Serval phosphates were identified as potentially good CO2 adsorbents, but the high cost of their synthesis must be addressed in order to develop these adsorbents for applications. / <p>At the time of the doctoral defence the following papers were unpublished and had a status as follows: Papers 4-8: Manuscripts.</p>

The ever increasing global demand for materials has placed aluminium as the world’s second most used metal, with world annual production currently >24 million tons. Consequently, the global alumina industry is perpetually striving to meet demands in conjunction with research, development and implementation of more efficient and sustainable processes and practises. Of specific concern for many proponents within the industry is that increased alumina production inadvertently results in increased Bayer Process-derived alkaline solid and liquid waste loads. Furthermore, in-house power generation at all Australian alumina refineries contributes to acid gas emissions, particularly SOx and NOx, both of which have environmental and anthropogenic impacts of global concern. The focus of this work is SO2 emission. SOx emission control measures can be achieved before, during or after combustion; the latter is termed flue gas desulphurisation (FGD). Commercially available FGD systems are dominated by once-through wet processes whereby the flue gas passes up through an absorbtion tower. The most favourable medium for industrial use is seawater, followed by limestone, and in some cases, a combination of both. However, the ever-increasing stringency of environmental emission legislation continues to inflict tighter controls on power production and is forcing industry to investigate alternative cost-effective FGD mediums. Therefore much research is currently dedicated to the utilisation of high volume, alkaline waste streams over manufactured sorbents. Modern environmental engineering approaches to waste product minimisation, neutralisation and/or reuse have lead to many new processes which change the view of many materials from waste product to environmental resource. Subsequently, this work examines the application of an isolated Bayer Process waste product, tricalcium aluminate hexahydrate (TCA6), as a FGD medium. Initial research assessed the dissolution behaviour and performance of the proposed medium with sulphuric acid, followed by batch reactor trials with a simulated flue gas. Data derived from this research indicated the suitability of TCA6 as a FGD medium and was subsequently applied to a preliminary model and proposed design parameters required for further pilot scale investigations. This work provides strong support for an economically viable and more sustainable approach to FGD for the alumina industry.

The ever increasing global demand for materials has placed aluminium as the world’s second most used metal, with world annual production currently >24 million tons. Consequently, the global alumina industry is perpetually striving to meet demands in conjunction with research, development and implementation of more efficient and sustainable processes and practises. Of specific concern for many proponents within the industry is that increased alumina production inadvertently results in increased Bayer Process-derived alkaline solid and liquid waste loads. Furthermore, in-house power generation at all Australian alumina refineries contributes to acid gas emissions, particularly SOx and NOx, both of which have environmental and anthropogenic impacts of global concern. The focus of this work is SO2 emission. SOx emission control measures can be achieved before, during or after combustion; the latter is termed flue gas desulphurisation (FGD). Commercially available FGD systems are dominated by once-through wet processes whereby the flue gas passes up through an absorbtion tower. The most favourable medium for industrial use is seawater, followed by limestone, and in some cases, a combination of both. However, the ever-increasing stringency of environmental emission legislation continues to inflict tighter controls on power production and is forcing industry to investigate alternative cost-effective FGD mediums. Therefore much research is currently dedicated to the utilisation of high volume, alkaline waste streams over manufactured sorbents. Modern environmental engineering approaches to waste product minimisation, neutralisation and/or reuse have lead to many new processes which change the view of many materials from waste product to environmental resource. Subsequently, this work examines the application of an isolated Bayer Process waste product, tricalcium aluminate hexahydrate (TCA6), as a FGD medium. Initial research assessed the dissolution behaviour and performance of the proposed medium with sulphuric acid, followed by batch reactor trials with a simulated flue gas. Data derived from this research indicated the suitability of TCA6 as a FGD medium and was subsequently applied to a preliminary model and proposed design parameters required for further pilot scale investigations. This work provides strong support for an economically viable and more sustainable approach to FGD for the alumina industry.

The ever increasing global demand for materials has placed aluminium as the world’s second most used metal, with world annual production currently >24 million tons. Consequently, the global alumina industry is perpetually striving to meet demands in conjunction with research, development and implementation of more efficient and sustainable processes and practises. Of specific concern for many proponents within the industry is that increased alumina production inadvertently results in increased Bayer Process-derived alkaline solid and liquid waste loads. Furthermore, in-house power generation at all Australian alumina refineries contributes to acid gas emissions, particularly SOx and NOx, both of which have environmental and anthropogenic impacts of global concern. The focus of this work is SO2 emission. SOx emission control measures can be achieved before, during or after combustion; the latter is termed flue gas desulphurisation (FGD). Commercially available FGD systems are dominated by once-through wet processes whereby the flue gas passes up through an absorbtion tower. The most favourable medium for industrial use is seawater, followed by limestone, and in some cases, a combination of both. However, the ever-increasing stringency of environmental emission legislation continues to inflict tighter controls on power production and is forcing industry to investigate alternative cost-effective FGD mediums. Therefore much research is currently dedicated to the utilisation of high volume, alkaline waste streams over manufactured sorbents. Modern environmental engineering approaches to waste product minimisation, neutralisation and/or reuse have lead to many new processes which change the view of many materials from waste product to environmental resource. Subsequently, this work examines the application of an isolated Bayer Process waste product, tricalcium aluminate hexahydrate (TCA6), as a FGD medium. Initial research assessed the dissolution behaviour and performance of the proposed medium with sulphuric acid, followed by batch reactor trials with a simulated flue gas. Data derived from this research indicated the suitability of TCA6 as a FGD medium and was subsequently applied to a preliminary model and proposed design parameters required for further pilot scale investigations. This work provides strong support for an economically viable and more sustainable approach to FGD for the alumina industry.