Research estimated toxicity of refuse-derived fuel fly ash (RDF-FA) on two earthworms species, Lumbricus terrestris and Eisenia foetida. Specific objectives were to: (1) Compare their 14-day LC50s under light and dark conditions; (2) separate toxicity due to osmotic, pH and physical factors from that of heavy metal contaminants; (3) compare relative differences of artificial soil and commercial soil as exposure media for evaluating toxicity to earthworms. The 14-d LC50s for L. terrestris in dark and light were 57.0 and 48.34 % RDF-FA, and 59.25 and 41.00 % RDF-FA for E. foetida using artificial soil. All of the toxicity resulted from heavy metals within the RDF-FA. Using L. terrestris, the LC50s for artificial soil and commercial soil were 52.30 and 64.34%.

The thesis deals with the determination of ash fusion temperatures. The first part of the thesis consist of research about the properties of ash, ash fusion temperatures and test methods, including a description of the problems associated with ash and their solution. In the second part, the ash fusion temperatures of the selected fuels are determined first experimentally and then by elemental analysis of ash. The results of both methods are compared at the end of the thesis.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

South Africa has large coal reserves and produces approximately 74% of its primary energy from coal. Coal gasification using moving bed gasifiers is one of the most important coal utilisation technologies, consuming ± 17.5% of locally produced coal. This study was motivated by the need to investigate alternative coal gasification technologies for the utilisation of fine, high-ash and caking coals for future Integrated Gasification Combined Cycle (IGCC) and coal to liquids (CTL) plants. These coals are estimated to form a large percentage of the remaining coal reserves in South Africa and could be difficult to utilise efficiently in moving bed gasifiers. Fluidised bed gasification was identified as a technology that could potentially utilise these coals. Coals from the New Vaal and Grootegeluk collieries were selected as being suitable for this investigation. The coals were subjected to detailed characterisation, bench-scale and pilot-scale fluidised bed gasification tests. The results of the pilot-scale atmospheric bubbling fluidised bed gasification tests show that stable gasification is possible at temperatures between 880 °C and 980 °C. The maximum fixed carbon conversion achievable in the pilot plant is, however, limited to ± 88% due to the low reactivity of the coals tested and to thermal fragmentation and attrition of the coal in the gasifier. It was found that oxygen enrichment of the gasification air from 21% to 36% by means of oxygen addition produces a significant increase in the calorific value of the gas (3.0 MJ/Nm3 to 5.5 MJ/Nm3). This observation has not previously been reported at pilot-plant scale. A mathematical model for a bubbling fluidised bed coal gasifier was developed based on sub-models for fluidised bed hydrodynamics, coal devolatilisation, chemical reactions, transfer processes and fines generation. A coal devolatilisation sub-model to predict the products of coal devolatilisation in a fluidised bed gasifier was developed and incorporated into the model. Parameters associated with the rates of the gasification reactions and the devoltilisation process were obtained by means of bench-scale tests. The heat loss parameter (Q) in the model was estimated by means of a heat loss calculation. The results from the pilot-scale gasification tests were used to evaluate the predictive capability of the model. It was found that for temperature, fixed carbon conversion and calorific value of the gas the difference between measured and predicted values was less than 10%. Recommendations are made for further refinement of the model to improve its predictive capability and range of application. The model was used to study the effect of major operating variables on gasifier performance. It was found that increasing the reactant gas (air, oxygen and steam) temperature from 250 °C to 550 °C increases the calorific value of the gas by ± 9.3% and the gasification efficiency by ± 6.0%. Increasing the fluidised bed height has a positive effect on fixed carbon conversion; however, at higher bed heights the benefit of increasing the bed height is less due to the inhibiting effects of H2 and CO on the rates of char gasification. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

South Africa has large coal reserves and produces approximately 74% of its primary energy from coal. Coal gasification using moving bed gasifiers is one of the most important coal utilisation technologies, consuming ± 17.5% of locally produced coal. This study was motivated by the need to investigate alternative coal gasification technologies for the utilisation of fine, high-ash and caking coals for future Integrated Gasification Combined Cycle (IGCC) and coal to liquids (CTL) plants. These coals are estimated to form a large percentage of the remaining coal reserves in South Africa and could be difficult to utilise efficiently in moving bed gasifiers. Fluidised bed gasification was identified as a technology that could potentially utilise these coals. Coals from the New Vaal and Grootegeluk collieries were selected as being suitable for this investigation. The coals were subjected to detailed characterisation, bench-scale and pilot-scale fluidised bed gasification tests. The results of the pilot-scale atmospheric bubbling fluidised bed gasification tests show that stable gasification is possible at temperatures between 880 °C and 980 °C. The maximum fixed carbon conversion achievable in the pilot plant is, however, limited to ± 88% due to the low reactivity of the coals tested and to thermal fragmentation and attrition of the coal in the gasifier. It was found that oxygen enrichment of the gasification air from 21% to 36% by means of oxygen addition produces a significant increase in the calorific value of the gas (3.0 MJ/Nm3 to 5.5 MJ/Nm3). This observation has not previously been reported at pilot-plant scale. A mathematical model for a bubbling fluidised bed coal gasifier was developed based on sub-models for fluidised bed hydrodynamics, coal devolatilisation, chemical reactions, transfer processes and fines generation. A coal devolatilisation sub-model to predict the products of coal devolatilisation in a fluidised bed gasifier was developed and incorporated into the model. Parameters associated with the rates of the gasification reactions and the devoltilisation process were obtained by means of bench-scale tests. The heat loss parameter (Q) in the model was estimated by means of a heat loss calculation. The results from the pilot-scale gasification tests were used to evaluate the predictive capability of the model. It was found that for temperature, fixed carbon conversion and calorific value of the gas the difference between measured and predicted values was less than 10%. Recommendations are made for further refinement of the model to improve its predictive capability and range of application. The model was used to study the effect of major operating variables on gasifier performance. It was found that increasing the reactant gas (air, oxygen and steam) temperature from 250 °C to 550 °C increases the calorific value of the gas by ± 9.3% and the gasification efficiency by ± 6.0%. Increasing the fluidised bed height has a positive effect on fixed carbon conversion; however, at higher bed heights the benefit of increasing the bed height is less due to the inhibiting effects of H2 and CO on the rates of char gasification. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

Master of Science / Department of Civil Engineering / Kyle Riding / Fly ash is a by-product of coal-fired power plants. This material can be used as a partial cement substitute in portland cement concrete. Use of fly ash can improve concrete durability as well as utilize an industrial by-product that would otherwise be discarded in landfills. However, research on fly ash concrete has shown that in some cases, concrete with high volumes of fly ash can have deicer salt scaling problems. Salt-scaling is the flaking of a concrete surface that when severe enough may result in lower skid resistance and service life of the concrete. In this study, concrete mixtures with six different fly ashes were tested in a laboratory using the ASTM C 672 standard. Curing compound, a wax-based coating sprayed on the fresh concrete surface to reduce evaporation, was used to compare the effects of curing on salt scaling of concrete containing high volumes of fly ash. Different variables measured were the type of fly ash, curing conditions, and total paste volume included in the mix. Results showed that curing compounds will improve the salt-scaling resistance of concrete containing a fly ash that only marginally exhibits salt scaling. However, the salt-scaling performance of concrete that contains fly ash from a source that performs poorly in ASTM C 672 is not markedly improved by using a curing compound. Additionally, results showed that salt-scaling resistance of concrete containing fly ash performs better when the total paste volume is not increased by the addition of fly ash to the mixture. The Kansas Outdoor Concrete Exposure Site (KOCE) at the Kansas State University Civil Infrastructure Systems Laboratory (CISL) was constructed to compare laboratory results to actual field conditions in the future. The site was developed based on experiences from the University of Texas-Austin outdoor exposure site and the CANMET exposure site in Ottawa, Canada. Alika silica reaction blocks were made to develop the procedure for future concrete durability testing at KOCE.

The high temperature interactions of alkali metal compounds with solids present in coal conversion processes are investigated. A temperature and concentration programmed reaction method is used to investigate the mechanism by which organically bound alkali is released from carbonaceous substrates. Vaporization of the alkali is preceded by reduction of oxygen-bearing groups during which CO is generated. A residual amount of alkali remains after complete reduction. This residual level is greater for potassium, indicating that potassium has stronger interactions with graphitic substrates than sodium. Other mineral substrates were exposed to high temperature alkali chloride vapors under both nitrogen and simulated flue gas atmospheres to investigate their potential application as sorbents for the removal of alkali from coal conversion flue gases. The compounds containing alumina and silica are found to readily adsorb alkali vapors and the minerals kaolinite, bauxite and emathlite are identified as promising alkali sorbents. The fundamentals of alkali adsorption on kaolinite, bauxite and emathlite are compared and analyzed both experimentally and through theoretical modeling. The experiments were performed in a microgravimetric reactor system; the sorbents were characterized before and after alkali adsorption using scanning Auger microscopy, X-ray diffraction analysis, mercury porosimetry and atomic emission spectrophotometry. The results show that the process is not a simple physical condensation, but a complex combination of several diffusion steps and reactions. There are some common features among these sorbents in their interactions with alkali vapors: In all cases the process is diffusion influenced, the rate of adsorption decreases with time and there is a final saturation limit. However, there are differences in reaction mechanisms leading to potentially different applications for each sorbent. Bauxite and kaolinite react with NaCl and water vapor to form nephelite and carnegieite and release HCl to the gas phase. However, emathlite reacts to form albite and HCl vapor. Albite has a melting point significantly lower than nephelite and carnegieite; therefore, emathlite is more suitable for lower temperature sorption systems downstream of the combustors/gasifiers, while kaolinite and bauxite are suitable as in-situ additives.

Theoretical and experimental studies of the chemical and physical factors which affect molecular diffusion of dissolved substances from fractures into a tuffaceous rock matrix have been made on rocks from G Tunnel and Yucca Mountain at the Nevada Test Site (NT8). Although a number of physical/chemical processes may cause nonadvective transport of dissolved species from fractures into the tuff matrix, diffusion in these rocks is controlled by the composition of the groundwater through multicomponent effects and several rock properties. The effective molecular diffusion coefficient of a particular species in the tuff can be related to its free aqueous diffusion coefficient by Dₑ = θ(m)(α/τ²)D₀ where bm is matrix porosity, α is the constrictivity, and τ is the tortuosity. The porosities of the samples studied ranged from 0.1 to 0.4. The parameter (α/τ²) ranged from 0.1 to 0.3, and effective matrix dif— fusion coefficients were measured to be between 2 to 17. x 10⁻⁷ cm²/s for sodium halides and sodium pentafluorobenzoate. Total porosity was found to be the principle factor accounting for the variation in effective diffusion coefficients. The constrictivity— tortuosity factor was found to have a fair correlation with the median pore diameters measured by mercury intrusion. Measurements of bulk rock electrical impedance changes with frequency indicate that the constrictivity factor, a, has a maximum value of 0.8 to 1, but may be smaller. If the larger values are correct, then the diffusion paths in tuff are more tortuous than in granular media. The diffusion coefficient matrix computed for various tracers in J-13 well water from the NTS indicates coupling of the diffusion fluxes of all ionic species. Multicomponent diffusion is a second order effect, however, which does not significantly affect experimental results. The results of a bench—scale fracture flow experiment revealed that the transport of ionic tracers (SCN ⁻ and pentafluorobenzoate) was affected by diffusion into the tuff matrix. The transport of a particulate tracer did not appear to be affected by diffusion.

Master of Science / Department of Animal Sciences and Industry / Joel DeRouchey / Jason Woodworth / Two experiments using a total of 646 nursery pigs were used to determine the effects of increasing phytase on nursery pig growth performance and bone ash characteristics. Two experiments using a total of 821 sows were used to determine the impact of increasing standardized ileal digestible (SID) lysine (Lys) in lactating sows. Experiment 1 determined the available phosphorus (aP) release of Natuphos E 5,000 G phytase in nursery pigs. Increasing phytase from 0 to 1,000 FTU/kg in phosphorus deficient diets improved nursery pig performance and bone ash characteristics. Using percentage bone ash and formulated phytase concentrations, an equation was developed to predict aP release up to 1,000 FTU/kg of Natuphos E phytase. Experiment 2 was conducted to determine the effect of Superdosing Natuphos E 5,000 G phytase on nursery pig performance and bone ash characteristics. Increasing phytase in diets marginal in P improved pig performance and bone ash values. Increasing phytase in P sufficient diets improved bone ash percent and tended to improve feed efficiency. Experiments 3 and 4 determined the impacts of increasing SID Lys in primiparous and multiparous lactating sows and their litters. In Exp. 3, increasing SID Lys above 0.80% in primiparous sows decreased backfat loss, but had no effect on sow BW loss, ADFI or litter gain. Conception rate at d 30 and percentage born alive tended to improve at 0.95% SID Lys. In Exp. 4 with mixed parity sows, increasing SID Lys to 1.05% increased sow weaning BW, litter gain, and reduced weight loss in lactation. Sow backfat loss increased as SID Lys increased from 0.75 to 1.20%, however loin eye depth loss was reduced as SID Lys increased. Percentage of females bred by d 7 after weaning was improved in primiparous females with increasing SID Lys, however no difference was observed in multiparous sows.

This thesis compares ash collected from different boilers cleaned using infrasound cleaning. The samples were evaluated from their physical properties, in an attempt to find connections between the difficulty to remove ash and its physical appearance. To get a deeper understanding of the mechanisms behind adhesion and fouling, and possibly explain results from the study of the ash samples, a literature review was carried out. The ash was also evaluated to see if any connections could be drawn between the physical properties of the ash and its fouling capabilities. A strong connection was found between ash density and its fouling capabilities. It was found that no dry ash with a density higher than 0.4 g/ml were difficult to remove with infrasound cleaning, and no ash with lower density was easy to remove. The ash density was calculated from a measurement of the weight of a certain volume of ash on a scale. Optical microscopy was used to study the ash samples, and gave an estimation of particle size, shape, and porosity. However, no clear connection could be observed with this method between the different samples and which were difficult to remove. The particle size for a few of the samples were also measured by a wet laser sieving method, and while it does give a good picture of particle size, the size was not found to be a useful prediction of the ash fouling behaviour. The exact mechanism giving rise to the density dependence need to be further investigated.