Дисертації з теми "Coal gasification Waste disposal"

Modern coal preparation facilities incorporate a wide array of solid-solid and solid-liquid separation processes for rejecting mineral matter to meet market specifications. The coarse mineral matter is typically placed into engineered refuse piles whereas the fine refuse is either stored in impoundments or co-disposed with the coarse refuse. The discharge water from the refuse material represents an environmental concern due to the potential release of trace elements, and the subsequent elevation of total dissolved solids and conductivity. The research findings reported in this dissertation addresses sustainable coal processing waste disposal through using strategies aimed at minimizing the environmental impacts. To provide an accurate and inexpensive method to assess the potential environmental effects of a given waste material, a conductivity screening-level test was modified to incorporate the impact of particle surface area. The test was used on various waste streams as well as the particle size and density fractions of each waste stream to identify environmentally sensitive components that can be separated from the bulk and isolated to prevent negative environmental impacts. The results were subsequently evaluated for long term mobility of trace elements under different disposal scenarios: (i) static leaching tests designed to simulate the quiescent conditions in a stable impoundment, and (ii) a dynamic test to simulate waste materials exposed to the atmosphere in variable wet/dry storage conditions. The results indicated that liberating, separating and isolating the highest density fractions (>2.68 SG) which represents less than 5% of the coal refuse materials results in significant abatement of total dissolved solids and conductivity. Required modifications of the coal processing plants were suggested to segregate and subsequently isolate the environmentally sensitive fractions from the remaining refuse material.

In South Africa most of the municipal solid waste is currently removed and taken to land fill sites for engraving. A very small percentage of this is recycled due to lack of exploration of alternative means of further processing. In 2011 approximately 108 million tonnes of waste, mostly being general waste was generated in South Africa. Ninety eight (98) million tonnes of this waste was disposed of at landfill sites (The Department of Environmental Affairs [DEA], 2012). Environmental engineers are finding municipal solid waste management to be a challenge, similarly do the city planners and local administration. The main reason being the difficulty brought about by the complexity in composition of the waste material, no availability of waste minimization technologies and the scarcity of land for landfill sites and their environmental impact (Lal & Singh, 2012). Anyaegbunam (2013) recommend that there is a disposal technique that can convert most of the landfill waste at reduced amount of money to what is being paid on other disposal techniques nowadays, regardless of its form or composition and produce an excess of clean energy, and that technique is called Plasma Gasification which carries a high capability of being economically efficient. According to Young (2010), plasma arc Gasification is a high-temperature pyrolysis process whereby the organics of waste solids (carbon-based materials) are converted into syngas. The syngas can also be sent to gas turbines or reciprocating engines to produce electricity. Few of these plants exist in the world, however there is none in South Africa due to municipal budgetary constraints and lack of evidence for return on investment. Gasification can be described as a thermo-chemical process wherein carbonaceous or carbon-rich feed stocks, for instance tree trimmings or biomass, coal, and petro-coke are transformed into a complex gas containing hydrogen and carbon monoxide (and smaller quantities of carbon dioxide and other trace gases) under high pressure, oxygen exhausted, strong heat and/or steam environments (SRS Energy Solutions, 2016) The problem of electricity shortages continues to increase and communities are unable to cope with the continuous rising electricity bills. It is forecast that electricity demand will grow by approximately 85% and thereby reaching 31 700TWH (terawatt hours) in the year 2035. This growth rate is anticipated at an annual rate of 2.4% of which the economic and population growth will be the driving force, while on the other hand the daily increase of waste at landfill sites poses many problems with regards to the lifespan of the landfill in case green technological disposal processes are not introduced.

The depletion of more attractive thicker and easily accessible coal seams in the central Appalachia will direct attention towards the extraction of coal seams thinner than 28 in. This thesis investigates the feasibility of an integrated mining and backfilling system applicable to thin seams. Two conceptual mining systems, namely Auger mining and Self Advancing Miner, have been proposed for this purpose. Both these systems are designed to remotely mine coal from the seams. Several attempts were made in the past to mine coal in a similar fashion but were not very successful due to several problems inherent to thin seams. The lack of effective steering techniques, accurate coal/rock interface and pillar thickness detection techniques were the main shortcomings of the systems. These problems were addressed in the proposed conceptual mining systems. Several coal/rock interface and rib thickness detection techniques currently available in the market or in the prototype stage have been discussed. Recent developments in coal/rock interface detection and direction sensing techniques have good potential in alleviating the previously encountered problems. Sensitivity analyses have been performed to assess the of effect critical mining parameters on the production potential of these systems. The self advancing miner has been found to be more promising than auger mining. Conceptual panels and face layouts for both systems have been included. Two types of filling methods namely pneumatic and hydraulic are considered applicable under thin seam conditions. A backfilling technique using rubber hoses for fill placement can be applied with both methods. Sensitivity analysis have been performed to establish the relationship between face operation cost, filling cost per ton and development cost per foot. Resulting analyses indicate that panel cost per short ton of coal is more sensitive to filling cost than on development cost.
Master of Science

Today’s problems with emissions of green house gases, land filling of waste and depletion of the oil reserves calls for new energy systems based on alternative fuels like biomass and waste. Gasification is an attractive technology for the use of such solid fuels. Conventional gasification, in the vast majority of cases, uses in-reactor heat release from combustion of part of the feedstock, possibly coupled with a limited preheating of the agent, to obtain the necessary temperatures in the gasifier bed. During recent years, a new gasification technology, using highly preheated gasification agents (> 1273 K), has been developed. The extra heat brought into the process by the high temperature agent reduces the amount of feedstock that has to be oxidized to supply the necessary heat and the use of highly preheated agents has previously proven to have several positive effects on the fuel gas quality.In difference to the previous work on gasification with highly preheated agents, this thesis primarily focuses on the fundamental aspects namely, mass conversion, heating and ignition. It starts by considering single fuel particles or thin beds of fuel particles inserted into highly preheated agents. Mass conversion, heating and ignition are reported in function of the temperature and oxygen concentration of the agent and formulas for the prediction of ignition time and ignition mechanism are developed. The perspective is then widened to include the whole gasifier bed. Simulations of fixed bed batch gasification using highly preheated agents are performed with a mathematical model and used to study how the high agent temperature influences the mass conversion, devolatilisation front rate and the temperature distribution in the fixed fuel bed. Further, the gas quality and gasification efficiency are studied by means of large scale experiment. Ultimately, a thermodynamic analysis of the whole autothermal gasification system, including both a regenerative preheating system and the gasifier, is made.The particle study reports results from experiments with wood and coal and agents consisting of mixtures of nitrogen and oxygen in various proportions. It is shown that an increase in agent temperature from 873 K to 1273 K make the conversion process faster, mostly due to an early onset of the devolatilisation (fast drying) but also due to an increased devolatilisation rate (at least in the case of wood). The time to ignition also decreases significantly, particularly so between 873 and 1073 K. Further, it is shown that the higher the agent temperature, the more pronounced was also the tendency of the coal particles to heat significantly faster in oxygen diluted conditions (5,10 and 21% oxygen) than in inert (0% oxygen) or oxygen rich conditions (30, 50, 80 and 100% oxygen). An increase in agent temperature is also shown to reduce the dependency of the process on the oxygen concentration, at least in diluted conditions (5-21% oxygen). The results also indicate that for coal an increase in the oxygen concentration, specifically in the region above the atmospheric concentration, leads to a decreased dependency on the agent temperature. It is finally shown in the experiments with agent temperatures of 1073 and 1273 K that a flame is promptly formed even in very low concentrations of oxygen.The gasifier study reports results from simulation of batch air gasification and experiments in both batch and continuous up-draft fixed bed gasifier with wood and waste derived fuel and air and mixtures of air and steam. It is shown that the conversion process is faster the higher the air temperature. In particular somewhere between air temperatures of 623 K and 803 K the process behaviour changes. In fact, the devolatilisation rate is significantly increased in this region while it increases less sharply with air temperature below and above this temperature window. The temperature distribution in the bed shows less sharp gradients at high temperature (> 803 K) than at low temperatures (< 623 K). It is also showed experimentally and in fairly large scale that the use of highly preheated air for the gasification of biomass and waste derived fuels can produce - in continuous mode – relatively high yields of product syngas with relatively high fractions of combustible gases and probably also low content of tar. The efficiency of the gasification under these conditions, even when the extra heat input in the preheated agent is considered in the computation of the gasification efficiency, is shown to be comparable to that of conventional gasification techniques. The results also shows that with the use of steam in the agent, the content of hydrogen can be further increased with respect to gasification with only preheated air.In base of the results of the particle study and the gasifier study it is shown that a there exists two regimes of operation in function of the agent temperature, separated by the minimum agent temperature to guarantee spontaneous ignition regardless of the particle temperature. The value of this temperature depend on material properties and the kinetics of the reaction, thus also on the oxygen concentration. When agent temperatures below the minimum agent temperature to guarantee spontaneous ignition regardless of the particle temperature are used, the drying and devolatilisation are mainly controlled by the heat released by reactions. The heating of the fuel particles and their devolatilisation are relatively slow and the devolatilisation rate is highly oxygen dependent. In a fixed bed, the devolatilisation front rate is low and the bed is characterised by significant temperature gradients.When the agent temperature is higher than the minimum agent temperature to guarantee spontaneous ignition regardless of the particle temperature, the drying and devolatilisation are mainly controlled by the convective heat transfer from the preheated agent and the released volatiles ignite very fast even in diluted conditions. This results in very efficient heat transfer to the fuel particles. In the fixed fuel bed the process is characterized by a high devolatilisation front rate. Thus, the temperature gradients in the bed are significantly reduced and the gasification can be said to be thermally homogeneous. Thanks to high rates of heat transfer and mass conversion, the heating value of the dry produced syngas is high with high concentrations of combustible species. The ignition of the volatiles and the high temperatures all along the bed presumably contributes to the reduction of the tar content even in up-draft configurations. The high temperatures also allows for operation with reduced air – to – fuel ratios which further increased the value of the produced gas (thanks to less dilution by nitrogen).The system study presents a concept for an autothermal system including both preheating and gasification. Results from a thermodynamic analysis of such a system are reported. Autothermal operation of a thermally homogeneous gasifier is possible only in a twin component system in which the gasifier is coupled to a preheating system able to reach preheating temperatures well above the minimum agent temperature to guarantee spontaneous ignition regardless of the particle temperature. It is shown that to reach certain temperature levels of the gasification air, heat exchange between product gas and air is not enough and the preheating system has to improve the temperatures involved, for example by burning part of the produced gas in a regenerative preheater. Further, it is shown that in comparison to gasifier without such a system for additional preheating, the autothermal Thermally Homogeneous Gasification system has the ability to significantly improve the gas quality (in terms of heating value of the dry gas) without losing energy- or exergy efficiency to an appreciable extent.
QC 20100903

This thesis presents details of investigations into the potential for co-disposal of the two rejects from Clarence Colliery and Kable's Transport Sand Mine. Column experiments were undertaken to simulate field conditions. The experiment consisted of: 1/. creating the required co-disposal arrangement and structure in containers 2/. infiltrating water through each container and measuring the rates of infiltration and overflow 3/. measuring the chemical properties of the leachate water. Geotechnical tests of co-disposal pile stability were undertaken using a specially constructed shear box. Results of this study suggest the co-disposal of course coal washery reject from Clarence Colliery with clay tailings from Kable's Transport Sand Mine is a feasible option for managing the generation of acetic drainage. It is recommended that field trials comprise layers of coal reject and clay tailings in a 9:1 ratio. Layering the coal reject with clay tailings creates a semi-permeable barrier which acts to restrict water percolation through the reject as well as reacting with the leachate to increase the leachate pH and adsorb metals
Master of Engineering (Hons)

Thesis (MTech (Electrical Engineering))--Cape Peninsula University of Technology, 2016.
The generation of municipal solid waste has increased significantly due to the exponential population growth and it has become a global issue. Gasification technology, an alternative method for waste treatment is a thermochemical process where carbon-based material are exposed to an environment deprived in oxygen, was used for this project. The aim of this thesis is to study the gasification of plastic waste which is a potential alternative energy source using infrared heaters. To achieve this goal, fundamental studies have been numerically and experimentally conducted for an infrared gasifier and subsequently establishing the temperature profile for gasification using a small scale reactor. A detailed study on low density polyethylene was conducted using Infrared Spectrometry and thermal decomposition techniques such as Thermogravimetry and Differential Scanning Calorimetry were performed to establish the temperature at which plastic pellets sample used for this research gasify. The gasification behaviour of pelletized low density polyethylene (plastic pellets) was tested and three case studies were done to evaluate the most suitable temperature profile for the reactor to gasify the low density polyethylene at high temperature for less amount of time. Subsequently, the reactor model was simulated and results validate the use of reactor at an optimum temperature of 800 °C for a gasification process with less residue content. The reactor designed for this research is fully functional and validates the temperature behaviour predicted during simulation. The experimental results show infrared heaters are suitable for gas production using this gasification process.

It was hypothesized that South African FA and brine could sequester CO2 through mineral carbonation. A statistical approach was undertaken to optimize the % CaCO3 formed from FA/brine/CO2 interaction with input parameters of temperature, pressure, particle size and solid/liquid ratio (S/L) being varied. The ranges adopted for the input parameters were: temperature of 30 º
C or 90 º
C
pressure of 1 Mpa or 4 Mpa
four particle sizes namely bulk ash, >
150 &mu
m, <
20 &mu
m and 20 &mu
m- 150 &mu
m particle size range
S/L ratios of 0.1, 0.5 or 1. The FA/ brine dispersions were carbonated in a high pressure reactor varying the above mentioned input parameters. The fresh Secunda FA of various size fractions was characterized morphologically using scanning electron microscopy, chemically using X-ray fluorescence and mineralogically using qualitative X-ray diffraction. The carbonated solid residues on the other hand were characterized using quantitative X-ray diffraction, scanning electron microscopy, thermal gravimetic analysis and Chittick tests. The raw brine from Tutuka together with the carbonation leachates were characterized using inductively coupled mass spectrometry and ion chromatography. Total acid digestion was carried out to evaluate the differences in the total elemental content in both the fresh ash and the carbonated solid residues. The results suggested that South African FA from Secunda belongs to class F based on the CaO content as well as the total alumina, silica and ferric oxide content, while the RO brine from Tutuka were classified as NaSO4 waters...

Thesis (Doctor of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2017.
The search for alternatives to fossil fuel is necessary with a view to reducing the negative environmental impact of fossil fuel and most importantly, to exploit an affordable and secured fuel source. This study investigated the viability of municipal solid waste gasification for a fuel cell system. Potential solid fuels obtained from the study in the form of refuse-derived fuel (RDF) had high heating value (HHV) between 18.17 MJ/Kg - 28.91 MJ/Kg with energy density increased from 4142.07 MJ/m3 to 10735.80 MJ/m3. The molecular formulas of RDF derived from Ladies Smith drop-off site, Woodstock drop-off site and an average molecular formula of all thirteen municipal solid waste (MSW) disposal facilities were CH1.43O1.02, CH1.49O1.19, and CH1.50O0.86 respectively. The comparative ratios of C/H were in the range of 7.11 to 8.90. The Thermo Gravimetric Analysis showed that the dehydration, thermal decompositions, char combustions were involved in the production of gaseous products but flaming pyrolysis stage was when most tar was converted to syngas mixture. The simulation of RDF gasification allowed a prediction of the RDF gasification behaviour under various operating parameters in an air-blown downdraft gasifier. Optimum SFR (steam flowrate) values for RDF1, RDF2 and RDF3 were determined to be within these values 2.80, 2.50 and 3.50 and Optimum ER values for RDF1, RDF2 and RDF3 were also determined to be within these values 0.15, 0.04 and 0.08. These conditions produced the desired high molar ratio of H2/CO yield in the syngas mixture in the product stream. The molar ratios of H2/CO yield in the syngas mixture in the product stream for all the RDFs were between 18.81 and 20.16. The values of H2/CO satisfy the requirement for fuel cell application. The highest concentration of heavy metal was observed for Al, Fe, Zn and Cr, namely 16627.77 mg/Kg at Coastal Park (CP), 17232.37 mg/Kg at Killarney (KL), 235.01 mg/Kg at Tygerdal (TG), and 564.87 mg/Kg at Kraaifontein (KF) respectively. The results of quantitative economic evaluation measurements were a net return (NR) of $0.20 million, a rate of return on investment (ROI) of 27.88 %, payback time (PBP) of 2.30 years, a net present value (NPV) of $1.11 million and a discounted cash flow rate of return (DCFROR) of 24.80 % and 28.20 % respectively. The results of the economic evaluations revealed that some findings of the economic benefits of this system would be viable if costs of handling MSW were further quantified into the costs analysis. The viability of the costs could depend on government responsibility to accept costs of handling MSW.

Gasification of black liquor is an alternative to the combustion of black liquor, which is currently the dominant form of chemical recovery in the paper industry. Gasification of black liquor offers the possibility of higher thermal efficiencies than combustion, reducing manufacturing costs and creating new revenue streams through a forest biorefinery. Pressurizing the gasification reactor further enhances the efficiency advantage of gasification over combustion. This study uses a pressurized entrained flow reactor (PEFR) to study black liquor gasification behavior under pressures, temperatures, and heating rates similar to those of next-generation high-temperature black liquor gasifiers. The effects of pressure on black liquor char morphology, gasification rates, pyrolysis carbon yields, and sulfur phase distribution were studied. These characteristics were investigated in three main groups of experiments at 900oC: pyrolysis (100% N2), gasification with constant partial pressure (0.25 bar H2O and 0.50 bar CO2), and gasification with constant mole fraction (10% CO2, 2% H2O, 1.7% CO, 0.3% H2), under five, ten, and fifteen bar total pressure. It was found that pressure had an impact on the char physical characteristics immediately after the char entered the reactor. Increasing pressure had the effect of decreasing the porosity of the chars. Pressure also affected particle destruction and reagglomeration mechanisms. Surface areas of gasification chars decreased with increasing pressures, but only at low carbon conversions. The rate of carbon conversion in gasification was shown to be a function of the gas composition near the particle, with higher levels of inhibiting gases slowing carbon conversion. The same phenomenon of product gas inhibition observed in gasification was used to explain carbon conversions in pyrolysis reactions. Sulfur distribution between condensed and gas phases was unaffected by increasing total pressure in the residence times investigated. Significant amounts of sulfur are lost during initial devolatilization. With water present this gas phase sulfur forms H2S and did not return to the condensed phase.

The separate land disposal of coal refuse and fly ash presents difficulties throughout the Appalachian region, both in terms of disposal costs per acre and in terms of its potential environmental impacts on soil, ground water, revegetation, and slope stability. The purpose of this study was to determine how fly ash addition to coal refuse would impact on certain geotechnical properties of the refuse disposal piles, and whether the refuse-fly ash blends would be suitable as co-disposed materials. Accordingly, the compaction, permeability and shear strength characteristics of the refuse-fly ash blends were experimentally determined for varying fly ash percentages. The compaction test results indicated that, with increasing fly ash, the maximum dry density of these blends marginally decreased. The permeability test results showed that the permeability of the test specimens progressively decreased with the increase in fly ash. The shear strength results demonstrated that the addition of fly ash did not significantly influence the shear strength of the refuse. The critical factor of safety determined during slope stability analysis revealed that the tested slope geometries were stable for long term, drained conditions (using the STABGM computer program). The volume change analysis determined that there was a minimal expansion in the volume of refuse when it was blended with fly ash. However, it may be noted that all the stated results depend on a number offactors, including the nature of the refuse and fly ash used. Therefore, these findings would be specific to bulk blends of coal refuse and fly ash only. In general, this study indicates that fly ash can be beneficially reused with respect to the geotechnical properties evaluated. Co-disposal of fly ash and coal refuse may be a reasonable alternative to present disposal methods.
Master of Science

Coarse coal refuse is difficult to reclaim due to high potential acidity and coarse fragment content, low water holding capacity, low fertility, and other problems. Little is known about coal refuse properties, particularly as they relate to revegetation potential. This study was undertaken to determine the physical and chemical properties of composite samples from 27 coal waste piles of varying age. Selected physical and chemical properties varied widely across this sample set. The mean coarse fragment (>2mm) content of these materials was 60%. The average texture of the fine (<2mm) fraction was a sandy loam with 15% clay. The mean water retention difference, between 0.03 MPa and 1.5 MPa of soil moisture tension, on a whole sample basis was 0.08 g water/g refuse. The pH values varied from 8.3 to 3.0, and the older piles generally had lower pH values than the more recent piles. The saturated paste electrical conductivity (EC) was higher in the younger coal waste materials. Total elemental analysis revealed that Si, Al, Fe, and K were the most abundant elements in these materials. The mineralogy of three selected samples was found to be dominated by quartz in the sand and silt fraction and mica in the clay fraction. The physical factor most limiting to plant growth was found to be low water holding capacity. Low pH was found to be the chemical factor most limiting to plant survival. These findings indicate that some refuse piles may be suitable for direct seeding, but many will require heavy lime and/or organic treatments.
Master of Science

To assess strategies aimed at minimizing the release of trace elements and the impact of disposal of coal waste materials on the environment, two long-term leaching experiments of up to five months duration were performed using waste materials from two plants cleaning high and low sulfur bituminous coal. The tests evaluated the mobility of major trace elements under different disposal scenarios: (i) a static leaching test designed to simulate the quiescent conditions encountered by coal waste material stored under water in a stable impoundment, and (ii) a dynamic test to simulate waste materials exposed to the atmosphere, either in variable wet/dry storage conditions, or in unusual circumstances like those resulting from breaching of an impoundment containment wall. The results indicate that different refuse streams have different leaching characteristics due to difference in their mineralogy and the mobility of most elements is enhanced under highly alkaline or acidic conditions with a few being mobilized under both conditions, suggesting that the minimization of element mobility requires the pH value of the medium to be maintained around neutral. In addition, most of heavy metals were associated with the illite and pyrite minerals. Two strategies of treating coal refuse were evaluated: fly ash mixed with coarse refuse and co-disposal of coarse and fine refuse. Both methods were found to neutralize the pH conditions and thus reduce mobility of the trace elements in static leaching tests whereas the opposite was found from dynamic experiments. The results indicate that such controlled storage under water could retard acid generation and the mobility of trace elements.

The need for effective disposal of huge volumes of industrial waste is becoming more challenging due to expected imposition of stringent pollution control regulations in the near future. Thermochemical conversion, particularly gasification of organics in the waste is considered the best route from the perspective of volume reduction and prevalent eco-friendly concept of waste-to-energy transformation. It is considered imperative to have adequate understanding of basic combustion features as a part of the thermochemical conversion process, leading to gasification. The aim of this thesis is to understand the fundamental combustion processes associated with one of the top listed hazardous wastes from distilleries (Biochemical Oxygen Demand (BOD) ~ 40,000 - 50,000 mg/L), commonly known as vinasse, stillage or spent wash, through experiments and modeling efforts. Specially designed experiments on distillery effluent combustion and gasification are conducted in laboratory scale reactors. As an essential starting point of the studies on ignition and combustion of distillery effluent containing solids consisting of 62 ± 2 % organics and 38 ± 2 % inorganics (primarily sugarcane derivatives), the roles of solids concentration, drop size and ambient temperature were investigated through experiments on (1) liquid droplets of 65 % and 77 % solids (remaining water) and (2) spheres of dried effluent (100 % solids) of size 0.5 mm to 20 mm diameter combusted at ambient temperatures of 773 to 1273 K. The investigation reveals that the droplets burn with two distinct regimes of combustion, flaming and char glowing. The ignition delay ‘t1’ of the droplets increased with size as is in the case of non-volatile droplets, while that of bone-dry spheres was found to be independent of size. The ‘t1’ decreased with increase in solids concentration. The ignition delay has showed an Arrhenius dependence on temperature. The initial ignition of the droplets and the dry spheres led to either homogeneous (flaming) or heterogeneous (flameless) combustion, depending on the ambient temperature in the case of sphere and on solid concentration and the ambient temperature, in the case of liquid droplets. The weight loss during the flaming combustion was found to be 50 - 80 % while during the char glowing it was 10-20 % depending on the ambient temperature. The flaming time tc is observed as tc~ d2c , as in the case of liquid fuel droplets and wood spheres. The char glowing time tc' is observed as tc ~ d2c as in the case of wood char, though the inert content of effluent char is as large as 50 % compared to 2 - 3 % in wood char. In the case of initial flameless combustion, the char combustion rate is observed to be lower. The heterogeneous char combustion in quiescent air in controlled temperature conditions has been studied and modeled using one-dimensional, spherico-symmetric conservation equations and the model predicts most of the features of char combustion satisfactorily. The measured surface and core temperatures during char glowing typically are in the range of 200 to 400 K and are higher than the controlled temperature of the furnace. Based on the results of single droplet combustion studies, combustion experiments were conducted in a laboratory scale vertical reactor (throughput ranging from 4 to 10 g/s) with the primary aim of obtaining sustained combustion. Spray of effluents with 50 % and 60 % solids (calorific value 6.8 - 8.2 MJ/kg), achieved by an air blast atomizer, was injected into a hot oxidizing environment to determine the parameters (ambient temperature and air-fuel ratio) at which auto-ignition could occur and subsequently studies were continued to investigate pre-ignition, ignition and combustion processes. Effluent with lower solids concentration was considered first from the point of view of the less expensive evaporator required in the field conditions for concentration and a spin-off in terms of better atomization consequently. Three classes of experiments were conducted: 1) Effluent injection from the wall with no auxiliary heat input, 2) Effluent injection with auxiliary heat input and 3) effluent injection within kerosene enveloping flame. Though individual particles in the spray periphery were found to combust, sustained spray combustion was not achieved in any of the three sets of experiments even with fine atomization. While conducting the third class of experiments in an inclined metallic reactor, sustained combustion of the pool resulting of accumulated spray seemed to result in large conversion of carbon. This led to the adoption of a new concept for effluent combustion in which the residence time is controlled by varying reactor inclination and the regenerative heat transfer from the product gases supplies heat for endothermic pre-ignition process occurring on the bed. Combustion and gasification experiments were conducted in an inclined plate reactor with rectangular cross section (80 mm x 160 mm) and 3000 mm long. A support flame was found necessary in the injection zone in addition to the regenerative heat transfer. Effluent with 60% solids was injected as film on the reactor bed. This film disintegrated into fine particles due to induced aerodynamic stretching and shear stripping. Combustion of individual particles provided exothermic heat profile and resulted into high carbon conversion. However, effluent clogging in the cold injection zone hindered system from attaining steady state. Effluent injected directly on the hot zone caused it to remain mobile due to the spheroidal evaporation and thus assuaging this problem. Improved mass distribution was achieved by displacing nozzle laterally in a cycle, actuated by a mechanism. Consistent injection led to sustained effluent combustion with resulting carbon conversion in excess of 98 %. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 14.0 %, CO = 7.0 %, H2 = 12.9 %, CH4 - 1 % H2S = 0.6 - 0.8 % and about 2 % of saturated moisture. This composition varied due to variation in temperature (± 30 K) and is attributed to combined effect of local flow variations, shifting zones of endothermic processes due to flowing of evaporating effluent over a large area. In order to minimize this problem, experiments were conducted by injecting effluent at higher solids (73 % solids is found injectable). The effluent was found to combust close to the injection location-due to the reduced ignition delay and lower endothermic evaporation load helped raising the local temperature. This caused the pyrolysis to occur in this hottest zone of the reactor with higher heating rates resulting in larger yield of devolatilized products and improved char conversion. Effluent combustion was found to sustain temperature in the reactor under sub-stoichiometric conditions without support of auxiliary heat input and achieved high carbon conversion. These results inspired the use of higher concentration effluent, which is also known in the case of wood to have improved gasification efficiency due to reduction in moisture fraction. In addition, the recent studies on the sulfur emission in the case of black liquor combustion in recovery boilers have revealed that with increase in solids concentration, release of sulfur in gas phase is reduces. The required concentration can be carried out using low-grade waste heat from the reactor itself. It was found through experiments that, even though spray ignition occurred at this concentration, the confined reactor space prevented the spray from attaining sustained combustion. This led to the conduct of experiments in a new vertical reactor with adequate thermal inertia, essential to prevent variations in local temperature to reach a steady state gasification and required space to accommodate the spray. The results of the experiments conducted in the vertical reactor in which effluents with 73 % solids, heated close to the boiling point and injected as fine spray in a top-down firing mode are consolidated and reported in the thesis in detail. Single particle combustion with enveloping faint flame was seen unlike stable flame found in coal water slurry spray combustion. Sustained gasification of gas-entrained particles occurred at reactor temperature in the range of 950 K - 1000 K and sub-stoichiometric air ratio 03 - 0.35 without the support of auxiliary fuel. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 10.0 -11.5 %, CO - 10.0 - 12.0 %, H2 - 6.7 - 8.0 %, CH4 = 1.75 % H2S = 0.2 - 0.4 % and about 2 % of saturated moisture. The carbon conversion obtained was in the range of 95 - 96 %. These experiments have provided the conditions for gasification. The extraction of potassium salts (mostly sulfates, carbonate and chloride) from the ash, using a simple water leaching process, was found to recover these chemicals to as high an extent as 70 - 75 % of total ash. In summary it is concluded that increasing the solid concentrations to as high levels as acceptable to the system (~ 75 %) and introducing as a fine spray of heated material (~ 363 K) into furnace with air at sub-stoichiometric conditions in a counter current combustion reactor will provide the frame work for the design of a gasification system for vinasse and similar effluent material. The thesis consists of seven chapters. Chapter 1 introduces the problem and motivation of the work presented in the thesis. Literature review is presented in Chapter 2. The Chapter 3 deals with the single particle combustion studies. The results of effluent spray combustion experiments conducted in a laboratory scale vertical reactor are presented in Chapter 4. The results of combustion and gasification experiments conducted in another variant of a reactor, namely, inclined flat plate rectangular reactor is consolidated in Chapter 5. The results of gas-entrained spray gasification experiment of higher concentration effluent injected as spray in the vertical reactor are presented in Chapter 6. The general conclusions and scope for the future work are presented in the concluding chapter 7.

Thesis (Ph. D.)--University of Missouri-Columbia, 1998.
Trademark symbol follows Chemchar in title. Typescript. Vita. Includes bibliographical references (leaf 130). Also available on the Internet.

This dissertation examines the contestations over the politics of knowledge, risk, and environmental justice in three fenceline sites. Mobilizing the fenceline standpoint to study risk strengthens our objective understanding of the social situatedness of risk. To illustrate how a fenceline standpoint contributes to stronger objectivity of risk contestations, I survey public discourse of coal slurry extraction in Black Mesa, Arizona using an environmental justice framework. Discursive justifications for the construction of the slurry pipeline reveal how environmental injustice in the fenceline community emerged through urban controversies over water and power generation that excluded a fenceline standpoint. Insights from Black Mesa frame the next two cases: open burning hazardous waste at Radford Army Ammunition Plant, and M6 Disposal at Camp Minden, Louisiana. At Radford, scholar-activist research examines the contestations of risk at one of the most hazardous waste facilities in the nation. I analyze the construction of risk from open burning of hazardous waste from a fenceline standpoint. I discursively situate the controversy over fenceline community risk from open burning, by showing the inadequacies of official risk assessments. Critical discourse analysis of risk shows the extant contestations over the practice of open burning. In juxtaposition to Radford, the Camp Minden open burn controversy demonstrates how a fenceline movement successfully constructed alternatives to open burning. Fenceline success in Minden is forcing scrutiny over the risks produced by the practice of open burning explosives across the United States. The activation of fenceline knowledge and expertise, through grassroots organizing, is propelling inquiry from scientific and technical experts of the American Chemical Society who are questioning why the Department of Defense and the Environmental Protection Agency have approved the use of open burning at other sites despite safer alternative technology. Synthetically, each case illustrates the importance of fenceline knowledge as a crucial site of expertise. I present an argument for how a fenceline standpoint can challenge regulatory and producer constructions of fenceline risk. The creation of a program of research: Critical Risk Analysis, offers a model for scholar-activist intervention on the fenceline. The Camp Minden Dialogue demonstrates a successful example of how fenceline expert-activists can influence the construction of risk. Normatively, I build the argument that environmental justice research within Science and Technology Studies ought to situate the fenceline standpoint as equal to the competing epistemological claims of production and regulatory experts in order to strengthen the objectivity of our research in contested fenceline sites.
Ph. D.

With increasing energy demand globally and, in particular, in South Africa coupled with depletion of the earth’s fossil energy resources and growing problem of disposal of nonbiodegradable waste such as waste tyres, there is a need and effort globally to find alternative energy from waste material including waste tyres. One possible way of exploiting waste tyre for energy or chemicals recovery is through gasification for the production of syngas, and this is what was investigated in this study. The possibility of gasification of waste tyre blended with coal after pyrolysis was investigated and two Bituminous coals were selected for blending with the waste tyre in co-gasification. A sample of ground waste tyre / waste tire, WT, a high vitrinite coal from the Waterberg coalfield (GG coal) and a high inertinite coal from the Highveld coalfield (SF coal) were used in this investigation. The waste tyre sample had the highest volatile matter content of 63.8%, followed by GG coal with 27% and SF coal with 23.8%. SF coal had the highest ash content of 21.6%, GG coal had 12.6% and waste tyre had the lowest of 6.6%. For the chars, SF char still had the highest ash of 24.8%, but WT char had higher ash, 14.7%, when compared to GG char with 13.9% ash. The vitrinite content in GG coal was 86.3%, whilst in SF coal it was 25% and SF coal had a higher inertinite content of 71% when compared to GG coal with 7.7%. SF char had the highest BET surface area of 126m2/g, followed by GG char with 113m2/g, and WT had the lowest value of 35.09m2/g. The alkali indices of the SF, WT and GG chars were calculated to be 8.2, 4.2 and 1.7 respectively. Coal samples were prepared by crushing and milling to particle sizes less than 75μm before charring in a packed bed balance reactor at temperatures up to 1000oC.Waste tyre samples were charred at the same conditions before milling to < 75μm particle size. Coal and WT chars were blended in ratios of 75:25, 50:50 and 25:75 before gasification experimentation. Carbon dioxide gasification was conducted on the blends and the pure coal and WT chars in a Thermogravimetric analyser (TGA) at 900oC, 925oC, 950oC and 975oC and ambient pressure. 100% CO2 was used at a flow rate of 2L/min. Reactivity of the pure char samples was found to be in the order SF > GG > WT, and the relationship between the coal chars’ reactivities could be explained by the high ash content of the SF char and low reactivity of the WT char corresponds to its low BET surface area. In general, the coal/WT char mixtures were less reactive than the respective coal, but more reactive than the pure WT char, the only exception being the 75% GG char blend which was initially more reactive than the GG char, and reactivity decreased with increasing WT content. For all samples reactivity increased with increasing temperature. The relationship between the reactivities of the GG char and its blends and that of the SF char and its blends was found to be affected by the amount of WT char added, especially at the lower temperatures 900oC and 925oC. SF coal is more reactive than GG coal, but at 900oC and 925oC, the reactivity of GG/WT blends improves in relation to the SF/WT blends with an increase in the ratio of WT in the blends, i.e. the 25% GG char blend is more reactive than the 25% SF char blend. The reactivity of the coal/WT blends was also checked against predicted conversion rates based on the conversion rates of the pure WT and coal samples. At 900oC and 925oC, the reactivities of the blends of both coal chars with WT char were found to be greater than the predicted conversion rates, and for the GG/WT blends the deviation increased with increasing WT ratios, while for the SF/WT blends the deviation increased with increasing SF ratios. These findings suggest the presence of synergism or enhancement between the coal chars and WT char in gasification reactions. The random pore model (RPM) was used to model the gasification results and it was found to adequately describe the experimental data. Activation energies determined with the RPM were found to be 205.4kJ/mol, 189.9kJ/mol and 173.9kJ/mol for SF char, WT char and GG char respectively. The activation energies of the coal/WT blends were found to be lower than those of both the pure coal and the pure WT chars. For the GG/WT blends the activation energy decreased with increasing WT char ratio, while for the SF/WT blends the activation energy decreased with increasing SF char ratio. The trends of the activation energies and conversion rates of the blends point to synergism or enhancement between the coal and WT chars in CO2 gasification reactions, and in the GG/WT blends this enhancement is driven more by the WT char, while in SF/WT blends it is driven by SF chars. It is possible that enhancement of the reactions is caused by mineral matter catalysis of the gasification reactions. The ash contents and alkali indices of the pure samples follow the order SF > WT > GG.
MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Yes
In order to evaluate the feasibility of using CO2 as a gasifying agent in the conversion of carbonaceous materials to syngas, gasification characteristics of coal, a suite of waste carbonaceous materials, and their blends were studied by using a thermogravimetric analyser (TGA). The results showed that CO2 gasification of polystyrene completed at 470 °C, which was lower than those of other carbonaceous materials. This behaviour was attributed to the high volatile content coupled with its unique thermal degradation properties. It was found that the initial decomposition temperature of blends decreased with the increasing amount of waste carbonaceous materials in the blends. In this study, results demonstrated that CO2 co-gasification process was enhanced as a direct consequence of interactions between coal and carbonaceous materials in the blends. The intensity and temperature of occurrence of these interactions were influenced by the chemical properties and composition of the carbonaceous materials in the blends. The strongest interactions were observed in coal/polystyrene blend at the devolatilisation stage as indicated by the highest value of Root Mean Square Interaction Index (RMSII), which was due to the highly reactive nature of polystyrene. On the other hand, coal/oat straw blend showed the highest interactions at char gasification stage. The catalytic effect of alkali metals and other minerals in oat straw, such as CaO, K2O, and Fe2O3, contributed to these strong interactions. The overall CO2 gasification of coal was enhanced via the addition of polystyrene and oat straw.

M.Sc. (Geography)
Coal mined in South Africa for the competitive international market, has to be selected to meet the many quality specifications of customers. This upgrading is done by washing the coal in a heavy medium separation plant. Marketable coal, discard and slurry are produced from this washing. Discard consists mainly of poor quality coal, carbonaceous shale and waste rock. Iron pyrite (FeS2) occurs in all of the above in higher concentrations than in the marketable coal. Both the carbonaceous materials and pyrites generate heat when oxidizing. If this oxidation is not arrested at an early stage on a discard dump and the temperature of the dump increases above BOoC, spontaneous combustion is quite likely. The South African Council for Scientific and Industrial Research (CSIR) has estimated that smouldering discard dumps in the Eastern Transvaal highveld region contribute approximately 400 000 tons of S02 per annum to the atmospheric pollution in that area. As a result, significant localized acid rain occurs, Louw (1990). The oxidation of iron pyrites to sulphuric acid, and the oxidation of other trace elements, is accelerated under the high temperature conditions generated by spontaneous combustion. Leaching of these oxidation products results in local groundwater and surface water contamination. This study describes different disposal technique and pilot study aimed at minimising the oxidation within the dumps. Slurry, which consists of discard and/or coal of less than 1 mm in diameter is co-deposited with discard in sequential layers of approximately 200 mm thick. This has resulted in reducing the permeability, porosity and air and water exchange within the dump. This in turn has led to a reduction in spontaneous combustion, pollution and costs. A visual increase in stability of the discard dumps, moisture content and operational ease of placement were experienced. The saleable value of the dump as a low value heat source is also preserved.

A project report submitted to the Faculty of Engineering, University of the Witwatersrand, Johannesburg in partial fulfilment of the requirements for the degree of Master of Science in Engineering Johannesburg, 1993
Superfines of less than 200 micron are generated when mining coal. They have not been successfully beneficiated in the past and are not acceptable to the consumer. A processh as been developed whereby the superfines are beneficiated, briquetted without the use of binders and devolatilised to produce a premium smokeless briquette which will attract a premium price in the export market. [Abbreviated abstract. Open document to view full version]
MT2017

Although products of coal combustion (PCCs) such as coal ash are currently exempted from classification as a hazardous waste in the United States under the 1976 Resource Conservation and Recovery Act (RCRA), the U.S. Environmental Protection Agency (EPA) is now revising a proposed rule to modify disposal practices for these materials in order to prevent contamination of ground- and surface water sources by leached trace elements. This paper analyzes several aspects of EPA’s scientific reasoning for instating the rule, with the intent of answering the following questions: 1) Are EPA’s cited values for PCC production and disposal accurate estimates of annual totals?; 2) In what ways can EPA’s leaching risk modeling assessment be improved?; 3) What is the total quantity of trace elements contained within all PCCs disposed annually?; and 4) What would be the potential costs and feasibility of reclassifying PCCs not under RCRA, but under existing NRC regulations as low-level radioactive waste (LLRW)? Among the results of my calculations, I found that although EPA estimates for annual PCC disposal are 20% larger than industry statistics, these latter values appear to be closer to reality. Second, EPA appears to have significantly underestimated historical PCC disposal: my projections indicate that EPA’s maximum estimate for the quantity of fly ash landfilled within the past 90 years was likely met by production in the last 30 years alone, if not less. Finally, my analysis indicates that while PCCs may potentially meet the criteria for reclassification as low-level radioactive waste by NRC, the cost of such regulation would be many times that of the EPA June proposed disposal rule ($220-302 billion for PCCs disposed in 2008 alone, versus $1.47 billion per year for the Subtitle C option and $236-587 million for Subtitle D regulatory options).
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Waste rocks (WRs) from coal mining and fly ash (FA) from coal combustion were studied to determine the potential of the WRs to generate AMD, FAs to neutralise it and estimate their impacts on environment. The ultimate goal was to develop a methodology based on co-disposal to mitigate the environmental problems associated to both wastes. Two methods for co-disposal were tested: i) Mixing WRs and FAs and ii) covering WRs with FAs. WRs were sampled from the Lakhra coal mines in Pakistan (PK), which has an estimated coal reserves of 1.3 Btonne, varying from lignite to sub-bituminous quality. The FA was sampled from a power plant utilising coal from Lakhra coal mines and is situated in close vicinity (15km) of the mine site. For comparative purposes a bituminous FA from Finland (FI) and biomass FA from Sweden (SE) were also characterised. The WRs and FA samples were characterised by mineralogical and geochemical methods. Besides organic material (coal traces), quartz, pyrite, kaolinite, hematite, gypsum and traces of calcite, lime, malladerite, spangolite, franklinite and birnessite were identified in WRs by XRD. The major elements Si, Al, Ca and Fe were in the range (wt. %) of 8 – 12, 6 – 9, 0.3 – 3 and 1 – 10, respectively, with high S concentrations (1.94 – 11.33 wt. %) in WRs. The AMD potential of WRs ranged from -70 to -492 kg CaCO3 tonne-1. All FAs contained quartz, with iron oxide, anhydrite and magnesioferrite in PK, mullite and lime in FI and calcite and anorthite in SE. The Ca content in SE was 6 and 8 times higher compared to PK and FI, respectively. FAs were enriched in As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn compared to continental crust. The acid neutralising potential of PK was equivalent to 20 kg CaCO3 tonne-1 compared to 275 kg CaCO3 tonne-1 (SE) and 25 kg CaCO3 tonne-1 (FI). During the period of 192 days in weathering cell experiments (WCE), the pH of leachates from most acidic WRs was maintained from 1 to 2.5, whereas, the less acidic WRs produced leachates of mildly acidic (2.7) to neutral (7.3) pH. The leachates from very acidic WRs ranged in the concentrations of Fe, SO24− and Al from mg L-1 to g L-1. The samples were subjected to column leaching experiments (CLE) in which mixture (FA:WR; 1:3) and cover (FA:WR; 1:5) cases were mimicked (with 10mm particle size) and effects of particle size (2, 5 and 10mm) on element leaching were studied. Despite having the lowest acid-neutralisation potential compared to FI and SE, co-disposal of PKFA as mixture readily provides acid buffering minerals, resulting in better start-up pH conditions and leachate quality. However, acidity produced by secondary mineralisation contributes towards the acidification of the system, causing stabilisation of pH at around 4.5−5. Secondary mineralisation (especially Fe- and Al-mineral precipitation) also removes toxic elements such as As, Pb, Cu, Zn, Cd, Co, Ni and Mn, and these secondary minerals can also buffer acidity when the pH tends to be acidic. In contrast, the pH of the leachates from the PKFA cover scenario gradually increased from strongly acidic to mildly acidic and circumneutral along with decrease in EC and elemental leaching in different WRs. Gradually increasing pH can be attributed to the cover effect, which reduces oxygen ingress, thus sulphide oxidation, causing pH to elevate. Due to the fact that pH~4–5 is sufficient for secondary Fe- and Al-mineral precipitation which also removes toxic elements (such as Cd, Co, Cu, Zn and Ni) by adsorption and/or co-precipitation, the FA cover performs well enough to achieve that pH until the conclusion of the CLE. However, due to the slower reactivity of the buffering system (additional to the initial flush-out), leaching in the beginning could not be restricted. The co-disposal of FA as cover and/or mixture possesses potential for neutralisation of AMD and improving leachate quality significantly. Particle size of the WRs affected the leaching of the sulphide related elements (such as Fe, S, Zn, Co, Cr, Cu, Mn and Ni) in CLE and WCE. Experiments with ≤1mm particle size constantly produced acidic and metal laden leachates. Co-disposal of FA and WRs as cover and mixture need to be investigated on pilot-scales before full-scale application.

The use of black liquor gasification as an alternative to conventional chemical and energy recovery systems for spent liquors is an area of particular interest to the pulp and paper industry. The motivation to explore this technology is to improve the thermal efficiency of the recovery process by utilizing the energy content of the spent black liquor more effectively and provide chemical recovery for sodium and sulphur containing liquors for a local pulp and paper mill. A study of the available gasification technologies showed that the steam reforming process marketed by ThermoChem Recovery International is particularly suited to the mill in that it can handle a change to a sulphite pulping chemistry and also handle silica removal which is an inherent problem with the bagasse raw material that the mill uses. However the technology required further development and confirmation of process suitability before implementation at the mill. This aim of this project was to build and operate a gasifier based on the TRI concept to determine if this process is suitable for recovery of SASAQ black liquor from bagasse pulping. This included gaining an understanding of the process variables like the black liquor solids composition and the non-process element levels and required carrying out a mass balance on inorganic components across the reactor as well. The focus of this investigation was primarily on the front end of the project and entailed basic and detailed design of a pilot gasification unit. The pilot unit was subsequently constructed, commissioned and operated to prove the unit met the design intent. Preliminary results showing the conceptual proof of the technology are presented as well as performance tests showing the unit capability of gasifying a 3.1 1Ihr 60% solid content black liquor feed. Problematic areas that could influence the design of a scale-up unit were identified and highlighted for further development, with proposed solutions.
Thesis (M.Sc.)-University of KwaZulu-Natal, Durban, 2005.

Geological carbon sequestration, as a method of atmospheric greenhouse gas reduction, is at the technological forefront of the climate change movement. During sequestration, carbon dioxide (CO���) gas effluent is captured from coal fired power plants and is injected into a storage saline aquifer or depleted oil reservoir. In an effort to fully understand and optimize CO��� trapping efficiency, the capillary trapping mechanisms that immobilize subsurface CO��� were analyzed at the pore-scale. Pairs of proxy fluids representing the range of in situ supercritical CO��� and brine conditions were used during experimentation. The two fluids (identified as wetting and non-wetting) were imbibed and drained from a flow cell apparatus containing a sintered glass bead column. Experimental and fluid parameters, such as interfacial tension, fluid viscosities and flow rate, were altered to characterize their relative impact on capillary trapping. Computed x-ray microtomography (CMT) was used to identify immobilized CO��� (non-wetting fluid) volumes after imbibition and drainage events. CMT analyzed data suggests that capillary behavior in glass bead systems do not follow the same trends as in consolidated natural material systems. An analysis of the disconnected phases in both the initial and final flood events indicate that the final (residual) amount of trapped non-wetting phase has a strong linear dependence on the original amount of non-wetting phase (after primary imbibition), which corresponds to the amount of gas or oil present in the formation prior to CO��� injection. More importantly, the residual trapped gas was also observed to increase with increasing non-wetting fluid phase viscosity. This suggests that CO��� sequestration can be optimized in two ways: through characterization of the trapped fluid present in the formation prior to injection and through alterations to the viscosity of supercritical CO2.
Graduation date: 2013

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg In fulfillment of the requirements for the degree of Master of Science in Geography and Environmental Studies 31 May 2018
South Africa will be dependent on coal for power generation for many decades to come, before a complete transition is achieved where more energy will be generated from non-fossil fuel sources. Through case studies of Hendrina and Kendal Power Stations, this study explored how the management of fly ash (FA) waste in South Africa can be improved to minimise its impact on the environment and human health and examined the potential recycling applications that can benefit local communities. The study drew insights from an environmental justice framework to examine the pollution impacts that FA is exposing to the local community. The environmental justice theory is based on the principle that all people have a right to live in an environment that enhances their wellbeing. Empirical evidence obtained from local community’s in-depth interviews revealed that FA is impacting on the health of communities by exposing them to respiratory and other illnesses and it is also affecting their livelihoods which primarily involves farming. A just transition theory was employed to examine potential socio economic opportunities that can be derived from FA recycling to fulfil redistributive measures that can reduce inequality and eradicate poverty in local communities. Some of Eskom’s power stations like Hendrina are nearing the end of their lifespan since their commissioning in the 1960’s and 1970’s. To aid a just transition, ash recycling was found to have the potential to address the socio economic situation of the power station’s employees and the local communities. The study found that local communities generally lack knowledge about coal ash recycling and need to be empowered and supported to partake in ash recycling ventures. The study argues that a shift in the ash recycling regime is needed in order to benefit local communities and facilitate a just transition to a clean energy production.
MT 2018

Manure-based biomass (MBB) has the potential to be a source of green energy at large coal-fired power plants and on smaller-scale combustion systems at or near confined animal feeding operations. Although MBB is a low quality fuel with an inferior heat value compared to coal and other fossil fuels, the concentration of it at large animal feeding operations can make it a viable source of fuel. Mathematical models were developed to portray the economics of co-firing and reburning coal with MBB. A base case run of the co-fire model in which a 95:5 blend of coal to low-ash MBB was burned at an existing 300-MWe coal-fired power plant was found to have an overall net present cost of $22.6 million. The most significant cost that hindered the profitability of the co-fire project was the cost of operating gas boilers for biomass dryers that were required to reduce the MBB's moisture content before transportation and combustion. However, a higher dollar value on avoided nonrenewable CO2 emissions could overrule exorbitant costs of drying and transporting the MBB to power plants. A CO2 value of $17/metric ton was found to be enough for the MBB co-fire project to reach an economic break-even point. Reburning coal with MBB to reduce NOx emissions can theoretically be more profitable than a co-fire project, due to the value of avoided NOx emissions. However, the issue of finding enough suitable low-ash biomass becomes problematic for reburn systems since the reburn fuel must supply 10 to 25% of the power plant?s heat rate in order to achieve the desired NOx level. A NOx emission value over $2500/metric ton would justify installing a MBB reburn system. A base case run of a mathematical model describing a small-scale, on-the-farm MBB combustion system that can completely incinerate high-moisture (over 90%) manure biomass was developed and completed. If all of the energy or steam produced by the MBB combustion system were to bring revenue to the animal feeding operation either by avoided fueling costs or by sales, the conceptualized MBB combustion system has the potential to be a profitable venture.

Two coal utility plants in South Africa selected (one from Sasol and another from Eskom) for this study produce large volumes of fly ash (over 40 Mt from Eskom at Tutuka, and 3 Mt from Sasol Synfuels at Secunda annually), and brines as by-products during coal processing. Co-disposal of the brines and fly ashes has been a normal practice in these coal-utility plants for decades. Long-term management of fly ash is necessary and requires an understanding and knowledge of how the different waste materials interact with water and brines in different chemical situations. However the geochemistry of their interactions, the leaching and mobility of elements in these disposal systems has not been fully understood. This work gives insights into the chemical processes taking place in the brine-water/brines systems that govern the concentrations of major and minor elements in ash leachates under different environmental conditions. The possible presence of organic compounds (subsequently referred to as 'organics') in brines and their effects on the leaching chemistry of fly ash was also studied. Sustainability and long term impact of the co-disposal of fly ash and brines on the environment was studied through static (batch tests) modeling of the pH-dependent acid neutralization capacity (ANC) tests and columns modeling for dynamic leach tests. The modeling was based on experimental results from other Sasol-Eskom ashbrine project collaborators. Modeling results of the ANC tests were in good agreement with the reported experimental results, which revealed that the release trends of various elements (including trace, heavy elements and contaminants) contained in fly ash into solution is highly pH dependent. However Na, K, Mo and Li exhibited constant solubilisation which was independent of pH changes from all the scenarios. The presence of different constituents of brines subjected to ANC resulted to different ANC capacities ranging from 0.98 moles H⁺/Kg dry ash (of ash-organics mixed with Mg-brines) to 3.87 H⁺/Kg dry ash for those with the C(4) brines. As expected, those constituents from the cationic brines were found on the lower region of acid addition (in the order Mg-brines < Ca-brines < Na-brines) while the anionic brines were found at the upper region of acid addition (in the order S(6)-brines < Cl-brines < C(4)-brines). In the middle region of acid addition were three important scenarios: that of ash with brine, ash without brines (i.e. ash with DMW) and ash with both ASW organics and combined brines. It was from these three scenarios that a generalization of the effect of brines and organics on the ANC was inferred. The ANC of ash with demineralised water (DMW) was 2.33 mol H⁺/Kg dry ash and that of ash with ASW organics lower at 2.12 mol H⁺/Kg dry ash which was the same value as that of ash with combined brines. This indicated that brines decreased the ANC of ash by about 9.01 % and which could be attributed to the acid-base neutralization process and the dynamics of solid phase dissolutions in response to the acid addition. Both fly ashes exhibited a typical pH > 12 (suspension in demineralised water) and the predominant cation even at this high pH is Ca²⁺ (at concentration > 0.002 mmol/L). This indicates that dissolution of CaO and formation of OH⁻ species at pH > 10 contributes to acid neutralisation capacity of both fly ashes and is the greatest contributor to the acid neutralizing capacity of both fly ashes. Two broad leaching behaviours as a function of pH were observed from the three fly ash-ASW organics-brines scenarios (i) leaching of Ca, Mg, Ni and Sr follows a cationic pattern where the concentration decreases monotonically as pH increases; (ii) leaching of Al, Fe, Ti and Zn follow an amphoteric pattern where the concentration increases at acidic and alkaline pH, although Al showed some anomaly from pH 11 where the concentration decreased with the increase in pH. Al showed an amphoteric pattern in which its release increased between pH 12.8 and 11 for all the scenarios and then decreased with decrease in pH down to neutral pH of 7. The batch leaching simulation results from hydrogeochemical modeling also showed that mineral dissolution, precipitation and new phase formation during ash-organics-brines interactions was controlled by pH. The newly formed phases however remain in equilibrium with the ash-brines-organics mixture. Each individual mineral phase dissolution/precipitation/formation system controls the concentration and speciation of the respective constituent elements as evidenced by the log C-pH diagrams obtained from the modeled scenarios. The ash-brines-organics interactions do exhibit and affect the mineralogical chemistry of fly ash. However the extent to which these interactions occur and their effect, varies from one scenario to another, and are dependent on the amounts and type of the constituent brine components. Organics do have a significant effect on dissolution characteristics of few minerals such as calcite, mullite, kaolinite, Ni₂SiO₄, and SrSiO₃ due to complexation effect. The effect is quantitatively conspicuous for calcite mineral phase and for the formation of some new phases such as Fe(OH)₃(am)-CF and portlandite. The composition of the liquid phase from acid neutralisation capacity experiments was successful.Hydrogeochemical modeling was used as a means to provide insights and understanding of the complex reactions taking place, speciation and mineralogical changes occurring. These changes would serve to predict future environmental scenarios when pH conditions change. In this study, an extension of the application field of PHREEQC hydrogeochemical code for modeling and simulation of equilibrium; kinetic and transport mechanisms associated with the interaction of water; and organics and brines with fly ash during their co-disposal is successfully demonstrated. The parameters associated with these mechanisms were used as inputs into the PHREEQC program using modified Lawrence Livermore National Laboratory (LLNL) database for inorganic brines and MINTEQ.V4 database for organics, and used to model the results of ANC test data for the fly ashes. A special reference is made to two separate modeled mineralogical ash recipes from two of the South African power utility plants' fly ash systems, namely, Tutuka and Secunda. The effects of brines in the leaching of major, minor and trace elements at various pH values and the mineralogical changes associated with the intermediate and final products from the interactions of ash-brines systems under different scenarios are qualitatively and quantatively discussed. Multiphase saturation characteristics have been determined for mineral species in contact with water and brines. The modeling results indicated that several mineral phases could be controlling the species concentration in the leachates, and the ANC and column modeling results corroborated well in many aspects with the experimental results obtained from collaborating institutions (South Africa Universities and Research institutions). In addition, application of the PHREEQC model to the ash heap under different disposal systems was carried out to predict the heap leachate composition and geochemical transformations taking place in a period of time. Pore water chemical analysis, and moisture content analysis revealed that contact of the ash with water is a crucial factor in the mobilization of the contaminants with time. Maximum weathering/dissolution of the ash is observed in the top layer (1-3) m and at the point of contact with the subsurface water level which was in good agreement with the model results. The surface layer and the very lowest layers of the dump in contact with lateral flows experience the highest degree of weathering leading to depletion of species. The geophysical transformation of fly ash was also captured through the porosity change calculations and the results revealed that geochemical reactions do affect the porosity of fly ash during the weathering processes. These modelling results were in agreement with the hydraulic tests and salt leaching tests conducted during Sasol-Eskom ashbrine project in Phase I which suggested that salts captured in the ash will become mobile and leach from the fly ash over time. The data therefore indicates that ash dumps may not act as sustainable salt sinks. These findings may have some bearing on engineering decisions on fly ash reuse. From the above observations, it is apparent that release of large quantities of the salts in the ash depends on the extent of its interaction with brines being used for irrigation or with water, either through plug-in flow after a rainfall event or contact with groundwater. The results revealed effects of brine-water contact time with fly ash, the flow volume and velocity, the pH, the degree of saturation, hydrogeology and ash heap geometry as important factors that affect fly ash transformation and weathering. Overall, the ash heap modeling enhanced the understanding of the ash-brines interactions and demonstrated that leachate composition is determined by the following factors; (i) the mass flows from the pores of fly ash, (ii) the surface dissolution of the mineral phases, (iii) the various chemical reactions involved during the ash-brine and ash-water interactions, (iv) the interactions with a gas phase (atmospheric CO₂), (v) the composition of the initial fly ash, and (vi) by the leachate flow and hydrodynamics as captured in the conceptual model. Any ash handling system should therefore be designed to take these criteria into consideration to prevent environmental contamination. The modeling results also gave indications that the ash-brine co-disposal in dry ash systems would be an unsustainable way of locking up brine salts in the long run. In this Thesis, modeling results were used to support experimental data which further reaffirmed the important role hydrogeochemical modeling plays in liquid and solid waste management. Furthermore, hydrogeochemical modeling complements the work of analytical/environmental scientists as well as guiding the future solid waste management and engineering decisions.
Thesis (Ph.D.)-University of KwaZulu-Natal, Westville, 2012.