Дисертації з теми "Coal liquefaction 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.

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

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)

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...

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.

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.

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).
text

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.

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.