In power plants using large utility coal-fired boilers for generation of electricity the coal is pulverised in coal mills and then it has to be pneumatically transported and distributed to a larger number of burners (e.g. 30-40) circumferentially arranged in several rows around the burning chamber of the boiler. Besides the large pipework flow splitting devices are necessary for distribution of an equal amount of pulverised fuel (PF) to each of the burners. So called trifurcators (without inner fittings or guiding vanes) and ''riffle'' type bifurcators are commonly used to split the gas-coal particle flow into two or three pipes/channels with an equal amount of PF mass flow rate in each outflow cross section of the flow splitting device. These PF flow splitting devices are subject of a number of problems. First of all an uneven distribution of PF over the burners of a large utility boiler leads to operational and maintenance problems, increased level of unburned carbon and higher rates of NOX emissions. Maldistribution of fuel between burners caused by non uniform concentration of the PF (particle roping) in pipe and channel bends prior to flow splitting devices leads to uncontrolled differences in the fuel to air ratio between burners. This results in localised regions in the furnace which are fuel rich, where insufficient air causes incomplete combustion of the fuel. Other regions in the furnace become fuel lean, forming high local concentrations of NOX due to the high local concentrations of O2. Otherwise PF maldistribution can impact on power plant maintenance in terms of uneven wear on PF pipework, flow splitters as well as the effects on boiler panels (PF deposition, corrosion, slagging). In order to address these problems in establishing uniform PF distribution over the outlet cross sections of flow splitting devices in the pipework of coal-fired power plants the present paper deals with numerical prediction and analysis of the complex gas and coal particle (PF) flow through trifurcators and ''riffle'' type bifurcators. The numerical investigation is based on a 3-dimensional Eulerian- Lagrangian approach (MISTRAL/PartFlow-3D) developed by Frank et al. The numerical method is capable to predict isothermal, incompressible, steady gas- particle flows in 3-dimensional, geometrically complex flow geometries using boundary fitted, block-structured, numerical grids. Due to the very high numerical effort of the investigated gas-particle flows the numerical approach has been developed with special emphasis on efficient parallel computing on clusters of workstations or other high performance computing architectures. Besides the aerodynamically interaction between the carrier fluid phase and the PF particles the gas-particle flow is mainly influenced by particle-wall interactions with the outer wall boundaries and the inner fittings and guiding vanes of the investigated flow splitting devices. In order to allow accurate quantitative prediction of the motion of the disperse phase the numerical model requires detailed information about the particle-wall collision process. In commonly used physical models of the particle-wall interaction this is the knowledge or experimental prediction of the restitution coefficients (dynamic friction coefficient, coefficient of restitution) for the used combination of particle and wall material, e.g. PF particles on steel. In the present investigation these parameters of the particle-wall interaction model have been obtained from special experiments in two test facilities. Basic experiments to clarify the details of the particle-wall interaction process were made in a test facility with a spherical disk accelerator. This test facility furthermore provides the opportunity to investigate the bouncing process under normal pressure as well as under vacuum conditions, thus excluding aerodynamically influences on the motion of small particles in the near vicinity of solid wall surfaces (especially under small angles of attack). In this experiments spherical glass beads were used as particle material. In a second test facility we have investigated the real impact of non-spherical pulverised fuel particles on a steel/ceramic target. In this experiments PF particles were accelerated by an injector using inert gas like e.g. CO2 or N2 as the carrier phase in order to avoid dust explosion hazards. The obtained data for the particle-wall collision models were compared to those obtained for glass spheres, where bouncing models are proofed to be valid. Furthermore the second test facility was used to obtain particle erosion rates for PF particles on steel targets as a function of impact angles and velocities. The results of experimental investigations has been incorporated into the numerical model. Hereafter the numerical approach MISTRAL/PartFlow-3D has been applied to the PF flow through a ''riffle'' type bifurcator. Using ICEM/CFD-Hexa as grid generator a numerical mesh with approximately 4 million grid cells has been designed for approximation of the complex geometry of the flow splitting device with all its interior fittings and guiding vanes. Based on a predicted gas flow field a large number of PF particles are tracked throughout the flow geometry of the flow-splitter. Besides mean quantities of the particle flow field like e.g. local particle concentrations, mean particle velocities, distribution of mean particle diameter, etc. it is now possible to obtain information about particle erosion on riffle plates and guiding vanes of the flow splitting device. Furthermore the influence of different roping patterns in front of the flow splitter on the uniformness of PF mass flow rate splitting after the bifurcator has been investigated numerically. Results show the efficient operation of the investigated bifurcator in absence of particle roping, this means under conditions of an uniform PF particle concentration distribution in the inflow cross section of the bifurcator. If particle roping occurs and particle concentration differs over the pipe cross section in front of the bifurcator the equal PF particle mass flow rate splitting can be strongly deteriorated in dependence on the location and intensity of the particle rope or particle concentration irregularities. The presented results show the importance of further development of efficient rope splitting devices for applications in coal-fired power plants. Numerical analysis can be used as an efficient tool for their investigation and further optimisation under various operating and flow conditions.

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils and Digitaria eriantha in the vicinity of three South African coal-fired power plants, Matla, Lethabo and Rooiwal were determined by gas chromatography–mass spectrometry. An ultrasonic assisted dispersive liquid-liquid microextraction (UA-DLLME) method was developed for the extraction of polycyclic aromatic hydrocarbon in soil, followed by determination using gas chromatography mass spectrometry. The study showed that an extraction protocol based on acetonitrile as dispersive solvent and C2H2Cl2 as extracting solvent, gave extraction efficiencies comparable to conventional soxhlet extraction for soil samples. The extraction time using ultrasonication and the volume of the extraction solvent was also investigated. Using a certified reference material soil (CRM), the extraction efficiency of UA-DLLME ranged from 64 to 86% in comparison with the Soxhlet result of 73 to 95%. In comparison with the real sample, the CRM result did not show a significant difference at 95% C.I. The UA-DLLME proved to be a convenient, rapid, cost-effective and greener sample preparation approach for the determination of PAHs in soil samples. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/ Phen + Anth) were used to provide a reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g−1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g−1 for a significantly contaminated site. Calculated values of the Phen/Phen + Anth ratio were 0.48±0.08, 0.44±0.05, and 0.38+0.04 for Matla, Lethabo and Rooiwal, respectively. The flouranthene/fluoranthene + pyrene (Flan/ Flan + Pyr) levels were found to be 0.49±0.03 for Matla, 0.44±0.05 for Lethabo, and 0.53±0.08 for Rooiwal. Such values indicate a xx pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25, indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can, therefore, be concluded that the soils were contaminated with PAHs originating from coal-fired power stations. Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr and Zn) were analysed in soil and the Digitaria eriantha plant around three coal power plants (Matla, Lethabo and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05 ± 0.02 to 1835.70 ± 70 μg g-1, 0.08 ± 0.05 to 1743.90 ± 29 μg g-1 and 0.07 ± 0.04 to 1735.20 ± 91 μg g-1 at Matla, Lethabo and Rooiwal respectively. The total metal concentration in the plant (Digitaria eriantha) ranged from 0.005 ± 0.003 to 534.87 ± 43 μg g-1 at Matla, 0.002 ± 0.001 to 400.49 ± 269 μg g-1 at Lethabo and 0.002 ± 0.001 to 426.91 ± 201 μg g-1 at Rooiwal. The accumulation factor (A) of less than 1 (i.e. 0.003 to 0.37) at power plants indicates a low transfer of metal from soil to plant (excluder). The enrichment factor values obtained (2.4 – 5) indicate that the soils are moderately enriched, with the exception of Pb that had significant enrichment of 20. The Geo-accumulation Index values of metals indicate that the soils are moderately polluted (0.005 – 0.65), except for Pb that showed moderate to strong pollution (1.74 – 2.53). / Chemistry / D. Phil. (Chemistry)