The swelling and caking propensity of coals may cause operational problems such as channelling and excessive pressure build-up in combustion, gasification and specifically in fluidised-bed and fixed-bed operations. As a result, the swelling and caking characteristics of certain coals make them less suitable for use as feedstock in applications where swelling and/or caking is undesired. Therefore, various studies have focused on the manipulation of the swelling and/or caking propensity of coals, and have proven the viability of using additives to reduce the swelling and caking of powdered coal (<500 μm). However, there is still a lack of research specifically focused on large coal particle devolatilisation behaviour, particularly swelling and caking, and the reduction thereof using additives. A comprehensive study was therefore proposed to investigate the swelling and caking behaviour of large coal particles (5, 10, and 20 mm) of typical South African coals, and the influence of the selected additive (potassium carbonate) thereon. Three different South African coals were selected based on their Free Swelling Index (FSI): coal TSH is a high swelling coal (FSI 9) from the Limpopo province, GG is a medium swelling coal (FSI 5.5-6.5) from the Waterberg region, and TWD is a non-swelling coal (FSI 0) from the Highveld region. Image analysis was used to semi-quantitatively describe the transient swelling and shrinkage behaviour of large coal particles (-20+16 mm) during lowtemperature devolatilisation (700 °C, N2 atmosphere, 7 K/min). X-ray computed tomography and mercury submersion were used to quantify the degree of swelling of large particles, and were compared to conventional swelling characteristics of powdered coals. The average swelling ratios obtained for TWD, GG, and TSH were respectively 1.9, 2.1 and 2.5 from image analysis and 1.8, 2.2 and 2.5 from mercury submersion. The results showed that coal swelling measurements such as FSI, and other conventional techniques used to describe the plastic behaviour of powdered coal, can in general not be used for the prediction of large coal particle swelling. The large coal particles were impregnated for 24 hours, using an excess 5.0 M K2CO3 impregnation solution. The influence of K2CO3-addition on the swelling behaviour of different coal particle sizes was compared, and results showed that the addition of K2CO3 resulted in a reduction in swelling for powdered coal (-212 μm), as well as large coal particles (5, 10, and 20 mm). For powdered coal, the addition of 10 wt.% K2CO3 decreased the free swelling index of GG and TSH coals from 6.5 to 0 and from 9.0 to 4.5, respectively. The volumetric swelling ratios (SRV) of the 20 mm particles were reduced from 3.0 to 1.8 for the GG coal, and from 5.7 to 1.4 for TSH. In contrast to the non-swelling (FSI 0) behaviour of the TWD powders, the large particles exhibited average SRV values of 1.7, and was found not be influenced by K2CO3-impregnation. It was found that the maximum swelling coefficient, kA, was reduced from 0.025 to 0.015 oC-1 for GG, and from 0.045 to 0.027 oC-1 for TSH, as a results of impregnation. From the results it was concluded that K2CO3-impregnation reduces the extent of swelling of coals such as GG (medium-swelling) and TSH (high-swelling), which exhibit significant plastic deformation. Results obtained from the caking experiments indicated that K2CO3-impregnation influenced the physical behaviour of the GG coal particles (5, 10, and 20 mm) the most. The extent of caking of GG was largely reduced due to impregnation, while the wall thickness and porosity also decreased. The coke from the impregnated GG samples had a less fluid-like appearance compared to coke from the raw coal. Bridging neck size measurements were performed, which quantitatively showed a 25-50% decrease in the caking propensity of GG particles. Coal TWD did not exhibit any caking behaviour. The K2CO3-impregnation did not influence the surface texture or porosity of the TWD char, but increased the overall brittleness of the devolatilised samples. Both the extent of caking and porosity of TSH coke were not influenced by impregnation. However, impregnation resulted in significantly less and smaller opened pores on the surface of the devolatilised samples, and also reduced the average wall thickness of the TSH coke. The overall conclusion made from this investigation is that K2CO3 (using solution impregnation) can be used to significantly reduce the caking and swelling tendency of large coal particles which exhibits a moderate degree of fluidity, such as GG (Waterberg region). The results obtained during this investigation show the viability of using additive addition to reduce the caking and swelling tendency of large coal particles. Together with further development, this may be a suitable method for modifying the swelling and caking behaviour of specific coals for use in fixed-bed and fluidised-bed gasification operations. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

The swelling and caking propensity of coals may cause operational problems such as channelling and excessive pressure build-up in combustion, gasification and specifically in fluidised-bed and fixed-bed operations. As a result, the swelling and caking characteristics of certain coals make them less suitable for use as feedstock in applications where swelling and/or caking is undesired. Therefore, various studies have focused on the manipulation of the swelling and/or caking propensity of coals, and have proven the viability of using additives to reduce the swelling and caking of powdered coal (<500 μm). However, there is still a lack of research specifically focused on large coal particle devolatilisation behaviour, particularly swelling and caking, and the reduction thereof using additives. A comprehensive study was therefore proposed to investigate the swelling and caking behaviour of large coal particles (5, 10, and 20 mm) of typical South African coals, and the influence of the selected additive (potassium carbonate) thereon. Three different South African coals were selected based on their Free Swelling Index (FSI): coal TSH is a high swelling coal (FSI 9) from the Limpopo province, GG is a medium swelling coal (FSI 5.5-6.5) from the Waterberg region, and TWD is a non-swelling coal (FSI 0) from the Highveld region. Image analysis was used to semi-quantitatively describe the transient swelling and shrinkage behaviour of large coal particles (-20+16 mm) during lowtemperature devolatilisation (700 °C, N2 atmosphere, 7 K/min). X-ray computed tomography and mercury submersion were used to quantify the degree of swelling of large particles, and were compared to conventional swelling characteristics of powdered coals. The average swelling ratios obtained for TWD, GG, and TSH were respectively 1.9, 2.1 and 2.5 from image analysis and 1.8, 2.2 and 2.5 from mercury submersion. The results showed that coal swelling measurements such as FSI, and other conventional techniques used to describe the plastic behaviour of powdered coal, can in general not be used for the prediction of large coal particle swelling. The large coal particles were impregnated for 24 hours, using an excess 5.0 M K2CO3 impregnation solution. The influence of K2CO3-addition on the swelling behaviour of different coal particle sizes was compared, and results showed that the addition of K2CO3 resulted in a reduction in swelling for powdered coal (-212 μm), as well as large coal particles (5, 10, and 20 mm). For powdered coal, the addition of 10 wt.% K2CO3 decreased the free swelling index of GG and TSH coals from 6.5 to 0 and from 9.0 to 4.5, respectively. The volumetric swelling ratios (SRV) of the 20 mm particles were reduced from 3.0 to 1.8 for the GG coal, and from 5.7 to 1.4 for TSH. In contrast to the non-swelling (FSI 0) behaviour of the TWD powders, the large particles exhibited average SRV values of 1.7, and was found not be influenced by K2CO3-impregnation. It was found that the maximum swelling coefficient, kA, was reduced from 0.025 to 0.015 oC-1 for GG, and from 0.045 to 0.027 oC-1 for TSH, as a results of impregnation. From the results it was concluded that K2CO3-impregnation reduces the extent of swelling of coals such as GG (medium-swelling) and TSH (high-swelling), which exhibit significant plastic deformation. Results obtained from the caking experiments indicated that K2CO3-impregnation influenced the physical behaviour of the GG coal particles (5, 10, and 20 mm) the most. The extent of caking of GG was largely reduced due to impregnation, while the wall thickness and porosity also decreased. The coke from the impregnated GG samples had a less fluid-like appearance compared to coke from the raw coal. Bridging neck size measurements were performed, which quantitatively showed a 25-50% decrease in the caking propensity of GG particles. Coal TWD did not exhibit any caking behaviour. The K2CO3-impregnation did not influence the surface texture or porosity of the TWD char, but increased the overall brittleness of the devolatilised samples. Both the extent of caking and porosity of TSH coke were not influenced by impregnation. However, impregnation resulted in significantly less and smaller opened pores on the surface of the devolatilised samples, and also reduced the average wall thickness of the TSH coke. The overall conclusion made from this investigation is that K2CO3 (using solution impregnation) can be used to significantly reduce the caking and swelling tendency of large coal particles which exhibits a moderate degree of fluidity, such as GG (Waterberg region). The results obtained during this investigation show the viability of using additive addition to reduce the caking and swelling tendency of large coal particles. Together with further development, this may be a suitable method for modifying the swelling and caking behaviour of specific coals for use in fixed-bed and fluidised-bed gasification operations. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015