Advances in the knowledge of chemical structure of coal and development of high performance computational techniques led to more than hundred and thirty four proposed molecular level representations (models) of coal between 1942 and 2010. These models were virtually on the carboniferous coals from the northern hemisphere. There are only two molecular models based on the inertinite- and vitrinite-rich coals from the southern hemisphere. The current investigation is based on the chars derived from the Permian-aged coals in two major South African coalfields, Witbank #4 seam and Waterberg Upper Ecca. The two coals were upgraded to 85 and 93% inertinite- and vitrinite-rich concentrates, on visible mineral matter free basis. The coals were slow heated in inert atmosphere at 20 ℃ min-1 to 450, 700 and 1000 ℃ and held at that temperature for an hour. After the HCl-HF treatment technique at ambient temperatures, the characteristics of the coals and chars were examined with proximate, ultimate, helium density, porosity, surface area, petrographic, solid-state 13C NMR, XRD and HRTEM analytical techniques. The results largely showed that substantial transitions occurred at 700-1000 ℃, where the chars became physically different but chemically similar. Consequently, the chars at the highest temperature (1000 ℃) drew attention to the detailed study of the atomistic properties that may give rise to different reactivity behaviours with CO2 gas. The H/C atomic ratios for the inertinite- and vitrinite-rich chars were respectively 0.31 and 0.49 at 450 ℃ and 0.10 and 0.12 at 1000 ℃. The true density was respectively 1.48 and 1.38 g.cm-3 at 450 ℃ and 1.87 and 1.81 g.cm-3 at 1000 ℃. The char form results from the petrographic analysis technique indicated that the 700-1000 ℃ inertinite-rich chars have lower proportions of thick-walled isotropic coke derived from pure vitrinites (5-8%) compared with the vitrinite-rich chars (91-95%). This property leads to the creation of pores and increases of volume and surface area as the softening walls expand. It was found that the average crystallite diameter, La, and the mean length of the aromatic carbon fringes from the XRD and HRTEM techniques, respectively, were in good agreement and made a definite distinction between the 1000 ℃ inertinite- and vitrinite-rich chars. The crystallite diameter on peak (10) approximations, La(10), of 37.6Å for the 1000 ℃ inertinite-rich chars fell within the HRTEM’s range of minimummaximum length boundary of 11x11 aromatic fringes (27-45Å). The La (10) of 30.7Å for the vitrinite-rich chars fell nearly on the minimum-maximum length range of 7x7 aromatic fringes (17-28Å.) The HRTEM results showed that the 1000 ℃ inertinite-rich chars comprised a higher distribution of larger aromatic fringes (11x11 parallelogram catenations) compared with a higher distribution of smaller aromatic fringes (7x7 parallelogram catenations). The mechanism for the similarity between the 700-1000 ℃ inertinite- and vitrinite-rich chars was the greater transition occurring in the vitrinite-rich coal to match the more resistant inertinite-rich coal. This emphasised that the transitions in the properties of vitrinite-rich coals were more thermally accelerated than those of the inertinite-rich coals. The similarity between the inertinite- and vitrinite-rich chars was shown by the total maceral reflectance, proximate, ultimate, skeletal density and aromaticity results. Evidence for this was the carbon content by mass for the inertinite- and vitrinite-rich chars of respectively 90.5 and 85.3% at 450 ℃ and 95.9 and 94.1% at 1000 ℃. The aromaticity from the XRD technique was respectively 87 and 77% at 450 ℃ and 98 and 96% at 1000 ℃. A similar pattern was found in the hydrogen and oxygen contents, the atomic O/C ratios and the aromaticity from the NMR technique. The subsequent construction of large-scale molecular structures for the 1000 ℃ inertinite-rich chars comprised 106 molecules constructed from a total of 42929 atoms, while the vitrinite-rich char model was made up of 185 molecules consisting of a total of 44315 atoms. The difference between the number of molecules was due to the inertinite-rich char model comprising a higher distribution of larger molecules compared with the vitrinite-rich char model, in agreement with the XRD and HRTEM results. These char structures were used to examine the behaviour on the basis of gasification reactivity with CO2. The density functional theory (DFT) was used to evaluate the interactions between CO2 and the atomistic representations of coal char derived from the inertinite- and vitrinite rich South African coals. The construction of char models used the modal aromatic fringes (fringes of highest frequencies in size distributions) from the HRTEM, for the inertinite- and vitrinite-rich chars, respectively (11x11 and 7x7 parallelogram-shaped aromatic carbon rings). The structures were DFT geometrically optimized and used to measure reactivity with the Fukui function, f+(r) and to depict a representative reactive carbon edge for the simulations of coal gasification reaction mechanism with CO2 gas. The f+(r) reactivity indices of the reactive edge follows the sequence: zigzag C remote from the tip C (Czi = 0.266) > first armchair C (Cr1 = 0.087) > tip C (Ct = 0.075) > second armchair C (Cr2 = 0.029) > zigzag C proximate to the tip C (Cz = 0.027). The DFT simulated mean activation energy, ΔEb, for the gasification reaction mechanism (formation of second CO gas molecule) was 233 kJ mol-1. The reaction for the formation of second CO molecule is defines gasification in essence. The experimental activation energy determined with the TGA and random pore model to account essentially for the pore variation in addition to the gasification chemical reaction were found to be very similar: 191 ± 25 kJ mol-1 and 210 ± 8 kJ mol-1; and in good agreement with the atomistic results. The investigation gave promise towards the utility of molecular representations of coal char within the context of fundamental coal gasification reaction mechanism with CO2. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Advances in the knowledge of chemical structure of coal and development of high performance computational techniques led to more than hundred and thirty four proposed molecular level representations (models) of coal between 1942 and 2010. These models were virtually on the carboniferous coals from the northern hemisphere. There are only two molecular models based on the inertinite- and vitrinite-rich coals from the southern hemisphere. The current investigation is based on the chars derived from the Permian-aged coals in two major South African coalfields, Witbank #4 seam and Waterberg Upper Ecca. The two coals were upgraded to 85 and 93% inertinite- and vitrinite-rich concentrates, on visible mineral matter free basis. The coals were slow heated in inert atmosphere at 20 ℃ min-1 to 450, 700 and 1000 ℃ and held at that temperature for an hour. After the HCl-HF treatment technique at ambient temperatures, the characteristics of the coals and chars were examined with proximate, ultimate, helium density, porosity, surface area, petrographic, solid-state 13C NMR, XRD and HRTEM analytical techniques. The results largely showed that substantial transitions occurred at 700-1000 ℃, where the chars became physically different but chemically similar. Consequently, the chars at the highest temperature (1000 ℃) drew attention to the detailed study of the atomistic properties that may give rise to different reactivity behaviours with CO2 gas. The H/C atomic ratios for the inertinite- and vitrinite-rich chars were respectively 0.31 and 0.49 at 450 ℃ and 0.10 and 0.12 at 1000 ℃. The true density was respectively 1.48 and 1.38 g.cm-3 at 450 ℃ and 1.87 and 1.81 g.cm-3 at 1000 ℃. The char form results from the petrographic analysis technique indicated that the 700-1000 ℃ inertinite-rich chars have lower proportions of thick-walled isotropic coke derived from pure vitrinites (5-8%) compared with the vitrinite-rich chars (91-95%). This property leads to the creation of pores and increases of volume and surface area as the softening walls expand. It was found that the average crystallite diameter, La, and the mean length of the aromatic carbon fringes from the XRD and HRTEM techniques, respectively, were in good agreement and made a definite distinction between the 1000 ℃ inertinite- and vitrinite-rich chars. The crystallite diameter on peak (10) approximations, La(10), of 37.6Å for the 1000 ℃ inertinite-rich chars fell within the HRTEM’s range of minimummaximum length boundary of 11x11 aromatic fringes (27-45Å). The La (10) of 30.7Å for the vitrinite-rich chars fell nearly on the minimum-maximum length range of 7x7 aromatic fringes (17-28Å.) The HRTEM results showed that the 1000 ℃ inertinite-rich chars comprised a higher distribution of larger aromatic fringes (11x11 parallelogram catenations) compared with a higher distribution of smaller aromatic fringes (7x7 parallelogram catenations). The mechanism for the similarity between the 700-1000 ℃ inertinite- and vitrinite-rich chars was the greater transition occurring in the vitrinite-rich coal to match the more resistant inertinite-rich coal. This emphasised that the transitions in the properties of vitrinite-rich coals were more thermally accelerated than those of the inertinite-rich coals. The similarity between the inertinite- and vitrinite-rich chars was shown by the total maceral reflectance, proximate, ultimate, skeletal density and aromaticity results. Evidence for this was the carbon content by mass for the inertinite- and vitrinite-rich chars of respectively 90.5 and 85.3% at 450 ℃ and 95.9 and 94.1% at 1000 ℃. The aromaticity from the XRD technique was respectively 87 and 77% at 450 ℃ and 98 and 96% at 1000 ℃. A similar pattern was found in the hydrogen and oxygen contents, the atomic O/C ratios and the aromaticity from the NMR technique. The subsequent construction of large-scale molecular structures for the 1000 ℃ inertinite-rich chars comprised 106 molecules constructed from a total of 42929 atoms, while the vitrinite-rich char model was made up of 185 molecules consisting of a total of 44315 atoms. The difference between the number of molecules was due to the inertinite-rich char model comprising a higher distribution of larger molecules compared with the vitrinite-rich char model, in agreement with the XRD and HRTEM results. These char structures were used to examine the behaviour on the basis of gasification reactivity with CO2. The density functional theory (DFT) was used to evaluate the interactions between CO2 and the atomistic representations of coal char derived from the inertinite- and vitrinite rich South African coals. The construction of char models used the modal aromatic fringes (fringes of highest frequencies in size distributions) from the HRTEM, for the inertinite- and vitrinite-rich chars, respectively (11x11 and 7x7 parallelogram-shaped aromatic carbon rings). The structures were DFT geometrically optimized and used to measure reactivity with the Fukui function, f+(r) and to depict a representative reactive carbon edge for the simulations of coal gasification reaction mechanism with CO2 gas. The f+(r) reactivity indices of the reactive edge follows the sequence: zigzag C remote from the tip C (Czi = 0.266) > first armchair C (Cr1 = 0.087) > tip C (Ct = 0.075) > second armchair C (Cr2 = 0.029) > zigzag C proximate to the tip C (Cz = 0.027). The DFT simulated mean activation energy, ΔEb, for the gasification reaction mechanism (formation of second CO gas molecule) was 233 kJ mol-1. The reaction for the formation of second CO molecule is defines gasification in essence. The experimental activation energy determined with the TGA and random pore model to account essentially for the pore variation in addition to the gasification chemical reaction were found to be very similar: 191 ± 25 kJ mol-1 and 210 ± 8 kJ mol-1; and in good agreement with the atomistic results. The investigation gave promise towards the utility of molecular representations of coal char within the context of fundamental coal gasification reaction mechanism with CO2. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015