Applications of chromium vary widely (refractories, chemicals and metallurgical); however, the greatest benefit of chromium is its ability to improve the corrosion resistance, strength and hardness of steel. South Africa possesses approximately 75% of the viable global chromite reserves and, as a result, dominates the ferrochrome market with production in excess of 5 million mega tonnes per year - making it an industry of extreme importance to the South African economy Submerged arc ferroalloy production furnaces mainly use Soderberg electrodes - self–baking continuous electrodes that are produced in situ during furnace operation. Electrode breakings may affect a furnace in a number of ways depending on the nature and location of the break. Low furnace power input, abnormal charging and tapping conditions, as well as loss of production are among the more common negative implications associated with electrode breaks. The successful operation of Soderberg electrodes is dependent on two main factors: high quality electrode paste and effective electrode management procedures. This study focused on electrode paste quality. The raw materials utilised in the production of Soderberg electrode paste consists of calcined anthracite mixed with a tar pitch binder. In this study the focus was on the development of an experimental procedure to measure the dimensional changes of electrode paste raw materials as a function of temperature by means of thermomechanical analysis (TMA). Three uncalcined anthracite (Zululand chips, Zululand duff, and Tendele duff) and two tar pitch samples (low and high softening point pitches, i.e. LSP and HSP) were obtained from a local paste producer. Electrode graphite samples were also obtained from a local pre–baked electrode supplier. The experimental procedure for both the anthracite and tar pitches consisted of two phases: sample preparation and TMA measurements. During the sample preparation procedure for the tar pitches, the two tar pitches were heat treated in order to prevent softening in the TMA (preventing possibly damage the instrument), where after pellets were pressed for TMA measurement. The anthracite samples were calcined at 1200, 1300 and 1400°C in the anthracite sample preparation phase. TMA sample pellets of calcined and uncalcined anthracite were pressed using only water as a binder. TMA was performed on pellets produced from the heat–treated tar pitch samples, uncalcined and calcined anthracite samples, as well as core drilled pellets of the pre–baked electrode graphite. The dimensional changes of these pellets were measured, as a function of temperature, through three consecutive heating (room temperature to 1300°C) and cooling (1300°C to approximately 100°C) cycles under a N2 atmosphere. A significant shrinkage (> 12%) for both the LSP and HSP tar pitches occurred during the first TMA heating cycle. During the second and third heating cycles of the LSP and HSP tar pitches, dimensional changes were approximately 2%. This indicates that substantial structural reordering of the carbonaceous binder takes place during the first heating cycle. TMA results obtained for all three the calcined anthracite samples investigated indicated thermal dimensional changes of less than 1%. The anthracite samples calcined at the highest experimental calcination temperature (1400°C) prior to TMA analysis had the smallest dimensional changes. This confirmed that higher calcination temperatures result in a higher level of structural ordering and dimensional stability. Considering the combined calcined anthracite and tar pitches TMA results, the importance of the initial baking of a Soderberg electrode at temperatures exceeding the baking isotherm temperature (475°C) becomes apparent - the dimensional behaviour of the tar pitch binder and the calcined anthracite differ dramatically, making the newly–formed electrode very susceptible to breakage. Once structural reordering of the pitch had taken place, thermal dimensional behaviours of the materials are much more similar, significantly reducing the risk of thermal shock–induced electrode breakages. In contrast to the relatively small dimensional changes measured for the calcined anthracite samples, the shrinkages measured for the uncalcined samples during the first TMA heating/cooling cycle were substantial (6–8%). This indicates the importance of the anthracite calcination process, before the electrode paste is formulated. Improperly calcined anthracite present in electrode paste would result in additional dimensional shrinkage that would have to be accommodated in the baking of a new electrode section. Considering the large shrinkage of the tar pitch that already takes place, it is unlikely that a strong enough electrode would be formed if this occurs. From the results, it also became apparent that the anthracite with the highest fixed carbon and lowest ash contents exhibited the smallest shrinkage during in situ TMA calcination. High fixed carbon, low ash type anthracites are therefore less prone to dimensional instabilities in Soderberg electrodes, as a result of poor calcination. The dimensional changes observed in the calcined anthracites were very similar to those observed for the electrode graphite samples. The expansions/shrinkages observed in the graphite samples were mostly less than 0.5%, whereas the expansions/shrinkages observed in the various calcined anthracites were approximately 0.6 to 0.9%. The difference in the magnitude of the dimensional behaviour between the calcined anthracites and the graphite can be attributed to the fact that the graphite had already undergone maximum structural ordering (having been pre–baked at 3000°C). / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

As a result of increasing cost, efficiency and environmental pressures ferrochrome producers strive towards lower overall energy consumption. Increases in local electricity prices have placed particular pressure on South African ferrochrome producers. Pelletised chromite pre–reduction is likely the currently applied ferrochrome production process option with the lowest specific electricity consumption. In this process fine chromite, together with a carbonaceous reductant and a clay binder is milled, pelletised and pre–reduced. In this dissertation it is demonstrated that the functioning of the clay binder in this process is not as straightforward as in conventional metallurgical pelletisation processes, since the cured pre–reduced pellets are characterised by an oxidised outer layer and a pre–reduced core. Conventional performance characteristics of clay binders (e.g. compressive strength and abrasion resistance) therefore have to be evaluated in both oxidative sintering and reducing environments. Two clay samples, i.e. attapulgite and bentonite, were obtained from a local ferrochrome producer and investigated within the context of this study. Results indicated that the compressive and abrasion resistance strengths of oxidative sintered pellets for both clays were substantially better than that of pre–reduced pellets. Thus, although the objective of the chromite pre–reduced process is to achieve maximum pre–reduction, the strength of pre–reduced chromite pellets is significantly enhanced by the thin oxidised outer layer. The strength of the bentonite–containing pellets was found to be superior in both pre–reducing and oxidative sintering environments. This is significant, since the attapulgite clay is currently the preferred option at both South African ferrochrome smelting plants applying the pelletised chromite pre–reduction process. Although not quantitatively investigated, thermo–mechanical analysis indicated that the hot strength of the attapulgite pellets could be weaker than the bentonite–containing pellets. The possible effects of clay binder selection on the level of pre–reduction were also investigated, since it could have substantial efficiency and economic implications. For both case study clays investigated, higher clay contents resulted in lower pre–reduction levels. This has relevance within the industrial process, since higher clay contents are on occasion utilised to achieve improved green strength. The average pre–reduction of the bentonite–containing pellets were also consistently higher than that of the attapulgite–containing pellets. Again, this is significant, since the attapulgite clay is currently the preferred option. In general the case study results presented in this dissertation indicated that it is unlikely that the performance of a specific clay binder in this relatively complex process can be predicted; based only on the chemical, surface chemical and mineralogical characterisation of the clay. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

As a result of increasing cost, efficiency and environmental pressures ferrochrome producers strive towards lower overall energy consumption. Increases in local electricity prices have placed particular pressure on South African ferrochrome producers. Pelletised chromite pre–reduction is likely the currently applied ferrochrome production process option with the lowest specific electricity consumption. In this process fine chromite, together with a carbonaceous reductant and a clay binder is milled, pelletised and pre–reduced. In this dissertation it is demonstrated that the functioning of the clay binder in this process is not as straightforward as in conventional metallurgical pelletisation processes, since the cured pre–reduced pellets are characterised by an oxidised outer layer and a pre–reduced core. Conventional performance characteristics of clay binders (e.g. compressive strength and abrasion resistance) therefore have to be evaluated in both oxidative sintering and reducing environments. Two clay samples, i.e. attapulgite and bentonite, were obtained from a local ferrochrome producer and investigated within the context of this study. Results indicated that the compressive and abrasion resistance strengths of oxidative sintered pellets for both clays were substantially better than that of pre–reduced pellets. Thus, although the objective of the chromite pre–reduced process is to achieve maximum pre–reduction, the strength of pre–reduced chromite pellets is significantly enhanced by the thin oxidised outer layer. The strength of the bentonite–containing pellets was found to be superior in both pre–reducing and oxidative sintering environments. This is significant, since the attapulgite clay is currently the preferred option at both South African ferrochrome smelting plants applying the pelletised chromite pre–reduction process. Although not quantitatively investigated, thermo–mechanical analysis indicated that the hot strength of the attapulgite pellets could be weaker than the bentonite–containing pellets. The possible effects of clay binder selection on the level of pre–reduction were also investigated, since it could have substantial efficiency and economic implications. For both case study clays investigated, higher clay contents resulted in lower pre–reduction levels. This has relevance within the industrial process, since higher clay contents are on occasion utilised to achieve improved green strength. The average pre–reduction of the bentonite–containing pellets were also consistently higher than that of the attapulgite–containing pellets. Again, this is significant, since the attapulgite clay is currently the preferred option. In general the case study results presented in this dissertation indicated that it is unlikely that the performance of a specific clay binder in this relatively complex process can be predicted; based only on the chemical, surface chemical and mineralogical characterisation of the clay. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Applications of chromium vary widely (refractories, chemicals and metallurgical); however, the greatest benefit of chromium is its ability to improve the corrosion resistance, strength and hardness of steel. South Africa possesses approximately 75% of the viable global chromite reserves and, as a result, dominates the ferrochrome market with production in excess of 5 million mega tonnes per year - making it an industry of extreme importance to the South African economy Submerged arc ferroalloy production furnaces mainly use Soderberg electrodes - self–baking continuous electrodes that are produced in situ during furnace operation. Electrode breakings may affect a furnace in a number of ways depending on the nature and location of the break. Low furnace power input, abnormal charging and tapping conditions, as well as loss of production are among the more common negative implications associated with electrode breaks. The successful operation of Soderberg electrodes is dependent on two main factors: high quality electrode paste and effective electrode management procedures. This study focused on electrode paste quality. The raw materials utilised in the production of Soderberg electrode paste consists of calcined anthracite mixed with a tar pitch binder. In this study the focus was on the development of an experimental procedure to measure the dimensional changes of electrode paste raw materials as a function of temperature by means of thermomechanical analysis (TMA). Three uncalcined anthracite (Zululand chips, Zululand duff, and Tendele duff) and two tar pitch samples (low and high softening point pitches, i.e. LSP and HSP) were obtained from a local paste producer. Electrode graphite samples were also obtained from a local pre–baked electrode supplier. The experimental procedure for both the anthracite and tar pitches consisted of two phases: sample preparation and TMA measurements. During the sample preparation procedure for the tar pitches, the two tar pitches were heat treated in order to prevent softening in the TMA (preventing possibly damage the instrument), where after pellets were pressed for TMA measurement. The anthracite samples were calcined at 1200, 1300 and 1400°C in the anthracite sample preparation phase. TMA sample pellets of calcined and uncalcined anthracite were pressed using only water as a binder. TMA was performed on pellets produced from the heat–treated tar pitch samples, uncalcined and calcined anthracite samples, as well as core drilled pellets of the pre–baked electrode graphite. The dimensional changes of these pellets were measured, as a function of temperature, through three consecutive heating (room temperature to 1300°C) and cooling (1300°C to approximately 100°C) cycles under a N2 atmosphere. A significant shrinkage (> 12%) for both the LSP and HSP tar pitches occurred during the first TMA heating cycle. During the second and third heating cycles of the LSP and HSP tar pitches, dimensional changes were approximately 2%. This indicates that substantial structural reordering of the carbonaceous binder takes place during the first heating cycle. TMA results obtained for all three the calcined anthracite samples investigated indicated thermal dimensional changes of less than 1%. The anthracite samples calcined at the highest experimental calcination temperature (1400°C) prior to TMA analysis had the smallest dimensional changes. This confirmed that higher calcination temperatures result in a higher level of structural ordering and dimensional stability. Considering the combined calcined anthracite and tar pitches TMA results, the importance of the initial baking of a Soderberg electrode at temperatures exceeding the baking isotherm temperature (475°C) becomes apparent - the dimensional behaviour of the tar pitch binder and the calcined anthracite differ dramatically, making the newly–formed electrode very susceptible to breakage. Once structural reordering of the pitch had taken place, thermal dimensional behaviours of the materials are much more similar, significantly reducing the risk of thermal shock–induced electrode breakages. In contrast to the relatively small dimensional changes measured for the calcined anthracite samples, the shrinkages measured for the uncalcined samples during the first TMA heating/cooling cycle were substantial (6–8%). This indicates the importance of the anthracite calcination process, before the electrode paste is formulated. Improperly calcined anthracite present in electrode paste would result in additional dimensional shrinkage that would have to be accommodated in the baking of a new electrode section. Considering the large shrinkage of the tar pitch that already takes place, it is unlikely that a strong enough electrode would be formed if this occurs. From the results, it also became apparent that the anthracite with the highest fixed carbon and lowest ash contents exhibited the smallest shrinkage during in situ TMA calcination. High fixed carbon, low ash type anthracites are therefore less prone to dimensional instabilities in Soderberg electrodes, as a result of poor calcination. The dimensional changes observed in the calcined anthracites were very similar to those observed for the electrode graphite samples. The expansions/shrinkages observed in the graphite samples were mostly less than 0.5%, whereas the expansions/shrinkages observed in the various calcined anthracites were approximately 0.6 to 0.9%. The difference in the magnitude of the dimensional behaviour between the calcined anthracites and the graphite can be attributed to the fact that the graphite had already undergone maximum structural ordering (having been pre–baked at 3000°C). / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.