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The reaction between carbon and iron oxide-containing slag is crucial to efficient electric arc furnace steelmaking. The reaction occurs via gaseous intermediates, and the rate of gas generation by carbon gasification is limited by the chemical reactions at the slag-gas and carbon-gas interfaces. The aim of the present study was to obtain an understanding of the gasification rate limiting factors and slag foaming behaviour that could be readily applied to industrial electric arc furnace situations. The rate of carbon gasification was measured in experimental simulations of an electric arc furnace heat with slags containing between 21.6 and 48.2 wt% 'FeO'. It was found that rate control was dominated by the carbon-gas chemical reaction. A model was developed which describes the carbon gasification rate, amount of residual carbon in the slag, gas composition, slag-gas interfacial area and bubble diameter during carbon injection into slag. The model predicts rate control by the carbon-gas chemical reaction, in agreement with experimental observations. The slag foaming behaviour was investigated, and it was found that the foaming index is a useful parameter in quantifying foam height only if void fraction is constant with respect to gas flow rate. The average bubble size was observed to be an important factor in determining foam stability, with smaller bubble size resulting in greater foam height. / Thesis / Master of Applied Science (MASc)

Thermodynamic calculations are used to study the alkali reactions in coal gasifier atmospheres. The reactive alkali and sulfur species released from coal are first calculated at temperatures from 800 K to 1900 K and pressures from 1 atm to 100 atm. Four P-T diagrams are constructed for the stable alkali and/or alkali-sulfur species at differ-ent temperatures and pressures. Alkali vapors are generated by the reactions Na₂CO₃_(s) + 2C_(s) = 2Na_(g) + 3CO_(g) Na₂CO₃_(s) + H₂O_(g) + C_(s) = 2NaOH_(g) + 2CO_(g) or K₂CO₃_(s) + 2C_(s) = 2K_(g) + 3CO_(g) K₂CO₃_(s) + H₂O_(g) + C_(s) = 2KOH_(g) + 2CO_(g) The phases formed from alkali-cement, and alkali-sulfur-cement reaction are also predicted. For both 53% and 72% alumina cement, calcium aluminate (CaO•Al₂O₃) is decomposed by the reactions CaO•Al₂O₃ + 2Na + 1/20₂ = Na₂O•Al₂O₃ + CaO CaO•Al₂O₃ + 2K + 1/20₂ = K₂O•Al₂O₃ + CaO or CaO•Al₂O₃ + 2Na + l/2S₂ = Na₂0•Al₂O₃ + CaS CaO•Al₂O₃ + 2K + 1/2S₂ = K₂•Al₂O₃ + CaS / M.S.

Master of Science / Department of Biological and Agricultural Engineering / Wenqiao Yuan / Gasification is an efficient way to produce energy from biomass, which has significant positive impacts on the environment, domestic economy, national energy security, and the society in general. In this study, a lab-scale updraft biomass gasifier was designed, built, and instrumented for stable gasification using low-bulk density biomass. Related accessories, such as a biomass feeder, inlet air temperature controller, air injection nozzle, and tar cracking system, were also developed to enhance gasifier performance. The effect of operation parameters on gasifier performance was studied. Two operational parameters, including air flow rate and feed-air temperature, were studied on three sources of biomass: prairie hay, sorghum biomass, and wood chips. Results showed that higher air flow rate increased tar contents in syngas for all three types. It was also found that different biomasses gave significantly different tar contents, in the order of wood chips>sorghum biomass>prairie hay. Feed-air temperature did not have a significant effect on tar content in syngas except for prairie hay, where higher feed air temperature reduced tar. A statistical model was implemented to study differences on syngas composition. Results showed that different biomasses produced syngas with different high heating value, e.g., wood chips > prairie hay > sorghum biomass. CO composition also showed differences by feed air temperature and biomass, e.g. prairie hay>wood chips>sorghum biomass, but H[subscript]2 did not show significant differences by either biomass type or operating conditions. Moreover, because of the downstream problems caused by tars in syngas such as tar condensation in pipelines, blockage and machinery collapse, an in-situ tar cracking system was developed to remove tars in syngas. The tar cracking device was built in the middle of the gasifier’s combustion using gasification heat to drive the reactions. The in-situ system was found to be very effective in tar removal and syngas enhancement. The highest tar removal of 95% was achieved at 0.3s residence time and 10% nickel loading. This condition also gave the highest syngas HHV increment of 36% (7.33 MJ/m[superscript]3). The effect of gas residence time and Ni loading on tar removal and syngas composition was also studied. Gas residence of 0.2-0.3s and Ni loading of 10% were found appropriate in this study.

In this work, SCWG of glucose, cellulose and pinewood was studied at different operating conditions with and without catalyst. Three parameters studied included temperature (400, 470, 500 and 550oC), water to biomass weight ratio (3:1 and 7:1) and catalyst (Ni/MgO, Ni/activated carbon, Ni/Al2O3, Ni/CeO2/Al2O3, dolomite, NaOH, KOH, activated carbon and olivine), which were varied for gasification of glucose, cellulose and pinewood. By comparing the results from model compound (glucose and cellulose) with that from real biomass (pinewood), the mechanism of how the individual compounds are gasified was explored. For catalytic runs with glucose, NaOH had the best activity for improving H2 formation. H2 yield increased by 135% using NaOH compared to that for run without catalyst at 500oC with a water to biomass weight ratio of 3:1. At the same operating conditions, the presence of Ni/activated carbon (Ni/AC) contributed to an 81% increase in H2 yield, followed by 62% with Ni/MgO, 60% with Ni/CeO2/Al2O3 and 52% with Ni/Al2O3. For catalytic runs with cellulose, the H2 yield increased by 194% with KOH compared to that for run without catalyst at 400oC with a water to biomass ratio of 3:1. At the same operating conditions, the presence of Ni/CeO2/Al2O3 contributed to a 31% increase in H2 yield followed by a 28% increase with dolomite. When the water to biomass ratio was increased from 3:1 to 7:1, H2 yield from glucose gasification was increased by 40% and 33% at 400 and 500oC, respectively, and the H2 yield of cellulose gasification was increased by 44%, 11% and 22% at 400, 470 and 550oC, respectively. The higher heating value of the oil products derived from SCWG of both glucose and cellulose incresed in the presence of catalysts. As real biomass, pinewood was gasified in supercritical water at the suitable operation conditions (550oC with water to biomass ratio of 7:1) obtained from previous experiments, using three kinds of catalyst: Ni/CeO2/Al2O3, dolomite and KOH. At the same operating conditions, the gasification of pinewood had smaller yields of H2 (20 to 41%) compared with that from cellulose. The effect of the catalyst on H2 production from SCW in the absence of biomass was studied. The results showed that a trace amount of H2 was formed with Ni based catalyst/dolomite only while some CO2 was formed with Ni/AC. Most of the runs presented in this report were repeated once, some of the runs had been triplicated, and the deviation of all results was in the range of ±5%.

The increased use of fossil fuels during the last centuries has caused elevated levels of carbon dioxide in the atmosphere. There is significant evidence that this is the cause of global warming. To mitigate the global warming, measures has to be taken to use renewable fuels and make processes more efficient. Catalytic gasification and downstream upgrading of synthesis gas is a promising technology for biofuel production, where previous research in black liquor gasification is currently expanding into a wider fuel feedstock. This work focuses on co-gasification of black liquor and by-products from other biofuel production technologies. The interesting by-products were crude glycerol from biodiesel production and spruce fermentation residue from ethanol production. The main goals were to study if the fuels can mix homogeneously and study the char reactivity. CO2 char gasification for mixtures of black liquor and glycerol or fermentation residue respectively was studied using thermogravimetric analysis (TGA) for four temperatures between 750°C and 900°C. The results show that glycerol can be mixed in all proportions with black liquor and indicate that the char reactivity is unchanged. The sustained char reactivity for blends is attributed to the volatility of glycerol. The fermentation residue does not produce a homogeneous mixture with black liquor and the char is less reactive. More studies should be performed to further elucidate the validity of the results.

This paper examines an overview of the economic and environmental aspects of Underground Coal Gasification (UCG) as a viable option to the above ground Surface Coal Gasification (SCG). In addition, some highlights, hurdles and opportunities from early investment to successful commercial application of some worldwide UCG projects will be discussed. Global energy demands have prompted continual crude oil consumption at an astronomical pace. As such, the most advanced economies are looking for local and bountiful resources to challenge crude oil's dependence for which coal provides the best alternative so far. In the U.S, the Department of Energy (DOE), the National Energy Transportation Laboratory (NETL) along with the Lawrence Livermore National Laboratory (LLNL) continue to support pilot programs that develop improved methods for clean coal technologies to produce coal derived fuels competitive with crude oil fuels at about $30 per barrel. Lignite, the softest of the four types of coal, is the best candidate for underground coal gasification due to its abundance, high volatility and water to carbon content in its rock formation. The biggest challenge of modern humans is to find a balance of energy consumption, availability of resources, production costs and environmental conservation. Additionally, UCG has environmental benefits that include mitigating CO₂ emissions through Carbon Capture and Storage (CCS) and reduced overall surface pollutants, making it the preferred choice over SCG. / text

The prime objective of a current research project at the University of Natal is to develop a novel autothermal fluidised bed coal gasifier which is capable of efficiently producing synthesis quality gas (rich in hydrogen and carbon monoxide) from discard of duff coal resources using air and steam as the reactant gases. The development of this gasifier was initially motivated to utilise the ever increasing supply of discard coal in South Africa which represents a significant potential source of energy and currently poses severe environmental pollution hazards caused by spontaneous combustion and wind erosion of the discard coal dumps. Recently, however, the gasifier has been considered for the conversion of more general coal resources in an Integrated Coal Gasification Combined Cycle process (IGCC) for the production of electricity. The knowledge of the kinetics of steam gasification of local coal resources is of vital importance to the design of this gasifier. However, no such kinetic data are available of which the author is aware. This thesis presents the following contributions to the overall knowledge of the gasifier (a) The development of a micro reactor to measure the rate of reaction of the steam gasification of coal-char at temperatures of up to l000oC and pressures up to 5 bar absolute; (b) Kinetic studies using the microreactor on the steam gasification of coal-chars derived from Bosjesspruit and Transvaal Navigation coal samples. The following principal results were obtained with Bosjesspruit coal-char : The rate of steam-char gasification is very sensitive to variations in the temperature of reaction in the range 840°C to 920°C. Neither the rate of steam-char gasification nor the product gas composition are affected by the steam partial pressure in the range 1.8 to 4.8 bar absolute; The concentrations of the H2 and CH4 components of the product gas stream rapidly approached their respective equilibrium compositions, whereas the concentrations of CO and CO2 gradually approach their respective equilibrium compositions during gasification at a rate which is typical of the stoichiometry of the Boudouard reaction. The average product gas composition is independent of the temperature of reaction in the range 840°C to 920°C and is approximately 49% H2, 32% CO, 17% CO2 and 2% CH4 on a molar basis; The steam gasification kinetic data are well described by a fundamental Arrhenius-type volumetric reaction model at (c) temperatures of up to 920°C. The value of the activation energy for the reaction is 146 kJ/gmol, which indicates that the gasification kinetics are controlled by the rates of the chemical reactions (ie. C + H2O = CO + H2 and C + CO2 = 2CO) at temperatures up to 920o C; There are no major differences between the kinetics measured for Bosjesspruit coal-char and those reported in the literature for foreign coal-chars. The experimental results obtained for the steam gasification of char derived from Transvaal Navigation coal show that the concentrations of both the Hz and the CH4 in the product gas stream rapidly attain their respective equilibrium values and remain approximately constant throughout gasification, whereas the concentrations of CO and CO2 gradually approach their respective equilibrium values during the course of gasification and almost attain equilibrium concentrations as the conversion of carbon nears completion. The rate of steam gasification of this char is therefore also controlled by the rate of the Boudouard reaction. The mathematical development of a steady-state, one-dimensional compartment model of the gasifier. The model is also presented in the form of a Fortran 77 computer program which is designed to run on a personal computer. The program is capable of simultaneously solving the overall material and energy balances of the gasifier to a tolerance of l% within 15 minutes when using a microprocessor which operates at 10 Mhz. (d) The gasifier simulation program is currently being used in the design of a pilot scale gasifier which is intended to demonstrate the capability of the process on a continous basis of operation. (e) Experimentation on the air-steam gasification of Bosjesspruit coal using a mini-pilot scale gasifier. These experiments have successfully demonstrated the feasibility of the production of a gas stream which is rich in hydrogen and carbon monoxide. The composition of the product gas stream compares well with the predictions of the simulation model of the gasifier. / Thesis (Ph.D.)-University of Natal, Durban, 1990.

The aim of this thesis is to describe the process of biomass gasification using gas simulating the composition of flue gas – a mixture of oxygen, carbon dioxide and water vapor. In the research part of the thesis the issue of gasification with the focus on fluidized bed gasification and the effect of the gasification medium used on the gasification process is discussed. In the practical part the thesis deals with the design, realization and evaluation of the experiment on a real device. The aim of the experiment is to determine the effect of the exact composition of the mixture of these three media on the gasification process and on the quality of the gas generated. The aim is to find the optimum composition for obtaining gas with the highest possible lower heating value, which contains as little tar as possible. At the end of the work, the results from the experiment are presented and described.

This master’s thesis deals with the process of biomass gasification using mixture of CO and O2 as gasification agent. First part describes the gasification process itself, used devices, gasification medium and its influence on the generated gas. Following section covers the experimental part of the work, which is focused on change properties of the generated gas using different ratios of CO2, O2, H2O and air in the gasification mixture. This part also includes processing and evaluation of the results.