Glycerol is a waste by-product obtained during the production of biodiesel. Biodiesel is one of the alternative fuels used to meet our energy requirements and also carbon dioxide emission is much lesser when compared to regular diesel fuel. Biodiesel and glycerol are produced from the transesterification of vegetable oils and fats with alcohol in the presence of a catalyst. About 10 wt% of vegetable oil is converted into glycerol during the transesterification process. An increase in biodiesel production would decrease the world market price of glycerol. The objective of this work is to produce value added products such as hydrogen or syn gas and medium heating value gas from waste glycerol using pyrolysis and steam gasification processes. <p> Pyrolysis and steam gasification of glycerol reactions was carried out in an Inconel®, tubular, fixed bed down-flow reactor at atmospheric pressure. The effects of carrier gas flow rate (30mL/min-70mL/min), temperature (650oC-800oC) and different particle diameter of different packing material (quartz - 0.21-0.35mm to 3-4mm; silicon carbide 0.15 to 1mm; Ottawa sand 0.21-0.35mm to 1.0-1.15mm) on the product yield, product gas volume, composition and calorific value were studied for the pyrolysis reactions. An increase in carrier gas flow rate did not have a significant effect on syn gas production at 800oC with quartz chips diameter of 3-4mm. However, total gas yield increased from 65 to 72wt% and liquid yield decreased from 30.7 to 19.3wt% when carrier gas flow rate decreased from 70 to 30mL/min. An increase in reaction temperature, increased the gas product yield from 27.5 to 68wt% and hydrogen yield from 17 to 48.6mol%. Also, syn gas production increased from 70 to 93 mol%. A change in particle size of the packing material had a significant increase in the gas yield and hydrogen gas composition. Therefore, pyrolysis reaction at 800oC, 50mL/min of nitrogen and quartz particle diameter of 0.21-0.35mm were optimum reaction parameter values that maximise the gas product yield (71wt%), hydrogen yield (55.4mol%), syn gas yield (93mol%) and volume of product gas (1.32L/g of glycerol). The net energy recovered at this condition was 111.18 kJ/mol of glycerol fed. However, the maximum heating value of product gas (21.35 MJ/m3) was obtained at 650oC, 50mL/min of nitrogen and with a quartz packing with particle diameter of 3-4mm. <p>The steam gasification of glycerol was carried out at 800oC, with two different packing materials (0.21-0.35mm diameter of quartz and 0.15mm of silicon carbide) by changing the steam to glycerol weight ratio from 0:100 to 50:50. The addition of steam to glycerol increased the hydrogen yield from 55.4 to 64mol% and volume of the product gas from 1.32L/g for pyrolysis to 1.71L/g of glycerol. When a steam to glycerol weight ratio of 50:50 used for the gasification reaction, the glycerol was completely converted to gas and char. Optimum conditions to maximize the volume of the product gas (1.71L/g), gas yield of 94wt% and hydrogen yield of 58mol% were 800oC, 0.21-0.35mm diameter of quartz as a packing material and steam to glycerol weight ratio of 50:50. Syn gas yield and calorific value of the product gas at this condition was 92mol% and 13.5MJ/m3, respectively. The net energy recovered at this condition was 117.19 kJ/mol of glycerol fed. <p>The steam gasification of crude glycerol was carried out at 800oC, quartz size of 0.21-0.35mm as a packing material over the range of steam to crude glycerol weight ratio from 7.5:92.5 to 50:50. Gasification reaction with steam to glycerol weight ratio of 50:50 was the optimum condition to produce high yield of product gas (91.1wt%), volume of gas (1.57L/g of glycerol and methanol), hydrogen (59.1mol%) and syn gas (79.1mol%). However, the calorific value of the product gas did not change significantly by increasing the steam to glycerol weight ratio.

Glycerol is a waste by-product obtained during the production of biodiesel. Biodiesel is one of the alternative fuels used to meet our energy requirements and also carbon dioxide emission is much lesser when compared to regular diesel fuel. Biodiesel and glycerol are produced from the transesterification of vegetable oils and fats with alcohol in the presence of a catalyst. About 10 wt% of vegetable oil is converted into glycerol during the transesterification process. An increase in biodiesel production would decrease the world market price of glycerol. The objective of this work is to produce value added products such as hydrogen or syn gas and medium heating value gas from waste glycerol using pyrolysis and steam gasification processes. <p> Pyrolysis and steam gasification of glycerol reactions was carried out in an Inconel®, tubular, fixed bed down-flow reactor at atmospheric pressure. The effects of carrier gas flow rate (30mL/min-70mL/min), temperature (650oC-800oC) and different particle diameter of different packing material (quartz - 0.21-0.35mm to 3-4mm; silicon carbide 0.15 to 1mm; Ottawa sand 0.21-0.35mm to 1.0-1.15mm) on the product yield, product gas volume, composition and calorific value were studied for the pyrolysis reactions. An increase in carrier gas flow rate did not have a significant effect on syn gas production at 800oC with quartz chips diameter of 3-4mm. However, total gas yield increased from 65 to 72wt% and liquid yield decreased from 30.7 to 19.3wt% when carrier gas flow rate decreased from 70 to 30mL/min. An increase in reaction temperature, increased the gas product yield from 27.5 to 68wt% and hydrogen yield from 17 to 48.6mol%. Also, syn gas production increased from 70 to 93 mol%. A change in particle size of the packing material had a significant increase in the gas yield and hydrogen gas composition. Therefore, pyrolysis reaction at 800oC, 50mL/min of nitrogen and quartz particle diameter of 0.21-0.35mm were optimum reaction parameter values that maximise the gas product yield (71wt%), hydrogen yield (55.4mol%), syn gas yield (93mol%) and volume of product gas (1.32L/g of glycerol). The net energy recovered at this condition was 111.18 kJ/mol of glycerol fed. However, the maximum heating value of product gas (21.35 MJ/m3) was obtained at 650oC, 50mL/min of nitrogen and with a quartz packing with particle diameter of 3-4mm. <p>The steam gasification of glycerol was carried out at 800oC, with two different packing materials (0.21-0.35mm diameter of quartz and 0.15mm of silicon carbide) by changing the steam to glycerol weight ratio from 0:100 to 50:50. The addition of steam to glycerol increased the hydrogen yield from 55.4 to 64mol% and volume of the product gas from 1.32L/g for pyrolysis to 1.71L/g of glycerol. When a steam to glycerol weight ratio of 50:50 used for the gasification reaction, the glycerol was completely converted to gas and char. Optimum conditions to maximize the volume of the product gas (1.71L/g), gas yield of 94wt% and hydrogen yield of 58mol% were 800oC, 0.21-0.35mm diameter of quartz as a packing material and steam to glycerol weight ratio of 50:50. Syn gas yield and calorific value of the product gas at this condition was 92mol% and 13.5MJ/m3, respectively. The net energy recovered at this condition was 117.19 kJ/mol of glycerol fed. <p>The steam gasification of crude glycerol was carried out at 800oC, quartz size of 0.21-0.35mm as a packing material over the range of steam to crude glycerol weight ratio from 7.5:92.5 to 50:50. Gasification reaction with steam to glycerol weight ratio of 50:50 was the optimum condition to produce high yield of product gas (91.1wt%), volume of gas (1.57L/g of glycerol and methanol), hydrogen (59.1mol%) and syn gas (79.1mol%). However, the calorific value of the product gas did not change significantly by increasing the steam to glycerol weight ratio.

Cotton-gin trash (CGT) was pyrolyzed at different temperatures and reaction times using an externally-heated batch reactor. The average yields of output products (solid/char, liquid/bio-oil, and gaseous) were determined. The heating value (HV) of CGT was measured to be around 15-16 MJ kg- 1 (6500-7000 Btu lb-1). In the first set of tests, CGT was pyrolyzed at 600, 700, and 800°C and at 30, 45, and 60 min reaction period. The maximum char yield of 40% by weight (wt.%) was determined at 600°C and 30 min settings, however, the HV of char was low and almost similar to the HV of CGT. A maximum gas yield of 40 wt.% was measured at 800°C and 60 min and the highest liquid yield of 30 wt.% was determined at 800°C and 30 min. In the modified pyrolysis test, the effects of temperature (500, 600, 700, and 800°C) on the product yield and other properties were investigated. The experiment was performed using the same reactor purged with nitrogen at a rate of 1000 cm3 min-1. Gas yield increased as temperature was increased while the effect was opposite on char yield. The maximum char yield of 38 wt.% was determined at 500°C and 30 min. The char had the largest fraction in the energy output (70-83%) followed by gas (10-20%) and bio-oil (7- 9%). Maximum gas yield of 35 wt.% was determined at 800°C. The average yield of CO, H2 and total hydrocarbons (THC) generally increased with increased temperature but CO2 production decreased. Methane, ethane, and propane dominated the THC. The bio-oil yield at 600°C was the highest at about 30 wt.% among the temperature settings. The HV of bio-oil was low (2-5 MJ kg-1) due to minimal non-HC compounds and high moisture content (MC). A simple energy balance of the process was performed. The process was considered energy intensive due to the high amount of energy input (6100 kJ) while generating a maximum energy output of only 10%. After disregarding the energy used for preparation and pyrolysis, the energy losses ranged from 30-46% while the energy of the output represent between 55-70% of the input energy from CGT.

To examine the effects of operational parameters on syn-gas quality and biouel conversion rate under various running conditions, an experimental study of hardwood chip?s gasification in a downdraft gasifier was conducted. The resulting syn-gas had average low heating value of 5.79 ± 0.52 MJ/ Nm3, tar concentration of 14.06 ± 8.54 mg/Nm³, particulate concentration of 3.05 ± 1.79 mg/Nm³, hardwood conversion rate of 2.37±0.24 Nm³/kg, and carbon conversion rate of 98.01 ± 0.53%. This syn-gas is of acceptable quality to be used as a fuel source for internal combustion engine operations. The gasifier?s grate temperature had no evident effects on syn-gas quality and conversion rate within a range of 740 to 817oC. The particulate contents in preiltered syn-gas significantly increased when the gas flow rate changed from 36 to 56 Nm3/h. When the moisture content of hardwood chips increased, tar content of postiltered syn-gas significantly increased, and CO content significantly decreased.

The research institute ETC in Piteå is working with energy technical research and development. Today, much work revolves around research about renewable sources for fuel. In one project, biomass such as wood pellet is heated up while producing synthesis gas. The synthesis gas is then analyzed using three different GC techniques. ETC wanted to be able to make all their analysis on one instrument and with a faster speed. They contacted the company Rowaco in Linköping for help with developing a method on FTIR for analysis of the synthesis gas and that has been the aim for this thesis. A method has been developed for analysis of water, carbon monoxide, carbon dioxide and methane. The results from this thesis show that the concentrations of the molecules in the synthesis gas are outside the calibration curved that has been made and that the high concentrations give much interference to other molecules. The thesis also shows that many areas in the spectrum from the process are roof absorbers and there is also a contamination of water and carbon dioxide in the system. Suggested improvements are to find the source for the contamination, to develop calibration points with higher concentrations, to reduce the length of the gas cell and to dilute the gas before entering the FTIR.

Hydrocarbon conversion and synthesis gas production are two components of the power production process that require significant development and exploration in the advanced energy arena. To remain within our current fueling infrastructure, it is imperative that an efficient and reliable mechanism to facilitate these components of the power production process is developed for automotive applications. A honeycomb monolith rhodium based catalyst has been identified as a potential fuel reformer element for use in automotive hydrocarbon fuel conversion. Using the novel and minimally invasive SpaciMS (Spatially resolved capillary inlet Mass Spectroscopy), developed at Oak Ridge National Laboratories, and an internal temperature acquisition system, the impact of fuel inlet space velocity on the operating rhodium based catalytic fuel reformer of interest was parametrically studied. In situ temperature and species profiles of the catalyst during steady state operation were produced. The data acquired through these experiments was then used to demonstrate analytic capability by conducting thermodynamic analyses on the operating fuel reformer. Experimental and analytical results can be used in development of design considerations for fuel conversion systems.

As hydrogen is increasingly used as an energy carrier, gas sensors that can operate at high temperatures and in harsh environments are needed for fuel cell, aerospace, and automotive applications. The high temperature Fischer-Tropsch process also uses mixtures of hydrogen and carbon monoxide to generate synthetic fuels from non-fossil precursors. As the Fischer-Tropsch process depends upon particular gas mixtures to generate various fuels, a sensor which can determine the proper ratio of reactants is needed. To this end, gallium nitride (GaN) has been used to fabricate a resistive gas sensor. GaN is a suitable semiconductor to be used in hydrogen because of a wide, direct bandgap and greater stability than many other semiconductors. Additionally, resistive sensors offer several advantages in design compared to other types of sensors. Response time of resistive sensors is faster than those of other semiconductor sensors because catalytic and diffusion steps are not part of the response mechanism. Instead, a thermal detection mechanism is employed in resistive sensors. In this work, sensor response to changes in hydrogen concentration in nitrogen was measured at 200°C and 300°C. Sensor response was measured as change in current from a reference response to pure nitrogen at each temperature under a constant 2.5 V bias. Isothermal operation was achieved by controlling sensor temperature and pre-heating gas mixtures. Sensitivity to concentration increased upon an increase in temperature. Additionally, sensor response to concentration changes of H2 in CO at 50 °C was demonstrated. Sensors show similar responses to nitrogen and carbon monoxide mixtures, which have similar thermal properties. Using the thermal detection mechanism of the sensors, a correlation was shown between sensor response and a gas mixture thermal conductivity.

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