Fuel cells, hydrogen and energy supply in Australia

Australia is unique in terms of its geography, population distribution, and energy sources. It has an abundance of fossil fuel in the form of coal, natural gas, coal seam methane (CSM), oil, and a variety renewable energy sources that are under development. Unfortunately, most of the natural gas is located so far away from the main centres of population that it is more economic to ship the energy as LNG to neighboring countries. Electricity generation is the largest consumer of energy in Australia and accounts for around 50% of greenhouse gas emissions as 84% of electricity is produced from coal. Unless these emissions are curbed, there is a risk of increasing temperatures throughout the country and associated climatic instability. To address this, research is underway to develop coal gasification and processes for the capture and sequestration Of CO2. Alternative transport fuels such as biodiesel are being introduced to help reduce emissions from vehicles. The future role of hydrogen is being addressed in a national study commissioned this year by the federal government. Work at the University of Queensland is also addressing full-cycle analysis of hydrogen production, transport, storage, and utilization for both stationary and transport applications. There is a modest but growing amount of university research in fuel cells in Australia, and an increasing interest from industry. Ceramic Fuel Cells Ltd. (CFCL) has a leading position in planar solid oxide fuel cells (SOFCs) technology, which is being developed for a variety of applications, and next year Perth in Western Australia is hosting a trial of buses powered by proton-exchange fuel cells. (C) 2004 Elsevier B.V. All rights reserved.

Technoeconomic modelling of coal conversion processes for liquid fuel production

Since the oil crisis of 1973 considerable interest has been shown in the production of liquid fuels from alternative sources. In particular processes utilizing coal as the feedstock have received considerable interest. These processes can be divided into direct and indirect liquefaction and pyrolysis. This thesis describes the modelling of indirect coal liquefaction processes for the purpose of performing technical and economic assessment of the production of liquid fuels from coal and lignite, using a variety of gasification and synthesis gas liquefaction technologies. The technologies were modeled on a 'step model' basis where a step is defined as a combination of individual unit operations which together perform a significant function on the process streams, such as a methanol synthesis step or a gasification and physical gas cleaning step. Sample results of the modelling, covering a wide range of gasifiers, liquid synthesis processes and products are presented in this thesis. Due to the large number of combinations of gasifier, liquid synthesis processes, products and economic sensitivity cases, a complete set of results is impractical to present in a single publication. The main results show that methanol is the cheapest fuel to produce from coal followed by fuel alcohol, diesel from the Shell Middle Distillate Synthesis process,gasoline from Mobil Methanol to Gasoline (MTG) process, diesel from the Mobil Methanol Olefins Gasoline Diesel (MOGD) process and finally gasoline from the same process. Some variation in production costs of all the products was shown depending on type of gasifier chosen and feedstock.

Pyrolysis liquids and gases as alternative fuels in internal combustion engines:a review

Liquids and gases produced through biomass pyrolysis have potential as renewable fuels to replace fossil fuels in conventional internal combustion engines. This review compares the properties of pyrolysis fuels, produced from a variety of feedstocks and using different pyrolysis techniques, against those of fossil fuels. High acidity, the presence of solid particles, high water content, high viscosity, storage and thermal instability, and low energy content are typical characteristics of pyrolysis liquids. A survey of combustion, performance and exhaust emission results from the use of pyrolysis liquids (both crude and up-graded) in compression ignition engines is presented. With only a few exceptions, most authors have reported difficulties associated with the adverse properties of pyrolysis liquids, including: corrosion and clogging of the injectors, long ignition delay and short combustion duration, difficulty in engine start-up, unstable operation, coking of the piston and cylinders and subsequent engine seizure. Pyrolysis gas can be used more readily, either in spark ignition or compression ignition engines; however, NO reduction techniques are desirable. Various approaches to improve the properties of pyrolysis liquids are discussed and a comparison of the properties of up-graded vs. crude pyrolysis liquid is included. Further developments in up-gradation techniques, such as hydrocracking and bio-refinery approaches, could lead to the production of green diesel and green gasoline. Modifications required to engines for use with pyrolysis liquids, for example in the fuel supply and injection systems, are discussed. Storage stability and economic issues are also reviewed. Our study presents recent progress and important R&D areas for successful future use of pyrolysis fuels in internal combustion engines.

Combustion of fuel blends containing digestate pyrolysis oil in a multi-cylinder compression ignition engine

Digestate from the anaerobic digestion conversion process is widely used as a farm land fertiliser. This study proposes an alternative use as a source of energy. Dried digestate was pyrolysed and the resulting oil was blended with waste cooking oil and butanol (10, 20 and 30 vol.%). The physical and chemical properties of the pyrolysis oil blends were measured and compared with pure fossil diesel and waste cooking oil. The blends were tested in a multi-cylinder indirect injection compression ignition engine.Engine combustion, exhaust gas emissions and performance parameters were measured and compared with pure fossil diesel operation. The ASTM copper corrosion values for 20% and 30% pyrolysis blends were 2c, compared to 1b for fossil diesel. The kinematic viscosities of the blends at 40 C were 5–7 times higher than that of fossil diesel. Digested pyrolysis oil blends produced lower in-cylinder peak pressures than fossil diesel and waste cooking oil operation. The maximum heat release rates of the blends were approximately 8% higher than with fossil diesel. The ignition delay periods of the blends were higher; pyrolysis oil blends started to combust late and once combustion started burnt quicker than fossil diesel. The total burning duration of the 20% and 30% blends were decreased by 12% and 3% compared to fossil diesel. At full engine load, the brake thermal efficiencies of the blends were decreased by about 3–7% when compared to fossil diesel. The pyrolysis blends gave lower smoke levels; at full engine load, smoke level of the 20% blend was 44% lower than fossil diesel. In comparison to fossil diesel and at full load, the brake specific fuel consumption (wt.) of the 30% and 20% blends were approximately 32% and 15% higher. At full engine load, the CO emission of the 20% and 30% blends were decreased by 39% and 66% with respect to the fossil diesel. Blends CO2 emissions were similar to that of fossil diesel; at full engine load, 30% blend produced approximately 5% higher CO2 emission than fossil diesel. The study concludes that on the basis of short term engine experiment up to 30% blend of pyrolysis oil from digestate of arable crops can be used in a compression ignition engine.

Catalysing sustainable fuel and chemical synthesis

Concerns over the economics of proven fossil fuel reserves, in concert with government and public acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from such combustible carbon, are driving academic and commercial research into new sustainable routes to fuel and chemicals. The quest for such sustainable resources to meet the demands of a rapidly rising global population represents one of this century’s grand challenges. Here, we discuss catalytic solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels, and oxygenated organic molecules for the manufacture of fine and speciality chemicals to meet future societal demands.

Computational modeling of intermediate temperature proton exchange membrane (PEM) fuel cells

A two-phase three-dimensional computational model of an intermediate temperature (120--190°C) proton exchange membrane (PEM) fuel cell is presented. This represents the first attempt to model PEM fuel cells employing intermediate temperature membranes, in this case, phosphoric acid doped polybenzimidazole (PBI). To date, mathematical modeling of PEM fuel cells has been restricted to low temperature operation, especially to those employing Nafion ® membranes; while research on PBI as an intermediate temperature membrane has been solely at the experimental level. This work is an advancement in the state of the art of both these fields of research. With a growing trend toward higher temperature operation of PEM fuel cells, mathematical modeling of such systems is necessary to help hasten the development of the technology and highlight areas where research should be focused.^ This mathematical model accounted for all the major transport and polarization processes occurring inside the fuel cell, including the two phase phenomenon of gas dissolution in the polymer electrolyte. Results were presented for polarization performance, flux distributions, concentration variations in both the gaseous and aqueous phases, and temperature variations for various heat management strategies. The model predictions matched well with published experimental data, and were self-consistent.^ The major finding of this research was that, due to the transport limitations imposed by the use of phosphoric acid as a doping agent, namely low solubility and diffusivity of dissolved gases and anion adsorption onto catalyst sites, the catalyst utilization is very low (∼1--2%). Significant cost savings were predicted with the use of advanced catalyst deposition techniques that would greatly reduce the eventual thickness of the catalyst layer, and subsequently improve catalyst utilization. The model also predicted that an increase in power output in the order of 50% is expected if alternative doping agents to phosphoric acid can be found, which afford better transport properties of dissolved gases, reduced anion adsorption onto catalyst sites, and which maintain stability and conductive properties at elevated temperatures.^

New fuel cells system for portable application with low temperature cofired ceramic (LTCC) technology

Miniature direct methanol fuel cells (DMFCs) are promising micro power sources for portable appliction. Low temperature cofired ceramic (LTCC), a competitive technology for current MEMS based fabrication, provides cost-effective mass manufacturing route for miniature DMFCs. Porous silver tape is adapted as electrodes to replace the traditional porous carbon electrodes due to its compatibility to LTCC processing and other electrochemical advantages. Electrochemical evaluation of silver under DMFCs operating conditions demonstrated that silver is a good electrode for DMFCs because of its reasonable corrosion resistance, low passivating current, and enhanced catalytic effect. Two catalyst loading methods (cofiring and postfiring) of the platinum and ruthenium catalysts are evaluated for LTCC based processing. The electrochemical analysis exhibits that the cofired path out-performs the postfiring path both at the anode and cathode. The reason is the formation of high surface area precipitated whiskers. Self-constraint sintering is utilized to overcome the difficulties of the large difference of coefficient of thermal expansion (CTE) between silver and LTCC (Dupont 951) tape during cofiring. The graphite sheet employed as a cavity fugitive insert guarantees cavity dimension conservation. Finally, performance of the membrane electrode assembly (MEA) with the porous silver electrode in the regular graphite electrode based cell and the integrated cofired cell is measured under passive fuel feeding condition. The MEA of the regular cell performs better as the electrode porosity and temperature increased. The power density of 10 mWcm-2 was obtained at ambient conditions with 1M methanol and it increased to 16 mWcm -2 at 50°C from an open circuit voltage of 0.58V. For the integrated prototype cell, the best performance, which depends on the balance methanol crossover and mass transfer at different temperatures and methanol concentrations, reaches 1.13 mWcm-2 at 2M methanol solution at ambient pressure. The porous media pore structure increases the methanol crossover resistance. As temperature increased to 60°C, the device increases to 2.14 mWcm-2.

Combustion Instability and Active Control: Alternative Fuels, Augmentors, and Modeling Heat Release

Experimental and analytical studies were conducted to explore thermo-acoustic coupling during the onset of combustion instability in various air-breathing combustor configurations. These include a laboratory-scale 200-kW dump combustor and a 100-kW augmentor featuring a v-gutter flame holder. They were used to simulate main combustion chambers and afterburners in aero engines, respectively. The three primary themes of this work includes: 1) modeling heat release fluctuations for stability analysis, 2) conducting active combustion control with alternative fuels, and 3) demonstrating practical active control for augmentor instability suppression. The phenomenon of combustion instabilities remains an unsolved problem in propulsion engines, mainly because of the difficulty in predicting the fluctuating component of heat release without extensive testing. A hybrid model was developed to describe both the temporal and spatial variations in dynamic heat release, using a separation of variables approach that requires only a limited amount of experimental data. The use of sinusoidal basis functions further reduced the amount of data required. When the mean heat release behavior is known, the only experimental data needed for detailed stability analysis is one instantaneous picture of heat release at the peak pressure phase. This model was successfully tested in the dump combustor experiments, reproducing the correct sign of the overall Rayleigh index as well as the remarkably accurate spatial distribution pattern of fluctuating heat release. Active combustion control was explored for fuel-flexible combustor operation using twelve different jet fuels including bio-synthetic and Fischer-Tropsch types. Analysis done using an actuated spray combustion model revealed that the combustion response times of these fuels were similar. Combined with experimental spray characterizations, this suggested that controller performance should remain effective with various alternative fuels. Active control experiments validated this analysis while demonstrating 50-70\% reduction in the peak spectral amplitude. A new model augmentor was built and tested for combustion dynamics using schlieren and chemiluminescence techniques. Novel active control techniques including pulsed air injection were implemented and the results were compared with the pulsed fuel injection approach. The pulsed injection of secondary air worked just as effectively for suppressing the augmentor instability, setting up the possibility of more efficient actuation strategy.

Environmental assessment of proton exchange membrane fuel cell platinum catalyst recycling

International audience

CHARACTERIZATION OF THERMAL AND MECHANICAL PROPERTIES OF POLYPROPYLENE–BASED COMPOSITES FOR FUEL CELL BIPOLAR PLATES AND DEVELOPMENT OF EDUCATIONAL TOOLS IN HYDROGEN AND FUEL CELL TECHNOLOGIES

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Experimental studies on comparison of microwave curing and thermal curing of epoxy resins used for alternative mould materials

In this present work attempts have been made to study the glass transition temperature of alternative mould materials by using both microwave heating and conventional oven heating. In this present work three epoxy resins, namely R2512, R2515 and R2516, which are commonly used for making injection moulds have been used in combination with two hardeners H2403 and H2409. The magnetron microwave generator used in this research is operating at a frequency of 2.45 GHz with a hollow rectangular waveguide. In order to distinguish the effects between the microwave and conventional heating, a number of experiments were performed to test their mechanical properties such as tensile and flexural strengths. Additionally, differential scanning calorimeter technique was implemented to measure the glass transition temperature on both microwave and conventional heating. This study provided necessary evidences to establish that microwave heated mould materials resulted with higher glass transition temperature than the conventional heating. Finally, attempts were also made to study the microstructure of microwave-cured materials by using a scanning electron microscope in order to analyze the morphology of cured specimens.