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.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

Performance Comparison of MATLAB and Neuro Solution Software on Estimation of Fuel Economy by Using Artificial Neural Network

In the world, scientific studies increase day by day and computer programs facilitate the human’s life. Scientists examine the human’s brain’s neural structure and they try to be model in the computer and they give the name of artificial neural network. For this reason, they think to develop more complex problem’s solution. The purpose of this study is to estimate fuel economy of an automobile engine by using artificial neural network (ANN) algorithm. Engine characteristics were simulated by using “Neuro Solution” software. The same data is used in MATLAB to compare the performance of MATLAB is such a problem and show its validity. The cylinder, displacement, power, weight, acceleration and vehicle production year are used as input data and miles per gallon (MPG) are used as target data. An Artificial Neural Network model was developed and 70% of data were used as training data, 15% of data were used as testing data and 15% of data is used as validation data. In creating our model, proper neuron number is carefully selected to increase the speed of the network. Since the problem has a nonlinear structure, multi layer are used in our model.

Free water in fuel sensor using fiber long period grating

A fiber optic free water in fuel (WIF) sensor is proposed by utilizing a long period fiber grating (LPFG). The existence of free water in fuel is indicated by the appearance of a characteristic loss band. The free water level in fuel can be determined by measuring the transmissions of two characteristic loss bands.

Increasing the electrolyte capacity of alkaline Zn-air fuel cells by scavenging zincate with Ca(OH)2

The use of calcium hydroxide for scavenging zincate species is demonstrated to be a highly effective approach for increasing the electrolyte capacity and improving the performance of the zinc-air fuel cell system. A fundamental approach is established in this study to quantify the formation of calcium zincate as the product of scavenging and the amount of water compensation necessary for optimal performance. The good agreement between predicted and experimental results proves the validity of the proposed theoretical approach. By applying the results of theoretical predictions, both the electrolyte capacity and the cell longevity have been increased by more than 40%. It is also found that, using Ca(OH)2 to scavenge zincate species in concentrated KOH solutions, affects mostly the removal of zincate, rather than ZnO, from the electrolyte, whereas the presence of excess, free, mobile H2O plays a key role in dissolving ZnO and forming zincate. The results obtained in this study demonstrate that the proposed approach can widely and effectively be applied to all zinc-air cell systems during their discharge cycle.

Effect of Cu and Sn promotion on the catalytic deoxygenation of model and algal lipids to fuel-like hydrocarbons over supported Ni catalysts

The ability of Cu and Sn to promote the performance of a 20% Ni/Al2O3 catalyst in the deoxygenation of lipids to fuel-like hydrocarbons was investigated using model triglyceride and fatty acid feeds, as well as algal lipids. In the semi-batch deoxygenation of tristearin at 260 °C a pronounced promotional effect was observed, a 20% Ni-5% Cu/Al2O3 catalyst affording both higher conversion (97%) and selectivity to C10-C17 alkanes (99%) in comparison with unpromoted 20% Ni/Al2O3 (27% conversion and 87% selectivity to C10-C17). In the same reaction at 350 °C, a 20% Ni-1% Sn/Al2O3 catalyst afforded the best results, giving yields of C10-C17 and C17 of 97% and 55%, respectively, which contrasts with the corresponding values of 87 and 21% obtained over 20% Ni/Al2O3. Equally encouraging results were obtained in the semi-batch deoxygenation of stearic acid at 300 °C, in which the 20% Ni-5% Cu/Al2O3 catalyst afforded the highest yields of C10-C17 and C17. Experiments were also conducted at 260 °C in a fixed bed reactor using triolein − a model unsaturated triglyceride − as the feed. While both 20% Ni/Al2O3 and 20% Ni-5% Cu/Al2O3 achieved quantitative yields of diesel-like hydrocarbons at all reaction times sampled, the Cu-promoted catalyst exhibited higher selectivity to longer chain hydrocarbons, a phenomenon which was also observed in experiments involving algal lipids as the feed. Characterization of fresh and spent catalysts indicates that Cu enhances the reducibility of Ni and suppresses both cracking reactions and coke-induced deactivation.

Experimental investigation of the fuel properties of glidfuel, palm oil mill effluent biodiesel and blends

Biofuels derived from industry waste have potential to substitute fossil fuels (Diesel and Gasoline) in internal combustion (IC) engines. Use of waste streams as fuels would help to reduce considerably life-cycle greenhouse gas emissions and minimise waste processing costs. In this study an investigation into the fuel properties of two waste derived biofuels were carried out, they are: (i) Glidfuel (GF) biofuel - a waste stream from paper industry, and (ii) Palm Oil Mill Effluent (POME) biodiesel - biodiesel produced from palm oil industry effluent through various treatment and transesterification process. GF and POME was mixed together at various proportions and separately with fossil diesel (FD) to assess the miscibility and various physical and chemical properties of the blends. Fuel properties such as kinematic viscosity, higher heating value, water content, acid number, density, flash point temperature, CHNO content, sulphur content, ash content, oxidation stability, cetane number and copper corrosion ratings of all the fuels were measured. The properties of GF, POME and various blends were compared with the corresponding properties of the standard FD. Significance of the fuel properties and their expected effects on combustion and exhaust emission characteristics of the IC engine were discussed. Results showed that most properties of both GF and POME biodiesel were comparable to FD. Both GF and POME were miscible with each other, and also separately with the FD. Flash point temperatures of GF and POME biodiesel were 40.7°C and 158.7°C respectively. The flash point temperature of GF was about 36% lower than corresponding FD. The water content in GF and FD were 0.74 (% wt) and 0.01 (% wt) respectively. Acidity values and corrosion ratings of both GF and POME biodiesel were low compared to corresponding value for FD. The study concluded that optimum GF-POME biofuel blends can substitute fossil diesel use in IC engines.

Aviation fuel gauging sensor utilizing multiple diaphragm sensors incorporating polymer optical fiber Bragg gratings

A high-performance fuel gauging sensor is described that uses five diaphragm-based pressure sensors, which are monitored using a linear array of polymer optical fiber Bragg gratings. The sensors were initially characterized using water, revealing a sensitivity of 98 pm/cm for four of the sensors and 86 pm/cm for the fifth. The discrepancy in the sensitivity of the fifth sensor has been explained as being a result of the annealing of the other four sensors. Initial testing in JET A-1 aviation fuel revealed the unsuitability of silicone rubber diaphragms for prolonged usage in fuel. A second set of sensors manufactured with a polyurethane-based diaphragm showed no measurable deterioration over a three month period immersed in fuel. These sensors exhibited a sensitivity of 39 pm/cm, which is less than the silicone rubber devices due to the stiffer nature of the polyurethane material used.

Gázolaj-jövedékiadó verseny az Európai Unióban (Fiscal competition on the market for diesel fuel in the European Union)

A tanulmány azt a kérdést vizsgálja, hogy versenyeznek-e az európai kormányok gázolajra vonatkozó jövedékiadó-kulcsaikkal a nagyobb adóbevételekért, és ha igen, befolyásolja-e az országok mérete kormányaik adóztatási stratégiáját. Az üzemanyagturizmussal szembesülő kormányok adókivetési magatartását egy kétországos adóverseny modellel jelezzük előre, amelyben a standard modellektől eltérően a fogyasztók kereslete árrugalmas. Megmutatjuk, hogy ha a kereslet nem teljesen rugalmatlan, mint Nielsen [2001], illetve Kanbur-Keen [1993] modelljeiben, akkor a nagy ország kormányának egyensúlyi viselkedése nemcsak abban különbözik a kicsiétől, hogy nagyobb adót állapít meg, hanem abban is, hogy válaszfüggvénye meredekebb. Az aszimmetrikus adóverseny általunk használt modelljét a dízelüzemanyagoknak 16 európai ország 1978 és 2005 közötti jövedékiadó-adatain vizsgáljuk. Az 1995 és 2005 közötti időszakra vonatkozó becslési eredményeink megerősítik, hogy az európai országok szomszédaik adókulcs-változtatásának hatására változtattak saját adókulcsaikon, és hogy a területileg/gazdaságilag kisebb országok kisebb intenzitással reagáltak szomszédaik adóváltoztatásra, mint a nagyobbak. Tanulmányunk ezzel magyarázatot nyújt arra is, hogy miért erősödött fel a tagállamok jövedéki adókulcsainak méret szerinti differenciálódása az elmúlt bő tíz évben, valamint hogy miért nem sikerült az Európai Uniónak a minimumadószintre vonatkozó előírásával előbbre lépnie az egységes adóztatás megvalósításában. / === / The paper assesses spatial competition in diesel taxation among European governments. By adding an extension to the standard model, it is shown that asymmetric competition – small countries undercutting large – implies that small countries respond less strongly to tax changes by their neighbours than large countries do. An estimate is then made of the fiscal reaction functions for national governments, employing a first-difference regression model with a weighting scheme constructed from road-traffic density data at national borders. Data from 16 countries (EU-15 minus Greece plus Norway and Switzerland) between 1978 and 2005 provides evidence that European governments set their diesel tax interdependently, and moreover, that small European countries tend to react less strongly to changes in their competitors' tax rate than large countries do.

The use of methane as automotive fuel – a step to sustainable economy?

The introduction of CNG (Compressed Natural Gas) as automotive fuel began in Italy as early as in mid- 1930s, and ever since the Italian market has always been highly advanced in this regard. Many other countries followed, some of them quite recently, but nevertheless with impressive results. The appeal of this automotive fuel is based on the fact that compared to gasoline, diesel and LPG (Liquefied Petroleum Gas), CNG is cleaner and cheaper; even more so, this fuel is renewable – it can be produced locally from biogas. Despite its obvious benefits, CNG is barely present in Hungary. This article provides an insight into the topic, highlights obstacles to introduction and suggests appropriate governmental steps. The information is intended to support the activities and the decision-making process of governmental officials, municipalities, car-fleet managers, car dealers and their service departments.

Capillary siphons and their application in the fuel delivery system of direct methanol fuel cells

The objective of the work is to develop a fuel delivery system for potable direct methanol fuel cell. Currently, one of the most fundamental limitations of direct methanol fuel cells is that the fuel supplied to the anode of the DMFC must be a very dilute aqueous methanol solution (usually 0.5∼1.5 M). If a DMFC is filled with a dilute aqueous methanol solution, the fuel cell operation time per refuel would be very short, which would considerably diminish the advantage of a DMFC over a conventional battery. To overcome this difficulty, a complex fuel delivery system based on the modern micro system technology was proposed by the author. The proposed fuel delivery system would include micro-pumps, a methanol sensor, and a control unit. The fuel delivery system adds considerable costs to the fuel cell system and consume considerable amount of electricity from the fuel cell, which in turn significantly reduces the net power output of the fuel cell. As a result, the DMFC would have tremendous difficulty to compete with the conventional battery technology in terms of costs and power output. ^ This work presents a novel passive fuel delivery system for direct methanol fuel cells. In this particular system, a methanol fuel and an aqueous methanol solution are stored separately in two containers and a wick is disposed between the two containers in a siphon fashion, with the container of the aqueous methanol solution communicating with the anode of the DMFC. Methanol is siphoned from the methanol container to the aqueous solution container in-situ when the methanol in the aqueous methanol solution is consumed during the operation of the fuel cell. Through a proper selection of the wick and the containers, the methanol concentration near the anode of the DMFC could be maintained within a preferable range. ^

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.

Use of active power filter to reduce the effects of harmonics in solid oxide fuel cells

The Solid Oxide Fuel Cell (SOFC) is a class of fuel cells that is capable of generating very high levels of power at high temperatures. SOFCs are used for stationary power generation and as Combined Heat and Power (CHP) systems. In spite of all the beneficial features of the SOFC, the propagation of ripple currents, due to nonlinear loads, is a challenging problem, as it interferes with the physical operation of the fuel cell. The purpose of this thesis is to identify the cause of ripples and attempt to eliminate or reduce the ripple propagation through the use of Active Power Filters (APF). To this end, a systematic approach to modeling the fuel cell to account for its nonlinear behavior in the presence of current ripples is presented. A model of a small fuel cell power system which consists of a fuel cell, a DC-DC converter, a single-phase inverter and a nonlinear load is developed in MATLAB/Simulink environment. The extent of ripple propagation, due to variations in load magnitude and frequency, are identified using frequency spectrum analysis. In order to reduce the effects of ripple propagation, an APF is modeled to remove ripples from the DC fuel cell current. The emphasis of this thesis is based on the idea that small fuel cell systems cannot implement large passive filters to cancel the effects of ripple propagation and hence, the compact APF topology effectively protects the fuel cell from propagating ripples and improves its electrical performance.