Documente Academic
Documente Profesional
Documente Cultură
1. Introduction ..................................................................................... 5
1.1. 1.2. 1.3. 1.4. 1.5. Options to Conventional Transport Fuels .............................................................. 6 Reasons for Promoting Non Fossil Fuel Derivatives............................................. 8 Comparison of Non Fossil Fuels ............................................................................... 9 Hydrogen ..................................................................................................................... 10 Main Aims of Study ................................................................................................... 12
3.2.1. 3.2.2. 3.3. 3.3.1. 3.3.2. 3.4. 3.4.1. 3.4.2. 3.4.3. 3.5. 3.5.1. 3.5.2. 3.5.3. 3.5.4.
Table of Contents
4. Chemical Kinetics of Methane Oxidation ................................ 30
4.1. 4.2. 4.3. 4.4. 4.5. 4.6. 4.7. 4.8. Carbon Bonding ......................................................................................................... 30 Hydrocarbon Chemistry Explosion Limits ........................................................ 32 Methane High Temperature Oxidation ................................................................. 34 Side Path with CH2 Radicals ................................................................................... 36 CH2OH Formation ...................................................................................................... 37 CH4 Low Temperature Oxidation .......................................................................... 38 Aldehyde Decomposition......................................................................................... 39 CO Oxidation .............................................................................................................. 40
List of Figures
Figure 1 (a): UK emissions by sector...........................................................................................3 Heating content of various fuels...........................................................................7 Comparison of properties of hydrogen and conventional fossil fuels..........8
Carbon dioxide release: Gas vs. Hydrogen...................................................................9
Figure 1.3 (a): Figure 1.4 (a): Figure 1.4 (b): Figure 1.5 (a): Figure 3.1(a): Figure 3.4 (a): Figure 3.5 (a): Figure 4 (a):
Laminar burning velocity for methane-, ethylene- and hydrogen-air............10 Simplified version of H2/O2 Mechanism.............................................................20 Explosion Limits of H2/O2 mechanism................................................................23 Detailed H2/O2 mechanism....................................................................................27 Hierarchical structure of hydrocarbon oxidation...............................................28 Explosion limits of Methane, Ethane and Propane..............................................30 Backbone of methane oxidation under high temperature.................................33 Side path reaction with CH2 radicals.....................................................................34 Aldehyde formation...................................................................................................35 CH4 low temperature oxidation..............................................................................36 Aldehyde decomposition to radical.........................................................................37 Geometry for computation.......................................................................................41
Figure 4.2 (a) Figure 4.3 (a): Figure 4.4 (a): Figure 4.5 (a): Figure 4.6 (a): Figure 4.7(a): Figure 5.1 (a):
Figure 5.1 (b): Geometry in x-y plane: 0.03m mesh size...............................................................42 Figure 5.3 (a): Laminar burning velocity of hydrogenmethane/air mixtures........................45
Figure 5.3 (b): The normalised laminar burning velocity and maximum H concentration...48
List of Graphs
Graph 5.2 (a): Mass Fraction of H2 vs. Curved Length..................................................................43 Graph 5.2 (b): Mass Fraction of CH4 vs. Curved Length...............................................................44
List of Tables
Table 1.1 (a): Table 4.2 (a): Table 5.3 (a): Major fossil fuel/non fossil fuel alternatives........................................................4 Different mechanisms for methane oxidation from various sources..............32 Reactant mole fraction of calculated flames.........................................................47
1. Introduction
Securities of supply and climate change are high on the global energy agenda. Transport emissions are the fastest rising cause of greenhouse gases. The emission by sectors in the U.K is shown below:
From the above [Figure 1(a)], transport contributes about 20% of the overall U.K emissions. The numbers of cars in the world are growing rapidly. In general, four options are considered to reduce these emissions: Alternative fuels Reducing the need to travel Promotion of public transport Improving fuel efficiency
A major influence in road congestion and accidents currently is convenience. The ease of mobility that personal transport offers is favoured by the majority, as opposed to public transport or less driving, albeit facts about health risks and fuel prices. Extreme difficulty is faced when trying to promote mileage reduction strategies and the automobile industry does not play a part in the influence for fear of harming its consumers. For these reasons, most transportation emission reduction programs focus on changing vehicle and fuel type rather than the amount people drive.
This drives the need to find alternates to conventional fuels, which could consequently aid the U.K in abiding to stringent emission regulations and reduce its dependence on oil from politically unstable regions. However, modern society is driven by its dependence on oil to fuel its transport needs. With increasing concern over fossil fuel shortages, researches on improving thermal efficiency in order for vehicles to run on cleaner fuels to produce fewer harmful emissions are being conducted, as they offer some savings on fuel costs and counteract the issue high power demand.
Considering fossil fuels, ultra-low sulphur versions of petrol and diesel represent options to the traditional versions, as they are around 97% cleaner, which imply they are better for the environment and operate at higher efficiencies in engines [Brevitt, B. (2002)]. However, to encourage their adoption, governing bodies have to cut excise duty rates relative to the standard product. Also, dwindling supplies of fossils is driving the quest for sustainable or non fossil fuel derivatives. Natural gas may prove to be the most important short term option because it produces fewer emissions than other conventional fossil fuels. This is depicted below:
On the other hand, successful implementation of natural gas gives rise to some problems. These are discussed below: Natural gas is a finite fossil fuel meaning its supply is limited Natural gas in itself is mainly methane, which is a greenhouse gas. Although there is less of it in the atmosphere, it is far more powerful in trapping heat than carbon dioxide (CO2).
When natural gas is burnt, it produces CO2 and water. On the contrary, natural gas industry pumps methane into the atmosphere when mining and through huge pipelines.
Non fossil fuels have the potential to be an environmentally friendly option to traditional fossil fuels, and even prove to have higher efficiencies when combusted. Ongoing research by the combustion and engine development society are currently being conducted into making non fossil fuel derivatives less expensive and more readily available, in order to make it a viable competitor in the fuel industry.
However, in terms of transportation, a key performance factor of a fuel is energy (heat) content. The heating content may be defined as the amount of energy released from combustion of a unit quantity of fuel. The heating content of various fuels are depicted below:
As noticed from [Figure 1.3(a)] above, hydrogen has the highest heating content, implying it contains more energy potential than any other fuel source.
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1.4. Hydrogen
Hydrogen is a fuel which has a potential for future use in transportation. It holds significant promise as a supplement fuel to improve performance and emissions of spark ignited and compression ignited engines. Transportation applications for hydrogen include buses, trucks, passenger vehicles, aircrafts, and trains, with technologies being developed to use hydrogen in both fuel cells and internal combustion engines, including methanol systems. Almost all major carmakers have a hydrogen-fuelled vehicle demonstration programme. Hydrogen-fuelled internal-combustion engine vehicles are viewed by some as a near-term, lower-cost option that could assist in the development of hydrogen infrastructure and hydrogen storage technology [Turner, J.A. (1999)]. A key advantage of this option is that hydrogen-fuelled internalcombustion engines vehicles can be made in larger numbers The table below shows the properties of hydrogen in comparison to traditional fossil fuels methane and gasoline, which are currently used in transport engines.
Figure 1.4(a): Comparison of properties of hydrogen and conventional fossil fuels [Skottene M., Rian K.E. (2007)]
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Hydrogen has several important properties that have an impact on its applicability as a fuel. It combines with oxygen (O2) to form water. It has high energy content per weight and the flame velocity of hydrogen is much faster than other fuels allowing oxidation with less heat transfer to the surroundings. This improves thermal efficiencies. Efficiencies are also improved because hydrogen has a very small gap quenching distance, allowing fuel to burn more completely. Hydrogen has the ability to burn at extremely lean equivalence ratios. Hydrogen will burn at mixtures seven times leaner than gasoline and five times leaner than methane [R. Choudhuri Ahsan & S.R. Gollahalli]. Hydrogen is highly flammable and only requires a small amount of energy to ignite it and make it burn. It also has a wide flammability range hence can burn when it makes up 4% to 74% of the air by volume [S. Gauthier, E. Lebas and D. Baillis.]. The combustion of hydrogen does not produce CO2, particulate or sulphur dioxide (SO2) emissions. A graph showing the CO2 release of gasoline compared to hydrogen is shown below as justification:
Figure 1.4(b): Carbon dioxide release: Gas vs. Hydrogen [Douglas, K. (2008)]
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Figure 1.5 (a): Laminar burning velocity for methane-, ethylene- and hydrogenair. [Choudhuri, R. & Gollahalli,, S.R (2000)]
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As noticed from [Figure 1.5 (a)], the laminar burning velocity of hydrogen is significantly higher than the rest of the other fuels. However, there are few studies which depict what happens when the fuels are mixed. From this, the program of work is as follows: 1. A literature review will be carried out based on the detailed chemical kinetic reactions involved in the combustion of hydrogen. 2. A literature review will be carried out based on the chemical kinetics of hydrogen combustion in air. 3. A literature review will be carried out to study the laminar burning velocities of hydrogen-methane mixtures in air. The effects of hydrogen addition on the mixtures laminar burning velocities will also be discussed.
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Monitoring the behaviour of individual species under a variety of conditions leads to further understanding of the combustion process, and can give insight on how to improve the efficiency and determine under what conditions various additives can be harmful.
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2.3.1.
Macroscopic Level
More global quantities are considered at this level, like temperature and pressure changes, corresponding to heat release from the process. At an engineering level, modelling is done at the macroscopic level because of the simplified modelling involved.
2.3.2.
Microscopic Level
If the origins of macroscopic properties are to be understood more thoroughly, then the microscopic level has to be considered. As a result of bond making and bond breaking, alterations in individual molecules can be examined at the molecular level by conducting detailed kinetic studies. These bond making and breaking methods will usually result in energy being released or absorbed, and consequently affect the global temperature of a system. Another consequence to bond making and bond breaking is pressure, as the number of molecules within the system changes. More importantly, the emphasis in the combustion and fuel community is on reducing emissions, understanding kinetic systems at microscopic levels are imperative.
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The origins of pollutants such as soot and NOx can only be investigated at this level, as the individual source molecules involved can be identified. Understanding the source of pollutants can lead to investigations on conditions, under which fewer pollutants are formed.
The structure of the molecule can be detailed from the set of reactions as well as thermodynamic information. The origins of this information are either directly from experiment or equivalence with similar molecules, where no direct information is available or from thorough calculations. [Baulch, DL (2007)] elaborates the data needs for combustion modelling. It was emphasised that in modelling applications, whilst the principal focus is on the mechanisms and the rate of reactions, the thermodynamic and transport data of species are just as as important or in some cases, more important, and must not be neglected.
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According to [Goswami, M. et al. (2008)], in the presence of sensitizers (Cl, N2O, NH3), a set of secondary reactions take place and form H atoms. The H atoms enter into a reaction with activated oxygen thus forming H2O. The oxidation of hydrogen can be divided into two sub-mechanisms: 1. The first sub-mechanism involves combinations of simple hydrogen and oxygen species, such as H. H2, O, H2O, O2, OH; and this includes some pressure sensitive reactions. 2. The second sub-mechanism involves the oxidation of H2O2 and evolves additional intermediate species HO2. Accepted standardised values are used to predict the rate of control of these reactions. For initial understanding, a simplified version of the mechanism is shown:
Figure 3.1(a): Simplified version of H2/O2 Mechanism. Rate constants k1, k2... 20
Each of the branching reactions (i.e. 2 & 3), produce two radical chain carriers for each chain carrier consumed. The two steps combine to give an overall branching coefficient of 3, corresponding to the hypothetical reaction:
3.2.1.
Bonding of Hydrogen
Hydrogen has a valency of one. This implies it has the tendency to lose an electron while combining with an element, giving it a positive valency. The hydrogen radical is formed when the valence electron is not bonded (i.e. lone). The hydrogen bond is formed when this valence electron is linked with another atom.
3.2.2.
Bonding of Oxygen
Oxygen has six electrons in its outer shell. For it to have a complete outer shell (i.e. eight electrons in its outer shell), it can either loose six electrons or gain two electrons. It is obviously easier to gain only two electrons and for this reason, the valency of oxygen is two. The bonding of oxygen is much more diverse as it can result in radicals, single or even double bonds.
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O (Oxygen atom single or triplet) : comprising of two electron pairs along with two unpaired electrons O- (Single bonded oxygen): comprising of a single bond and a single electron in addition to two electron pairs O= (Double bonded oxygen): comprising of two bonds as well as two electron pairs.
3.3.1.
H2 O2 H OH Reactions
The analogy of the hydrogen mechanism being a chain branching process has been mentioned and validated by various researches. The different types of reactions can be represented based on the number of radicals created and destroyed between the reactants and products.
[Reaction 3.31 (a)]: Initiation Reactions: Fuel and Oxidiser
H2+M H+H+M
The initiation reactions are those where stable species such as H2 and O2 form radicals. The dissociation energy of H2 is much lower than O2 and so the initiation step must be related to the former. Shock tube experiments have also been carried out at low pressures and different compositions by [Wang et al (2003)]. In these studies, a different reaction is captured, which depicts the auto ignition delay more accurately and might be the most probable initiation step.
H2+O2 HO2+H
Because of the fact that the hydroperoxy radical, HO2 is a relatively stable radical, it does not readily participate in the rest of the necessary chain reactions.
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3.3.2.
The first sub-mechanism of simple hydrogen and oxygen radicals has a transition, through the recombination to the mechanism of more complex species such as HO2, H2O2. Since HO2 is a radical, formation of HO2 are chain branching reactions. On the other hand, the formation of H2O2 can be both terminating and branching. Since radicals are highly reactive, their concentrations are minute and the backward reactions of all the branching and recombination chain steps are usually neglected. The rate of chain branching reactions increases with temperature. On the other hand, since the radical recombination steps require a third body, the rate of these reactions decreases with increasing temperature.
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H+O2+M HO2+M
Active hydrogen atoms can be removed by oxygen molecules in the threebody recombination reaction as shown above. Studies conducted by [Markides, N. (2006)] at the University of Cambridge suggest that [Reaction 3.32 (a)] is kinetically favoured at lower temperatures and higher pressures.
[Reaction 3.32 (b)]: HO2 Reactions
The hydrogen combustion reaction results in a net increase of two hydrogen atoms in the reactive system, as conclusively established by various research institutes. Unless these two hydrogen atoms are used up in the same length of time, the reaction rate increases exponentially with time and eventually leads to an explosion. Such circumstances can be evaded if the termination process is rapid. Of particular interest in combustion systems, typically considering fuel integration, it is necessary to understand the explosion limits of the H2/O2 mechanism. This is displayed below:
Figure 3.4(a): Explosion Limits of H2/O2 mechanism [Lu, T. & Law, C.K. (2009)]
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The graph above [Figure 3.4(a)] shows the different limits of hydrogen ignition with respect to temperature and increasing pressure. A general trend noticed is that increasing pressure of the system results in the mixture transitioning from explosive to non- explosive to explosive, as it pass through the first, second and third explosion limits.
3.4.1.
First Limit
The first limit is at very low pressures and the mean free path in the gas is rather large. Experimental evidence clearly depicts the explosive limits dependence on the size of the vessel. These points the inhibitors are the destruction of radicals H, O, OH at the walls. The reactions with the walls are more prominent at low pressure. This implies that the number of collisions to produce the chain reactions is relatively low. A reaction with the wall acts as a termination reaction thus lowering the explosive tendency. If termination balances initiation, a steady reaction occurs and explosion is avoided
3.4.2.
Second Limit
At higher pressures, the size of the vessel is less significant. The chain carriers react and combine prior to reaching the walls, As pressure increases, three body termination reactions are more significant because of the increased collision frequency between molecules. Within the hydrogen mechanism, as pressures go above the second explosion limit, HO2 is somewhat un-reactive, thus its formation can be thought of as a terminating reaction, as it is able to move towards the walls of the vessel. The inhibition of the HO2 reaction dominating above the second explosion limit implies it requires a higher temperature to result in an explosion. The peak pressure, which requires the highest temperature, is about half an atmosphere.
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3.4.3.
Third Limit
Taking into account simple density considerations, the initial density of the reactants increases as pressure goes up. For this reason, the temperature requirement for the reaction to reach a critical state to result in an explosion is low. This means the inhibiting effect of the second limit, namely the HO2 inhibition, is no longer relevant in this regime. As pressure increases, even the inhibiting effect of HO2 formation is countered with the formation of H2O2, which in turn is a noteworthy source of hydroxyl radicals; in fact two for every HO2 radical: HO2+H2 H2O2+H H2O2+M OH+OH+M [Reaction 3.43 (a) ALL REVERSIBLE] In essence, from the above reaction, as pressure increases, HO2 reacts with H2. In addition, H2O, the major final product is an excellent third body.
3.5.1.
The Gas Research Institute developed the well known GRI-Mech 3.0, which contains 26 reversible reactions for H2/O2 kinetics. It is also optimised for natural gas combustion.
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It was also validated against experimental data for ignition delay. Conversely, the Gas Research Institute discontinued support for the GRIMech project due to lack of funding, in the year 2000. In view of this fact, significant work has been implemented regarding the H2/O2 chemical kinetic mechanism by various research institutes.
3.5.2.
Yetter et al
[Yetter, R.A et al (1994)] presented a detailed CO/H2/O2 mechanism consisting of 19 reversible reactions for the H2/O2 system that was validated against experimental data at different temperatures and equivalence ratios. The measurements, which were carried out assuming plug flow and adiabatic conditions, have been extensively validated for the hydrogen mechanism. The mechanism, however, was extensively studied at flow reactor conditions, but was not tested against or modified as a result of comparisons with experimental data derived in other types of experiments and in other parameter ranges.
3.5.3.
Mueller et al
Based on an improvement on the chemical kinetic mechanism presented by [Yetter et al (1994)], an updated version was handed by [Mueller et al (1999)]. This revised mechanism is validated against a wide range of experimental conditions including those found in shock tubes, flow reactors and laminar premixed flame models. Excellent agreement of the model predictions with experimental observations demonstrates that the mechanism is comprehensive and has good predictive capabilities for different experimental systems.
3.5.4.
Li et al
The study of [Li et al (2004)] provides an updated version of the H2/O2 mechanism, based on previous works of [Yetter, R.A & Mueller, M.A (1999)]. This improvement is based upon new thermodynamic data and rate
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coefficients, and has been compared over a wide range of experimental data including VPFR data, shock tube ignition delay data and new flame speeds. This updated comprehensive detailed H2/O2 mechanism consists of 19 reversible elementary reactions, and is shown in [FIGURE 3.5 (a)]. All reactions are reversible.
As clearly depicted in various literatures, combustion mechanisms have a clear hierarchical structure.
As mentioned before, the hydrogen mechanism forms the base where many of the critical radicals driving ignition are formed, such as OH. A critical sub-mechanism for hydrocarbons including the methane mechanism, as conclusively established by many research institutes, is the carbon monoxide (CO) mechanism. All hydrocarbon mechanisms, including methane produce intermediates that further react with these submechanisms.
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Hydrocarbon mechanisms are essentially many combinations of transformations between these states. Carbon has four electrons available for bonding in its valence shell. The main stable carbon bonded states have either 4 single bonds; a double bond with 2 single bonds or a triple bond with a single bond. These are illustrated below: Single Bonded Carbon
Simple radicals of carbon are usually of the same configurations; just one of the bonds is replaced, by a non-bonded electron. Typical configurations are shown below: Methylene: Radical Carbon (Singlet or Triplet)
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Figure 4.2 (a): Explosion limits of Methane, Ethane and Propane. [Markides, N. (2006)] 32
The shape of the graph justifies how different the reactions involving hydrocarbons are from hydrogen. As expected and noticed from [Figure 4.2 (a)], the larger the molecule, the greater the explosion shifts towards lower temperatures and pressures. During the studies of [Miller JA & Kee RJ (1990)] on chemical kinetics and combustion modelling of hydrocarbons, it was noticed that intermolecular collisions are more prominent in heavier hydrocarbons and intermediates formed via these collisions break down forming radical pools, which initiate faster reactions. Also, key experimental characteristics from the explosion graph include: The very rapid reaction rates which proceed after induction levels The formation of formaldehyde, which tends to increase reaction rates and shorten ignition times
Excluding methane and ethane, it was also noticed that cool flames are exhibited which are associated with multiple ignitions and negative temperature coefficients of reaction rates.
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All the mechanisms presented in literature, however varying in number of reactions, have the same basic features. The illustration below shows the backbone of the methane oxidation under high temperature condition.
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H is abstracted initially, and with the addition of oxygen along with the loss of H, an aldehyde is formed. This aldehyde decomposes to CO. Through the CO sub-mechanism, the final equilibrium products are made.
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The aldehyde starts as a double bond, with two single bonds, one of which is hydrogen. The hydrogen is abstracted or lost, and an aldehyde radical is produced with a double bonded carbon, with a single electron radical and a single bond, as can be seen in [Figure 4.6 (a)] above.
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4.8. CO Oxidation
CO2, the ultimate product, is produced via the two propagating steps of the CO mechanism. The significance to these steps is that at the same time, the number of important radicals such as H and OH in the system is not diminished, hence it is propagation. Important reactions found in the hydrogen mechanism involve further propagation and branching. Reactions with the original oxidiser, O2 produce radicals important to the two CO oxidation reactions, namely OH and HO2, one of which is a branching reaction evolving more radicals into the system. This complementary set of reactions substantiates the observation that H is the catalyst for CO oxidation. Below shows the major steps in CO oxidation, made up of branching, propagating and termination steps. CO Mechanism:
TERMINATION CO + O + M CO2 + M
[Reaction 4.8 (a) ALL REVERSIBLE]: CO oxidation reactions
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The laminar burning velocities of hydrogen-methane with air premixed flames have been experimentally and numerically measured at different values of equivalent ratios and fuel compositions by various research institutes. Majority of these investigations on burning velocity conducted can be classified under two categories: 1. The effect of hydrogen addition to methane 2. The effect of substitution of hydrogen by methane Of particular interest are The works of [Yu et al (1986)], whose results of the hydrogen-methane hybrid mixture showed a linear increase of the laminar burning velocity with the increase of hydrogen fraction in the fuel blends. The effects of initial pressure and hydrogen fraction of hydrogenmethane flame was investigated by [Halter et al (2005)].
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The results for this investigation showed that the laminar burning velocity increased with the increase of hydrogen fraction. A counter effect was noticed with the increase in initial pressure. [Scholte and Vaags (1959)] first carried out measurement of the laminar burning velocity by means of a tube burner method. Together with more recent work by [Lui et al (2007)], this study is known to be extensive since a wide array of equivalence ratios and fuel compositions were investigated, varying form pure methane to pure hydrogen.
Also efforts regarding the laminar burning velocities of hydrogen-methane flames have been made on the computational side. Simulations of the premixed hybrid flames have been carried out extensively with CHEMKIN or COSILAB laminar premixed flames codes. There are still many discrepancies on reactions and species which are dominant in hydrogen enriched methane flames. Following prior investigations in this project, the chemical kinetics of both methane and hydrogen have been reasonable well understood and outlined. For this study, remaining uncertainties of the laminar burning velocity of hydrogen-methane flames will be considered. The chemical kinetic effects of hydrogen addition to methane will be analysed by investigating the reaction paths which would most likely occur in the premixed flames.
Ultimately, these findings will be related to the laminar burning velocities of other experiments found in literature and the dominant reactions and species will be identified from chemical kinetic mechanisms. By means of two jet inlets, hydrogen and methane will be issued into a cylindrical geometry with a pressure outlet. This is illustrated below:
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In this simulation, swirl was also induced. The imposition of swirl was necessary to increase jet spread, jet width, jet growth, jet decay and entrainment, turbulence level and mixing with the surrounding fluid. The Swirl angle was set to 45 degrees.
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In order to resolve an appropriate mesh size which will consequently lead to obtaining more accurate results, contours of y+ were plotted over the wall surfaces. Y+ is a mesh-dependent dimensionless distance that quantifies to what degree the wall layer is resolved. Plotting contours of y+ determines values of turbulent viscosity and thermal conductivity at the centres of cells having a face on the wall. The logarithmic wall treatment was used for these computations. This model is appropriate when these near wall centres are placed in the range of 20 <y+<200. Y+ values for a mesh size of 0.03m are shown in [Figure 5.1 (b)]. After careful analysis of contour plots for this size mesh, it was realised that y+ values lie within a range of 38 and 24. Hence the logarithmic wall treatment is appropriate as the y+ value lies between the range of 20 <y+<200. For this reason, the chosen mesh size for computations was 0.03m, as this resolves solutions adequately for turbulent regimes.
NB: The flow rates of hydrogen and methane were kept equal and the study was based on cold flow stoichiometric simulations.
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5.2. Results
0.8
Mass Fraction of H2
0.6
0.4
0.2
0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 Curved Length (m)
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0.3
0.25
0.2
0.15
0.1
0.05
0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 Curved Length (m)
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5.3. Discussion
As can be seen from [Graph 5.2 (b)], the mass fraction of CH4 along the curved length decreases. This decrease is steady till about a distance of around 0.25m, when the mass fraction falls suddenly. On the other hand, from [Graph 5.2 (a)], the mass fraction of H2 long the curved length increases. This opposing trend can be ascribed to an increase in CH4 consumption by the reaction, and H2 switching from an intermediate species to a reactant. A study conducted by [Salari, V. Di & Benedetto, A. Di (2007)] further validates this trend in relation to burning velocity. Their results for an experiment based on the laminar burning velocity of hydrogen-methane and air premixed flames are shown below:
Figure 5.3 (a): Laminar burning velocity of hydrogenmethane/air mixtures as function of the hydrogen content at three values of the equivalence ratio. [Salari, V. Di & Benedetto, A. Di (2007)]
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As seen from the results above, as the mass fraction of hydrogen in the mixture increases, so does the burning velocity. The following elementary reactions contribute to the kinetic control of the hybrid mixture: From these results in [Figure 5.3 (a)], three regimes can be identified at all equivalence ratios, depending on hydrogen mole fraction in the hybrid mixture: The first regime is a region of methane dominated combustion, where the hydrogen content is relatively low. The methane laminar burning velocity increases linearly and slightly. In this region, it was identified that methane conversion is dominated by:
Further investigations based on numerical studies of the effect of hydrogen addition on methane air flames have also been conducted. Of relevance, is a recent publication in the International Journal of Hydrogen Energy by [Wang, J. Et al (2009)], based on a numerical study of the effect of hydrogen addition on methaneair mixtures combustion. The results of the reactant mole fraction of the calculated flames are shown below:
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Table 5.3 (a): Reactant mole fraction of calculated flames. [Wang, J. Et al (2009)]
It can be that the mole fraction of methane in the flame is reduced as the mole fraction of hydrogen increases. This effect will in turn affect the mole fraction of carbon related species in the flame. The reason for reduction of methane in the flame can be attributed to the enhancement of the chemical reaction as hydrogen is added. From these findings, the dominant reactions contributing to the consumption of CH4 have been identified. These reactions are shown below:
OH + CH4 CH3 + H2O (1) H + CH4 CH3 + H2 (2) O + CH4 OH + CH3 (3) H + CH3 + M CH4 + M (4)
[Reaction 5.3 (d) ALL REVERSIBLE]
It is noticed from these reactions that the main consumption reactions of methane are the abstraction reactions attacked by H, O and OH, which are free radicals. From sensitivity analyses conducted by [Wang, J. Et al (2009)], methane mole fractions have the highest sensitivity to reactions:
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Free radicals (H, O, and OH) are extremely active due because they poses an unpaired electron and are short lived during the combustion reaction. The chain branching and chain propagating reactions play an important role in this chemical reaction. The normalised laminar burning velocity and maximum H concentration in the reaction zone as a function of hydrogen content, constructed by [Salari, V. Di & Benedetto, A. Di (2007)] is shown in the figure below:
Figure 5.3 (b): The normalised laminar burning velocity and maximum H concentration in the reaction zone as a function of hydrogen content. [Salari, V. Di & Benedetto, A. Di (2007)] 50
Mole fractions and rate of production of free radicals increase as hydrogen is added. This also accounts to the enhancement of the combustion of methane and air. From the [Figure 5.3 (b)] above, it is noticed that significant enhancement to the laminar burning velocity occurs only starting at hydrogen mole fractions higher than about 0.5. From this, it can be deduced that only at these values of fuel composition, the methane request for H radicals can be compensated by the hydrogen presence in the blend. It can also be deduced that the H radical concentration as well as the normalised laminar burning velocity are higher in rich mixtures. The main reactions forming these radicals are:
The first reaction listed in [Reaction 5.3 (F)] is promoted with the increase in hydrogen mole fraction and thus forms more hydrogen atoms which promote the reaction rate of the second reaction. As formerly discussed in the previous chapter, carbon monoxide (CO) plays an important role in the oxidation of methane. As the hydrogen fraction is increased, the CO mole fraction is reduced. This is due to a decrease in methane mole fraction as this reactant is used up quicker. The main CO consumption reaction has been identified to be:
OH + CO H + CO2
[Reaction 5.3 (g) REVERSIBLE]
This reaction has also been identified as the most important reaction for hydrocarbon combustion and nearly all of the heat release associated with the overall combustion process will occur in this step. C1 to C3 species associated with the combustion of methane also experience a similar trend to CO.
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6. Conclusions
Concerns about dwindling fossil fuel supplies have raised the need to investigate into alternate fuels. Considering the enormous ecological and economic importance of the transport sector, the question of what fuel will be used in vehicles tomorrow touches upon core elements of sustainable development. This research project was carried out on two fuels, natural gas (methane) and hydrogen, as both posses qualities to help mitigate the problem of global emissions. The study was mainly conducted to investigate the potential of hydrogen improving fuel properties. As convalescing vehicular combustion was of particular interest, the effect of hydrogen addition on improving the laminar burning velocity was delved into, basing the findings on chemical kinetics. By comparing computational fluid dynamic simulations on the hybrid mixture of hydrogen and methane, to experimental evidence found in literature, it was discovered that hydrogen is an excellent additive to improve the combustion of natural gas. Simulation results showed that hydrogen in the hybrid mixture changes roles from being an intermediate species to being a reactant in the system. This is mainly because hydrogen has a low ignition energy and high reactivity and diffusivity. Relating this feature to chemical kinetics, the promotion of the chemical reaction was discovered to be majorly attributed to the increase in radicals (H, OH, O) in the flame as hydrogen is added. Substantiating simulation results to experiments on laminar burning velocity found in literature, it can be concluded that the addition of hydrogen to natural gas gives a good alternative fuel to conventional hydrocarbon fuels as it significantly enhances the chemical reaction (i.e. combustion) and also improves flame stability and burning velocity. This project further validates the potential hydrogen has on sustainable development predominantly in the transport sector. Further research is necessary however in order to incorporate it fully in vehicles. A major focus can be on combustion chamber technology and investigating necessary modifications required to successfully incorporate hydrogenated fuels in spark ignition engines.
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7. References
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