2011

FINAL YEAR PROJECT REPORT

WISDOM PATRICK ENANG
UNIVERSITY OF BATH 4/19/2011

April 19, 2011

[FINAL YEAR PROJECT REPORT]

Department of Mechanical Engineering FACULTY OF ENGINEERING AND DESIGN FINAL YEAR MEng PROJECT REPORT

PROJECT TOPIC: INVESTIGATING THE IMPACT OF BIODIESEL ON AUTOMOTIVE CATALYST PERFORMANCE

AUTHOR’S NAME: WISDOM PATRICK ENANG

DATE OF SUBMISSION: 19/04/2011

DECLARATION:

“I certify that I have read and understood the entry in the Student Handbook for the Department of Mechanical Engineering on Cheating and Plagiarism and that all material in this assignment is my own work, except where I have indicated with appropriate references. I agree that, in line with Regulation 15.3(e), if requested I will submit an electronic copy of this work for submission to a Plagiarism Detection Service for quality assurance purposes.”

AUTHOR’S SIGNATURE: ………………………………………………………………………….

SUPERVISOR: DR C.D BANNISTER

ASSESSOR: DR NGWOMPO

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ABSTRACT

The use of biodiesel as a preferred fuel is rapidly expanding around the world, owing to it role in the reduction of emissions compared to petroleum diesel. This rapid growth has created an imperative demand on the need for several studies with regards, the impact of biodiesel use on different engine technologies, as well as the impact of its emissions on the performance of diesel after treatment systems. This study aims to quantify the impact of biodiesel emissions on the performance of an automotive oxidation catalyst. As part of the study, 3 tests were performed on a 2.0 Litre Ford Puma engine, with a common rail fuel injection system. The first 2 tests, which are the ramp test and steady state test, were carried out in a somewhat idealised laboratory condition, where adjustment were made to the EGR settings, exhaust flow rates and engine speed, in an attempt to match the CO, THC and NOx emissions across all the fuel blend ratio tested. The 3rd test (NEDC TEST), models the performance of an automotive oxidation catalyst in real life drive cycle, where no adjustments were made at all. The lights off curve data for the NEDC test analysis were all taken at idle periods. Results obtained from the steady state and ramp test do show a decrease in the light off temperature of the catalyst with increasing biodiesel fuel blend ratio. In the steady state test, the presence of an EGR was found to promote the catalyst conversion efficiency. Investigations in to the performance of the oxidation catalyst under the New European drive cycle; found that the amount of torque needed to induce catalyst light off tended to increase with increasing biodiesel blend ratio.

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ACKNOWLEGDMENTS

Wisdom Enang, April 2011. ‘’INVESTIGATING THE IMPACT OF BIODIESEL ON THE AUTOMOTIVE CATALYST PERFORMANCE’’. The author expresses his in depth appreciation to his supervisor: Dr Chris Bannister and assessor: Dr Ngwompo, department of Mechanical Engineering, University of Bath, for their dedicated help towards making this research work a success.

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CONTENTS
ABSTRACT ............................................................................................................................................... 2 ACKNOWLEGDMENTS ............................................................................................................................ 3 1. INTRODUCTION .............................................................................................................................. 9

1.1 LAYOUT OF RESEARCH WORK ......................................................................................................... 11 2. LITERATURE REVIEW .................................................................................................................... 13

2.1 LITERATURE REVIEW ON BIODIESEL EMISSIONS AND DIESEL AFTER TREATMENT SYSTEMS ......... 13 2.2 EVOLUTION OF DIESEL OXIDATION CATALYST AND OXIDIZING ELEMENTS ................................... 17 2.3 AUTOMOTIVE CATALYSIS ................................................................................................................ 20 2.3.1 Diesel oxidation catalyst literature review .................................................................................. 22 2.3.2 Absorption desorption and oxidation of CO on Catalyst monolith ............................................. 23 2.3.4 Effect of HC ratio and O2 concentration on light off characteristics............................................ 30 2.4 STATEMENT OF RESEARCH ............................................................................................................. 32 3. EXPERIMENTAL SECTION .............................................................................................................. 33

3.1 FACILITIES AND ENGINE TYPE USED ................................................................................................ 33 3.2 FUEL TYPE USED .............................................................................................................................. 34 3.3 CATALYST PREPARTION................................................................................................................... 36 3.4 TEST PORCEEDURES ........................................................................................................................ 36 3.4.1 Ramp test ..................................................................................................................................... 36 3.4.2 Steady state Test .......................................................................................................................... 37 3.4.3 NEDC Test..................................................................................................................................... 37

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RESULTS AND DISCUSSION........................................................................................................... 39

4.1 RAMP TEST ...................................................................................................................................... 39 4.1.1 Ramp Test Overview .................................................................................................................... 39 4.1.2 Effect of Ramp test on the Pre and Post Catalyst emissions ....................................................... 40 4.1.3 Catalyst conversion efficiency under the Ramp test condition ................................................... 46 4.1.4 Effect of Hydrocarbon trappings ‘’Zeolites’’ on the Oxidation of THC Emissions ........................ 48 4.2 STEADY STEATE TEST ....................................................................................................................... 51 4.2.1 Catalyst conversion efficiency under steady state test condition ............................................... 51 4.2.2 Effect of Hydrocarbon trappings on the Oxidation of THC under steady state test condition ... 54 4.2.3 Effect of EGR on the performance of an oxidation catalyst ........................................................ 54 4.3 NEDC ............................................................................................................................................... 58 4.3.1 Effect of Increased fuel Consumption with increasing blend ratio on vehicle emissions ........... 60 4.3.2 Catalyst conversion efficiency under the NEDC test condition. .................................................. 66 4.3.3 Effect of torque on the performance of an oxidation catalyst .................................................... 71 4.4 CATALYST CONVERSION EFFICIENCY PREDICTION MODEL FOR NEDC ........................................... 73 5. 5.1 CONCLUSIONS AND FURTHER WORK .......................................................................................... 78 CONCLUSIONS ........................................................................................................................... 78

5.2 RESEARCH CHALLENGES AND LIMITATIONS TO RESEARCH FINDINGS ........................................... 80 5.3 RECOMMENDED FURTHER WORK ............................................................................................ 81

REFERENCES .......................................................................................................................................... 82 NOMENCLATURE .................................................................................................................................. 88

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LIST OF FIGURES
Figure 1 – Research logic process flow chart ........................................................................................ 12 Figure 2 - Diesel Oxidation Catalyst ...................................................................................................... 17 Figure 3 - Three way oxidation catalyst ................................................................................................ 18 Figure 4 - Cross-section of diesel oxidation catalyst, with platinum formulation only ........................ 19 Figure 5 - Cross-section of diesel oxidation catalyst with palladium added to a platinum based oxidation catalyst .................................................................................................................................. 19 Figure 6 - CO covered surface pre - pre light off................................................................................... 24 Figure 7 - O covered surface post light off............................................................................................ 24 Figure 8 - Plot of the CO - O2 specific rates of reaction (TOF) for (a) single crystal (Pd, Lr and Pt) and their supported catalyst ........................................................................................................................ 25 Figure 9 - Light off characteristics of DOC formulations for different combustion modes and HC ratios (13 per cent O2 for conventional combustion, * per cent O2 for PCI combustion) .............................. 26 Figure 10 - HC ratio and O2 concentration effects on T50 temperature for the Pt. only catalyst ......... 28 Figure 11 - HC ration and O2 concentration effects on T50 temperature for the Pt.-Pd. catalyst ......... 29 Figure 12 - CO, C2H4 and C11H24 light off comparison with different HC ratios and O2 concentration for Pt-Pd catalyst ................................................................................................................................... 31 Figure 13 - Plot of Vehicle Speed vs time, for the NEDC....................................................................... 38 Figure 14 - A plot of pre-catalyst and post catalyst CO emissions versus time for B(0) (Ramp test) ... 41 Figure 15 - A plot of pre and post catalyst CO emissions versus time for B(50) (Ramp test) ............... 42 Figure 16 - A plot of pre and post catalyst THC emissions versus time for B(0) (Ramp test) ............... 42 Figure 17 - A plot of pre and post catalyst THC emissions versus time for B(50) (Ramp test) ............. 43 Figure 18 - A plot of pre and post catalyst NOx emissions versus time for B(0) (Ramp test) ............... 44 Figure 19 - A plot of pre and post catalyst NOx emissions versus time for B(50) (Ramp test) ............. 44

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Figure 20 - A graph of comparison between the CO light off curve for B(0), and B(50) (Ramp test) ... 47 Figure 21 - A graph of comparison between the THC light off curve for B(0), and B(50) ..................... 47 Figure 22 - A graph of comparison between the NOx light off curve for B(0), and B(50) (Ramp test). 48 Figure 23 - A plot of pre and post catalyst THC emissions versus catalyst temperature for B(0) (Ramp test) ....................................................................................................................................................... 49 Figure 24 - A plot of pre and post catalyst THC emissions versus catalyst temperature for B(50) (Ramp test)............................................................................................................................................ 49 Figure 25 - A graph of comparison between the CO light off curve of B(0), B(25) and B(50) (Steady state test) .............................................................................................................................................. 52 Figure 26 - A graph of comparison between the THC light off curve of B(0), B(25) and B(50) (Steady state test) .............................................................................................................................................. 53 Figure 27 - A graph of comparison between the NOx light off curve of B(0), B(25) and B(50) (Steady state test) .............................................................................................................................................. 53 Figure 28 - A plot showing the effect of EGR on CO conversion efficiency for B(25) ........................... 56 Figure 29 - A plot showing the effect of EGR on THC conversion efficiency for B(25) ......................... 56 Figure 30 - A plot showing the effect of EGR on NOx conversion efficiency for B(25) ......................... 57 Figure 31 - The impact of biodiesel blend ration on fuel consumption under the NEDC ..................... 59 Figure 32 - A plot of pre and post catalyst NOx emissions versus time for B(0) (NEDC test) ............... 61 Figure 33 - A plot of pre and post catalyst NOx emissions versus time for B(25) (NEDC test) ............. 61 Figure 34 - A plot of pre and post catalyst NOx emissions versus time for B(50) (NEDC test) ............. 62 Figure 35 - A plot of pre and post catalyst CO emissions versus time for B(0) (NEDC test) ................. 63 Figure 36 - A plot of pre and post catalyst CO emissions versus time for B(25) (NEDC test) ............... 63 Figure 37 - A plot of pre and post catalyst CO emissions versus time for B(50) (NEDC test) ............... 64 Figure 38 - A plot of pre and post catalyst THC emissions versus time for B(0) (NEDC test) ............... 64 Figure 39 - A plot of pre and post catalyst THC emissions versus time for B(25) (NEDC test) ............. 65 Figure 40 - A plot of pre and post catalyst THC emissions versus time for B(50) (NEDC test) ............. 65 WISDOM PATRICK ENANG Page 7

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Figure 41 - A graph of comparison between the CO light off curve for B(0), B(25) and B(50) (NEDC test) ....................................................................................................................................................... 67 Figure 42 - A graph of comparison between the PPM levels of CO converted for B(0), B(25) and B(50) (NEDC test) ............................................................................................................................................ 67 Figure 43 - A graph of comparison between the THC light off curve for B(0), B(25) and B(50) (NEDC test) ....................................................................................................................................................... 68 Figure 44 - A graph of comparison between the PPM levels of THC for B(0), B(25) and B(50) (NEDC test) ....................................................................................................................................................... 68 Figure 45 - A graph of comparison between the NOx light off curve for B(0), B(25) and B(50) (NEDC test) ....................................................................................................................................................... 69 Figure 46 - A graph of comparison between the PPM levels of NOx converted for B(0), B(25) and B(50) (NEDC test) .................................................................................................................................. 69 Figure 47 - Impact of Torque on the CO conversion efficiency B(0), B(25) and B(50) (NEDC test) ...... 71 Figure 48 - Impact of Torque on the THC conversion efficiency B(0), B(25) and B(50) (NEDC test)..... 72 Figure 49 - Impact of Torque on NOx conversion efficiency B(0), B(25) and B(50) (NEDC test) .......... 72 Figure 50 - The impact of biodiesel blend ratio, and exhaust temperatures on NEDC CO catalyst conversion efficiency ............................................................................................................................ 74 Figure 51 - The impact of biodiesel blend ration, and exhaust temperatures on NEDC THC conversion efficiency ............................................................................................................................................... 75 Figure 52 - Plot showing the relative cycle time for different CO conversion efficiencies ................... 76 Figure 53 - Plot showing the relative NEDC cycle time for different THC conversion efficiencies ....... 76

LIST OF TABLES
Table 1 - Physical and chemical properties of the B(0) fuel.................................................................. 34 Table 2 - Physical and chemical properties of the B(100) fuel.............................................................. 35

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1. INTRODUCTION

Increasing cost of fossil fuels, in addition to the government’s pursuit for reduced emissions and environmental conservation, has drawn attention of researchers and government environmental agencies, to consider biofuels as a clean alternative to petroleum fuel. Reports according to the biofuels research council show that by 2030 the EU could replace 25% of its transportation fuels with biofuels. Mono-ester diesel fuels collectively referred to as ‘’biodiesel’’, are made mostly from domestic renewable sources such as oils from vegetables, peanuts, soybeans and canola/rape seeds, through the process of Tran esterification, using potassium hydroxide as the catalyst, mixed with alcohol (ethanol or methanol) A publication by the United States Environment protection Agency, claims that biodiesels could be used in late models of diesel engines (models after 1992), without any further major modification in the engine technology. Biodiesel properties are similar to those of diesel fuel, although it has very low sulphur content and as well free of aromatic compounds. It is also, non-toxic and possesses a higher flash point, better lubricity performance, than petroleum based diesel. Besides the enormous amount of advantages associated with the use of biodiesels, it has a poor oxidation stability when compared to petroleum diesel, although much of the fuel stability characteristics is associated more with its production feed stocks, and storage conditions. Biodiesel also has a lower heating value than conventional petroleum diesel, which implies that with biodiesel, more fuel consumption is needed to provide the same energy in an engine, compared to conventional petroleum diesel. The potential of using biodiesel in blended ratios with petroleum diesel, for reducing the environmental impact of diesel emissions as well as optimizing diesel engine functionality, has WISDOM PATRICK ENANG Page 9

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widely been investigated, although most of those studies have been centred on biodiesel emissions such as CO (Carbon Monoxide), THC (Total hydrocarbons), NOx (Nitrogen oxides) and particulate matter. Most reviewed literature do show a general decline in the level of emitted CO and THC emissions with increasing biodiesel ratio, although the reverse could be inferred for NOx emissions. A lot of researches are currently on going with regards, the significance of biodiesels emissions in the environment, and the need for the incorporation of an after treatment system as part of the diesel engine, in order to help reduce the emissions levels entering in to the atmosphere from the engine. Most of the published and unpublished literatures currently available do tend to concentrate more on diesel particulate filters, with very little being said about the impact of biodiesel emissions on the performance of an oxidation catalyst. Even the few studies that do exist on the performance of an oxidation catalyst in reducing CO and THC emissions levels from diesel engines do not go in depth in to investigating the potentials of the oxidation catalyst in real driving conditions, thus rendering most of their findings and inferences, somewhat impractical in reality. It is in the light of this need, that this research work has been put together in order to quantify the impact of biodiesel blend ratio on the performance of an automotive oxidation catalyst, both in idealised laboratory test conditions, and in the real life driving condition under the New European Drive Cycle (NEDC). The main objectives of this research project are: (i) Data analysis with regards the influence of biodiesel fuel emissions on the performance of an oxidation catalyst. (ii) (iii) Identification of evolving graphical trends from the analysis made Building of experimental models to help predict the characteristics of biodiesel emissions on the performance of an automotive oxidation catalyst.

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1.1 LAYOUT OF RESEARCH WORK

This research work is divided in to (5) chapters. The first chapter (Chapter 1) features introductory information on biodiesel fuels and its evolution till date. (Chapter 2) highlights some important research attempts in the field. Research findings and propose explanations are also stated in this chapter, in order to further facilitate the understanding of the impact of biodiesel emissions on engine technologies and in the environment at large. In this chapter, on-going and already published research work In the field of ‘’diesel after treatment systems’’ are also reviewed with particular emphasis laid on those related with ‘’Diesel Oxidation Catalyst’’, so as to create an overall appreciation of the topic, as well as highlight the unrivalled need for this research. The third chapter (Chapter 3) describes the experimental apparatus, test fuels and procedures which were used to perform the necessary experiments. Any test assumptions or approximations made are highlighted in this section. Chapter 4 will focus on the identification of evolved trends from all tests performed, which will be observed using sets of graphs correlated based on the light off data, and NEDC data. In this Chapter, an attempt is made to further investigate the impact of a diesel oxidation catalyst, when used in cars driving under the New European drive cycle, with particular emphasis on the influence of cold starts on the performance of the oxidation catalyst. In Chapter 4 also, the overall conversion efficiency data for CO, and THC emissions, will be used to create very basic prediction models of the sort of conversion efficiency which a real car’s oxidation catalyst will expect to experience at different exhaust temperatures whilst driving under the New European Drive Cycle. Overall limitations to research findings and the proposed models will also be discussed in this chapter. Chapter 5 will feature the summary of this research work, where both general and specific conclusions are made on the entire research findings. In addition to this, recommendations for further work will also be made in this chapter. Detailed in Figure 1 is a research logic process flow chart, which highlights the main areas of investigation in this research work. WISDOM PATRICK ENANG Page 11

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Figure 1 – Research logic process flow chart

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2. LITERATURE REVIEW

2.1 LITERATURE REVIEW ON BIODIESEL EMISSIONS AND DIESEL AFTER TREATMENT SYSTEMS

Stringent diesel emissions regulations around the world have put much pressure on the shoulders of manufactures to reduce the level of emissions entering the atmosphere from diesel engines. Much of the initial attempt to achieve this by the manufactures was by the substitution of biodiesel in place of the conventional petroleum diesel. In order to create a balance between the vehicle performance and the imposed emissions regulations, many manufacturers prefer to blend petroleum diesel with biodiesel in a proportion which is deemed suitable to run on their engines. In a statement from the diesel fuel injection systems manufacturer’s association, they suggested that diesel fuel specification should be updated on a regular basis, to allow for the gradually increasing percentage of biodiesel. By so doing injection components could be manufactured such that they are protected from the possible secondary effect of the fatty acid methylesthers, which includes filter plugging due to softening and corrosion of zinc or aluminium parts in the fuel injection system due to the presence of free menthol residues. Whilst biodiesel has been highlighted as a plausible substitute for petroleum diesel, great concerns still arise over the effects of its emissions on health and environment, considering the fact that only a few of its hydrocarbon emissions are yet known. Studies about the effects of increasing biodiesel blend ratio on the operation and emissions of diesel engines have been documented in a vast amount of published and unpublished literature since the 1980’s (1), (2), (3). A general trend of observation amongst most of the literatures reviewed is a reduction in CO and THC emissions with increasing biodiesel blend ratio, like wise increasing NOx emissions have also been observed for increasing biodiesel blend ratio. The most proposed reason for the observed decrease in CO and THC emissions with increasing biodiesel blend ratio includes increased oxygen content with increasing biodiesel blend ratio (4), and high centane number associated with increased biofuel blend ratio (5),

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thus inducing a combustion delay. Other generally proposed reasons for this observation include; the advanced combustion associated with the higher biodiesel blend ratio, and its combustion timing. A study according to Choi et al (6) showed that CO emissions from biodiesel were remarkably affected by the engine load conditions. They specifically observed that, at low load conditions, there was no difference in the CO emissions recorded between the blend ratios tested, whereas at high load conditions, a decrease in CO emissions was observed with increasing biodiesel blend ratio. In a similar research, Charlet et al (7) found that although there was a decrease in emissions of CO with biodiesel, the reverse seemed to be the case in idle conditions, where values as high as 60% increase in CO emissions was observed whilst using biofuels in place of petroleum diesel. Research according to Lapuerta et al (8), and Rakopoulous et al (9), have found engine load to be a decisive factor in the reduction of THC emissions observed with increasing biodiesel blend ratio. These findings were further confirmed when Munoz et al, (10) recorded THC reductions while substituting conventional diesel with biodiesel at low load conditions. Rakopoulous in his studies applauded the high oxygen content of the biodiesel molecules, as being responsible for a more complete combustion of fuel, thus resulting in the reduction in THC emissions. Researchers like Turrio-Baldasaari et al (11) and Murillo et al (12), further added that the volatile nature of biodiesel compared to petroleum diesel makes the process of combustion in biodiesel much easier. Most of the literatures reviewed either showed a slight increase in NOx emissions with increasing biodiesel blend ratio or no important effect at all. In a study carried out by Cardom M et al (13), it was concluded that increasing trends of NOx emissions with increasing biodiesel blend ratio, was mainly an issue with older engine technologies due to the advancement in injection derived from the physical properties of biodiesel such as (viscosity, density, compressibility and sound velocity). Hamaski et al (14), in a similar research reported slight decrease in NOx emissions at low WISDOM PATRICK ENANG Page 14

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loads and increase with high loads. Krahl et al (15), in their research concluded that, neither an increase nor decrease in the level of NOx emissions will be observed regardless of the fuel used, should an indirect injection diesel engine under transient conditions be used for the test. In an investigation of the effect of biodiesel oxygen content on the observed increasing NOx emissions, Lapuerta et al (16) concluded that the oxygen content of biodiesel could not cause any increase in NOx formation as a result of the fact that diffusion combustion occur mainly in regions of oxygen-fuel ratio, of about 2.81 for biodiesel and, 3.58 for a standard diesel, making it impossible for the internal oxygen in the biodiesel fuel molecule to be enough to compensate for this difference. The effect of PM has been highly debated in the research field of ‘'energy and fuels’’, with some researchers (17), (18) recording an increase, and some recording a decrease (19), (20) with increasing biodiesel blend ratio. According to M. Lapuerta et al’s (16) review, a decrease in PM emissions, with biodiesel is the ‘’Unanimous trend’’. Krahl et al (15) from his research inferred that there are no significant reductions in PM emissions if biodiesel are used in heavy duty engines, but there will be if a light duty engine is used. Similar experiments from Lapuerta et al (20) and (21) confirmed Krahl et al’s conclusions. Researchers like (14) and (22) have used parameter like loading conditions, quality of biodiesel, engine type and engine temperature, to investigate the impact of biodiesel blend ratio, on particulate emissions. Leung et al (22), tested a single cylinder engine, with petroleum diesel and pure biodiesel from rapeseed at different load conditions. In that study they observed larger decreases of PM emissions for biodiesel at high load conditions. In their explanations, they said that the particle formation during diffusion and high loads were responsible for making the oxygen content of biodiesel molecule more effective in reducing the PM emissions. Other studies (23), (24) , further confirmed this by saying that the oxygen content of biodiesel molecule is responsible for the complete combustion and oxidation of the exhaust soot. Studies according to Gerpen et al (25) found that PM emissions reduced with the use of oxygenated compounds, compared to using oxygen enriched compound, compared to using oxygen enriched air,

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thus they concluded that the need for additional oxygen is strongly emphasised in order to achieve required reductions in PM emissions. Boehman et al (26) through their themo-gravimetric study of biodiesel soot particles found that the variance in the soot particles between biodiesel and petroleum diesel was responsible for the higher tendency of soot oxidation with biodiesel. A combination of after treatment systems have been proposed by some researches, as a viable solution in reducing CO, THC and NOx emissions to a non-harmful level. Some of these proposed after treatment systems include DPF (Diesel particulate filter) and DOC (Diesel Oxidation Catalyst). Amy et al’s (27) research in to effect of biodiesel emissions on the performance of a diesel particulate filter in a diesel engine, showed that increased biodiesel blend ratio produced less soot and thus required a lesser regenerative temperature, when compared to the conventional petroleum diesel. Their conclusions indicated the fact that with biodiesel fuels, the regeneration of particulate filters could be carried out without the fear of causing an over heat in the exhaust system. They applauded the reactive nature of the biodiesel soot, as a major contributor to this trend.

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2.2 EVOLUTION OF DIESEL OXIDATION CATALYST AND OXIDIZING ELEMENTS

Automotive catalytic converters made their first appearance in to automobiles, in the 1970s, and were initially fitted in to automobiles in America in 1975, in an attempt to reduce the emissions from vehicles. First catalysts were composed of simple formulations of platinum deposited on aluminium oxide, which essentially functioned as a 2 way catalyst (Figure 2) responsible for reducing tail pipe emissions of both carbon monoxide and hydrocarbons by oxidizing them to carbon dioxide and water. As years went by, the 3 way catalyst (Figure 3) was developed for gasoline engines, in which carbon monoxide, and unburnt hydrocarbons are oxidized at the same time as NOx emissions.

Figure 2 - Diesel Oxidation Catalyst

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Figure 3 - Three way oxidation catalyst

The operating requirements for a two way diesel oxidation catalyst are typically very different from that of the three way catalysts. Platinum group metals are currently being considered by manufacturers as ‘’preferable’’ compared to palladium group metals, as the main oxidizing agent in a DOC. This is as a result of the fact that the exhaust stream of a diesel engine is very oxidizing, and in such a condition, palladium easily gets converted in to a less catalytic – active palladium oxide, whereas platinum retains it metallic nature. Gaseous sulphur species from the combustion of diesel and gasoline fuels have been proven to poison platinum based catalysts compared to palladium based catalysts, which tend to be more tolerant under a sulphur rich conditions. Research in to the possibility of combining palladium and platinum group metals in a diesel oxidation catalyst, show that the presence of palladium tend to thermally support the platinum based catalyst when they are subjected to high exhaust temperatures. At very high exhaust temperatures, platinum if used alone as an oxidizing element in the catalyst, tend to sinter, thus its Nano scale particles start to move around the support and as a result merge to form larger particle aggregates, which leads to a fall in catalyst conversion efficiency. However, with the addition of palladium, the size of the precious metal particles are stabilised, thus ensuring an efficient and more durable performance of the oxidation catalyst as shown in Figure 4 and Figure 5. WISDOM PATRICK ENANG Page 18

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Figure 4 - Cross-section of diesel oxidation catalyst, with platinum formulation only

Figure 5 - Cross-section of diesel oxidation catalyst with palladium added to a platinum based oxidation catalyst

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2.3 AUTOMOTIVE CATALYSIS

The installation of catalytic converters in the exhaust of diesel engines has now been widely practiced by manufacturers of automobiles, in an attempt to comply with the current legislations that govern the emissions from cars. When an engine starts from a cold state the exhaust manifold and catalytic converter also appear cold. During this period limited conversion of the exhaust emissions are expected to occur. This is due to the fact that most of the exhaust products get emitted before the catalyst has the chance to warm up to the required light off temperature. This therefore suggests that allowing the catalyst to warm up quickly is very important in order to reach the cold-start emissions regulations. As the engine warms up, the exhaust manifold and catalyst monolith also heats up to, making it possible for the conversion of the exhaust emissions to commence. The working of an oxidation catalyst is very dependent on the amount of oxygen in the exhaust pipe, the temperature of the catalyst, the size and design of the catalyst, although beyond the light off temperature, the light off curves are limited by oxygen absorption on the catalyst (28). Diesel oxidation catalyst (DOC) function by oxidizing Carbon monoxide to Carbon dioxide, and by oxidizing the total un burnt hydrocarbons to water and Carbon dioxide, over the ‘’platinum’’ or ‘’palladium’’ group metals. Recently many manufacturers find it a lot more advantageous to manufacture catalysts with a combination of both group metals. When heated the combination of platinum and palladium group metals within the catalyst, do create a bimetallic effect, thus ensuring the thermal stability of the catalyst. There is evidence to suggest that without the presence of the diesel oxidation catalyst, the oxidation for carbon monoxide and unburnt hydrocarbons will still take place but at much higher exhaust temperatures. The presence of the oxidation catalyst makes it possible, for the oxidation of the emissions to proceed at lower temperatures. Recently, much of the development of DOCs has been targeted towards the reduction of the amount of un-converted emissions from the diesel WISDOM PATRICK ENANG Page 20

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exhaust at temperatures lower than what is needed for light off. When diesel engines, operates at idle or low engine load conditions, the temperature of the engine exhaust is often lower than the light off temperature required for any oxidation activity. At such conditions it is noted that most exhaust pollutants could easily pass through the catalyst unconverted, without the use of a new diesel catalyst technology which has been developed to enhance the performance of diesel oxidation catalyst at cold start conditions. This technology incorporates hydrocarbon trapping materials ‘’Zeolites’’ in to the catalyst wash coat. The Zeolites traps and store diesel exhaust hydrocarbons during periods of low exhaust temperatures and then as the exhaust temperature increases above the light off temperature, the Zeolite traps releases the stored hydrocarbons, which then get oxidized by the catalyst. With this technology, periods of high exhaust temperatures are needed for the desorption of the hydrocarbons from the ‘’Zeolites’’ as well as the regeneration of the oxidation catalyst in order to avoid the saturation of the unburnt hydrocarbons on the catalyst, which could result in increasing hydrocarbon emissions passing through the catalyst unconverted. Above the light off temperature, the performance of oxidation catalyst rapidly increases towards a steady state level with increasing temperature. Although this is true, but continuous exposure of the diesel oxidation catalyst to high temperatures, cause damages to the catalyst performance on the long run. At high catalyst temperatures, the catalytically active Nano scale platinum or palladium particles and their aggregated surface area decreases, and with less of the oxidizing metal surface exposed to the exhaust gases, the conversion efficiency of the overall oxidation catalyst will fall as a result.

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April 19, 2011 2.3.1 Diesel oxidation catalyst literature review

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Diesel oxidation catalysts (DOC) are increasingly being considered as a very important component in the diesel exhaust architecture used to reduce diesel emissions. Besides its main function of oxidizing THC and CO emissions, it has been proven to assume multiple roles of generating equi-molar mixtures of NO and NO2 for optimal operation of the selective catalytic reduction (SCR) after treatment system. In addition, the production of heat from the oxidation reaction also helps in oxidizing soot in the diesel particulate filter (DPF). The functionality of the DOC activity is strictly dependent on the exhaust temperature, and it shows low or no oxidation activity at low exhaust temperatures. Yamamoto et al. (29) in their study found that diesel oxidation catalyst generally have little or no effect on NOX emissions. However they did also find that some of the catalysts used for DOC applications tend to promote the conversion of NO to NO2. In a similar study Ambs et al (30) and Ferrauto (31), found that the rate of NO oxidation to NO2 depended on factors such as catalyst formation, monolith geometry, as well as the exhaust temperature. Farrauto (31) in his study, found that vanadium and palladium based catalyst were capable of suppressing the conversion of NO to NO2, whilst catalyst formulation based on platinum were shown to have a high NO to NO2 conversion. In a similar study to the one conducted by Farrauto (31), Layer et al (32) found that an 80% conversion of NO to NO2 could be reached with the use of an optimised DOC system operated at an average exhaust temperature of approximately 300oC.

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2.3.2 Absorption desorption and oxidation of CO on Catalyst monolith

Several studies in to the oxidation of CO in an oxidation catalyst claim that CO binds on the platinum terminally, on the top site (33), (34). In another study Makowa and Slichter (35) used platinum nuclear magnetic resonance to confirm the claim above, by explaining that the bond between CO occurs typically through the C atom, as show in Figure 6. In an analysis by Ford et al (36), lots of calculations of CO adsorption on Platinum were carried out, and in the end they reported that CO bounded in both top and bridged configurations. In a study by Stephen (37), he found that at low temperature (room temperature), CO molecules were found to dominate the oxidation sites of catalyst (Figure 6). In his explanation he stated that: ‘’The sticking coefficient for CO is much higher than for oxygen. If there is a small amount of oxygen on the catalyst surface, CO may slowly consume this oxygen, but the available free sites will be dominated by adsorbing CO.’’ He went on further to explain that as CO absorb on to the platinum catalyst, it tends to block the adsorption of oxygen on the catalyst site, thus leading to a ‘’no oxidation reaction’’ situation on the catalyst where CO tends to self-poison the catalyst the low temperatures. The self-poisoning effect of CO, at low temperatures, are however fully reversible at increased exhaust temperatures, where the rate of CO desorption increases, making available more free site for the absorption of oxygen atoms. Increase in absorption of oxygen on to the catalyst oxidation sites, leads to a proportionate increase in the rate of oxidation reaction, which in turn accelerates light off. Upon completion of the conversion reaction, subsequent reactions are only limited by flow rates of reactants. In another study Stephen (37) observed that an increase in light out temperature was recorded during increased PPMs of CO in to the DOC inlet gas. In his explanation, he claimed that this was as a result of the fact that ‘’ When more CO is present in the feed gas, more CO is present in the bulk ready, to adsorb to the catalyst surface, reducing the relative competitiveness of oxygen adsorption and increasing the light-off temperature’’. WISDOM PATRICK ENANG Page 23

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Beyond the light off temperatures, the reaction of CO proceeds to completion, with molecules reacting as fast as they are brought in to the catalyst. At this point oxygen dominates the catalyst site as shown in Figure 7 below. Below the catalyst light off temperature, the rate of surface reaction tends to decrease, up until a critical temperature is reached where the rate CO absorption exceeds the rate of CO oxidation. At this point, CO begins to dominate the surface again as shown in Figure 6, and the rate of relative competitiveness of oxygen adsorption on to the catalyst monolith decreases.

Figure 6 - CO covered surface pre - pre light off

Figure 7 - O covered surface post light off

Source: Stephen (37)

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In a study conducted by Santra et al (38), they correlated the oxidation rate of CO to CO2 as function of inverse temperature (1/T) as shown in Figure 8, and observed that as (1/T) got bigger, the rate of CO2 formation from CO was reduced, which there for implies that the oxidation of CO to CO2 is directly proportional to catalyst temperature (T).

Figure 8 - Plot of the CO - O2 specific rates of reaction (TOF) for (a) single crystal (Pd, Lr and Pt) and their supported catalyst Source: Santra et al (38)

Oxygen adsorption on the oxidation catalyst typically occurs in a dissociative manner on the surface of platinum based catalyst monolith. Although, the kinetic characteristics of oxygen adsorption on Pt remains a topic under a lot research debate, the general agreement from all the reviewed literatures remain that oxygen adsorbs in a dissociative and irreversible manner on to the catalyst, in the temperature range of 250 – 800K.

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In a gas flow reactor test, Han et al (39)investigated the light off temperature of CO, C2H4 and C11H24, for 3 different DOC formulations with feed-gas compositions representative of conventional combustion, and PCI combustion. In their investigations, they found that for any DOC formulation tested, (Pt, Pt–Pd, and Pt–Pd + CeO2 catalysts) the light off temperature for conventional combustion appeared to be lower compared to that of PCI combustion for all 3 exhaust species tested (CO, C2H4 and C11H24 ) as shown in Figure 9 below.

Figure 9 - Light off characteristics of DOC formulations for different combustion modes and HC ratios (13 per cent O2 for conventional combustion, * per cent O2 for PCI combustion) Source: Han et al (39)

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In their explanations they said that this behaviour was as result of the lower partial pressures of CO and C2H4 in conventional combustion, such that there was less adsorptive competition between CO and C2H4 to occupy the active catalyst sites. They explained that the higher partial pressure of O2 in conventional combustion, leads to the dissociation of oxygen molecules in to oxygen atoms, which then get absorbed on to the catalyst active site, thus resulting in an earlier light off. In that same study they also found that irrespective of the combustion modes, and DOC formulation used, CO was observed to oxidize first, followed by C2H5, and C11H24, thus indicating that CO exhibited a more competitive characteristic in occupying the catalyst sites compared to the rest of the exhaust speciation tested. In a comparison of the two different HC ratios in the PCI exhaust, they found that C2:C11 ratio of 1:6 reduced the light-off temperature compared with the C2: C11 ratio of 1:2 for both the catalyst with Platinum formulation only and the catalyst with platinum and palladium formulation as shown in Figure 10 and Figure 11. According to their inferences they said that ‘’the light-off temperature is reduced by the lower C2: C11 ratio because less adsorptive competition occurs between CO and C2H4’’.

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Figure 10 - HC ratio and O2 concentration effects on T50 temperature for the Pt. only catalyst

Source: Han et al (39)

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Figure 11 - HC ration and O2 concentration effects on T50 temperature for the Pt.-Pd. catalyst

Source: Han et al (39)

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2.3.4 Effect of HC ratio and O2 concentration on light off characteristics

In another light off analysis Han et al (39) noticed that as CO and C2H4 were initially oxidized, a negative conversion efficiency of C11H24 was recorded, at around catalyst temperatures of 210oC – 240oC (Figure 12). Their comparative hydrocarbon analysis showed that the oxidation rate of C11H24 was not as fast as that of C2H4, which suggests that some hydrocarbons tend to promote a much faster rate of conversion than the others. Beyond 240oC, they observed that the partial oxidation of C2H4 and C11H24 due to insufficient oxygen concentration tended to produce more CO molecules, thus leading to a decline in the CO conversion efficiency as the temperature increased (Figure 12). Increased oxygen concentration was found to decrease the light off temperature at any given hydrocarbon mixture ratio (Figure 12), thus resulting in a more positive oxidation. They concluded that the higher partial pressure of oxygen resulted in a higher degree of dissociated oxygen atoms being adsorbed on the catalyst active sites, thus promoting the oxidation of CO and HC in the DOC.

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Figure 12 - CO, C2H4 and C11H24 light off comparison with different HC ratios and O2 concentration for Pt-Pd catalyst WISDOM PATRICK ENANG Page 31

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2.4 STATEMENT OF RESEARCH

Whilst the studies stated above have been made in order to explore the potential of diesel oxidation catalyst in diesel engines, much of their studies were centred on emissions produced from combusting petroleum diesel fuel and not biodiesel. The exhaust emissions of biodiesel appear to be more complex than that of petroleum, thus suggesting that most of the inferences made from the literatures reviewed above may not completely hold for biodiesel. Furthermore, there is an important need to investigate deep into the impact of biodiesel emissions such as CO and THC on the performance of a diesel oxidation catalyst both in idealised laboratory conditions, and in real driving conditions. It is in the light of this need that this investigation has been undertaken. As part of this research work, ramp tests and steady state tests will be carried out in order to identify general evolving trends and thus identify, the general characteristics of an oxidation catalyst in response to CO, THC and NOx emissions for each of the fuel blend ratio tested. In addition to that, the oxidation catalyst will be analysed over the New European Drive Cycle, with suitable explanations given to the observations made. These investigations will enable reasonable but very basic predictions to be made on the sort of conversion efficiencies an oxidation catalyst will have for different exhaust temperatures, in a car operating under the New European Drive Cycle.

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3. EXPERIMENTAL SECTION

3.1 FACILITIES AND ENGINE TYPE USED

The entire tests were carried out using a Zollner 2 independent 126KW Chassis Dynamometer, housed under a controlled environment where a penman climatic systems refrigeration plant was used to control the temperature within a -10oC to +50oC range. Two Horiba MEXA 7000 series were employed for continuous sampling of pre and post catalyst emissions as well as ‘’bag’’ emissions via the constant – volume sampling system. The engine used for this test was a 2.0 Litre Ford Puma engine, with a common rail fuel injection system. Temperature recordings of the catalyst monolith were made using a set of 20 different thermocouples arranged longitudinally across the length of the catalyst monolith.

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3.2 FUEL TYPE USED

For most of the tests carried out in this research, 3 blend ratios were used, which includes, B(0), B(25) and B(50). These fuel blend ratio were created using a combination of the B(0) fuel from Shell, with specifications as shown in Table 1 below and a B(100) fuel from BP with specifications as shown in Table 2. During this research there was no facility available for measuring the properties of the individual fuel blend ratios produced, and so for the subsequent light off analysis, it is assumed that the properties of the fuel blend ratios produced are in between that of the two parent fuels B(0) and B(100). Batch No: Fuel Type: Supplier: Specification: Fuel Certfied Date: PROPERTY Centane Number Initial Boiling Point 50% Evaporate 95% Evaporate Final Boiling point Residue Calorific Value - Gross Calorific Value - Nett Viscosity, Kinematic @ 40 degrees Sulphur Content (UVF) Lubricity Neut No. (Strong acid) Cloud Point Cold Filter Plugging Point Carbon Content Hydrogen H/C Ration Water Content Aromatics Density at 15 degress celcius REFERENCE / LINE FUEL - DK 2567 DIESEL B(0) SHELL XE - M4CX725-A 20-Jun-07 UNIT VALUE 52.8 165 270 349 359 1 45.52 42.59 2.748 7 234 <0.01 -11 -18 86.5 13.46 1.854 68 20 0.883

Degrees Celcius Degrees Celcius Degrees Celcius %Vol MJ/Kg MJ/Kg mm^2/s PPM mgKOH/g Degrees Celcius Degrees Celcius % mass

mg/Kg % v/v kg/l

Table 1 - Physical and chemical properties of the B(0) fuel

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B(100) RME FROM BP PROPERTY Net calorific value Density at 15 oC Kinematic Viscosity at 40 oC Flash Point Sulphur Content Microcarbon Residue 10% (ASTM D1160) Cetane Number Water Total Contamination Copper Corrosion Oxidation Stability, 110 oC Acid Number Iodine Value Linolenic Acid Methyl Ester Polyunsaturated Methyl Ester Ester Content Methanol Content Monoglyceride Content Diglyceride Content Triglyceride Content Free Glycerol Total Glycerol Sodium Potassium Calcium Magnesium Phosphorus Cold Filter Plugging Point UNIT Mj/kg kg/m3 mm2/s °C mg/kg % (m/m) mg/kg mg/kg METHOD D240 ISO 12185 EN ISO 3104 EN ISO 3679* EN ISO 20846* EN ISO 10370 EN ISO 5165 EN ISO 12937 EN 12662* EN ISO 2160 EN 14112* EN 14104* EN 14111* EN 14103* EN 14103* EN 14103* EN 14110* EN 14105* EN 14105* EN 14105* EN 14105* EN 14105* EN 14108* EN 14109* EN 14538* EN 14538* EN 14107* EN 116 VALUE 39.99 883.2 4.564 182.0 1.8 0.17 49.5 210 6 1 10.8 0.18 112 9.41 <1 97.7 0.01 0.57 0.15 0.03 <0.01 0.17 <0.1 <0.1 <0.1 <0.1 0.2 -20

Hours mgKOH/g g/100gFAME % m/m % m/m % m/m % (m/m) % m/m % m/m % m/m % m/m % m/m mg/kg mg/kg mg/kg mg/kg mg/kg °C

Table 2 - Physical and chemical properties of the B(100) fuel

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3.3 CATALYST PREPARTION

The catalyst used for this test, composed of a combination of platinum and palladium group metals, as the main oxidizing metals on the monolith core. Prior to any test, the catalyst was moderately heated a night before, so as to enable any stored emissions to be completely burnt out, in order to avoid errors in the recorded results.

3.4 TEST PORCEEDURES

Three tests in total were performed during this research. These tests include ramp test, steady state test, and the NEDC test.

3.4.1 Ramp test

2 Blend ratios of biodiesel, B(0) and B(50) were used for the ramp test. During this test, the temperature of the catalyst was increased at approximately 0.125OC/min at 7% pedal setting, thus raising the catalyst monolith temperature from 40OC to 127OC. After that, it was ramped over a minute, to a 14% pedal setting, and then held constant for another 10 minutes, thus allowing the catalyst monolith temperature to get high enough for the catalyst to light off. During the Ramp test adjustments were also made to the exhaust flow rate, vehicle speed and EGR valve setting in an attempt to match the CO, THC and NOx emissions levels coming from all the fuel blends, thus providing a neutral ground for the comparison of its impact on the performance of the oxidation catalyst. After several iterations, only the CO and THC emissions could be matched for the two fuel blend ratios used for the Ramp test. The NOx emissions were still observed to be slightly different between both fuels, although that did not have much of an effect on the accuracy of the catalyst conversion analysis subsequently made.

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3.4.2 Steady state Test

In the steady state test, the engine was switched on and set to automatically apply an increasing pedal% from 7% to 14%, in a span of 20 minutes. With this test 3 fuel blend ratios, B(0), B(25) and B(50) were tested and their pre and post-catalyst emissions levels were recorded as MEXA1 and MEXA 2 reading respectively. Just as in the case of the Ramp test, adjustments were also made to the throttle settings, vehicles speeds and EGR valve position in an attempt to match the CO, THC and NOx emissions levels coming from all the fuel blends, thus providing a neutral ground for the comparison of its impact of the performance of the oxidation catalyst. The greatest challenge encountered in trying to adjust settings of the engine components to match the emissions levels for all the tested fuels in the steady state test, was that only CO and THC emissions could be matched. Despite all attempts, there were slight differences in the NOx emissions between the fuels blend ratios, although these differences were not enough to affect the accuracy of the subsequent light off analysis.

3.4.3 NEDC Test

In the NEDC test, the engine was tested using 3 fuel blend ratios, B(0), B(25) and B(50) over the entire drive cycle. This drive cycle as shown below in Figure 13, consists of four repeated ECE-15 driving cycles and an Extra-Urban driving cycle, or EUDC, which represents the typical usage of a car in Europe. In this test no attempts were made to adjust the engine settings in order to achieve the same level of emissions between fuels blend ratios tested. This implies that the CO, THC and NOx emissions of all the biodiesel blend ratios tested over the NEDC cycle, were quite different from each other. In this test, torque and fuel consumption measurements were recorded for each blend tested. These values are later used in this research work to analyse their effects on the performance of an oxidation catalyst in a real driving cycle. WISDOM PATRICK ENANG Page 37

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Figure 13 - Plot of Vehicle Speed vs time, for the NEDC

Note: The engine speed versus time plot subsequently used for the NEDC light off analysis in this research work, has been smoothened a bit to enable easy observations of evolved trends.

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4. RESULTS AND DISCUSSION

4.1 RAMP TEST

4.1.1 Ramp Test Overview

As already discussed in the experimental section of this report, prior to this test, the catalyst was heated up enough to allow all emissions to be burnt out completely, thus maintaining a clean and clear monolith surface. During the ramp test, the temperature of the catalyst was increased at approximately 0.125OC/min using a 7% pedal setting, thus raising the catalyst monolith temperature from 40OC to 127OC after which it was ramped over a minute, to a 14% pedal setting, and then held constant for another 10 minutes allowing the catalyst monolith temperature to get high enough for light off. During all the tests made including the ramp test, the inlet temperature of the monolith catalyst were recorded using a 20 different thermocouples arranged across the length of the monolith length as shown below.

Temperature variations between the functioning thermocouples were not very pronounced before the light off temperature, but became more significant at much higher temperature values. However it is important to note that beyond the light off temperature, all emissions do quickly attend their

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peak conversion, therefore ruling out the significance of the differences in higher temperature values of the thermocouples, for the purpose of this analysis. In addition, the ramp down section of the test was ignored, as most of the subsequent analysis will be based on the light off characteristics of the catalyst.

4.1.2 Effect of Ramp test on the Pre and Post Catalyst emissions

During the Ramp, increasing levels of CO, THC and NOx emissions were noticed for both, B(0) and B(50) blend ratio used for the test as detailed in Figure 14 - Figure 19. The reason for this behaviour is as a result of the fact that during a pedal ramp more fuel than needed is drawn in to the engine in an attempt to match the available mass of air drawn in (which is solely based on engine speed and load). This creates an atmosphere where the engine runs initially rich at the beginning of the pedal ramp, and then tends to a lean run towards the end of the pedal ramp, thus leading to a more complete combustion of the contained fuel.

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15 800 14 13 600 12 11 400 10 9 8 0 0 2 4 6 8 10 12 14 16 7

CO (PPM)

200

TIME (MINS)
RAMP PEDAL % B(0) RAMP CO MEXA 1 B(0) RAMP CO MEXA 2

Figure 14 - A plot of pre-catalyst and post catalyst CO emissions versus time for B(0) (Ramp test)

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600

13 12

CO (PPM)

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9 8

0 0 2 4 6 8 10 12 14 16

7

TIME (MINS)
RAMP PEDAL % B(50) RAMP CO MEXA 1 RAMP CO MEXA 2

Figure 15 - A plot of pre and post catalyst CO emissions versus time for B(50) (Ramp test)

250

15 14

200 13 12 11 100 10 9 50 8 0 0 2 4 6 8 10 12 14 16 7

THC (PPM)

TIME (MINS)
B(0) RAMP THC MEXA 1 B(0) RAMP THC MEXA 2 RAMP PEDAL %

Figure 16 - A plot of pre and post catalyst THC emissions versus time for B(0) (Ramp test) WISDOM PATRICK ENANG Page 42

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THC (PPM)

TIME (MINS)
B(50) RAMP THC MEXA 1 B(50) RAMP THC MEXA 2 RAMP PEDAL %

Figure 17 - A plot of pre and post catalyst THC emissions versus time for B(50) (Ramp test)

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2D Graph 3

220 200 180

15 14 13

160

NOx (PPM)

120 100 80

11 10 9

60 40 20 0 2 4 6 8 10 12 14 16 8 7

TIME (MINS)
B(0) RAMP NOx MEXA 1 B(0) RAMP NOx MEXA 2 RAMP PEDAL %

Figure 18 - A plot of pre and post catalyst NOx emissions versus time for B(0) (Ramp test)

240 220 200

15 14 13

180

NOx (PPM)

140 120 100

11 10 9

80 60 40 0 2 4 6 8 10 12 14 16 8 7

TIME (MINS)
B(50) RAMP NOx MEXA 1 B(50) RAMP NOx MEXA 2 RAMP PEDAL %

Figure 19 - A plot of pre and post catalyst NOx emissions versus time for B(50) (Ramp test)

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PEDAL %

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Subsequently after the ramp it could be observed that both CO emissions (Figure 14 & Figure 15) and THC emissions (Figure 16 & Figure 17) for the B(0) and the B(50) fuel blend, did decrease suggesting the transition of the engine from rich combustion condition, to a lean combustion condition. However the same was not observed for the NOx emissions (Figure 18 and Figure 19). Subsequently after the ramp, NOx emissions (Figure 18 and Figure 19), were found to maintain at a somewhat peak level up until the end of the ramp. One possible reason for this observation could be that, towards the end of the ramp, the temperature of the exhaust got high enough for NOx emissions to form, which will be consistent with the findings of Cardone et al (13) As already discussed in the experimental section, for the ramp test, several adjustments were made to EGR settings, engine speed, and exhaust flow rate, in an attempt to match the emissions levels in all the fuels tested. In the end only the CO, and THC emissions (Figure 14- Figure 17) of both fuel blend ratios tested were closely matched. The NOx emissions (Figure 18 and Figure 19) however, were slightly different, but such differences were not enough to affect the accuracy of the subsequent light off analysis performed. Despites all attempts only CO and THC emissions for all fuel blend ratio tested were matched. NOx emissions on the other hand were found to slightly increase with increasing biodiesel blend ratio. The Increasing levels of NOx emissions observed during the ramp test, do also confirm the findings of Cardone M et al (13)and that of Tat ME et al (40). In line with Cardone’s proposal, this trend appears to be as a result of the complex combustion processes associated with increasing biodiesel blend ratio, due to the advanced injection derived from its properties like (viscosity, density, compressibility and sound velocity).

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4.1.3 Catalyst conversion efficiency under the Ramp test condition

In order to create a more comparative picture of the effect of CO, THC and NOx emissions, from the B(0) and B(50) fuel blend, on the performance of the oxidation catalyst in the ramp test, a set of light off comparison curves for both fuel blend ratios are shown in Figure 20 - Figure 22. For all emissions (CO and THC) emissions, the B(50) biodiesel blend showed a lower light off temperature when compared to the B(0) biodiesel blend. Conversion efficiencies of the catalyst were also found to increase, with increasing biodiesel blend ratio, for any particular catalyst temperature. The main reason for these observations is believed to stem from the increasing trend of high oxygen content of biodiesel. B(50) contains much more molecular oxygen content than B(0), which helps it facilitate a more complete combustion, compared to the B(0) fuel. A more complete combustion, reduces the overall CO and THC emissions produced, as well as promote the emission of more partially oxidized hydrocarbons, in B(50) fuel blend compared to the B(0) fuel blend. The presence of more partially oxidized hydrocarbons in the B(50) fuel blend, in addition to its lower CO emission levels, results in the low light of temperature observed. The presence of more partially oxidized hydrocarbons from the B(50) fuel blend compared to the B(0) fuel blend, implies that a lower catalyst temperature is required for the complete oxidation of the THC emissions from B(50). A similar logic could also be used to explain why B(50) has a higher level of peak THC conversion (80%) than that of B(0) which is (76%) as shown in Figure 21. This finding goes very much in line with the findings of Han et al. (39), who claimed in his study that ‘’Low CO emissions, partially oxidized HC’s and higher O2 concentration are necessary to lower the temperature of a diesel oxidation catalyst’’.

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100

80

Conversion %

60

40

20

0 100 120 140 160 180 200 220 240 260 280

Catalyst Temperature (Degrees)
B(0) RAMP CO Conversion B(50) RAMP CO Conversion

Figure 20 - A graph of comparison between the CO light off curve for B(0), and B(50) (Ramp test)

100

80

Conversion %

60

40

20

0 100 120 140 160 180 200 220 240 260 280

Catalyst Temperature (Degrees)

B(0) RAMP THC Conversion B(50) RAMP THC Conversion

Figure 21 - A graph of comparison between the THC light off curve for B(0), and B(50)

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Conversion %

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Catalyst Temperature (Degrees)
B(0) RAMP NOx Conversion B(50) RAM NOx Conversion

Figure 22 - A graph of comparison between the NOx light off curve for B(0), and B(50) (Ramp test)

4.1.4 Effect of Hydrocarbon trappings ‘’Zeolites’’ on the Oxidation of THC Emissions

Figure 23 and Figure 24 shows the variation between the Pre Catalyst (MEXA 1) and Post catalyst (MEXA 2) readings for THC emissions over increasing catalyst temperatures using the B(0) and the B(50) biodiesel fuel blend. From both curves, there appear to be a significant difference between the MEXA 1 and MEXA 2 readings for both biodiesel blend ratios, even at very low temperatures. According to Han et al (39) who under took a similar study, this observation holds up for very low temperatures, even much lower temperatures, than the THC light off temperature of the oxidation catalyst, thus ruling out the possibility that catalytic oxidation may have been responsible for the differences observed.

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200 13 12 11 100 10 9 50 8 0 140 160 180 200 220 240 260 7

THC (PPM)

CATALYST TEMPERATURE (DEGREES)
B(0) RAMP THC MEXA 1 B(0) RAMP THC MEXA 2 RAMP PEDAL %

Figure 23 - A plot of pre and post catalyst THC emissions versus catalyst temperature for B(0) (Ramp test)

250

15 14

200 13 12 11 100 10 9 50 8 0 140 160 180 200 220 240 7

THC (PPM)

CATALYST TEMPERATURE (DEGREES)
B(50) RAMP THC MEXA 1 B(50) RAMP THC MEXA 2 RAMP PEDAL %

Figure 24 - A plot of pre and post catalyst THC emissions versus catalyst temperature for B(50) (Ramp test)

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However a more plausible reason for the variation between the Pre Catalyst (MEXA 1) and Post catalyst (MEXA 2) readings observed, is that some of the pre-catalyst THC emissions got trapped at low exhaust temperatures, in the hydrocarbon trapping material of the Catalyst called ‘’Zeolites’’. As shown in Figure 21, at temperatures preceding about 135oC for the B(50) fuel, and about (138oC) for the B(0) fuel, the curve appears to be parallel to the X - axis, which suggest that most of the THC emissions for both fuels in that catalyst temperature region, were rather trapped in the Zeolites and not converted as would have initially been thought. At low temperatures, THC emissions tend to condense from gas to a somewhat liquid form on the catalyst traps where it is stored until the catalyst temperature becomes high enough to facilitate, the necessary conversion of THC to water and carbon dioxide. As it can be seen in Figure 21, beyond (140oC) a fall in conversion efficiency with increasing catalyst temperature up until (165oC) for B(0) and (160oC) for B(50) appears to be the dominant trend for both fuel blends. This effect it due to the change in state of THC emissions from the liquid stored state to a gaseous state where it is ready for oxidation as the temperature of the catalyst increases towards a light off point. During this stage, it is believed that most of the increase in catalyst temperature is used to generate the needed latent heat of vaporisation, in order to create a complete change in state of the stored THC emissions from liquid to a gaseous state. Beyond this stage, a significant increase in conversion efficiency with increasing catalyst temperature, is observed for both fuels, with B(0) having a peak conversion efficiency of 76% and B(50) having a peak conversion efficiency of 80% (Figure 21).

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4.2 STEADY STEATE TEST

Unlike the RAMP test, during the steady state test, the engine was switched on and set to apply an increasing pedal% from 7% to 14%, under a span of 20 minutes. With this test method 3 fuel blend ratios, B(0), B(25) and B(50) were tested and their pre and post-catalyst emissions levels were recorded as MEXA1 and MEXA 2 respectively. Adjustments were made to EGR valve settings, exhaust flow rates and vehicle speed, in an attempt to match all the 3 emissions (CO, THC and NOx) level for the fuel blend ratios tested. Only CO and THC emissions were successfully match in the end, for all the fuel blends tested. There were some slight differences in the NOx emissions from each of the fuel blend ratios tested, although such differences were found to be of minimal effect on the overall performance of the oxidation catalyst.

4.2.1 Catalyst conversion efficiency under steady state test condition

Figure 25 – Figure 27, shows a correlation of the catalyst temperature against, the oxidation catalyst conversion efficiency (light off curve) for CO, THC and NOx emissions under the steady state test condition. The light off curves for CO and THC emissions, in B(0), B(25) and B(50) appear to be very close to each other, and could arguably be concluded that: all three fuel blends possess the same light off characteristics. However, B50 appears to have a lower CO and THC light off temperature than B(25) and B(0), which again reinforces the role of higher molecular oxygen content in the production of partially oxidized THC molecules, thus lowering the temperature needed for its complete oxidation. This finding goes very much in line with the findings of Han et al. (39), who claimed in his study that ‘’Low CO emissions, partially oxidized HC’s and higher O 2 concentration are necessary to lower the temperature of a diesel oxidation catalyst’’. This trend also goes a long way to confirm similar observations made in the ‘’Ramp test’’. With the NOx emissions

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conversion curve (Figure 27) not much of a significant difference was observed between the 3 fuel blends tested.

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CONVERSION %

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20

0 100 120 140 160 180 200

CATALYST TEMPERATURE (Degrees)
B(0) STEADY STATE B(25) STEADY STATE B(50) STEADY STATE

Figure 25 - A graph of comparison between the CO light off curve of B(0), B(25) and B(50) (Steady state test)

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100

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CONVERSION %

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40

20 100 120 140 160 180 200

CATALYST TEMPERATURE (Degrees)

B(0) STEADY STATE THC B(25) STEADY STATE THC B(50) STEADY STATE THC

Figure 26 - A graph of comparison between the THC light off curve of B(0), B(25) and B(50) (Steady state test)

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CONVERSION %

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4

2

0 100 120 140 160 180 200

CATALYST TEMPERATURE (Degrees)
B(0) STEADY STATE NOx B(25) STEADY STATE NOx B(50) STEADY STATE NOx

Figure 27 - A graph of comparison between the NOx light off curve of B(0), B(25) and B(50) (Steady state test) WISDOM PATRICK ENANG Page 53

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4.2.2 Effect of Hydrocarbon trappings on the Oxidation of THC under steady state test condition The THC light off characteristics of the catalyst, before 120oC for B(50), 137oC for B(25) and 141oC for B(0) as shown in Figure 26, appears to be a straight line, which is similar to an observation in ramp test THC light off curve (Figure 21). As already explained under the ramp test, this trend suggests that most of the THC emissions within that temperature region were stored in the ‘’zeolites’’, of the catalyst as supposed to being converted.

4.2.3 Effect of EGR on the performance of an oxidation catalyst

Increased biodiesel blend ratios, have been found both in this research work, and that of Cardone M. et al (13) as being a cause of NOx emissions. Despite the earlier discussed potential of biodiesel in reducing CO and THC emissions, its role in the increase of NOx emissions which is very poisonous to the environment, have drawn the attention of government environmentalist, to put stringent rules on manufacturers who propose the use of biodiesel with their engine, to make use of alternative methods to reduce the NOx emissions, to environmentally accepted levels. NOx emissions tend to form more at high combustion temperatures, and so in an attempt to reduce the tendency of its formation, engine manufacturer have turned their attention to the use of EGR as an effective technique. With the EGR method, air from the exhaust, is drawn back in to the in-cylinder in order to reduce its temperature, thus reducing the tendency of NOx emissions to form. Although, this method has proven very successful in reducing NOx emissions, the down side of it is that EGR also leads to increase in the formation of THC, CO and PPM emissions, alongside an increase in the specific fuel consumption of fuel (41). In a research study, Ken Satoh et al (42), investigated on a single cylinder DI diesel engine, with various combinations of EGR, fuel injection and injection timing, and found that NOX reduction ratio has a strong correlation with the oxygen

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content of the fuel regardless of the injection pressure or timing. In their findings, they claimed that NOx reduction ratio was in direct proportion to the intake gas temperature, and so the use of an EGR, may lead to an incomplete combustion and subsequent increase in THC and CO emissions levels. No literature till date has been produced to further investigate the effect of the EGR on the performance of an oxidation catalyst. Oxidation catalysts are mainly known to oxidize THC and CO to water and CO2, and its functionality relies mainly on temperature, and so if the use of an EGR leads to increased CO and THC emissions, with decreasing exhausts temperature, it then primarily infers that the performance of the oxidation catalyst could be affected in some form. As a result, the next paragraph, will attempt to investigate just how much of an effect the use of an EGR in an engine will have on the performance of an oxidation catalyst. For this analysis a B25 fuel was used under the steady state test condition with different EGR settings. Figure 28 – Figure 30, shows some comparative correlations of the effect of an EGR on the performance of a diesel oxidation catalyst in an engine being run on the B25 fuel blend, under the steady state test condition. For this analysis, the EGR’s effect on the oxidation catalyst conversion efficiency has been investigated for the individual emissions CO, THC and NOx as shown in Figure 28 - Figure 30. The dominant effect of the EGR on the performance of the oxidation catalyst in this case, was a decrease in the light of temperature for CO and THC emissions, which tended to infer that at much lower temperatures, higher conversion efficiencies of THC and CO emissions were achieved by the catalyst, combusting the same fuel with a higher EGR setting.

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120

20 18

100 16 80 14 12 10 8 6 20 4 2 0 0

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B(25) WITH LOW EGR CO CONVERSION PLOT B(25) WITH HIGH EGR CO CONVERSION PLOT LOW EGR SETTING FOR B(25) HIGH EGR SETTING FOR B(25)

Figure 28 - A plot showing the effect of EGR on CO conversion efficiency for B(25)

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CONVERSION %

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12 10

EGR %
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50

40

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B(25) WITH LOW EGR THC CONVERSION PLOT B(25) WITH HIGH EGR THC CONVERSION PLOT LOW EGR SETTING FOR B(25) HIGH EGR SETTING FOR B(25)

Figure 29 - A plot showing the effect of EGR on THC conversion efficiency for B(25)

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12

20 18

10 16 8

CONVERSION %

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4

8 6 4

2

0

2 0 130 140 150 160 170 180 190

CATALYST TEMPERATURE (Degrees)
B(25) WITH LOW EGR NOx CONVERSION PLOT B(25) WITH HIGH EGR NOx CONVERSION PLOT HIGH EGR SETTING FOR B(25) LOW EGR SETTING FOR B(25)

Figure 30 - A plot showing the effect of EGR on NOx conversion efficiency for B(25)

This observed trend appears not to be in line with what was expected, as the use of EGR has been proven to increase THC and CO emissions (42). That notwithstanding the only plausible explanation for this rather surprising trend is that some of the exhaust gases drawn back in through the EGR contained hydrocarbons which tended to promote the activity of the catalyst at a much lower light off temperatures for CO and THC emissions. The use of an EGR tended to reduce the peak NOx conversion as shown in Figure 30. This overall decrease in the peak NOx conversion efficiency observed with the use of an EGR is thought to have been very much as expected and in line with the aims of using an EGR as part of an engine after treatment, which is to reduce the catalyst temperature and consequently reduce the tendency for NOx emissions to form.

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4.3 NEDC

During the steady state and ramp test, special efforts through repeated testing and adjustment of EGR settings, exhaust flow rates, and engine speed, were made in order to closely match the CO, THC and NOx emissions levels produced from all the fuel blend ratios tested (B(0), B(25) and B(50)). This was to enable, a clear and fair investigation to be made on the effect of the oxidation catalyst in the conversion of the CO, THC and NOx emissions for the entire blend ratios tested. However, this method of analysis did very little to model the effect of the oxidation catalyst in a real life drive cycle. In an attempt to understand the effect of an oxidation catalyst in a real life drive cycle, this section will investigate further, the potential of an oxidation catalyst in a car being driven under the New European Drive Cycle. During the NEDC test, the engine was being run such that similar levels of engine speed were obtainable from the engine; regard less of the fuel blend in use. As a result of the reduced calorific value associated with increased biodiesel fuel blend, more fuel was consumed with the B(50) blend, than with the B(0) blend as shown in Figure 31 below, in order to make up for the low energy content of the B(50) fuel blend. Although it is fair to say that the differences in the fuel consumption between the B(0), B(25) and B(50) in this test was not very significant, but its effect on the emissions produced, and sequent effect on the functionality of the oxidation catalyst, remains an area which demands much more detailed analysis, and so will be looked at subsequently.

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20 18

Fuel Consumption (mg/st)

16 14 12 10 8 6 4 2 50 100 150 200 250 300

Catalyst Temperatures (Degrees)
Fuel consumption B(0) Fuel consumption B(25) Fuel consumption B(50)

Figure 31 - The impact of biodiesel blend ration on fuel consumption under the NEDC

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4.3.1 Effect of Increased fuel Consumption with increasing blend ratio on vehicle emissions

Over the NEDC cycle, NOx emissions were found to increase, with increasing biodiesel fuel blend ratio as evident in Figure 32 - Figure 34. These results were however very consistent with the findings of Schumach LG et al. (43). This phenomenon is believed to be as a result of the advanced injection derived from biodiesel properties like (viscosity, density, compressibility and sound velocity). Regardless of the fuel type used for this test, a high spike in levels of NOx emissions was noticed towards the end of the cycle. This observation is believed to be as a result of the fact that NOx emissions tend to form in higher quantities, during periods of high in cylinder temperature. The subsequent quick fall in the NOx emissions towards the end of the NEDC test cycle, is consistent across all the NDEC profiles regardless of the fuel blend used, and is believed to have been as a result of the deceleration experienced by the engine towards the end of this cycle, which means that there was a drop in the amount of fuel injection regardless of the fuel blend used, and thus a fall in the amount of NOx emissions produced. All over the cycle, NOx emissions were found to increase proportionately with increased engine acceleration, as well decrease proportionately in periods where a fall in the engine acceleration was experienced. This observation appeared to hold true regardless of the fuel blend used during this test.

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600

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2500

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100

0 0 5 10 15 20

500

TIME (MINS)
B(0) NEDC NOx MEXA 1 B(0) NEDC NOx MEXA 2 B(0) NEDC ENGINE SPEED

Figure 32 - A plot of pre and post catalyst NOx emissions versus time for B(0) (NEDC test)

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200 1000

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500

TIME (MINS)
B(25) NEDC NOx MEXA 1 B(25) NEDC NOx MEXA 2 B(25) ENGINE SPEED

Figure 33 - A plot of pre and post catalyst NOx emissions versus time for B(25) (NEDC test)

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0 0 5 10 15 20

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TIME (MINS)
B(50) NEDC NOx MEXA 1 B(50) NEDC NOx MEXA 2 B(50) NEDC ENGINE SPEED

Figure 34 - A plot of pre and post catalyst NOx emissions versus time for B(50) (NEDC test)

CO and THC emissions throughout the NEDC test were found to decrease with increasing biodiesel blend ratio, despite the fact that with increased biodiesel fuel blend ratio, more fuel was consumed by the engine in order to produce the same level of power and torque like the low fuel blends (Figure 35 – Figure 40). This trend is however contrary to the findings of Bannister et al (44). This trend suggests that the presence of high oxygen content in the B(50), fuel compared to the B(25) and subsequently B(0), was sufficient enough to facilitate a more complete fuel combustion, thus leading to the low levels of CO and THC emissions observed with the increased biodiesel blends. Over the entire NEDC test cycle, THC and CO emissions regardless of the blend ratio used were observed to gradually decrease, over the entire cycle time. This trend suggests that the engine, tended to run rich at the beginning of the cycle, in order to compensate for its cold start, and then gradually transited to a lean run where most of the fuel was combusted in a more complete manner. WISDOM PATRICK ENANG Page 62

ENGINE SPEED (RPM)

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CO (PPM)

2000 2000 1500

1000 1000

0 0 5 10 15 20

500

TIME (MINS)
B(0) NEDC CO MEXA 1 B(0) NEDC CO MEXA 2 B(0) NEDC ENGINE SPEED

Figure 35 - A plot of pre and post catalyst CO emissions versus time for B(0) (NEDC test)

4000

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CO (PPM)

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1000 1000

0 0 5 10 15 20

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TIME (MINS)
B(25) NEDC CO MEXA 1 B(25) NEDC CO MEXA 2 B(25) NEDC ENGINE SPEED

Figure 36 - A plot of pre and post catalyst CO emissions versus time for B(25) (NEDC test) WISDOM PATRICK ENANG Page 63

ENGINE SPEED (RPM)

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4000

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CO (PPM)

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1000 1000

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TIME (MINS)
B(50) NEDC CO MEXA1 B(50) NEDC CO MEXA 2 B(50) NEDC ENGINE SPEED

Figure 37 - A plot of pre and post catalyst CO emissions versus time for B(50) (NEDC test)

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TIME (MINS)
B(0) NEDC THC MEXA 1 B(0) NEDC THC MEXA 2 B(0) NEDC ENGINE SPEED

Figure 38 - A plot of pre and post catalyst THC emissions versus time for B(0) (NEDC test) WISDOM PATRICK ENANG Page 64

ENGINE SPEED (RPM)

THC (PPM)

ENGINE SPEED (RPM)

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0 0 5 10 15 20

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TIME (MINS)
B(25) NEDC THC MEXA 1 B(25) NEDC THC MEXA 2 B(25) ENGINE SPEED

Figure 39 - A plot of pre and post catalyst THC emissions versus time for B(25) (NEDC test)

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TIME (MINS)
B(50) NEDC THC MEXA 1 B(50) NEDC THC MEXA 2 B(50) ENGINE SPEED

Figure 40 - A plot of pre and post catalyst THC emissions versus time for B(50) (NEDC test) WISDOM PATRICK ENANG Page 65

ENGINE SPEED (RPM)

THC (PPM)

ENGINE SPEED (RPM)

THC (PPM)

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CO and THC emissions as shown in Figure 35 - Figure 40 were also found to exhibit a proportionate increase and decrease in emissions levels as the engine accelerated and decelerated respectively. This is believed to be as a result of the fact that within an accelerating mode, more fuel is demanded for by the engine, which results in the combustion of more fuel at that instant. The increase in fuel demand causes the level of CO and THC emissions to increase, although the emission levels tend to fall once the engine is in a decelerating mode.

4.3.2 Catalyst conversion efficiency under the NEDC test condition.

During the NEDC test cycle, the engine experienced a combination of accelerations and decelerations, which turned out to cause a fluctuation in the general temperature profile of the oxidation catalyst over the entire cycle. As such the only way a light off curve profile could be modelled for the NEDC test was by considering the temperature values at idle periods, and thus determining the catalyst conversion at those points. As already discussed above, different levels of CO, THC and NOx emissions for the different fuel blend ratio were observed all over the NEDC test cycle (Figure 41 – Figure 46). This however creates a scenario where we are no more able to compare like for like. In this situation the use of just a light off curve (conversion efficiency vs catalyst temperature) alone, will not be able to fairly point out the effect of one fuel blend on the performance of the oxidation catalyst, over another fuel blend. Consequently, a combination of the NEDC light off curves for CO, THC and NOx emissions are detailed in Figure 41, Figure 43 and Figure 45 respectively, as well as curves correlating the catalyst temperatures, with actual emissions (PPM) converted by the catalyst (Figure 42, Figure 44, and Figure 46), are being used to draw a clearer picture of what is really going within the oxidation catalyst during the NEDC cycle. As previously stated the light off curves for the NEDC were constructed using the conversion efficiency data at idle periods, while the (converted PPM against Catalyst temperature plots), were constructed using data from all over the NEDC cycle.

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100

80

Conversion %

60

40

20

0 0 50 100 150 200 250 300

Catalyst Temperature (Degrees)

B(25) NEDC CO CONVERSION B(0) NEDC CO CONVERSION B(50) NEDC CO CONVERSION

Figure 41 - A graph of comparison between the CO light off curve for B(0), B(25) and B(50) (NEDC test)

1800 1600 1400 1200

CO (PPM)

1000 800 600 400 200 0 -200 50 100 150 200 250 300 350

CATALYST TEMPERATURE (Degrees)
B(0) NDEC CO PPM CONVERTED B(25) NDEC CO PPM CONVERTED B(50) NDEC CO PPM CONVERTED

Figure 42 - A graph of comparison between the PPM levels of CO converted for B(0), B(25) and B(50) (NEDC test)

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100

80

Conversion %

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20

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Catalyst Temperature (Degrees)

B(0) NEDC THC CONVERSION

B(25) NEDC THC CONVERSION B(50) NEDC THC CONVERSION

Figure 43 - A graph of comparison between the THC light off curve for B(0), B(25) and B(50) (NEDC test)

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THC (PPM)

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CATALYST TEMPERATURE (Degrees)
B(0) NEDC THC PPM CONVERTED B(25) NEDC THC PPM CONVERTED B(50) NEDC THC PPM CONVERTED

Figure 44 - A graph of comparison between the PPM levels of THC for B(0), B(25) and B(50) (NEDC test)

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30

25

Conversion %

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15

10

5

0 0 50 100 150 200 250 300

Catalyst Temperature (Degrees)

B(25) NEDC NOx CONVERSION B(0) NEDC NOx CONVERSION B(50) NEDC NOx CONVERSION

Figure 45 - A graph of comparison between the NOx light off curve for B(0), B(25) and B(50) (NEDC test)

40

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NOx (PPM)

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0

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-20 50 100 150 200 250 300 350

CATALYST TEMPERATURE (Degrees)
B(0) NEDC NOx PPM CONVERTED B(25) NEDC NOx PPM CONVERTED B(50) NEDC NOx PPM CONVERTED

Figure 46 - A graph of comparison between the PPM levels of NOx converted for B(0), B(25) and B(50) (NEDC test) WISDOM PATRICK ENANG Page 69

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Figure 42, shows a decrease in the overall CO (PPM) emissions converted by the catalyst with increasing biodiesel blend ratios. This same trend could be observed for THC emissions (Figure 44). Figure 41 on the other hand for the CO emissions, shows a decrease in the light off temperature, with increasing fuel blend ratio, and so does the THC light off curve in (Figure 43). In this case, it is important to note that, the high molecular oxygen content associated with increased biodiesel blends cannot be held responsible for the decrease in light off temperature experienced here. This is because, unlike the Ramp and the Steady state test, in the NEDC test, all fuels blend ratio tested did emit different PPMs of CO and THC, and so the difference in the oxygen content between the fuel blends tested becomes far less relevant in understanding why the light off temperature of the catalyst tended to decrease with increasing biodiesel blend ratio. One plausible explanation for this trend is that, as the CO and THC (PPM) emitted increases, some of the emitted CO and THC molecules tend to have partial access to the oxidizing catalyst sites, and as such tend to require a much higher oxidation temperature. In other words for the B(50) fuel which emitted the least PPMs of CO and THC, the surface area of its molecules would have more of a full access to the catalyst oxidation site than the rest of the tested fuel blends, and as such will be able to light off at a much lower temperature. In the case of NOx oxidation, the actual PPMs of NOx emissions converted (Figure 46) appears to be on the increase with increasing biodiesel blend ratio, whilst the reverse appears to be the case for the NOx conversion efficiency curve in Figure 45. This is believed to be as a result of the fact that unlike THC and CO emissions, NOx emissions do tend to form at high exhaust temperatures, Which means that with B(50) although much more NOx emissions were produced than any other fuel blend tested, the low catalyst temperature characteristics of the B(50) limited the overall conversion efficiency for the NOx emissions (Figure 45).

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4.3.3 Effect of torque on the performance of an oxidation catalyst

In a real drive cycle, the conversion efficiency of an oxidation catalyst does vary with torque. Figure 47 – Figure 49, shows that at the same torque value much higher conversion efficiency is obtainable with the lower biodiesel blend ratio, than with higher biodiesel blend ratio. This trend remains consistent all through the conversion efficiency curves for CO, THC and NOx (Figure 47 – Figure 49), and is thought to be as a result of the decreased energy content of biodiesel, which implies that a much higher engine torque is needed to light off the catalyst as the fuel blend ratio increases.

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CO CONVERSION %

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TORQUE (NM)
B(0) CO B(25) CO B(50) CO

Figure 47 - Impact of Torque on the CO conversion efficiency B(0), B(25) and B(50) (NEDC test)

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90

80

THC CONVERSION %

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60

50

40

30

20 0 5 10 15 20 25 30

TORQUE (NM)
B(0) THC B(25) THC B(50) THC

Figure 48 - Impact of Torque on the THC conversion efficiency B(0), B(25) and B(50) (NEDC test)

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NOx CONVERSION %

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TORQUE (NM)
B(0) NOx B(25) NOx B(50) NOx

Figure 49 - Impact of Torque on NOx conversion efficiency B(0), B(25) and B(50) (NEDC test)

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4.4 CATALYST CONVERSION EFFICIENCY PREDICTION MODEL FOR NEDC

Figure 50 and Figure 51 presents correlations of CO and THC conversion efficiency against, different biodiesel fuel blend ratio, at specific exhaust temperatures for the NEDC test cycle. It is important to note that these predictive correlations, were put together using data from all over the NEDC cycle, which is quite different from the Idle period data used to correlate the light off curves in Figure 41 and Figure 43. Inferring from Figure 50 and Figure 51, it is immediately clear that the CO conversion efficiency appears to increase with increasing biodiesel blend ratio. This observation goes a long way to further confirm the trends previously observed in Figure 41 and Figure 43, although those graphs were computed using conversion efficiencies at idle periods. As evident in Figure 50, a comparison of B(0) and B(50) do show that the overall CO conversion efficiency tend to increase by 26%, 11%, 20%, and 10% for 50oC, 100oC, 150oC and 200oC exhaust gas temperatures respectively. A similar trend of increasing conversion efficiency with increased biodiesel blend ratio could also be observed in the case of THC emissions as shown in Figure 51. A comparison of B(0) and B(50) in Figure 51, do show that the overall THC conversion efficiency between both fuels, tend to go up by 4%, 5%, 2%, 1% for 50oC, 100oC, 150oC and 200oC exhaust temperatures, respectively. Figure 52 and Figure 53, presents histograms, which give a clear picture of the proportion of cycle time spent at the different CO and THC conversion efficiencies respectively, for all the fuel blend ratios tested (B(0), B(25) and B(50)) during the NEDC test. Data from all over the NEDC test cycle were taken in to consideration during the construction of these histograms. The use of B(0), when compared with the rest of the fuels (B25 and B50), led to the highest cycle time at which the catalyst was operating at a 50 - 75% conversion efficiency. According to the Figure 52, at least a 75% CO conversion efficiency was experience for 70% of the cycle time.

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120

(NEDC) CO CATALYST CONVERSION (%)

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BLEND RATIO (%)
50 degrees celcius 100 degrees celcius 150 degrees celcius 200 degrees celcius x column vs y column x column 1 vs y column 1 x column 2 vs y column 2 x column 3 vs y column 3

Figure 50 - The impact of biodiesel blend ratio, and exhaust temperatures on NEDC CO catalyst conversion efficiency

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86

(NEDC) THC CATATLYST CONVERSION (%)

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BLEND RATIO(%)
50 degrees celcius 100 degrees celcius 150 degrees celcuis 200 degrees celcuis x column 1 vs y column 1 x column 2 vs y column 2 x column 5 vs y column 5 x column 6 vs y column 6

Figure 51 - The impact of biodiesel blend ration, and exhaust temperatures on NEDC THC conversion efficiency

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Relative Cycle Time (%)

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CO Conversion Efficiency (%)

Figure 52 - Plot showing the relative cycle time for different CO conversion efficiencies

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Relative Cycle Time (%)

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B(50)

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THC Conversion Efficiency (%)

Figure 53 - Plot showing the relative NEDC cycle time for different THC conversion efficiencies

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The distribution of the THC conversion efficiency histogram in Figure 53, does present a very different pattern to the CO conversion efficiency histogram in Figure 51. The cycle time spent on THC conversion efficiencies above 75% tended to fall. This observation is very consistent with an earlier observation in Figure 38 to Figure 40, where THC MEXA 2 (post catalyst emissions), tended toward 0 PPM value), just after 16 minutes of a 20 minutes cycle time. According Figure 53, the percentage of cycle time spent on THC conversion efficiencies above 75% for B(0), B(25) and B(50), was 18%, 12%, and 17% respectively. It is not clear why B(25) experienced the least relative cycle time for THC conversion above 75%, but it is believed that this could be as a result of fall in engine combustion efficiency, or change in the exhaust gas composition, or change in the gas concentration, which led to a less favourable oxidation environment within the catalyst.

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5. CONCLUSIONS AND FURTHER WORK

5.1 CONCLUSIONS

Whilst biodiesel possesses many similarities to conventional diesel, its unique property of increased oxygen content, makes it more preferable to conventional diesel by some engine manufacturers. A lot of research work currently exists about the characteristics of biodiesel in different engine technologies. Most of such reviewed literatures who attempt to talk on diesel after treatment systems, only centre on particulate filters with very little attention given to the oxidation catalyst. This paper aims to contribute to the understanding of the effect of biodiesel emissions on the performance of an oxidation catalyst; both in idealized laboratory test conditions, and in a real life drive cycle (NEDC). Two fuel blend ratio B(0) and B(50) were tested under the ramp test condition where adjustments were made to the experimental set up, in order to ensure equal levels of CO, THC and NOx emissions across the 2 tested blends. During the ramp, CO, THC and NOx emissions were found to increase proportionately across all biodiesel blends tested, up until the end of the ramp where CO and THC emission were found to later decrease, thus suggesting the engine’s transition from rich to lean combustion condition. NOx emissions for the two fuel blends tested increased during the ramp but continued at a somewhat peak level up until the end of the ramp. This trend is thought to be as a result of the fact that NOx emissions tend to form at high temperature, which was exactly the temperature condition of the exhaust towards the end of the ramp. In the ramp test, increased biodiesel blend ratio, were also found to promote catalytic conversion of CO and THC, at low light of temperatures. The high molecular oxygen content of increased biodiesel blends is thought to be responsible for this trend. Increased molecular oxygen in biodiesel, helps facilitate a more complete combustion of the fuel, as well produce partially oxidized CO and THC emissions, which require minimal light off temperature, to attain a complete conversion to carbon dioxide and water. At low

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start conditions, THC emissions were found trapped in the hydrocarbon trapping ‘’zeolites’’ of the catalyst as supposed to being converted. This trend was also observed in the THC light off curve correlated from the steady state test data. In another study under the steady state test conditions, increased EGR settings was found to promote catalytic conversion. This trend suggests that with the use of an EGR, the hydrocarbons drawn in to the exhaust manifold, tend to promote catalytic conversion. This conclusion remains questionable however; as there was facility for us to test the actual hydrocarbons that made up the exhaust, and also confirm how reactive they were to the catalyst monolith. Over the NEDC cycle, the light off temperature of the oxidation catalyst was found to decrease with increasing biodiesel blend ratio. Another investigation over the NEDC cycle found that whilst the light off temperature of the oxidation catalyst appeared to decrease with increasing biodiesel blend ratio, the actual amount of emissions (PPM) converted were also on the decrease with increasing biodiesel blend ratio. These two trends however made it clear, that the only reason the light off temperature tended to decrease with increasing biodiesel blend ratio for the NEDEC was as a result of the fact that fewer emissions were produced by the higher biodiesel blends compared to the lower biodiesel blends. The quantity of CO and THC emissions recorded during the test for B(50) were relatively lesser than that of B(25) and B(0), which means that the emitted CO and THC molecules of B(50), tended to have more of a full access to the oxidation site of the catalyst thus reducing the need for high light off temperatures. Over the NEDC test cycle, the effect of engine torque on the performance of the oxidation catalyst was also investigated. In that study, it was found that at any given torque the conversion efficiency of the catalyst appears to decrease, with increasing biodiesel fuel blend ratio, as a result of the low energy content of biodiesel.

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5.2 RESEARCH CHALLENGES AND LIMITATIONS TO RESEARCH FINDINGS

Regardless of the sort of research conducted, challenges and limitations to research work are inevitable. In this research several limitations were encountered. First, despite all attempts to match the CO, THC and NOx emissions from the fuel blends tested (B(0), B(25) and B(50)) during the Ramp and steady state test, only CO, and THC emissions could be matched. All efforts to match the NOx emissions for the entire fuel blends tested, alongside the CO, and THC emissions failed. However, the differences in NOx emissions between the fuels were found to be very little and subsequently assumed as being insignificant in the light off performance of the oxidation catalyst. The second challenge encountered during this research was the fact that, there was no facility available to determine exactly what type of hydrocarbons, were produce post combustion of each of the fuel blend. As such all HC carbon emissions were recorded as (THC) - Total hydrocarbons. According to some reviewed literature, some hydrocarbons tend to promote oxidation more than the others, and so it would have been more helpful if there was a facility for us to find out the oxidation characteristics of the exhaust hydrocarbons for each of the fuel blends tested, and relate it to how it impacts on the performance of the oxidation catalyst.

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5.3 RECOMMENDED FURTHER WORK

The research work presented in this write up, provides an insight in to the impact of biodiesel emissions on the performance of an oxidation catalyst, as well as possibilities for further work in order to enhance the overall understanding of the research topic. Some of those further research possibilities include: (1) Repetition of a similar research using different biodiesel blends from different feed stocks to the one used in this research. This will create a platform for confirmation of observed trends in this research, as well as identify any disagreeing trends, with reasons.

(2) Repetition of a similar research study with a different engine technology, operating conditions, or drive cycles, in order to validate the observations and proposed explanations documented in this research work.

(3) Kinetic modelling of the oxidation of CO, THC and NOx emissions, on a different types of catalyst monoliths like Pt (Platinum), Pd (Palladium), and Rd (Rhodium). This study will help facilitate more accurate predictions of the light off performance of an oxidation catalyst, in a real life drive cycle like NEDC.

(4) Investigations in to the impact of the competitive interaction amongst biodiesel emissions (CO, THC and NOx), within the catalyst oxidation site. This study will give a clearer understanding, as to how the various biodiesel emissions (CO, THC and NOx) affect each other’s oxidation rate, within the catalyst.

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REFERENCES

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10. Munoz M, Meroo F, Morea J. Emissions of an automobile diesel engine fuelled with sun flower methyl ester. Trans AA94SAE 2004,47 (1), 5 - 11. 11. L. Turrio-Baldassarri, C.L. Battistelli, L. Conti, R. Crebelli, B. De Berardis and A.L. Iamiceli et al., Emission comparison of urban bus engine fuelled with diesel oil and biodiesel blend, Sci Total Environ327 (2004), pp. 147–162. 12. S. Murillo, J.L. Míguez, J. Porteiro, E. Granada and J.C. Morán, Performance and exhaust emissions in the use of biodiesel in outboard diesel engines, Fuel 86 (2007), pp. 1765–1771. 13. M. Cardone, M.V. Prati, V. Rocco, M. Seggiani, A. Senatore and S. Vitolo, Brassica Carinata as an alternative oil crop for the production of biodiesel in Italy: engine performance and regulated and unregulated exhaust emissions, Environ Sci Technol 36 (20. 14. Hamasaki K, Kinoshita E, Tajima H, Takasaki K, Morita D. Combustion characteristics of diesel engines with waste vegetable oil methyl ester. In: The 5th international symposium on diagnostics and modeling of combustion in internal combustion engines, 2001. 15. Krahl J, Munack A, Bahadir M, Schumacher L, Elser N. Review: utilization of rapeseed oil, rapeseed oil methyl ester or diesel fuel: exhaust gas emissions and estimation of environmental effects. SAE paper 1996, 962096. 16. Lapuerta M, Armas O, Rodriguez‐Fernandez J. Effect of biodiesel fuels on diesel engine emissions. Progress in Energy and Combustion Science. 2008 and 34(2):198‐223. 17. T.D. Durbin, J.R. Collins, J.M. Norbeck and M.R. Smith, Effects of biodiesel, biodiesel blends, and a synthetic diesel on emissions from light heavy-duty diesel vehicles, Environ Sci Technol 34(3) (2000), pp.

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18. Munack A, Schröder O, Krahl J, Bünger J. Comparison of relevant gas emissions from biodiesel and fossil diesel fuel. Agricultural Engineering International: the CIGR Journal of Scientific Research and Development 2001 and 001., III: manuscript EE 01. 19. M.S. Graboski and R.L. McCormick, Combustion of fat and vegetable oil derived fuels in diesel engines, Progr Energy Combust Sci 24 (1998), pp. 125–164. 20. Lapuerta M, Armas O, Ballesteros R. Diesel particulate emissions from biofuels derived from Spanish vegetable oils. SAE paper 2002, 2002-01-1657. 21. S.T. Bagley, L.D. Gratz, J.H. Johnson and J.F. McDonald, Effects of an oxidation catalytic converter and a biodiesel fuel on the chemical, mutagenic, and particle size characteristics of emissions from a diesel engine, Environ Sci Technol 32 (1998),. 22. D.Y.C. Leung, Y. Luo and T.L. Chan, Optimization of exhaust emissions of a diesel engine fuelled with biodiesel, Energy Fuels (2006). 23. W.G. Wang, D.W. Lyons, N.N. Clark, M. Gautam and P.M. Norton, Emissions from nine heavy trucks fuelled by diesel and biodiesel blend without engine modification, Environ Sci Technol 34 (6) (2000), pp. 24. Chang DY, Van Gerpen JH. Fuel properties and engine performance for biodiesel prepared from modified feedstocks. SAE paper 1997, 971684. 25. Schmidt K, Van Gerpen JH. The effect of biodiesel fuel composition on diesel combustion and emissions. SAE paper 1996, 961086. 26. A.L. Boehman, J. Song and M. Alam, Impact of biodiesel blending on diesel soot and the regeneration of particulate filters, Energy Fuels 19 (2005), pp. 1857–1864.

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27. Amy Peterson, Po-Lee, and Ming Ching lai of Wayne State University Detroit. ‘’Effect of B20 on emissions and performance of a diesel particulate filter in a light-diesel engine’’ SME 2009 Internal Combustion Engine Division Fall Technical Conference. A : s.n. 28. Kinetic Models for a Diesel Oxidation Catalyst Stephen Salomons stephen.salomons@ualberta.net (http://catalysis.salomons.cc) University of Alberta, Edmonton, Alberta, Canada. 29. Yamamoto, K., Takada, K., Kusaka, J., Kanno, Y. and Nagata, M. (2006). Influence of diesel post injection timing on HC emissions and catalytic oxidatcion performance. In SAE Technical Paper,(013442). 30. Ambs, J. and McClure, T. (1993). The influence of the Oxidation Catalyst on NO2 in Diesel Exaust. In SAE Technical Paper,(932494). 31. Farrauto, R. J. (1997). Ceria-Alumina oxidation catalyst. U. Patent. 5462907. 32. Layer, J. (1994). Oxidative Diesel control catalyst. U. Patent. 5371056. 33. T. Engel and G. Ertl. Advances in Catalysis, volume 28, chapter Elementary Steps in the Catalytic Oxidation of Carbon Monoxide on Platinum Metals, pages 1–78. Elsevier Inc., 1979. ISBN 0-12007828-7.REFERENCES 262. 34. G. Rupprechter, T. Dellwig, H. Unterhalt, and H.-J. Freund. CO adsorption on Ni(100) and Pt(111) studied by infrared-visible sum frequency generation spectroscopy: design and application of an SFG-compatible UHV-high-pressure reaction cell (2001). 35. Claus D. Makowka, Charles P. Slichter, and J. H. Sinfelt. Probe of the Surface of a Heterogeneous Catalyst: Double NMR of Carbon Monoxide Chemisorbed on Highly Dispersed Platinum. Physical Review Letters, 49(6):379–382, 1982 doi:10.1103/PhysRevLett 49.379.

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36. Denise C. Ford, Ye Xu, and Manos Mavrikakis. Atomic and molecular adsorption on Pt(1 1 1). Surface Science, 587(3):159–174, 2005. doi:10.1016/j.susc.2005.04.028. . 37. Stephen Salomons ‘’Kinetic Models for a Diesel Oxidation Catalyst’’, stephen.salomons@ualberta.net ‘’http://catalysis.salomons.cc’’ University of Alberta, Edmonton, Alberta, Canada. 38. A. K. Santra and D. W. Goodman, ‘’Catalytic oxidation of CO by platinum group metals: from ultrahigh vacuum to elevated pressures’’ , Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, TX 77842-3012, USA. 39. Han M-B*, D Assanis and S Bohac ‘’Characterisation of heat-up diesel oxidation catalyst through gas flow reactor and in situ engine testing’’ General motors Collaborative Research laboratory, University of Michigan, Ann Arbor, MI, USA (2008). 40. TAT ME. Investigation of oxides of Nitrogen emissions from biodiesel fuel engines. PhD thesis 2003, Iowa state university. 41. Yasufumi Yoshimoto Masayuki Onodera and Hiroya Tamaki, “Reduction of NOx and Smoke and BSFC in a Diesel Engine Fuelled by Biodiesel Emulsion with Used Frying oil”, SAE paper 1999-013598,pp.no.1913-1929. 42. Ken Santoh, Long Zhang, Hirokazu Hatanaka, Toshiaki Takatsuki, Katsuhiko Yokoto, “Relationship between Nox and SM emissions from DI diesel engine with EGR”, Society of Automotive engineers of Japan, Vol.18 (1997),pp no.369-375. 43. Schumacher LG, Borgelt SC, Hires WG, Fosseen D, Goetz W. Fueling diesel engines with blends of methyl ester soybean oil andmdiesel fuel. 1994. Available on line: www.missouri.edu/~pavt0689/ASAED94.htm.

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44. C.D Bannister, J.G Hawley, H M Ali, C J Chuck, P Price, S S Chrysafi, A Brown and W Pickford. ‘’The impact of biodiesel blend ratio on vehicle performance and emissions’’. Department of Mechanical Engineering, University of Bath, Avon, Bath, UK. (2009).

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NOMENCLATURE

CO CO2 EGR DPF NOx PM PPM THC DOC NEDC RPM MINs Pd. Pt. O2 T50 MEXA 1 MEXA 2 Light off PCI Bx HC EUDC ECE

Carbon Monoxide Carbon Dioxide Exhaust Gas Recirculation Diesel Particulate Filter Oxides of Nitrogen Particulate Matter Parts Per Million Total Hydrocarbon Diesel Oxidation Catalyst New European Drive cycle Revolution per minute Minutes Palladium Platinum Oxygen Light off temperature Pre-catalyst emissions (PPM) Post catalyst emissions (PPM) Temperature at which catalyst achieves a 50% conversion efficiency Pre mixed compression ignition Biodiesel blend ratio x=0 i.e. B(0), x=50 i.e. B(50), x=25 i.e. B(25) Hydrocarbons European Extra Urban Drive cycle Former European ECE 15 drive cycle for urban driving

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