BLENDING OF ETHANOL IN GASOLINE FOR SPARK IGNITION ENGINES

PROBLEM INVENTORY and EVAPORATIVE MEASUREMENTS

REGISTRERINGSUPPGIFT
Utgivare: Projektbeteckning Utgivningsår/mån

Rapport nr

MTC 5407
ISSN: 1103-0240

AVL MTC Motortestcenter AB Uppdragsgivare: Box 223 EMFO SE-136 23 Haninge
Författare:

8050407

2005-05

Tel: +46 8 500 656 00 Fax: +46 8 500 283 28 e-post: magnus.henke@avlmtc.com

Prof. Karl-Erik Egebäck Mr Magnus Henke Mr Björn Rehnlund Mr Mats Wallin (coordinator) Associate Prof. Roger Westerholm Rapportens titel

ISRN:
ASB-MTC-R—05/2--SE

Språk:

Engelska:

Blending of Ethanol in Gasoline for Spark Ignition Engines – Problem Inventory and Evaporative Measurements.
Svenska:

ENG Antal sidor:

Inblandning av Etanol i Bensin för Ottomotorer – Probleminventering och Avdunstningsmätningar.

111+ 20

Sammanfattning: Presently all gasoline sold in Sweden contain 5 % of ethanol. Ethanol mixing above 5% is not possible because of the EU-fuel directive as well as The European standard EN 228. However, there is in Sweden an interest in further increasing the bio-ethanol content in gasoline up to at least 10 %. The main reason is that even relatively small percentage additions will result in a substantial total volume of gasoline substitution, and the present infrastructure for distributing fuels can be used largely unchanged. Based on that background the purposes of the study were to collect information on national and international findings and experience related to the use of blends of ethanol in gasoline as fuels in spark ignition engines. The project also included a first study on the impact of the evaporative emissions with different grades of base gasoline and different blending proportions of ethanol. The main conclusion from using ethanol-gasoline blends in practice is that blends with up to 15 percent ethanol will not have any significant negative effects on the wear of the engine or vehicle performance. No significant difference can be seen in regulated emissions when comparing the use of blended fuel (with up to 1015% ethanol) to the use of neat gasoline. Concerning unregulated emissions views differ. Regarding the emissions of benzene, toluene, ethyl benzene and xylene (BTEX) the main conclusion is that there is a slight decrease when using ethanol blends, while for aldehydes there is a significant increase, especially of acetaldehyde and (to a lesser extent) formaldehyde emissions. However, there is a serious lack of data describing the effects under Swedish conditions. There will be a slight increase (~2-3%) in fuel consumption when shifting from neat gasoline to a 10 percent ethanol-gasoline blend, depending on the design of the vehicle. Cold starts, in particular, will affect fuel consumption more when using blended gasoline than when using neat gasoline. There is a need to generate data and experience by running tests and analysing the environmental effects of blending ethanol with gasoline. The lack of data is more marked for blends with high ethanol contents (~20 %). Such blends should be avoided before a thorough analysis has been carried out and more data are available.

Förslag till nyckelord Engelska: Ethanol, Blending, Gasoline, Exhaust emissions, Regulated, Unregulated, LCA, Alcohol fuels, Alternative fuels, Evaporative emissions, Vapour pressure, RVP, Svenska: Etanol, Låginblandning, Bensin, Avgasemissioner, Reglerade, Oreglerade, LCA, Alkoholbränslen, Avdunstningsmätningar, Ångtrycksmätningar, RVP, Hälsoeffekt, Rapportseriens titel Rapport – MTC AB. www.avlmtc.com

BLENDING OF ETHANOL IN GASOLINE FOR SPARK IGNITION ENGINES

PROBLEM INVENTORY and EVAPORATIVE MEASUREMENTS

Study performed by Stockholm University, ATRAX AB, Autoemission KEE Consultant AB, AVL MTC AB. Financed by Swedish EMFO 2004-2005

......... Roger Westerholm Stockholm University roger......3.......................................com Coordinator: Mr Mats Wallin........................................... Data and Experience..........................................................5. 2................1.......... 2............se Mr Magnus Henke AVL MTC AB magnus............................7........................................... Mawalco (representing AVL MTC AB)...............1......................... 3.............4..... Fuel Energy Content – Engine Power...............................3. Karl-Erik Egebäck Autoemmission KEE Consultant AB karl-erik..................15 Fuel Ethanol in East Asia ...........................42 6........ 2........1.................................8 2.... 1.............Page 2 This study has been carried out by: Associate Prof.............. 5............................33 4................................. 3.........25 Impact of Fuel................................................................... 2..................................egeback@mailbox................ 2........................28 Impact on Service and Maintenance... 3.... 3................ 10 Prerequisites for the Literature Study...................................................6..37 Theoretical Discussion about HC Emissions............... 1......................2.............. 6 Background..7...10 Fuel ethanol in the USA/California ............................................................................................. 2...38 Characterisation of Exhaust Emissions ..17 Fuel Ethanol in Australia........se Mr Björn Rehnlund Atrax Energi AB bjorn.........................1............38 Unregulated Exhaust Emissions ........................... 37 Regulated exhaust emissions ...2...............4..........................25 Impact of Lube Oil ....................................................................................... 45 ...........15 Fuel ethanol in Brazil ........... 3.... Air Quality and Health Effects................................29 Compatibility and Wear.................................................................................................. 4 Introduction..........rehnlund@atrax.....................com Contents 0....se Prof.........................................11 Fuel Ethanol in Japan ....... 5.......................6 Alcohol Blended Fuels .............................................................................swipnet...............................................................westerholm@anchem................................................................................wallin@mawalco.......... 3........................................... 35 Emissions . 23 Vehicle Performance . 1............. Summary ...su........ 5..... 2.....6............ 3.......3...................................................2............4...................................................................................................30 Impact of Vapour Lock. 5...................5......................................... mats.........................19 3............... 5........henke@avlmtc.......... The Use of Ethanol in Different Countries..................10 Fuel Ethanol in Sweden..........................2.............................................23 Cold Starts and Driving ...........................................

.....1................. 10..... Appendix 2. 8....................................65 8..........................................................................59 Evaluation of Emissions in the USA ..............83 Findings .........................1....... 90 Abbreviations .USA ..................................................... 7........................................................ 8.... 14.................106 15........... 70 RVP ....88 Performance and Wear .............. Conclusions and Recommendations ........ 10........... Vapour Pressure ................ Risk for Explosions at Low Ambient Temperatures.................5..............2...................... 14...................... 105 14.......2..........................................87 Unregulated Emissions ....80 LCA Studies for Ethanol in Neat Form or Blended with Gasoline ....5................ 8. 7...........1......................................................... 111 15....................................................................... 8.......................................................................1....................2.....89 12................................................................Europe........................ 79 Life Cycle Analysis (LCA) of Gasoline and Ethanol Blends ............48 Evaluation of Emissions in Canada .............1.......3.........4................................................................4.........................111 ......62 Fuel Consumption..........................5.... References..........3............. 7................... LCA in the Context of This Project.........................................105 Emission tests in UK ..................................77 Theoretical Discussion on Vapour Pressure Using Raoult’s Law............86 Regulated Emissions.......Brazil ............Australia ................................. 8..75 RVP .............................................Page 3 7........................ 47 Evaluation of Emissions in Australia .................... Evaporation Test of Two Ethanol Blended RON 95 Summer Gasolines........................................ 7.............2.. 103 Appendix 1......................................... 85 11.52 Evaluation of Emissions in the UK .........................................................................................1.......56 Evaluation of Emissions in Sweden .....................................78 9................. 7...........6........ 11...........................3................................... Fuel Reid Vapour Pressure ................................................................... Evaluation of Emissions and fuel consumption .... 8.............................4..........................................72 RVP ....81 Discussion................................................. 13.........76 RVP ................6..................................................................................................... 10...................77 Findings .................. 11.......................................................... 10..........................................84 11..................................... Emission tests in Canada ............................................................2................. 80 10............................................3...................88 Life Cycle Analysis ........ 11....... 7......................4........................................................................ 11...........................................................

The results and experience presented in this report originate from Sweden. especially of acetaldehyde and (to a lesser extent) formaldehyde emissions. Japan. Regarding the emissions of benzene. The main conclusions of the study are as follows: • There is intense interest world-wide in using ethanol as an automotive fuel. No significant difference can be seen in regulated emissions when comparing the use of blended fuel (with up to 10-15% ethanol) to the use of neat gasoline. fuel energy content.Page 4 0. Another aim of the project was to study the impact of using such blends on evaporative emissions by carrying out measurements with different grades of base gasoline and different blending proportions of ethanol. • • • • . fuel and lubricating oil performance. SUMMARY The purpose of the study reported here was to collect information on national and international findings and experience related to the use of blends of ethanol in gasoline as fuels in spark ignition engines. vapour lock. will affect fuel consumption more when using blended gasoline than when using neat gasoline. fuel consumption. Thailand and Australia. However this can be partly offset by the higher octane value of ethanol. The main topics discussed are the effects of using blends on: vehicle performance. and the present infrastructure for distributing fuels can be used largely unchanged. toluene. Concerning unregulated emissions views differ. cold starts and drivability. Reid Vapour Pressure (RVP) and Life Cycle Analyses. in particular. the USA. emissions (regulated and unregulated). However. Blending bio fuels with a petroleum-based fuel has the twin advantages that even relatively small percentage additions will result in a substantial total volume of gasoline substitution. while for aldehydes there is a significant increase. ethyl benzene and xylene (BTEX) the main conclusion is that there is a slight decrease when using ethanol blends. India. Brazil. especially in blending ethanol with gasoline. Presently all gasoline sold in Sweden contain 5 % of ethanol (here and throughout the text such percentages refer to the alcohol content of blends by volume) and the relevant authorities are interested in further increasing the bio-ethanol content in gasoline. depending on the design of the vehicle. Cold starts. Blending ethanol in a commonly used fossil fuel is generally seen as an easy way to introduce an alternative such as bio-ethanol without costly changes of the fleet of vehicles on the road. Ethanol can easily be blended in gasoline by well known methods. service and maintenance. A report on these measurements can be found in the appendix to this report. The main reason for blending ethanol with gasoline is to reduce fossil carbon dioxide emissions (and thus the greenhouse effect) from vehicles by using bio-ethanol originating from renewable sources. Ethanol has a lower heating value than gasoline. which will reduce the energy content of the fuel. there is a serious lack of data describing the effects under Swedish conditions. China. There will be a slight increase (~2-3%) in fuel consumption when shifting from neat gasoline to a 10 percent ethanol-gasoline blend. The main conclusion from using ethanol-gasoline blends in practice is that blends with up to 15 percent ethanol will not have any significant negative effects on the wear of the engine or vehicle performance. compatibility and wear.

Such blends should be avoided before a thorough analysis has been carried out and more data are available. A third issue is whether blends with 10 to 15 percent ethanol in gasoline will affect human health and the environment (both local and regional). The report includes 181 references and was financed by the Swedish Emission Research Program (Emissionsforskningsprogrammet. either there must be an exemption for ethanol blended fuels or the base gasoline RVP must be adjusted. The lack of data is even more marked for blends with high ethanol contents (~20 %). A first issue to address is the problem that the RVP increases when ethanol is blended with gasoline since current gasoline standards impose limits on its RVP. Such adjustments are already made today to the base gasoline used in the 5 % ethanol gasoline blends. . Therefore. given the differences in conditions and regulations between Sweden. A second issue is concern about the performance and start-ability of vehicles at low temperatures. which commonly occur in wintertime.Page 5 There is a need to generate data and experience by running tests and analysing the environmental effects of blending ethanol with gasoline. other countries belonging to the European Union. and regions where there is long experience of running vehicles on blended fuels. In addition. In the light of the situation and conditions in Sweden and the other countries belonging to the European Union there are certain barriers to overcome in order to succeed with the intention to increase the content of ethanol in blended gasoline. a number of issues have to be addressed before the alcohol content of blends is increased. EMFO). especially in the northern parts of Sweden.

since the total transportation work load is steadily increasing such measures will not be sufficient if we really want to reduce the emissions of carbon dioxide. and almost 50 % of the total net emissions of carbon dioxide. especially in developing countries. to some extent. traffic levels.Page 6 1. If international and national goals (such as those set out in the Kyoto protocol) for reducing net emissions of carbon dioxide are to be met. the dwindling supply of petroleum fuels will sooner or later become a limiting factor. fairly drastic political decisions may have to be taken to address this problem in the future. the use of fossil fuels in the transport sector has to be substantially reduced. The two alternatives are not. of course. the transport sector is a major contributor to net emissions of greenhouse gases.1. This can be done. In order to reduce absolute amounts of these emissions we have to go further and an additional measure that will be required is to replace fossil vehicle fuels with renewable ones. although some originates from other types of fossil fuels such as natural gas and Liquefied Petroleum Gas (LPG). A major contributor to the greenhouse effect is the transport sector* due to the heavy. In the transport sector this means either introducing bio fuels and using adapted vehicles. and that the present infrastructure for distributing fuels can be used. However. especially in the short term. Primarily. Alcohols can be blended with gasoline or used as neat fuel in both optimised spark ignition engines and compression ignition engines. However. Today. by increasing the energy efficiency of engines and vehicles and thus reducing fuel consumption on a volume per unit distance travelled basis. or blending bio fuels with petroleum-based fuels for use with present vehicle fleets. An important step in efforts to solve the problem is to replace fossil source energy with bioenergy. and increasing. mostly gasoline and diesel oil in road transportation systems. 1. mutually exclusive. Probably the best candidate bio fuels to replace gasoline in the short term are alcohols. In spite of ongoing activity to promote efficiency. The carbon dioxide emissions originate mainly from the use of fossil fuels. blending bio fuels with petroleum-based fuels for use by the present conventional vehicle fleets has the advantages that even using quite low blending concentrations will result in substantial total volumes of gasoline being substituted by bio fuels. In Sweden this sector accounts for roughly 20 % of total energy consumption. INTRODUCTION Background A challenge that humanity must take seriously is to limit and decrease the greenhouse effect caused by various human activities. As transport levels are expected to rise substantially. In the medium term ethanol produced from grain will probably be * Approx 30% according to the Annual Report of Greenhouse Gas Emissions from the Swedish EPA. this means bio-based fuels. the sector is still generating significant increases in CO2 emissions. of which carbon dioxide is particularly important. Furthermore. 2002 .

it can be assumed that they mainly included vehicles with efficient emission control systems. follows the development. identified data as well as yet undocumented experience concerning emissions when using ethanol blended gasoline. almost all the alcohol fuel used is ethanol and it has three main uses in Sweden: as neat ethanol in ca 400 buses. thereby reducing dependence on imported petroleum. such as increasing the octane value of the fuel and reducing the benzene content of the exhaust gases. Be easily mixed with gasoline. established in 1974. but some studies were carried out on ethanol-gasoline blends. especially in Brazil. The first ISAF-symposium was organized in Stockholm 1978 and since then a symposium has been organized every 2 to 4 years. Assessing what (if any) emission studies are needed to estimate reliably the effects of using ethanol blended gasoline on total emissions. It should also be noted that for a long time 10% ethanol has been added to commercial gasoline in many parts of the USA. . Today. Be used (and already is on a wide scale) as an oxygenate in gasoline. This means that the most common alternative fuel used in Sweden is ethanol. Create new jobs in the country related to its production. but at the same time technical features of cars in the USA have historically differed. the USA and Sweden. The primary advantage of adding a biobased alcohol to gasoline is that it reduces net CO2 emissions but it also has other positive effects. The goal for the future is to increase the amount of domestically-produced ethanol from cellulose (ligno-cellulose) and one step toward this goal is research to be carried out at a pilot plant. Be produced domestically. in a gasoline blend (E85) for Flexible Fuelled Vehicles (FFVs). from those in Sweden. The use of alcohol blended gasoline and neat fuel alcohols as substitutes for neat gasoline have become matters of interest in many countries. The goals of the project presented in this report are to accumulate the data required to facilitate increased use of bio fuel by: • • • • Studying available literature.’ From an international perspective. at least in part. both qualitative and quantitative. and as a component of all of the other gasoline (E5) used throughout the country. Only approximately 65 000 m3 (50 000 m3 from wheat and 15 000 from cellulose) of this alcohol is domestically produced and at the time of writing around 165 000 m3 is imported from Brazil. The International Energy Agency (IEA). Measuring evaporative emissions from the combustion of different blends of ethanol and neat gasoline. ethanol accounts for a substantial part of the alternative fuel market. In the USA there is considerable experience of adding higher proportions of ethanol to gasoline than those allowed by gasoline regulations in Sweden (Europe). Evaluating the relevance of existing investigations and the data generated in them. and data and other experience from various trials have been presented and discussed at symposia organised by the International Symposium on Alcohol Fuels (ISAF).Page 7 the most important alternative fuel for replacing gasoline. Today. The advantages of ethanol are that it can: • • • • • Provide a viable alternative to reduce the greenhouse effect. Since these studies were carried out in the USA. of which approximately 17 000 were being used in Sweden in February 2005. collected knowledge. and in the long term ethanol produced from cellulose might take over from grain ethanol. most research up to 1990 was focused on blends of methanol and gasoline.

Of these “Ratio Blending” is designed for use when up to six components are to be blended. Launder. In Figure 1.4 %. According to these calculations. In his MSc thesis Launder described the development of the use of fuel alcohol. how and to what extent ethanol in gasoline may affect the materials in the vehicle and cause excessive wear of parts in the fuel system and the engine. Amongst other salient facts noted by Launder “Minnesota has also passed legislation requiring the use of 10% ethanol in all gasoline”. a mixture of 85 % ethanol and 15 % gasoline. albeit somewhat less so than methanol.Page 8 1. There is still debate about whether. Sweden (5 %) and the USA (up to 10 %). More sophisticated blending technologies such as Ratio Blending. Since methanol can be produced from natural gas at no great cost. especially the use of ethanol in the USA. “Sidestream Blending” is similar to ratio blending and is used when two or more components are to be mixed together and “Wildstream Blending” can be used when blending ethanol with gasolines of many different qualities simultaneously. when oil supplies were reduced and a search for alternative energy carriers began in order to replace gasoline and diesel fuel. Since both methanol and ethanol have considerably lower energy contents (15. Alcohol Blended Fuels The idea of adding low contents of ethanol or methanol to gasoline is not new. However. The interest in producing an alternative fuel based on biomass has also been a major factor in the early choice between methanol and ethanol. as shown in section 8. in the USA. such as plastic components and even metals in the fuel system. inter alia. A lesson learned was that new.7 MJ/l and 21. In section 6 the calculated effects on the energy content of the fuel of blending ethanol with a specific gasoline are presented. since even ethanol can be characterized as an aggressive fluid.2. and is quite easy to blend with gasoline. respectively) compared with gasoline (approximately 35 MJ/l) use of an alcoholcontaining blend may affect the power output of the engine to varying degrees. 2004. extending back at least to the 1970s. Sidestream Blending and Wildstream Blending are described and discussed in a paper by Toptech (2004). this alcohol was seen as an attractive additive. the increase in vapour pressure is considerably larger when blending methanol than when blending ethanol. more resistant materials had to be used in the fuel system of the vehicles as well as in the distribution system. Brazil (up to 25 %). “Sequential Blending” of ethanol in gasoline means that the two components are pumped to the delivery truck in sequence. methanol was considered the most attractive alcohol to be added to gasoline. depending on its design. . Initially. 2001).4 MJ/l. The use of E85. Blends with other percentages of ethanol in gasoline are commonly used in various countries around the world. when using methanol in practice it became clear that precautions had to be taken when handling it and that methanol is aggressive to some materials. Blending alcohol in gasoline will affect. Even if it is computer controlled there are some uncertainties about whether the resulting mixtures will fulfil their specifications. especially Australia (officially 10 %). car manufacturers have agreed that use of gasoline with up to 10 % ethanol will not affect the warranties of their vehicles (Science Fair Projects Encyclopaedia.1 the configuration of Sidestream Blending is shown. These experiences were also of great value when ethanol came to be more commonly used as an alternative to the commercial fuels. However. the vapour pressure of the fuel and. for FFVs has become common. adding ethanol to a final volume of 10 % to a gasoline with an energy content of 32. Canada (10 %).3 MJ/litre will decrease that value by 3. The alcohol is commonly added to gasoline when filling the tank of the vehicle that will deliver the fuel to the gas stations.

areas of the country where air pollution levels persistently exceed the national ambient air quality standards.5 73.1.8 145.6 IBP 36. 2. i.0 181. At least five major reasons for blending ethanol in gasoline are discussed. Reduction of net carbon dioxide emissions.736 0.3 86. Using the blended fuels reduces brake specific energy consumption.741 0.5 . including the following advantages of using ethanol as an alternative fuel: 1. 4. Fuel properties of ethanol gasoline fuel blends (He et al.1 selected fuel properties for a neat gasoline and ethanol blends with the neat gasoline are shown. also important to use cost-efficient methods. It is.2 82. RON and MON numbers and the IBP (initial boiling point) of the blended fuels increase as ethanol contents increase.2 49. The need to reduce the dependence on imported fuels.7 149.0 52. The need (especially in the US) to improve the air quality in non-attainment areas. 90 % and FBP (final boiling point) decrease.2 72.7 MON 81.5 40.751 Density at 19°C RON 92.4 95.0 10% 55. To create new jobs in the country by national production of ethanol.5 181.1.0 99. Density.0 37.e.7 FBP 184. while 10 %. Configuration of “Sidestream Blending” Since there are concerns related to the fact that ethanol is readily miscible with water it is important to use water-free systems when blending ethanol in gasoline. to mitigate global warming. 2003) Fuel parameters Neat gasoline E10 (10 % ethanol) E30 (30 % ethanol) 0.Page 9 Figure 1. Table 1. The need to replace petroleum fuels with a renewable fuel 3. In Table 1.. 5.5 90% 153.7 50% 92. of course.

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2.
2.1.

THE USE OF ETHANOL IN DIFFERENT COUNTRIES
Prerequisites for the Literature Study

When the parameters of the literature survey for this project were considered it soon became apparent that the foci should be on the influence of adding ethanol on the vehicle and emissions (and thus its effects on the environment, air quality and health). Consequently, it was concluded that the following subjects should be examined during the search and discussed in the report: • • • • • • Vehicle performance/wear. Fuel. Vapour pressure. Emissions. Air quality and health effects. Life cycle analyses.

2.2.

Fuel Ethanol in Sweden

Two sets of standards for fuel ethanol are presented here, one of which was developed by a small quantity ethanol producer in Sweden and one by the American Society for Testing and Materials (ASTM) as an industry standard. The Swedish producer of ethanol, Svensk Etanolkemi AB (SEKAB) has presented specifications for fuel ethanol to be used when blending ethanol with gasoline, see Table 2.1 (SEKAB, 2004). The oil crises of 1973 and 1976 prompted a search in Sweden for alternatives to gasoline for light duty vehicles and a project was initiated to study the possibility of replacing some gasoline with an alcohol. Since a governmental investigation had been launched in 1965 in order to study an introduction of emission regulations it was also seen as the use of an alcohol blended gasoline could be one measure to reduce especially the emission of CO To address practical issues associated with introducing an alcohol-based fuel a wide-ranging study was organized by the Swedish National Board for Technical Development (STU). Initially, this work was carried out by a small company named the Swedish Methanol Company, since it concentrated on the use of methanol as an additive to gasoline. Later, ethanol and other potential alternatives were included in the project and Sweden also became a member of the International Energy Agency (IEA). The company carrying out the work was then renamed the Swedish Motor Fuel Technology Co. (SDAB). The work within the project included both laboratory and field tests. The results of laboratory investigations and field trials that had been carried out in various locations around the world were reported to the IEA in 1986 by STU and SDAB. (STU, 1986;1987). The countries that helped prepare the report were Canada, Japan New Zealand, Sweden and the USA. A great deal of valuable experience concerning the use of alcohol and (especially) alcohol blended gasoline was gathered during this co-operative assessment of alternative fuels. However, at this time Brazil was the only country in the world that was focusing on ethanol as an alternative to gasoline.

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Table 2.1. Sales specification of technical ethanol 99.5% SPSE-Ethanol 99.5% 3 4 1 (1) 2004-11-03 SPSE-410. Limit Method of analysis Parameter Ethanol % by volume min 99.8 ASME 1112 % by weight min 99.7 Density (D 20/4) g/ml max 0.790 SS-ISO 758 Appearance Clear, without particles ASTM D 2090 Colour Hazel max 5 AMSE 1102 Water % by weight max 0.3 SS-ISO 760 Aldehydes (as acetaldehyde) % by weight max 0.0025 AMSE 1118 Acidity (as acetic acid) % by weight max 0.0025 AMSE 1114 Fusel oil mg/l max 50 AMSE 1107, GCmethod Methanol mg/l max 20 AMSE 1107, GCmethod Distillation interval*: ASTM D 1078 - starting point min 77 °C - drypoint max 81 °C Flashpoint* +12 SS-EN 22719 °C Explosion limits* % by volume in air 3.5 - 15 Accepted from literature Refractive index* 1.3618 Accepted from nD20 Literature Evaporation residue* mg/l max 10 AMSE 1124 *The seller guarantees these properties, although they are not tested on each delivery. During the 1980s the focus of investigations and trials with alcohol fuels in Sweden switched to ethanol, both as an alternative for diesel oil and as an additive to gasoline. At this time the main rationale for introducing an alternative was to reduce exhaust emissions. Since the introduction of emission control systems with catalysts for gasoline-fuelled vehicles had efficiently reduced exhaust emissions, most of the research on alternative fuels in Sweden during the 1980s and 1990s was related to diesel-fuelled vehicles. Several comparative reports on different fuels, including alcohol-gasoline blends, were prepared, and the most comprehensive investigations are summarised and discussed in the following text. In Sweden ethanol is currently used in the following three forms: 1. Blended in gasoline to a volume of 5 % according to the Swedish Petroleum Institute (SPI). 2. E85 in Flexible fuelled vehicles (FFVs). 3. E100 (including an ignition improver and other additives) for use in ethanol-fuelled buses.

2.3.

Fuel ethanol in the USA/California

In the year 2000 the projected consumption of gasoline in the US was 127.568 milliard US gallons (468.897 million m3), of which E10 accounted for 908.700 million gallons (ca 3.440 million m3) and the consumption of MTBE in gasoline amounted to 2.1115 milliard gallons (ca 11.780 million m3) according to the US department of energy (Yacobucci and Womach, 2000), see also Table 2.2. Since MTBE blending will be out by the end of 2005 according to MathPro (2002) there will be a need to increase the use of ethanol blended gasoline. According to

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MathPro “The mandate volume would increase on an annual schedule, reaching 5 billion gallons per year (bgy) in 2012” of ethanol. Thereafter, annual mandate volumes would be set to maintain the percentage share of the U.S. gasoline pool that ethanol held in 2012”. Table 2.2 Estimated US Consumption of Fuel Ethanol, MTBE and Gasoline (Thousand Gasoline Equivalent Gallons), (Department of Energy,1998). 1994 E85 E95 Ethanol in Gasohol (E10) MTBE in Gasoline Gasolineb 80 140 845 900 2 108 800 113 144 000 1996 694 2 699 660 200 2 749 700 117 783 000 1998 1,727 59a 916 000 2 915 600 122 849 000 2000 (projected) 3,283 59 908 700 3 111 500 127 568 000

The US Renewable Fuels Association (RFA) has presented industry guidelines for the use of ethanol in the American market and according to the Association the guidelines represent “a compilation of the key technical aspects of fuel grade ethanol use based on the collective experience and expertise of our member companies” (Renewable Fuels Association, 2002). The following industry standard is valid as the industry standard for fuel ethanol to be blended in gasoline to any rate in the USA, Table 2.3. Table 2.3. Industry standard for fuel ethanol to be blended in gasoline in the US. ASTM 4806 Property Specification ASTM Test Method Ethanol, vol% 92.1 D5501 Methanol, vol% 0.5 Solvent-washed gum, mg/100 ml max 5.0 D381 Water content, vol%, max 1.0 E203 Denaturant content, vol%, min 1.96 Denaturant content, vol%, max 4.76 Inorganic chloride content, mass ppm (mg/L), max 40 (32) D512 Copper content mg/kg, max 0.1 D1688 Acidity (as acetic acid, mass-% (mg/L), max 0.007 (56) D1613 pH 6.5 – 9.0 D6423 Appearance Visibly free of suspended or precipitated contaminants (clear & bright)

In the cited report the RFA gave certain recommendations and discussed a number of effects linked to the use of ethanol blended gasoline. The producers of ethanol and member companies of the RFA were recommended “to add corrosion inhibitors to all of their fuel grade ethanol at a treat rate to provide corrosion protection” comparable to the treatments applied to fuels such as neat gasoline

few reports on measurements of emissions obtained when using ethanol blended gasoline have been found. Ford and GM were in favour of the E10 (gasohol) and they stated that its use would be covered in their vehicle guarantees. 2002) the blending research octane number (RON) of ethanol is 129. Performance tests were carried out when using different percentages up to 40 % of ethanol in gasoline. including its octane number. and thus improves the performance of the vehicle. In the paper from RFA it is stated that the octane numbers (R+M)/2 will increase by 2 to 3 units. Progress towards the use of alcohol-gasoline blends as fuels has been underway since at least the 1970s. however. The Clean Air Act of 1990 mandated the use of reformulated gasoline (RFG) in certain areas of the USA to ameliorate air quality problems. During an experimental investigation of ethanol blends in gasoline AbelRahman and Osman found that the maximum engine indicated power improvement occurred with a 10 % ethanol blend when adapting the compression ratio of the engine to the fuel AbelRahman and Osman. Since fuel ethanol has a higher octane number than gasoline it may well be true that adding ethanol to gasoline increases the octane number. Since the environmental protection authorities also favour the use of ethanol blended gasoline it has became common in US to blend 10 % ethanol in commercial gasoline. but in the cited paper from RFA (Renewable Fuels Association. An issue that should be addressed is whether (and if so. A further recommendation is to “wear safety goggles when handling ethanol” Renewable Fuels Association.0 and the blending motor octane number (MON) 96. and here too opinions differ. (1997). Further valuable information on many aspects of using alcohols in gasoline can be found in literature from the USA/California. a move that was subsequently followed by almost all manufacturers. such as high ozone levels. to what degree) the octane numbers will increase when blending ethanol in gasoline. the RFA recommends that ethanol should be handled “with the same safety precautions as gasoline” and that sparks and flames should be avoided when handling ethanol. In the 1980s three additional Acts were passed that promoted production of ethanol from corn. However. and Procedures. according to a report by Launder (2001). inter alia. Unfortunately. exempting 10 % ethanol-gasoline blends from the 4% gallon tax on motor fuels applied at the time.Page 13 According to the RFA adding ethanol will affect several properties of gasoline. water solubility and oxygen content (the oxygen content of ethanol is approximately 33 % by weight). The Arab countries’ embargo in the 1970s against the USA was the main factor that initially prompted use of alcohol fuels (ethanol and methanol) as substitutes to compensate for the resulting drop in gasoline supplies. where experience in their use (especially ethanol) and test data (both laboratory and field based) have been gathered over a long time. 2001). volatility.0. It should be noted that the big automobile manufacturers Chrysler. and the use of oxygen blended fuel in areas with high levels of carbon monoxide during the winter. In addition. a guidebook released by the US Department of Energy (DOE) recommends that skin and vapour contact with E85 should be avoided and that ethanol-resistant gloves should be used (US Department of Energy. Specifications. Maintaining the safety of the working environment is an important issue when working with automotive fuels. 2002-2005). The octane numbers of ethanol quoted in various reports and other data sources differ. there is considerable uncertainty about the extent to which the engine power will improve and whether this improvement will occur across the whole range of ethanol contents in gasoline. In order to meet the demand for ethanol as a . Chevron has also reported that ethanol has a “Blending Research Octane Number (BRON)” of 129 (Chevron. In its Industry Guidelines. and these measures were reinforced by a “blender’s credit” of 40 cents per gallon. (2002). An Energy Tax Act was passed.

The Clean Air Act should authorize any State “for which a waiver is in effect to impose control of any fuels and fuel additive for the purpose of water quality protection.4. The State Governor should be authorized. (3) to complete a model which reflects the effects on the emissions that are related to the characteristics or components of the fuel used during 2005. the EPA has argued that no waiver should be applied. 1993). The Act eliminates the waiver that allows higher RVP limits for ethanol blended gasoline. The amendments require the Administrator to: (1) carry out tests in order to evaluate health and environmental effects of the use of fuel and fuel additives.Page 14 blending component a 1-psi waiver in the permitted vapour pressure parameter (RVP) has been allowed for ethanol-gasoline blends. which may in worst case scenarios result in enhanced levels of ozone (US EPA. Furthermore. This “Requires regulations to: (1) ensure that toxic air pollutant emissions reductions achieved under the reformulated gasoline program are maintained in such States. At the end of 2001 “A bill to amend the Clean Air Act to address problems concerning methyl tertiary butyl ether. Therefore. and for other purposes” was introduced to the US Senate concerning reformulated fuel. as can be seen in the following quotation: “EPA believes that ethanol can and will play an important role in reformulated gasoline without a 1. welfare and the environment and inspections of underground tanks should be carried out. The Act also authorizes “grants to MTBE merchant producers to assist in conversion of production facilities to the production of other fuel additives. “upon notification” of the EPA Administrator. .0 psi waiver. In a summary of the bill the following seven amendments (abbreviated here) were recommended to the Senate: • Actions should be taken concerning the leakage of MTBE from corrodible underground tanks. tests should be carried out in order to study the effects of using MTBE and other ethers which may be used to replace MTBE. “to waive oxygen content requirements for reformulated gasoline other than those regarding oxygen content to be reformulated gasoline”. and that granting such a waiver would therefore be unreasonable” (US EPA. “Allows State implementation plan revisions that apply conventional gasoline prohibitions to non classified areas”. Authorizes appropriations” (US Senate 2001). Fuel Ethanol in Japan It has been difficult to find information on investigations carried out in Japan concerning the introduction and use of ethanol in either neat or blended forms. Another is that the few relevant reports that have been found have nearly all been written in Japanese. although it has been shown that ethanol will raise the vapour pressure of the fuel. (2) to publish analysis showing changes of the air quality resulting from implementation of the Act. which represents a risk for public health. • • • • • • 2. 1993). Requires the Administrator of the Environmental Protection Agency to ban the use of MTBE in motor fuel within four years of this Act´s enactment”. An increase in vapour pressure has been shown to increase the emissions of VOCs (volatile organic components). One reason for this is that interest in ethanol has been low in Japan. and (2) establish performance standards”.

the program that initially introduced the use of ethanol as an automotive fuel in Brazil started in 1974 “as a consequence of the oil crisis”. China. according to some unconfirmed reports and personal communication with Jan Lindstedt. The Swedish Bioalkohol fuels Foundation. An important benefit of the program is that it has provided stable employment for approximately 500 000 workers in the sugar cane plantations and similar numbers in the alcohol/ethanol production industry and other activities connected to the use of ethanol fuels such as transportation. Ministry of Mines and Energy. Sugar cane plantations introduced by the Portuguese in the 16th century were. and still are. In recent years Japan has also shown increasing interest in so-called synthetic fuels. the Ministry of Industry and Commerce. However. the automobile industry. the fuel distributors. Thailand and Australia. BAFF. PETROBRÁS (state owned oil company). . A certain amount is also exported to Sweden and blended in gasoline. and the gas stations. There have also been considerable benefits in terms of greenhouse gas reductions since ethanol produced in Brazil is exported to and used in many countries. 2. According to this paper.5. Japan. blending etc. One of the main requirements linked to the introduction of PROALCOOL was that there should be close coordination amongst the authorities and other parties involved. Japan has started to introduce ethanol and is currently planning to increase its use. such as methanol and DiMethyl Ether (DME). namely “the Ministry of Agriculture and sugarcane planters. the automobile owners”. There was also a requirement that subsidies should be used to stimulate the production of cars to be run on alcohol.Page 15 However. especially India. Japanese interest in alternative fuels has been concentrated for many years on natural gas or liquid fuels that could be produced from natural gas. In the last few decades methanol has been the main Japanese alternative to gasoline. the Ministry of Science and Technology and research centres. used as sources for the ethanol production. the Ministries of Finance and Planning and. Fuel ethanol in Brazil In a paper released by the Brazilian embassy in India information about the national program for fuel alcohol in Brazil (PROALCOOL) can be found (Brazilian Embassy. such as paraffin (synthetic diesel) and (to some extent) alkylate (synthetic gasoline) fuels produced from natural gas (and maybe in the future from gasified biomass) by the so-called Fischer-Tropsch technique. 2002). and the relaxation of tax on industrialised products is seen to have been effective in this context. last but not the least.

. Growth in ethanol production (anhydrous and hydrous) in Brazil from 1975/76 to 2003/4.Page 16 . about 40 % are passenger cars and in total the 4. today more than 4. He noted that two types of ethanol fuels . Unfortunately.are produced under Brazilian regulations.98 %) .2 million cars are ethanol-powered according to data and information presented by Online TEFL. the effects that ethanol-gasoline blends with up to 25 % ethanol contents have had on the drivability. However. According to Szwarc. Of these. deterioration and wear of vehicles and last (but not least) the emissions and air quality in urban areas are not clear. as shown in Figure 2. the use of ethanol as a blending component has increased over the years and the content of ethanol in Brazilian gasoline blends has increased from 4. Anhydrous ethanol can be blended with gasoline up to 25 % by volume while hydrous ethanol is used either as a neat fuel or blended with gasohol (see section 13 for the definition of gasohol) for use in FFVs (Szwarc.5 % by volume in 1977 to 25 % in 2002.2 million vehicles annually consume approximately 14 million m3 of ethanol (Ethanol Curriculum Online TEFL Module 5. ethanol content 99.anhydrous (min.1. Therefore. Figure 2. 2005). few papers prepared in Brazil and written in English have been found.2.13 – 95. 2004).58 %) and hydrous (ethanol content 95. In a workshop on Mitigation (SBSTA 21/COP in December 2004 in Buenos Aires Alfred Szwarc (a consultant at the Ministry of Science and Technology) described Brazilian experience with fuel grade ethanol.

1977-2002 (Szwarc. . and when launching the program it was also said that “China may soon become an ethanol industry leader. Changes in the maximum ethanol content of ethanol-gasoline blends in Brazil. Fuel Ethanol in East Asia In addition to Japan several other countries in East Asia.. China In 2001 the Chinese State Development Commission launched an ethanol program and after careful consideration issued quality standards for denatured ethanol and ethanol blended gasoline.Page 17 % 30 25 20 15 10 5 0 BRAZIL: MAX PRECENT ETHANOL IN GASOLINE OVER TIME 1977 1979 1981 1985 1998 1999 2002 YEAR Figure 2. 2004). including China. This emphasises one of the reasons for the large-scale introduction of ethanol. In the same year Beijing (China) also organised a World fuel ethanol congress (2001). It is well known that there is an urgent need to improve the air quality in China. are investigating the effects of using ethanol blended gasoline on the environment. CO: Higher reduction in older E100 (up to 70%) and gasohol (up to 40%) vehicles in comparison with ethanol-free gasoline”.. “Vehicle Emission Reductions Related to Fuel Ethanol Use in Brazil: • • • • • Lead additives banned since 1990. 2. These countries have good opportunities to start ethanol production on varying scales. VOC´s with lower toxicity & photochemical reactivity.2. India and Thailand. especially in Beijing. and when it launched the program the Chinese government announced that “China plans to spend nearly $12 billion on a program to cut smog and pollution in Beijing by 2008. No actual data from emission tests in Brazil have been found. vehicles and other issues.” The program for the Congress also indicates that this event was considered a platform for initiating use of ethanol as an automotive fuel on a broader scale (Beijing World Fuel Ethanol Congress 2001). Reduction of PM (carbon and sulfate particles).6. but the following observations were made by Szwarc (2004) at the workshop in Buenos Aires. Reduction of SOx.

Saving of around 20 m3 of scarce gasoline. northeast China (Beijing Times. The test fleet included 93 vehicles and comprised cars.000 yuan (US$3.787 milj km. No adverse effect on engine oil. Bhanot and Chaudhari. there was a considerable shortage of oil and sharp rises in crude oil prices in the 1970s. These five cities are Zhengzhou. 2002).. according to the available literature considerable activity is now underway. 2002). all vehicles carrying a licence plate starting with “Yu A” have to use ethanol-based fuel according to an order by the Zhengzhou Municipal Government. Luoyang and Nanyang in Henan province and Harbin and Zhaodong in Heilongjiang province. 2001). but in another paper it is said that ethanol will be blended with lead-free gasoline in a 1:9 ratio (US Commercial Service. Based on recommendations by a committee for the development of alternative fuels for motor vehicles. 2003). Otherwise. 1994). plans have been developed to use ethanol-gasoline blends (Uppal. vehicles logged 1.Page 18 In China ethanol is commonly produced from corn and sorghum (Nan et al. trials were carried out in New Delhi in 1991. prompting interest in fuel ethanol. Winrock International India* initiated the formation of * Winrock International India (WII) is a non-profit organization working in the areas of natural resource management. 2003). In addition. According to the Beijing Times. China is “pushing” the use of ethanol as fuel by constructing a plant in the Henan province that will produce 300 000 tons of fuel per year (Beijing Times. In the province of Liaoning new regulations state that car owners must use ethanol as a fuel for their vehicles. The results of the field trials are summarised in the following quotation: • • • • • • “93 Delhi Admn. 2002). In India too. In order to force motorists to use fuel ethanol. 2004).600) since "Ethanol fuel can play an important role in easing consumption of traditional petrol and protecting the environment" according to the Liaoning Development and Reform Committee (People’s Daily. According to the specifications set by the Bureau of Indian Standards for Gasoline up to 5 % ethanol can be blended with gasoline (The Gazette of India. There seems to have been a lull in the development of fuel ethanol in India during the 1990s. Cooler and smoother operation of vehicles.. India In India. like other countries around the world. . 2002a). and even ethanol-diesel oil blends (Acharya et al. Overall fuel economy is comparable with neat gasoline operation” (Malhotra. The specification of “ethanol-based fuel” is not clear. If they do not switch to ethanol they will be fined between 5. Since the authorities in India found that the agriculture sector needed support and that air quality had to be improved the Ministry of Petroleum and Natural Gas Resolution started to examine issues related to the introduction of ethanol blended gasoline. Reduction in CO and HC emissions. vans and jeeps. However. clean energy and climate change. this should be changed to ‘The Beijing Times has also reported that China is promoting the use of ethanol-based fuel in five cities”.000 yuan (US$600) and 30. A headline in the Beijing Times also stated that “China Promotes Ethanol-Based Fuel in Five Cities”. 2002. The fuels used were blends of 5 % and 10 % ethanol in gasoline.

the ethanol production capacity in Australia amounted to 135 000 m3. by building three new production plants. 2001). There are plans to increase the production capacity of fuel grade ethanol incrementally by about 270 000 m3. including sugar cane. Fuel Ethanol in Australia In a literature review prepared by the Orbital Engine Company (2002a) for Environment Australia it is reported that the first Australian examination (“trial”) of a blend of ethanol (15%) in gasoline was carried out from 1980 to 1983. 2. In addition a number of relevant papers reporting investigations and other activities in Thailand have been found in Internet searches. in total.Page 19 an “Ethanol Coalition of India” in 2000 to promote the development of fuel ethanol (Mishra. 2002). production of ethanol from bagasse and rice straw has been studied by Siwarasak and Wirivutthikorn (2002). In November 2001 the RFA reported that the Government of Thailand had approved the use of a 10 % ethanol/gasoline blend in order to increase the production of ethanol in the country.. In 2004. some of which gave information on the development of fuel ethanol production in Thailand. 2004) and sweet sorghum (Thanonkeo et al. where it is stated that "The major automobile manufacturers have advised my Department that they accept the use of 10 per cent ethanol blends and that such blends will not affect vehicle warranties. Thailand In the autumn of 2002 Thailand hosted the 14th ISAF International Symposium on Alcohol fuels. About 30 – 35 000 m3 was exported for other purposes and the rest was used domestically. This is also reflected in a paper presented by Dr. entitled “The Role of Alcohol Fuels in Meeting the Energy. 2003) According to the paper and other reports from Australia there is interest in blends with higher alcohol contents." (Ministry for the Environment and Heritage. molasses and cassava (Ethanol Industry in Thailand. The scope for producing ethanol from sweet sorghum has been investigated via a process presented by Thanonkeo et al . At this symposium many papers prepared in Thailand were presented. 2002). around 55 000 m3 was used for blending with gasoline. since the American car manufacturers agreed to accept a blend of up to 10 % ethanol in gasoline without changing the warranty conditions of their vehicles. Of this. It has also been reported that there is an attempt in Thailand to replace MTBE by ethanol (World Association of Beet and Cane Growers. In addition. 2003. There was then a long time lag to the second trial. According to the literature there are five or six main potential sources of ethanol in Thailand. An interim production target will be half of this . The 10 % figure seems to have been related to the situation in the USA. 2001). One reason why the government wants to increase the content of ethanol in gasoline is the need to be less dependent on imported oil and to promote the use of domestically produced energy carriers (Renewable Fuels Association. but not as an automotive fuel. Kemp (the Australian Minister for the Environment and Heritage).7. The main results from these tests have been presented in comprehensive summaries in the cited reports. and investigations have been carried out with blends of up to 20 % ethanol in gasoline and some conclusions from these investigations will be discussed below (Orbital Engine Company. which was conducted in the years immediately preceding 1998 with a 10 % blend of ethanol in gasoline. 2004). One way to stimulate this replacement is seen to be a plan to decrease the excise tax on ethanol mixtures. Environmental and Economic Needs of the 21st Century”.

ethanol is produced from sugarcane and wheat. In September 2000 a paper entitled “Setting National Fuel Quality Standards” was released by the Natural Heritage Trust on the “Proposed Standards for Fuel Parameters (Gasoline and Diesel)” and the “Revised Commonwealth Position”. 2004). and the policy of labelling ethanol blends at the gasoline pump. to allow the continued use of a 10 % ethanol-gasoline blend already available on the market.Page 20 amount. but the possibility of using other feedstocks (such as barley. NRMA. 2002. Environment Australia published a paper entitled “Setting the Ethanol Limit in Petrol” which officially invited the public to send in their views on the limit for ethanol blends in gasoline (Environment Australia. 2000). The outcome of these discussions prevented Environment Australia (and thus the Government). The discussion about fuel ethanol in Australia has heavily focused on two issues: future gasoline quality standards and labelling of the gasoline pumps. for NRMA showed that 10 % ethanol could be accepted.7 %. various gasoline suppliers and the insurance company NRMA* (which covers cars inter alia). NRMA. but the use of a 20 % blend led to increased wear (see section 3. However the production of 270 000 m3 of ethanol. (Boswell. Today.1. The proposal by the Commonwealth was that an exemption should be made for ethanol so as the standard could be the following when referring to “Summary of revised Commonwealth proposal for fuel quality standards” where the specification for gasoline is: “Oxygen content: 2.e. 2002a. Noting the Commonwealth position. welcomed the opportunity to use gasoline with that of blended ethanol. 2003) and found that there could be problems with higher alcohol contents. i. in fact. 2003). The AAA says that they support ethanol contents in gasoline of up to 10 %. After years of discussions. in which representatives of the petroleum industry. as proposed in the standards for gasoline. less than the 360 million litres required to supply ethanol for an E10 blend in Queensland alone. from allowing higher alcohol contents than 10 % in blends with gasoline. There is also interest in producing ethanol from other biomaterials. below). NRMA has also been conducting research on ethanol gasoline blends used in motor vehicles (Australia Automobile Association. lignocelluloses (Cheung et al. corn and sorghum) is discussed. 2002).7 % (max) with an exemption for ethanol blends up to 10 %” (Natural Heritage Trust. such as wood. A study conducted by Apache Research Ltd. One of the main positions taken by the Commonwealth was that the oxygen content in gasoline must be higher than 2. have been involved (the authors of this report conclude that NRMA is not willing to cover the risk for damage to cars that may be caused by a high percentage of ethanol in gasoline). All those who were strongly opposed to higher ethanol contents than 10 % supported the 10 % limit and. 2002. the Australian Automobile Association (AAA). The opinion of the NRMA has been that no higher ethanol content than 10 % should be allowed “until comprehensive research shows that it will not damage fuel systems and engines” (Australian Automobile Association 2002. * National Roads and Motorists’ Association ..

A background paper for “Setting a Quality Standard for Fuel Ethanol” has been prepared by Hart Downstream Energy Services (Hart Downstream Energy Services. The position of the AIP is that the introduction of ethanol under the government policy should be viable if the consumers feel confidence in its use as a fuel (Shell. 18 February 2005 (Department of the Environment and Heritage. Shell notes that the Australian Institute of Physics* (AIP) has been “taking positive steps towards achieving the Government’s [350 000 m3] target for bio fuels” by participating in various activities related to the further introduction of bio fuels. 2004a). Federal Government. In December 2003 BP announced that it will limit its marketing to a 10 % blended regular unleaded gasoline in Queensland after the middle of December 2003. contains more than 1% ethanol”. the AAA and NRMA obviously created pressure on Environment Australia and the Australian government since it resulted in the Minister for the Environment deciding to set a 10 % limit for ethanol blends in gasoline in April 2003. and the Department of the Environment and Heritage has invited stakeholders to send in comments by by close of business. The actions taken by the petroleum industry. In a second paper the standards for some of the fuel parameters are presented and in a third paper the labelling requirements are listed and it is stated that “If you sell an ethanol blend you will have to display a label” (Department of the Environment and Heritage.Page 21 2002a). including ethanol. admitted that ethanol blended gasoline fuels “have a role to play in Australia as a renewable fuel and as an octane enhancer” (BP. When delivering blended fuel from a pump the label must be displayed “as close as practicable to each nozzle that dispenses the ethanol blend and for retail supply special requirements are to be followed”. * . However. 2003a).3 a replicate of the label is shown. One of the papers states that “ethanol blends for the Australian market means gasoline that. 2004). and a statement that the ethanol blend is the subject of this standard” (Kemp. 2003). 2003). 2003. In Figure 2. It is also stated that “the ethanol blend may contain up to and including 10% ethanol. The decision taken by the Minister for the Environment is explained in papers released by the Ministry. 2004 and 2004a). Attorney-General’s Department 2004) has started. Australian Institute of Physics (AIP has gained recognition as a key representative body of Australia's petroleum industry). as tested in accordance with the Fuel Standards (Gasoline) Determination 2001. Dr George Nicolaides of BP. Early in 2003 BP announced that it had been delivering a 10 % blend of ethanol in gasoline. but was going to stop producing it since consumer confidence in ethanol blended gasoline was low (BP. Preparation of the position paper for the “Fuel Quality Standards Act 2000” (Office of Legislative Drafting. 2003a). 2003). He also announced that he was going to appeal to the State Governments to require labelling at fuel pumps delivering ethanol blends (Federal Government. In a paper presented in 2003.

Page 22 Figure 2. The Australian label for ethanol blended gasoline. .3. 2004a). (Department of the Environment and Heritage.

DATA AND EXPERIENCE Data and experience related to the use of ethanol blended fuels are presented and evaluated. the position of WWFC is that the level of 3. Vehicle Performance One of the objectives for this project is to find out whether it is possible to increase the content of ethanol in Swedish gasoline from about 5 % to a higher percentage without creating problems that would be unacceptable to the car manufacturers. The materials selected for examination were largely reports and other papers presented during the last 10 years. 2002.1. WWFC Comments. When examining reports dealing with blended fuel. 200) The response from WWFC is that the WWFC Committee selected a limit of 2.7 % as the general mass of oxygen in gasoline in order to assure correct operation of the engine. applied to web-sourced materials was to exclude all texts that were not in report format. experience and data obtained in empirical studies have shown that the use of ethanol contents up to 10 to 15 % in gasoline should not create any serious wear of the vehicle/engine. There is a WWFC requirement for using co-solvents and inhibitors when methanol is used. 200) . below. Papers from lobby organizations were also often excluded since they tend to be prejudiced and to present conclusions without giving sufficient information about the basic conditions and data on which the conclusions are based.5% (by mass) in order to allow a blend of 10% ethanol in gasoline (WWFC. since they provide information about decisions taken or to be taken and research that will be presented eventually. wear of the vehicles and vehicle performance it soon becomes apparent that opinions differ among those concerned with the use of ethanol and the impact on vehicles of using ethanol.5% oxygen content for ethanol blends in gasoline is too high. Data on air quality. When searching via the internet a great number of papers can be found. a footnote to this statement indicates that the Committee accepts the use of 10% ethanol in gasoline if the fuel conforms to the requirements set for the fuel. (WWFC. 2002. many papers from various authorities. are presented and discussed in two separate sections. but may influence drivability. 3. 4 and 5. so a second selection criterion. It should be noted that this project does not consider the production of ethanol. health effects and emissions linked to the use of ethanol blended gasoline. Due to the maximum oxygen level in gasoline WWFC do not allow an addition of 10% ethanol to gasoline which may already contain 2% MTBE despite the fact that this is allowed by US EPA. the supply and delivery of ethanol blended fuel or associated costs. universities and institutions have been of great value even if they have not been written in the form of a report. WWFC Comments. However.Page 23 3. A comment on World Wide Fuel Charter (WWFC) was that WWFC should increase the maximum oxygen content in gasoline to 3. cars owners and/or drivers. However. However. even if they were based on empirical studies. Furthermore.

a fuel with a certain level of an alcohol in gasoline. respectively. metallic parts of the fuel regulator diaphragm. a closed loop control system and runs on ULP (“unleaded petrol”) gasoline. and the PCV valve/spool showed corrosion and pitting. as closely as possible. 2004) • A Holden Commodore VN. However. vehicles designed to be fuelled with up to 85 % ethanol in gasoline. a three-way catalyst. of varying importance. which has an electronic fuel injection system. focusing especially on its effects on the durability of their components (Orbital Engine Company. Many reports and other documents deal with the use of ethanol. especially its starting and drivability at low temperatures. 1985 model.g. the fuel sender unit. pitting and tarnishing. The general view derived from studying the international literature is that blends with up to 15 % ethanol do not have any serious effects on the performance and wear of the vehicle. tarnishing and pitting. e. tarnishing and the plastic filters were discoloured. standard SAE protocols (J1748 for polymeric material. The fuel tank metal. including its effects on performance and wear. i. thus improving their start-ability and emission performance when used with ethanol-gasoline blends. which has a carburettor and runs on LRP gasoline. In the Science Fair Projects Encyclopedia (2004) it is said that both of the ethanol-gasoline variants “E10 and "E15". • • According to the Orbital report the tests followed. 1985 model. ongoing development of engines and control systems for the fuel and emissions have resulted in considerable improvements related not only to emission performance but also to drivability. due to sub-optimal operation of the vehicle’s emission control systems during the time lag until the engine and catalyst reach the normal temperature for a continuously running engine. but the most extensive reports focus on flexible fuel vehicles (FFVs). Car owner/driver acceptance of a new fuel. .Page 24 The Orbital Engine Company in Australia has carried out extensive tests for the Australian government on vehicles fuelled with ethanol blended gasoline. The results from the 2000 hour testing and evaluation program can be summarized as follows: • • • Metallic fuel system: various parts of the fuel system such as the fuel pump. Adding a higher percentage of an alcohol like ethanol may affect the performance of the vehicle. These effects on the engine and vehicle may also result in increased emissions. many significant steps have been taken in recent years which will reduce these problems. Concerning drivability: “The most important aspect of performance (other than starting) is acceleration. containing 10 % and 15% ethanol in gasoline. open loop control systems and runs on LRP (low vapour pressure) gasoline. A Ford Falcon XE. which has electronic fuel injection. 1990 model. Various parts of the carburettors and associated components of the carburettor-equipped car showed corrosion. A Holden Commodore VK. is highly dependent on the cost of the fuel and the performance of the vehicle. J1748 for metallic material and J1681 for material/component immersion testing). Although vehicle performance and wear of the engine and its control systems are linked to a number of different factors. and the fuel pressure regulator showed corrosion. A 20 vol% ethanol gasoline blend was used as test fuel. both from a stop and at highway speeds in order to pass” and is a vital issue for customers according to McLean and Lave (2002). are “generally safe” for common usage in automobile engines. the fuel injectors.e. Further advances may solve some of the problems concerning the cold start parameters of the engines.

and a fuel with extremely high vapour pressure may cause problems with hot start ability. of alcohols in gasoline do not cause problems during cold starts and the warming-up phase of the engine. In Sweden an engine heater is commonly used to improve the cold starts and warming up of the engine. The properties considered are fuel volatility. hot drivability and vapour lock. distillation properties. Cold Starts and Driving High levels of an alcohol (over 20 %) usually adversely affect cold starts and warming up in low temperature conditions since more heat is needed to vaporize alcohol than gasoline. 3.1. especially for modern vehicles (US Department of Energy. water tolerance and gasoline additives. 1996). and vapour lock protection index in six classes (according to ASTM D 4814).5 T10 + 3. It has been shown that later models of fuel injected vehicles are less sensitive to a reduction in T50 than older cars.0 T90 Vapour lock protection index: ASTM D 4814 defines six classes of vapour lock production.Page 25 3. but this does not seem to be a good alternative for ethanol-gasoline blends with low alcohol contents. Normally low levels.0 T50 + 1. Vapour pressure: This is a measure of “front end” volatility. Distillation properties: Ethanol in gasoline will reduce the T50 value of the fuel. vapour pressure.2.3. decrease the 50 % distillation point (T50). . oxygen content. Fuel volatility: Adding ethanol to gasoline will increase the volatility. calculated drivability index. and affect both the drivability index and vapour lock protection. One recommended for use with FFVs is a specially designed catalyst presented by the National Renewable Energy Laboratory (NREL). A key feature of the catalyst tested by NREL is that it is insulated with a “Variable-conductance vacuum insulation” (NREL. as shown in Table 3. as discussed in the paper. Impact of Fuel In the RFA (2002) paper the impact of adding ethanol to the base fuel on the physico-chemical properties of the fuel is also discussed. Another suggestion is to use certain additives in the fuel. The following paragraphs summarise the impact of adding ethanol on these variables. Drivability index: The drivability index is based on the relationship between the distillation temperature of the fuel and the cold start and warming up parameters of the vehicle. < 10 %. which may cause problems with older vehicles in warm weather. Several methods and devices are available to improve the cold start and emissions during the warming up period. 1991). The following formula can be used to calculate the drivability index (DI): DI = 1.

7 2. A salient issue to consider is whether a 10 % ethanol content in Swedish summer gasoline would meet the ASTM vapour lock protection standards. test method D 2533 is to be used for oxygenategasoline fuel blends. max 1 60 20 2 56 20 3 51 20 4 47 20 5 41 20 6 35 20 * At 101.1.1.2 (Renewable Fuels Association. The authors of this report strongly believe that adding 10 % ethanol to Swedish winter grade gasoline would not create any problems in meeting the ASTM vapour lock protection standards. volume % Fuel Oxygen Content. The definition according to the ASTM standard ASTM D 4814 is that the Vapour Lock Index.7 2. ORNL. In practice this is reflected in the fact that the RVP standards for winter and summer grade gasoline in Sweden are 95 kPa and 70 kPa. meaning that higher TV/L temperatures are required for summer grades of ethanolgasoline blends and lower TV/L20 temperatures are required for winter grade blends. ASTM D 4814 Vapor Lock Protection Class Requirements (Oak Ridge National Laboratory. Fuel ethanol content. which is more volatile would have a TV/L20 temperature of 35°C. The requirement for each of the classes is that the maximum vapour to liquid ratio formed at the test temperature (TV) must be at most 20 (Oak Ridge National Laboratory. 2002). and that the vapour lock class depends not only on the climate but also the altitude. The vapour lock protection index is defined as TV/L20. The procedure for estimating temperature-V/L may only be used for gasoline (ASTM D 4814e). as can be seen in Table 3. Ethanol content and oxygenate content in fuels. according to the ASTM standard ASTM D “is the ratio of the volume of vapour formed at atmospheric pressure to the volume of fuel tested in Test Method D 2533” (Renewable Fuels Association. The ORNL has presented two examples.) #The mercury confining fluid procedure of test Method D 2533 shall be used for gasoline-oxygenate blends.2. Test Method D 5188 may be used for all fuels.5 Since there are differences in the density of different grades of gasoline compared to the density of ethanol the final content of oxygen will vary if the blending volume is fixed to a certain volume. 2002). Vapour Lock Vapour/Liquid (V/L)*# Protection Class Test Temperature °C V/L. Table 3. which are more volatile. 2002).3 kPa pressure (760 mm Hg. 2002). weight % 5.Page 26 Table 3. As can be seen in Table 3.0 7. which would have a TV/L20 temperature of 60°C while class 6. as shown in the table. respectively.7 10 3. one of which is related to vapour lock protection class 1. Oxygen content: The standard for the oxygenate content in gasoline is set on a weight basis. .

1991). for storage tanks. those who are responsible for delivering and blending alcohols in gasoline are aware of the risks and consequences of contamination of alcohol fuels by water.. For ethanol-blended gasoline the RFA recommends that ethanol producing member companies should “treat their ethanol with a corrosion inhibitor to ensure that any final blend is properly treated for corrosion protection”. and at customer delivery points. such as detergent/deposit additives. However one of the recommendations is of great importance for those filling cars with ethanol blended gasoline. According to the RFA the water tolerance of blended fuels is temperaturedependent. However. while the water tolerance is 0. It is well known that the concentrations of formaldehyde and acetic acid are relatively high in the combustion gases when methanol or methanol-gasoline blends are used in a combustion engine. namely that: “When first converting to an ethanol program it is advisable to recalibrate meters . The impact of the water-ethanol phase on the engine is greater in a twostroke engine than in a four stroke engine.5 °C or more. since the risk for water contamination of the fuel is a potentially serious problem Chevron in the US has decided to use ethanol only in areas where appropriate terminal facilities (i. containing both ethanol and water. Methods for blending alcohols in gasoline are discussed in section 1. in order to ensure the quality of the blended alcohol-gasoline fuel (Chevron. the tolerance is lower at low temperatures. However. Formic acid and water vapour in the combustion gases during low temperature combustion of alcohols containing high percentages of water may oxidize metal components in the engine. According to the US DOE.Page 27 Water tolerance: It is well known that ethanol has affinity to water. during the combustion of ethanol or ethanol-gasoline blends.e. In a report prepared by Krause and finalized by Korotney the possibility of phase separation occurring in ethanol-gasoline blends contaminated with water has been discussed.3 % (v/v) water at approximately -12 °C (Renewable Fuels Association.. since water in the fuel can also adversely affect the start ability and driving performance of the engine. were it may combust in the engine. forms in addition to the gasoline and ethanol phase. The RFA has established recommendations for blending ethanol in gasoline. where ethanol is properly distributed) are available. In a two-stroke engine the ethanol-water phase will compete with the gasoline-oil mixture and reduce the lubricating ability of the lubricating oil. In a study of a blend of anhydrous ethanol and unleaded gasoline the wear was not found to be unusually high (US Department of Energy. for distribution. However. certain amounts of these gases are also formed. The possibility of increased wear of components in the engine is not the only risk. in addition to considerable amounts of acetaldehyde and acetic acid. water starts to remove ethanol from the gasoline and another phase. with 11 % water in ethanol a significant increase in the wear occurred. When phase separation occurs in a blend of ethanol in gasoline. for protecting pumps and meters. since the engine temperature was reduced. The acidity of the combustion gases in combination with the lubricating ability of the lube oil will significantly increase the wear rate. i. 2002).5 % water (v/v) at temperatures of 15.2.e. phase separation normally only occurs in the presence of liquid water in the ethanol-gasoline blend (Krause and Korotney. 2004). Gasoline additives: Various additives may be used in gasoline. However. A 10 % ethanol blend in gasoline will tolerate approximately 0. Many of these recommendations are certainly known by suppliers of ethanol blended fuels. 1995). so appropriate measures must be taken when blending ethanol with gasoline and during the distribution of ethanolgasoline blends.

(2001) state that several modelling studies predict that the presence of ethanol in gasoline will probably increase the BTEX (i. 1998). which are addressed in a number of reports.Page 28 after 10-14 days to ensure that the change of product has not caused any meters to overdispense” (Renewable Fuels Association. inter alia.3) of ethanol blended gasoline with neat gasoline. According to Prakash this is somewhat offset by the fact that adding ethanol to gasoline results in a higher volume of combustion gases. According to Deeb et al. Ethanol and gasoline octane numbers. Besides pollution from exhaust emissions there are also issues related to the handling of ethanol/gasoline blends. Neither the true extent of the potential increase nor the risks for leakage to the ground soil have been well characterised. benzene toluene. since the presence of an alcohol in gasoline will lean out the fuel. These effects have been discussed in other sections of the present report. 1998). ethylbenzene and xylene) plume from a leakage. In such cases the fuel will be more efficiently matched to the engine. Table 3. (2002) and Lovanh et al.e. Property Ethanol Gasoline RON 102-130 90-100 MON 89-96 80-92 (RON+MON)/2 96-112 85-96 Blending RON 112-120 90-100 Blending MON 95-106 80-92 Her essential message concerning the octane number is that the high octane rate of ethanol increases the value of the blended fuel.3. fuel economy and the water miscibility of ethanol are also discussed in the cited report (Prakash. The effects of adding ethanol to gasoline on fuel properties have been discussed by Chandra Prakash in a report prepared for Environment Canada (Prakash. for instance their storage in underground fuel tanks and the potential contamination of groundwater due to leaks. In addition there are indications in the reports that biodegradation of benzene is severely inhibited by the presence of ethanol. resulting in some loss of engine power. Additives compatible with the engine oil must be used in order to avoid deposits building up. . enleanment (which affects the cold start ability). but not the risk for deposits forming in the engine caused by cold starts at low temperatures. (2002) simulations indicate that the benzene plume is likely to increase by 16 to 34% in the presence of ethanol. She also points out that the higher octane number of the blended fuel confers advantages in terms of fuel efficiency for later models of vehicles since they are commonly equipped with knock sensors. which retard the ignition timing in the event of knocking. the advantage of using ethanol as an enhancer of the octane number of the blended fuel. Powers et al. She notes. which increases the pressure in the cylinder and thus increases the power efficiency by 1 to 2 percent. The negative effects of blending ethanol in gasoline in terms of increased volatility. The fact that ethanol has a lower heating value than gasoline may affect the performance of the vehicle. As an example she refers to a comparison (summarized in Table 3. 2002).

Professor Mathur (Delphi) has reported that he has completed a three-year trial on the road using approximately one hundred government vehicles. Ford no longer require the use of synthetic oil for the lubrication of engines designed to be fuelled with E85. and the maintenance . although blends with up to 25 vol% ethanol in gasoline have been used in Brazil for many years. When ordering replacement parts for an FFV make sure to let the dealer know you are fuelling with ethanol”.Page 29 3. Impact on Service and Maintenance A marked lack of wide-ranging. Impact of Lube Oil During the survey of the international literature no report was found that specifically recommended the use of special oil when driving vehicles with up to 10 % ethanol in gasoline. see under section 3. This is espeally tru for studies of later years models of vehicles. 2004).4. fuelling the vehicles and other issues (Mathur. 2004). 2002). Exceptions are the investigations carried out in Australia referred to in sections 2. according to information from the National Ethanol Vehicle Coalition. They also recommended that data should be gathered on the effects of fuel oxygenates to provide a knowledge base for the California Air Resource Board (CARB) (AAM/AIAM. However. One interesting observation is that analyses of samples of lubricating oils have detected no differences in comparisons of the use of ethanol blended fuel and neat gasoline. check the owner's manual or consult with the vehicle manufacturer to be sure that you are using the right engine oil. A question to consider is whether (and if so to what extent) components in the lubrication oil like sulphur and other chemicals will react with acidic combustion products. He claims that there has not been any problem related to aspects such as storing the fuel. those with 10 % or less of ethanol. If you are driving a (FFV). In a Vehicle Buyer's Guide for Consumers published by the US DOE the owners of FFVs are advised to check their service manuals to ensure that the right fuel oils are used (US Department of Energy. 1999). according to the National Renewable Energy Laboratory (NREL) car manufacturers have agreed to apply the same warranties for FFVs as those of vehicles being run on neat gasoline. i. No such recommendations from the US DOE concerning low ethanol-gasoline blends.6). Two of their recommendations for a FFV when using ethanol gasoline blends are: • • “Special engine lubricants may be required when fuelling with ethanol. extensive studies of ethanol-gasoline blends with 10 to 30 % ethanol contents was found in the literature search.7 and 7. However.5. Other car manufacturers like Chrysler may still require special oil for their FFVs (National Ethanol Vehicle Coalition.1.e. 3. Additional service and maintenance instructions to be followed by the service personal and car owners have not been (and are still not) generally issued for FFVs. The Alliance of Automobile Manufacturers (AAM) and the Association of International Automobile Manufacturers (AIAM) have proposed that additional data on “fuel sulphur effects at near-zero” levels of sulphur should be compiled. have been found. For FFVs some vehicle manufacturers claim that a special lubricating oil is needed (still.

Manufacturers stand behind them with standard warranties equal to those of gasoline vehicles. • “FFVs have been used in private and government fleets for years. This is consistent with the view of the Australian Consumers Association (ACA) to its members. It has also been noted by Ford in literature concerning their Ford Taurus that no special service instructions are needed. may allow use of ethanol-gasoline blends with at least 10 % alcohol. Dealer maintenance practices for FFVs are very similar to those followed for gasoline vehicles” (NREL. This benefit has been noted by many authors. In the report by the US DOE the following materials are listed as subject to degradation due to high concentrations of alcohols since ethanol may not be compatible with them: • • Lubricating oils. in gasoline is the potential formation of water vapour and formic acid during low temperature combustion (US Department of Energy. . and General Motors stated that a blend of 10 % ethanol in gasoline would be covered by their warranties for their cars on the US market. but then the warranty may not be valid since increasing the compression ratio may damage the engine.Page 30 practises of dealers are very similar for these two types of vehicles. as stated in the following quotation. almost all US car manufacturers were recommending the use of 10 % ethanol in gasoline according to Launder. 2003). By 1995.The CRFA also says that a higher engine compression ratio is advisable for ethanol-gasoline blends above 10 %. The technology is proven. “surface treatment of engine parts” and more “frequent replacement of lubrication oil or higher quality synthetic oils or a redesign of conventional engine lubrication oils”. Many car manufacturers in Europe and Japan sell vehicles in North America. 1991). including Launder (2001) from Michigan State University in a study of the development of ethanol blends in gasoline in the USA from 1970 onwards. According to the CRFA’s website this warranty is valid for ethanol concentrations up to 10 % and no engine modification is needed (www. 2003). and their new car warranties won’t cover such damages” (Australian Consumers Association. especially methanol. 2003). Terne steel (in gas tanks). and for vehicles available on the US market the use of blends with up to 10 % alcohol has been accepted by the car manufacturers.html). According to the Canadian Renewable Fuel Association (CRFA) all automobiles sold in North America (the USA and Canada) are “designed with full warranty protection even when they are operated on ethanol-blended gasoline” (Canadian Renewable Fuel Association. As early as 1980 Chrysler.org/ethanolterms. and thus the assumption of the authors of the present report is that the design of vehicles on the European market. “Most of the manufacturers say gasoline containing more than 10 % ethanol can damage car engines. Compatibility and Wear Studies on engine wear have shown that there is only a slight risk that the use of blends with low alcohol contents will result in increased wear. Ford. 3. including Sweden. In the information given by Ford Motor Company concerning their FFVs there are: “no special service or maintenance issues with the Taurus Flexible Fuel Vehicle” (Ford Motor Company. 2004). and the knowledge base about them is strong. the same year that Ford started production of FFVs.greenfuels.6. • For vehicles using up to 10 % ethanol in gasoline there does not generally seem to be any need for special service instructions. The most serious reported risk associated with blending an alcohol. The proposed solutions of the problem are to use “acid neutralizers in lubrication oils”.

1998). which may especially apply to older cars. especially in the fuel system (Hammel-Smith et al. (2002) highlight the further potential problem.. Polymers.” In the investigation by Minnesota State University (referred to above) the use of a 30 % ethanolgasoline blend did not cause more than normal wear to the engines (Bonnema et al. it is also said that “few. fuel pumps. A possible solution could be to use a special corrosion-inhibiting additive. that alcohol tends to react with rubber and they advise that modern cars should be designed to be compatible with the use of alcohol blended gasoline. Specifications. 2004). following material tests extending over many years. 2002). Hsieh et al. Leather. the physico-chemical characteristics of alcohol are different from those of gasoline..3. 2002). as noted in section 2. rubbers. carburettors. Unfortunately. . has presented a study entitled “Vehicular Ethanol Fuel”. for example. plastics (hoses). In its Industry Guidelines. no information about the two other vehicles appears to be provided in the cited paper. it also advises that the meters should be recalibrated “10-14 days” after switching to the distribution of ethanol blended gasoline. In the report by Hammel-Smith et al. The cited paper also discusses findings reported by other authors. However. On the other hand it states that no accelerated wear has been seen in gasoline meters which are used for ethanolgasoline blends (Renewable Fuels Association. especially methanol. According to Hammel-Smith and his colleagues at the NREL. and Procedures the FRA states that o-rings and seals used in meters for neat ethanol should be “designed to withstand ethanol”.3 %w) and hydrous (93. Polyester bonded fiberglass laminates. representing the Brazilian Automobile Manufacturers Association. Joseph Jr. that these or similar materials may be used in modern vehicle systems. Eight out of ten carburetted cars tested showed more or similar wear when compared with gasoline fuelled vehicles. One aspect discussed was the effects of ethanol blended gasoline relative to neat gasoline. elastomers. Many authors of papers dealing with alcohol fuels claim that most problems associated with the use of alcohol. On the other hand it was felt that gasoline was as corrosive towards copper strips as a 10 % ethanol gasoline blend. It was also noted by the Oak Ridge National Laboratory that “Du Pont had found that highly fluorinated fluorohydrocarbons provided the best resistance to either highly aromatic gasoline or to ethanol”... The conclusion of the Joseph Junior presentation is that use of a 10 % ethanolgasoline blend had no apparent detrimental effect on vehicle performance. which may affect various components. The Oak Ridge National Laboratory has.Page 31 • • • • • • Cylinder walls. (2002) have reported. Hammel-Smith et al. describing experience with the use of ethanol-gasoline blends – both anhydrous (99. Another conclusion was that a 22 % ethanol blend is more corrosive towards metals than gasoline. if any incidents have been reported on 10% blends associated with ‘cylinder wall wash’. as a fuel for vehicles have occurred in older cars. reported that use of 15 % ethanol-gasoline blends appears to be incompatible with parts of the fuel system according to tests carried out by the Technical Research Centre (VTT) in Finland. Polymethane. Brazilian experience suggested that the relative compatibility of the blends with plastic materials was “good” and their tendency to cause the formation of gum deposits was “low”. Cork gasket material.2 %w) – in cars in Brazil (Joseph Jr.

oxygenate in the fuel may result in a too lean air-fuel mixture”. For example. on average. and that MTBE has been added to both of them to date. and that there was no increase in wear or reduction of TBN (total base number) compared to corresponding parameters when using neat gasoline (Apace Research Ltd. but not more. 10 %) there has been shown to be no difference between using them and neat gasoline. The essential message from Nissan is that the cost of MTBE can be saved by replacing MTBE with ethanol without decreasing the octane number of the fuel when compared with the gasoline used. The engine wear that occurs when using a 10 % ethanolgasoline blend was studied by Apache Research Ltd in Australia. it is stated that in “modern” motor vehicles equipped with engine control systems that adjust the air-fuel ratio. 2005). 1998). no need to wait until the tank is empty”. 2002). which noted approvingly. the Federal Chamber of Automotive Industries and the Australian Automobile Association that a 10 % ethanol content in gasoline is acceptable. in one of which. entitled “Oxygenated Gasoline”.. that it has been stated in “the News” that “the Minister “the Minister of the Energy Ministry together with the Thai Automotive Industry Association and major fuel suppliers such as the Petroleum Authority of Thailand (PTT). oxygenated gasoline will perform well. There are indications that one potential problem is excessive wear of the nozzles and hoses etc. loss of fuel economy and accelerated wear of engine components and fuel lines”. one of which may be to check the fuel facilities since their materials may be incompatible with the use of ethanol. who found that “there is no additional or unusual wear to that normally expected”. 2004). the Nissan Motor Co. in the equipment used (US Department of Energy. The ethanol production industry has not agreed to the ethanol content of ethanol-gasoline blends being limited to 10 %. . Bangchark Petroleum and Shell announced that the use of gasohol in cars is one way to reduce fuel imports and promote the production of gasohol in Thailand” (Nissan. In the cited paper Nissan says that two grades of gasoline are used in Thailand. because higher ethanol contents will result in “loss of drivability. and claims that 10 to 20 % ethanol in gasoline has been used in vehicle fleets since 1992. As early as 1978 gasoline containing 10 % ethanol was being marketed in Nebraska. according to Chevron when oxygenated gasoline is used. RON 91 and RON 95. in vehicles with carburettors or systems for fuel injection that do not control the air-fuel ratio. USA. Several vehicle manufacturers have stated that their vehicles can be run on ethanol-gasoline blends with a 10 % ethanol content without any problem. There seems to have been an ongoing agreement between the Australian Institute of Petroleum. In a series of papers Chevron has discussed. just open the fuel tank lid and fill it up.Page 32 The Guidebook from the US DOE mentioned above provides information on solutions to problems related (inter alia) to fuel sampling. You can change back to normal gasoline at anytime. issues related to oxygenated fuels and especially ethanol blends in gasoline (Chevron. For blends with low ethanol contents (max. the volumetric fuel consumption will increase by 2 to 3 percent. Ltd. However. inter alia. In addition. Furthermore Nissan states that “Nissan gasoline engines that are equipped with the injection system (EGI) can run on gasohol without any ensuing problem” and that “No modification is required to use gasohol. 2002). The industry also made an agreement with a university to study the effects of higher blends of ethanol in gasoline (Department of the Environment and Heritage. In addition it will have an effect on the warranty provisions for the vehicle (Australian Automobile Association. in a paper released in 2005. 2001).

In addition. The vapour pressure of a methanol-gasoline blend is significantly higher than that of a corresponding ethanol-gasoline blend. which can reduce drivability. depending on its aromatics content. Considering all the available information. Impact of Vapour Lock Vapour lock is caused by the fuel flow to the engine being reduced as a result of vapour formation.Page 33 In California the use of MTBE and other ethers has been banned since 2004. Some metal components in the engine fuel system will rust or corrode if water or acidic compounds are present in the fuel system. In the complete report (Chevron. Methanol-gasoline blends are not authorized by many manuals for vehicle owners. typically caused by high temperatures. if it is not adjusted for such blending may result in a fuel with too high volatility (in this context the alcohol’s previously mentioned effect on the VL = 20 temperature is relevant). the following performance-related issues have been highlighted by Chevron: • • • • • Compared to neat gasoline. • 3. it seems likely that ethanol will soon be the only oxygenate that can be used in the USA to satisfy federal requirements for oxygen in gasoline. This problem may be exacerbated in carburettorequipped vehicles. According to Chevron: • • • • Blends of gasoline with methanol are more corrosive towards metals and cause more rapid deterioration of elastomers in the fuel system. Fuels with extremely high vapour pressure may cause drivability and hot start problems as a result of vapour lock. while the vehicle is being driven. Conventional gasoline can dissolve up to 150 ppm water at 21 °C. since the resulting commingling will result in the RVP of the fuel in the tank exceeding standard limits. but water from the phase separation of gasoline oxygenated with ethanol will. According to Chevron “additional water dissolved in oxygenated gasolines does not cause rusting or corrosion. which is a measure of the front end volatility∗ of the fuel. . given time”. Ethanol blended gasoline is not to be mixed with neat gasoline that has not been adjusted for such blending. Blending ethanol in conventional gasoline. 2002a) Chevron discusses the implications of the observation that “Methanol is Not Ethanol” in that they have different physico-chemical characteristics. and other states are considering similar bans (Chevron. Vapour lock is linked to the vapour pressure of the fuel. Phase separation may occur if ethanol blended gasoline is transported in pipelines. Since the addition of an alcohol to gasoline will ∗ Front-end volatility: A term applied to the volatility of the lower boiling-point fractions of gasoline. from other sources as well as Chevron. adding it has not been a viable option for summer reformulated gasoline. Since ethanol increases the volatility of the fuel. Methanol is toxic. An ethanol-gasoline blend with 10 % ethanol can dissolve up to 6000 to 7000 ppm water at 21 °C.7. ethanol/gasoline blends need more heat to evaporate. Vapour lock can also make it impossible to start the engine. 2002a).

according to Chevron. 2002). and protection from vapour-linked problems is greatest at the lower end of the range (Chevron.Page 34 increase the volatility of the fuel. there is a risk that it will also cause vapour lock to occur in hot weather or at high altitudes. The following formula has been developed for calculating the VLI based on the vapour pressure (in kPa) and percent evaporated fuel at 70 °C: VLI=10(VP)+7(E70). . The normal range for the VLI. is 800 to 1250. A paper published by Chevron recommends that fuels should not exceed specified Vapour Lock Index (VLI) values in order to avoid problems such as vapour lock and hot fuel.

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4.

AIR QUALITY AND HEALTH EFFECTS

Air quality can be considered at three levels: global, regional and local. From a global perspective, the most important greenhouse gases are nitrous oxide, carbon dioxide and methane, all of which affect the global climate. Increased use of bio-based fuels, especially as blending components in gasoline, is expected to decrease the net production of carbon dioxide from fossil fuels in vehicles, which is an important issue for sustainable development. By introducing bio based fuels the net production of fossil carbon dioxide from vehicles is expected to decrease with increased amounts of bio based blending components in gasoline which is an important issue for sustainable developments. Colón et al. (2001) have compared the urban air levels of organic compounds in Sao Paulo, Brazil, and the Los Angeles basin, USA. In Sao Paulo it is estimated that ethanol or ethanolgasoline fuel blends account for approximately 40% of the total fuel used, but the corresponding level in the Los Angeles basin is much lower, hence the urban air in Sao Paulo is much more strongly affected by the use of ethanol as motor fuel.. It was found that the ambient air levels of volatile organic compounds measured in Sao Paulo were substantially higher than those in Los Angeles. For instance, mean concentrations of mono ring aromatics, volatile aldehydes and “simple” alcohols (mainly ethanol) were 2 - 3, 5 - 10 and 10 - 100 times higher, respectively. Alkanes (C4-C11, n-alkanes) were slightly increased in Sao Paulo. The ambient levels of organic compounds in the Los Angeles basin used by Colón in the comparisons were based on measurements made by the US EPA in the year 1997 (Lonneman, 1998). A study regarding carbonyls in urban air, collected in Rio de Janeiro, Brazil, revealed that of the 61 carbonyl compounds measured the most abundant were formaldehyde and acetaldehyde, with mean concentrations of 10.8 + 4.1 and 10.4 + 4.6 ug/m3, respectively (Grosjean et al., 2002). Maclean and Lave (2000) have investigated air quality trade-offs from automobiles fuelled by alternative fuels. They state that comparisons can be misleading if the vehicles used are dissimilar. One of the fuels considered was E85 i.e. 85% ethanol and 15% gasoline. Aakko and Nylund (2003) investigated an FFV running on E85 and found that when the temperature was lowered from 23 ºC to –7 ºC formaldehyde and acetaldehyde emissions increased (the latter approximately four-fold; from 4 to 15 mg/km driven). Exhausts from mobile sources such as motor vehicles are chemically very complex. The chemical compounds emitted range from gaseous, liquids to particles (solids) and may also be distributed between particles and the gas phase depending on the physical properties of the compounds. Particle emissions consist mainly of carbon particles onto which a variety of compounds are adsorbed. Up to 10-40 % by weight of the particles can be extracted from the carbon matrix with organic solvents (National Research Council, 1982). Such an extract is often referred to as the soluble organic fraction (SOF). Several factors affect the chemical composition of the exhaust emissions, including the fuel, fuel quality, engine lubricating oil, engine wear, exhaust after treatment, driving conditions and ambient temperatures. Ambient temperature driving conditions, which of course depend on seasonal variations, can have a major impact on emissions, especially for Otto engines, both with and without three-way catalysts (Almèn et al., 1997) at low ambient temperatures from +20 ºC down to –20 ºC or lower. Investigations of light duty diesel engines have indicated that they are relatively unaffected by the ambient temperature compared to investigated Otto engines. This

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could be due to the differences in the combustion mechanisms of Diesel and Otto engines. Aakko and Nylund (2003) investigated exhaust emissions from an FFV running on E85 at temperatures of +20, 0 and –7 ºC, and concluded that the emissions of CO, HC and total particles increased as the temperature was lowered while NOx emissions were only slightly increased. Another important factor affecting the chemical composition of exhaust emissions generated in the combustion process in an engine is the service and maintenance history of the vehicle/engine. Extremely high levels of both regulated and unregulated emissions have been detected in exhaust emissions from gasoline fuelled vehicles that have been poorly serviced and maintained, i.e. incorrectly functioning engines or so-called high emitters (Sjödin et al., 2000). High emitters should be mended or eliminated from the car fleet in general. Armstrong (1995) has evaluated ethanol as an individual compound and states that it is readily degraded in the environment, so human exposure to it is anticipated to be very low. Furthermore, abundant information is available on the metabolism of ingested ethanol, which strongly suggests that environmental exposure to ethanol will have no adverse health impact on humans. Average ambient levels of ethanol in Porto Alegre, Brazil, where 17% of the vehicles run on ethanol have been found to be 12 ppb. Animal studies have found that the Lowest Effect Level (the lowest level to give a detectable response) of ethanol is 45 ppm, which is approximately 4000 times higher. The dose for a person living in Puerto Alegre might be about 0.5 mg ethanol, which is a negligible dose. In section 5.3 a selection of exhaust constituents that may have adverse effects on the environment or health of animals and humans is listed and discussed.

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5.

EMISSIONS

In an investigation by the Swedish government entitled “Alternativbränsleutredningen*” (SOU, 1996) it was proposed that a thorough chemical characterization of exhaust emissions (regulated and unregulated exhaust constituents) of gasoline blended with alcohols should be carried out. Furthermore, it was suggested that bio assays, such as mutagenicity tests, TCDD-receptor affinity tests and neurotoxicity tests, should be included in the risk evaluation. The risk criterion was that the modified fuel alcohol/gasoline blend should not have any greater potential environmental and health impact than a baseline gasoline fuel. However, an updated set of compounds and classes of compounds that should be considered is discussed below.

5.1.

Regulated exhaust emissions

Emissions that are regulated by law (Lagen, 2001) are carbon monoxide (CO), unburned fuel hydrocarbons (HC), nitrogen oxides (NOx) and, for diesel cars, particles. The methods used to determine regulated pollutants have been developed for application to conventional fossil based gasoline and diesel fuels. These methods are: chemiluminescense detection for NOx, nondispersive infrared detection (NDIR) for CO, gravimetric analysis for particulates and flame ionization detection (FID) for HC. The chemical constituents of HC are, by definition, hydrocarbons which consist solely of carbon and hydrogen atoms. However, the chemical compounds emitted include compounds other than pure hydrocarbons (see below) in relative abundances that vary depending on the fuel used, so the “HC” signal from the FID tends to be underestimated. This is because the hydrocarbons and partially oxygenated compounds have different response factors, as widely reported in the scientific literature (Table 5.1). Consequently, to make a valid comparison of HC emissions from gasoline and ethanol blended gasoline as fuels the comparison must be made compound by compound to avoid over- or underestimations. This requires the development of a method enabling the separate detection of hydrocarbons and alcohols (at least) in exhaust emissions. Table 5.1. Sensitivity of the flame ionization detector towards selected compounds relative to that of the hydrocarbon n-heptane (C7H16), which is set to 1.00 (Diez, 1967). Hydrocarbons Alcohols Organic acids Methane 0.97 Methanol 0.23 Formic acid 0.01 Ethane 0.97 Ethanol 0.46 Acetic acid 0.24 Emission measurements must be carried out as part of the type approval of the vehicle according to relevant legislation, for example the European regulations (current EU Directive 70/220/EEG with amendments). There is also a need for emission testing to generate emission factors for use in emission inventories and air quality studies. Characterisation of emissions from vehicles is also essential for research purposes. Emission tests are commonly carried out according to standard procedures to enable data generated at different laboratories or during different projects to be compared. There may also be a need to generate emission factors for local traffic situations,

*

Investigation of alternative fuels.

due to the contribution of the alcohol* contents in the exhaust emitted from the vehicle.46. The corresponding value for ethanol is 0. 5. This means that reported HC emissions from vehicles fuelled with alcohol/gasoline blends are overestimated.Page 38 in which case specific driving patterns (driving cycles) may have to be followed when testing the vehicles.15 mg/km. depending on the regulations in force. addition of methanol to gasoline increases the exhaust emissions of unburned methanol. An updated method needs to be developed for HC measurements from a legal perspective. and that the same vehicle is run on a gasoline blend and the measured “HC” emissions are also 0. and methyl * Other compounds. if only ethanol is present in the exhaust the “HC” emission measured is still 0.1). but if only (100%) ethanol is present in the exhaust the ethanol emission factor from the vehicle is in reality 0. Assume. such as alcohols/aldehydes. and the larger the alcohol contents present in the exhaust. The above discussion highlights the need to distinguish between HC and alcohol contents in vehicle exhaust. the unburned fuel hydrocarbons (HC) in the exhaust consist mainly of unburned gasoline which itself largely consists of hydrocarbons. when using gasoline/ethanol blends as fuel the uncombusted fuel constituents include both unburned gasoline (which consists mainly of hydrocarbons as noted) and uncombusted ethanol.2. For instance. uncombusted fuel hydrocarbons).e.3. which can be regarded as a “carbon counter”.15 mg/km (i. Using these relative sensitivity factors. especially when alcohol gasoline blends are used as fuel. . The relative sensitivity of an FID for each of the hydrocarbons methane. When using gasoline as fuel in an Otto engine. formaldehyde. but not ethanol emissions.15 mg/km (consisting of both uncombusted fuel hydrocarbons and uncombusted ethanol) in comparative tests. 1967). also contribute to the signal from the FID. ethane. Theoretical Discussion about HC Emissions From a strictly chemical perspective. the HC emissions measured in the diluted exhaust consist of both hydrocarbons and ethanol (alcohol). for example. However. and assuming that only hydrocarbons are present in the exhaust the HC emission factor will be 0. HC emissions are regulated by law (see section 5. Unregulated Exhaust Emissions It is well known that the addition of alcohols to gasoline fuel affects the unregulated exhaust emission constituents (Egebäck and Bertilsson. propane and pentane is approximately 1 (Dietz.33 mg/km However. 5. Thus. This also means that a standardized method needs to be developed. hydrocarbons consist solely of the elements carbon and hydrogen. that a vehicle is run on gasoline and has HC emissions of 0. 1983). the greater the error in estimated HC emissions. The standard analytical method used for determining hydrocarbons in motor vehicle exhaust is to use a Flame Ionization Detector (FID).15 mg/km but should be practically zero as no hydrocarbon is present in the exhaust. From a legal perspective.

. they may induce allergic reactions and formaldehyde is considered to be a carcinogen (CARB. uncombusted alcohols from the fuel are emitted in the exhaust in various amounts. the compound 1. 1983. . formaldehyde. especially for ethanol-gasoline blended fuels.1). These uncombusted alcohols in the exhaust emissions should be measured since there is a risk that the “HC” signal from the FID will be overestimated. this hypothesis needs to be experimentally confirmed. and thus should be monitored and reduced in exhaust emissions from automotive sources. 1983). 1991). which have the potential to initiate cancer. suggesting that emissions of alkenes are reduced when it is used rather than neat gasoline. For instance. Alkenes Alkenes such as ethene. The list of such compounds is expected to be updated and modified according to future findings. (1994) significant sources of 1. Aldehydes Aldehydes are known to be irritants. methyl nitrite and ethyl nitrite. However. By blending gasoline with ethanol the “fuel olefin” content decreases. 1990). hence they are potential carcinogens.. 1983).3-butadiene is metabolized to ethylene oxide in both animals and humans (Törnqvist et al. The US EPA has estimated that more than 20.3-butadiene can be potentially metabolized by endogenous enzymes to reactive metabolites. Greenhouse gases and smog-forming compounds are also considered.. leading to estimates of HC emissions from alcohol blended gasoline fuels being higher than they really are (see Regulated exhaust emissions regarding HC section 5. acetaldehyde. From vehicles fuelled with methanol/gasoline blends and methanol/diesel blends methyl nitrite is formed (Johnsson and Bertilsson. Alkyl nitrites are formed from uncombusted alcohol reacting with nitrogen oxides (NOx) in exhaust plumes.000 individual chemical compounds are emitted from diesel fuelled vehicles (US EPA. This means that more than 97 % of the estimated compounds emitted from diesel vehicles are unknown (as are. Alkyl nitrites Methyl and ethyl nitrite are mutagenic (Törnqvist et al. therefore. Aldehydes of special interest are formaldehyde and acetaldehyde. 1983).3-butadiene are the olefins in the fuel. Corresponding additions of ethanol to gasoline increase the exhaust emissions of unburned methanol. Both methyl and ethyl nitrite are formed in exhaust plumes from vehicles fuelled with ethanolgasoline blends (Egebäck and Bertilsson. 1989). Wild et al. propene and 1. However. 1988. According to Schuetzle et al. Using ethanol as a blending component in gasoline results in increased emissions of both formaldehyde and acetaldehyde (Egebäck and Bertilsson. 2003) significant increases in aldehyde emissions occur at relatively low ambient temperatures (-7 ºC). 1982). According to Aakko and Nylund (Aakko and Nylund. a selection of unregulated exhaust constituents is considered below that are considered to be important and to have potential health effects on animals and humans.Page 39 nitrite. The effect is expected to be even greater at lower ambient temperatures than -7 ºC. Alcohols When alcohols are used as blending components in gasoline. their health effects). ethanol. approximately 500 of which have been positively/tentatively identified in the scientific literature.

dibenzo(a. BTEX can also be pyrosynthesised in the combustion process from the fuel or lubricating oil constituents. However. 1989. which are often collectively called BTEX. 1983: 1989). 1997). forming PAN in the atmospheric photochemical system.. Important particle parameters in general are their size. and acetaldehyde and ethanol minor roles. This conclusion is supported by the results of several other investigations. indeno(1. Peroxyacetyl nitrate In a study by Gaffney et al.e. (1995) indicate that particle size is a very important parameter. benzo(k)fluoranthene. (Grosjean et al.Page 40 Monoaromatics Monoaromatic compounds emitted from vehicles include benzene. Levels were measured before and after introduction of a 10% ethanol gasoline fuel blend (>99%) and the cited authors detected increased levels of PAN and aldehydes during the wintertime. Brazil. In the report it is stated that acetaldehyde emissions increase as the ethanol content in the blended gasoline fuel increases. benzo(b)fluoranthene.e. 1983. 1998) benzene is a known human carcinogen and may cause leukaemia through occupational exposure (Törnqvist and Ehrenberg.. However. with no genotoxic compounds adsorbed on them (i. Each PAH has a relatively large number of hydrocarbons with two or more condensed aromatic rings.l)pyrene. 1991. methyl anthracenes/phenanthrenes. 1997). retene and benzo(ghi)perylene recommended by the Swedish . 1993) interest in particles per se has increased. These neoplasms may be caused by the particle fraction of the exhaust (International Agency for Research on Cancer. as precursors to PAN in urban air – in contrast to a report prepared by the Orbital Engine Company (2002) for Environment Australia. through gravimetric determination using a dilution tunnel technique at a diluted exhaust temperature below 52 °C. Studies by Heinrich et al. IARC. Camner et al. toluene. fluoranthene. dibenz(a. A study which is more valid during summertime conditions in Porto Alegre.2. Due to the findings that TiO2 and carbon black particles. Exposure to diesel exhausts clearly induces lung tumours in rats. (1997) field measurements taken in Albuquerque. which states that acetaldehyde is particularly important since it reacts with NOx. emitted in the uncombusted fuel constituents.h)anthracene. New Mexico. benzo(a)pyrene. The Institute of Environmental Medicine (Karolinska Institute. number. 1990. Pott and Heinrich. 1994). in Sweden are the PAHs phenanthrene. Particulate emissions Particlulate emissions are measured on a weight basis i. surface area and chemical composition. Heinrich et al. of which a subgroup (Polycyclic Aromatic Hydrocarbons or PAHs). were used to compare atmospheric levels of peroxyacetyl nitrate (PAN) associated with the use of different fuels. A source of BTEX emissions from vehicles is the BTEX content of the fuel used. 2002) indicates that aromatics and alkenes have a major role. ethyl benzene and xylene. consists of mutagenic carcinogenic hydrocarbons (IARC.. “clean” particles) can also give rise to lung cancers in rats (Pott. pyrene. Sweden) has published a report which concludes that it is not currently possible to tell if a non-specific particle factor or a direct genotoxic effect of material adsorbed on the particles is responsible for causing lung cancer (Camner et al.3-cd)pyrene.. Therefore. Polycyclic Aromatic Compounds Polycyclic Aromatic Compounds (PACs) are a numerous group of mutagenic carcinogenic compounds. According to the California Air Resources Board (CARB. the particles emitted should be chemically analysed with respect to both their size and numbers.

for which GWP is set to one. It should be noted that nitrogen oxides (NOx) are regulated pollutants that are determined jointly. especially those of asthmatics and children (Nitschke. The GWP indicates the relative contribution of a molecule of a greenhouse gas compared to a molecule of carbon dioxide... 1981. thereby increasing the average temperature of the earth. respectively.2 ppmv). however published in 2002 (Boström et al. Table 5. According to Rodhe (2005).315 93. 2004)..Page 41 Environmental Protection Agency (SEPA) for air monitoring programs in 1999.e.75 40. methane (CH4) and nitrous oxide (N2O). Nitrogen dioxide (NO2) is a compound that plays a role in respiratory diseases. 2002). at present the European Parliament has not made a final decision about the limit value according to Kyrklund (Kyrklund. 2002). Global Warming Potential (GWP) and the relative contribution to the global warming effect (RCGWE) of selected compounds. N2O 296 0. Greenhouse gases Greenhouse gases of most interest are carbon dioxide (CO2).. the background concentration in the atmosphere of carbon dioxide is 375 ppmv (yearly variation. However. Compound GWP Concentratio GWP x ppm % RCGWE n ppmv Carbon dioxide. the most important greenhouse gas is carbon dioxide. 1999). Aromatic quinones have previously been identified and measured in gasoline particulate exhaust extracts (Schuetzle et al. while the background concentrations of methane and dinitrogen oxide (nitrous oxide) are 1. Clearly. Alsberg et al. 1981) and ambient air (Cho et al. By multiplying the concentration of a greenhouse gas and its respective GWP. An important parameter for the formation of nitrogen oxides is the combustion temperature i. The origin of the aromatic quinones is not fully understood if it is related to the gasoline fuel as uncombusted quinones (initially in the fuel) or if they are formed in the combustion . increased combustion temperature results in increased nitrogen oxide emissions. CO2 1 375 375 74 Methane..315 ppmv.7 cells macrophage-like cells derived from tumours induced in male BALB/c mice by the Abelson murine leukemia virus. due to its relative abundance in the atmosphere. its relative contribution to the global warming effect can be estimated. So far B(a)P is the only PAH whose concentration in ambient air will be regulated by European Commission and the limit value will most probably be set to 1 ng/m3.3 7. In Table 5. as the sum of NO and NO2 contents rather than as individual components. CH4 23 1.2 the Global Warming Potential (GWP) for selected greenhouse gases is shown. Nitrogen dioxide Nitrogen oxides (NO and NO2) are formed by the oxidation of nitrogen from the air in the combustion process..2 18 Quinones A recent publication by Xia (Xia et al.. 2004). 2004) shows that a quinone-enriched polar fraction from a diesel particulate extract was more potent than PAH with respect to toxic effects in RAW 264.2. 1985). Recommended guideline value concentrations in ambient air are set to 0. +/. Quinones are a group of organic compounds that consist of diketones (carbonyls) which contain oxygen and are present in both diesel particles (Schuetzle et al. all of which interact with the radiative energy fluxes in the atmosphere.75 ppmv and 0.1 ng/m3 for benzo(a)pyrene (B(a)P) and for fluoranthene 2 ng/m3 in Sweden (Boström et al.9 Dinitrogen oxide.

4. NOx.77 0. However..08 Benzene.3. For instance.3 mean emission factors are shown from three TWC-equipped cars running on 3.12 3.77 0.83 +/Formaldehyde.1).85 3. Characterisation of Exhaust Emissions In a relatively recent publication He et al.42 0. It is well known that fuel properties affect the chemical composition of the exhaust emitted from engines. 6 and 10 % ethanol-gasoline blends (Schifter et al. mg/km 0. but had a low conversion efficiency for ethanol.4.62 + In Table 5.22 7. Table 5. 5.87 4. mg/km 7. g/test . mg/km 1. It is possible that increasing the ethanol content of gasoline-ethanol blends causes similar increases in quinone emissions. % ethanol-gasoline blends (Schifter et al.4 the mean fuel economy and mean evaporative emissions from the three TWCequipped cars running on 3.68 Ethanol effect +/+/+ Fuel consumption l/10 km Evap.01 Acetaldehyde. Table 5. 2001).2.78 1.. benzene and acetaldehyde emissions increased with increasing ethanol contents. The engine was run on neat gasoline.25 1. CO and NOx emissions was reduced and ethanol and acetaldehyde emissions was increased. Table 1.Page 42 process. 3 vol % Ethanol 0.83 0. 6 and 10 vol. g/km 0.42 0. Mean fuel economy and mean evaporative (Evap) emissions from three TWCequipped cars running on 3..12 1.09 3. g/km 0.11 + Butadiene. 2001). Mean emission factors from three TWC-equipped cars running on 3. % ethanol gasoline blends (Schifter et al. (2003) present a study of exhaust emission characteristics from an engine with an electronic fuel injection (EFI) system with and without a three-way catalyst (TWC) system. The engine out emissions at idle speed using E30 as fuel it was observed that HC. and both 10 % ethanol(E10) and 30 % ethanol. In Table 5.21 0.89 2..23 0. It is difficult to interpret or to draw firm conclusions from the data in the table. while CO and formaldehyde emissions and the ozone formation factor (g O3/g Non Methane Organic Gases. It was also observed that the TWC system reduced acetaldehyde emissions. g/km 3. adding ethanol to gasoline increases the emission of aldehydes (carbonyls).(E30) gasoline blends (see section 1.97 HC. mg/km 1.48 + g O3/g NMOG 3. NMOG) decreased.60 0.11 2. but there are no empirical data related to this issue as yet.22 0 NOx.32 0.87 4. diurnal. 6 and 10 vol. 6 and 10 % ethanol gasoline blends are shown. as they are mean values from three cars. 2001). g/test Evap. Emission 3% 6 % Ethanol 10 % Ethanol Ethanol Ethanol effect CO. hot-soak.14 0.38 8.44 10 vol % Ethanol 0.46 6 vol % Ethanol 0.

GASOLINE VERSUS E20 EXHAUST EMISSIONS mg/km 8 7 6 5 4 3 2 1 0 E20 E20 6400 km 80 000 km E20 E20 Gasoline Gasoline Gasoline Gasoline HOLDEN FORD TOYOTA HYUNDAI SUBARU Figure 5. From the figure it can be seen that increased accumulate driving distance results in an increased acetaldehyde emission. 2002) by the dilution of the base gasoline. The benzene emission is lower when the E20 fuel is used as fuel and the emission is reduced at increased driving distance. Benzene emissions (mg/km) gasoline versus E20. BENZENE EMISSION .Page 43 Regarding emissions of benzene.2 shows average acetaldehyde emissions from all vehicles tested. This seems to be fuel independent. The emission measurements were made using fuels comprising of 20% ethanol (E20) in gasoline and neat gasoline. 2004) the unregulated emissions such as BTEX and aldehydes were measured.1 shows average benzene emissions from five tested cars. toluene. the vehicle emissions were determined at both 6400 and 80000 km odometer readings. In Figure 5. Gasoline E20 .1. however the Toyota car is excluded. ethyl benzene and xylene (BTEX) a general conclusion is that as the ethanol content of the blended fuel increases the BTEX emissions are reduced (Orbital Engine Company. The Holden car decreases its benzene emissions with increased driving distance. Comparative benzene emissions from the Hyundai car is that benzene emissions increase as the driving distance increases which is valid for both fuels tested. Because of this. it is difficult to make firm conclusions with respect to benzene emissions vehicle dependency. Furthermore. From the Figure 5. Furthermore. the Subaru car has larger benzene emissions from the E20 fuel compared to neat gasoline. In a study carried out in Australia (Orbital Engine Company.1 it can be concluded that the there is a relatively large variation in acetaldehyde emissions due to fuel and accumulated driving distance and vehicle tested. Figure 5. Because of this.1 it can be concluded that there is a relatively large variation in benzene emissions due to fuel and accumulated driving distance and vehicle tested. it is difficult to make firm conclusions with respect to formaldehyde emissions vehicle dependency. From the Figure 5.

acetaldehyde and formaldehyde emissions.4 0.5 1 0.8 0.GASOLINE VERSUS E20 1 EXHAUST EMISSIONS [mg/km] 0.Page 44 ACETALDEHYDE EMISSION . . All of the tested vehicles had increased formaldehyde emissions with respect to increased accumulative driving distance. FORMALDEHYDE EMISSION .6 0.1 0 E20 E20 Gasoline Gasoline 6400 km 80 000 km 0 E20 E20 Gasoline Gasoline Gasoline 0 E20 HOLDEN FORD TOYOTA HYNUDAI SUBARU Figure 5.3 shows average formaldehyde emissions from all vehicles tested.5 6400 km 80 000 km EXHAUST EMISSIONS [mg/km] 2 1. Acetaldehyde emissions (mg/km) gasoline versus E20. from Figures 5.3 0.5 0 Gasoline Gasoline Gasoline Gasoline Gasoline E20 E20 E20 E20 E20 HOLDEN FORD TOYOTA HYUNDAI SUBARU Figure 5.3.GASOLINE VERSUS E20 2.1 to 5.9 0. The relative emissions of formaldehyde are vehicle and fuel dependant. Summing up. The gasoline fuel used contains up to 500 ppm sulphur which is extremely large compared to gasoline available on the Swedish market which is expected to have an impact on the exhaust emissions. Figure 5.2.5 0.3 due to accumulative driving distance the function of the catalysts is deteriorating which results in increased emissions of benzene.7 0.2 0. Formaldehyde emissions (mg/km) gasoline versus E20.

1. vehicles produced today are designed to adjust the air-fuel ratio in order to compensate for changes in the fuel. When adding ethanol up to 25 % the energy change may be sufficient for the driver to clearly detect a change in the engine’s power* during acceleration of the vehicle. However. Furthermore. including exhaust gas recirculation rates.92 for MON (Prakash. to a certain degree.1. in the literature study it was not possible to find a * As the energy content (MJ/l) of ethanol gasoline blends is lower than that of neat gasoline the fuel consumption will most likely increase for the average driver. “Modern adaptive learning engine management systems control the combustion stoichiometry by monitoring various ambient and engine parameters. The reduction in energy content per unit volume fuel caused by adding five different percentages of ethanol to a certain blend of gasoline is shown in Figure 6. The engine’s power output depends on the energy content per unit volume fuel injected into its combustion chamber. M J/l % 35 30 25 20 15 10 5 0 -5 -10 CHA NGE OF ENERGY WHEN BLENDING DIFFERENT PERCENTA GES OF ETHA NOL IN GA SOLINE % EtO in gasoline H % change of fuel energy Fuel energy content [M J/l Figure 6. 2005). increase fuel consumption. Since ethanol has a significantly lower energy value than gasoline its addition may affect the engine’s power even though the octane number of ethanol is higher than that of gasoline. However. Since there has been a lack of standard protocols for measuring the octane numbers RON and MON for ethanol the presented range for them is quite wide: 102 – 130 for RON and 89 – 96 for MON according to Environment Canada. The effect of blending ethanol with Swedish Class 1 (MK1) gasoline on the fuel’s energy content.Page 45 6. Environment Canada. The conclusion is that an addition of 10 to 15 % ethanol to gasoline will. the air flow sensor. and exhaust oxygen sensor outputs” (Hamilton. . FUEL ENERGY CONTENT – ENGINE POWER. and according to information obtained from Web FAQs. The octane numbers presented for ethanol blended gasoline are 90 – 100 for RON and 80. It is well known that vehicles are equipped with systems for adaptive learning or adaptive memory. 1998. the octane numbers for gasoline vary depending on its composition. 2004).

7 % when driving according to the Highway cycle (Apache Research Ltd. the overall increase in fuel consumption when using E10 will be only 2 %. from an investigation of the use of a blend of 10% ethanol in gasoline show that fuel consumption increased by 2. of which the design of the fuel system of the vehicle and engine. 2004). the percentage of ethanol in the fuel and the driving pattern of the vehicle appear to be most important.5 % to 7 % depending on the cycle and the vehicle”. . Results presented by Apache Research Ltd. According to the statements by Orbital this increase in fuel consumption should not be detectable by an average driver.Page 46 definitive percentage for the increase since it depends on a number of factors. In a paper from the Transportation Office of Energy Efficiency in Canada it is said that adding 10% ethanol to gasoline (E10) will result in a blend with an energy content equivalent to 97 % of the energy content of the base gasoline. 2003).4 % when driving according to the US EPA City cycle and by 2. Since this decrease in energy content will be partly compensated by the “improved combustion efficiency” of the ethanol blended fuel. In the same report Orbital also states that “Increases in fuel consumption of 5% or more are considered to be recognisable to the average driver” (Orbital Engine Company. In comparison. increasing the speed of the vehicle from 100 km/h to 120 km/h will result in a 20 % increase in fuel consumption (Transport Office of Energy Efficiency in Canada. In a report prepared by the Orbital Engine Company for Environment Australia concerning an investigation into the use of 20 % ethanol in gasoline it is stated that the “increase in fuel consumption ranges from 2. 1998). An issue to consider is whether the owner of the vehicle will recognize the increase in fuel consumption that may occur when ethanol is added to gasoline.

will increase. resulting in an increase of the volumetric fuel consumption. The most important issue to clarify is whether. On the other hand it has been shown in section 6 of this report that blending ethanol in gasoline will decrease the energy content of the fuel. In the paper the EPA also declare that “Some vehicle fuels. Hammel-Smith and his colleagues at NREL have indicated that a key aspect concerning vehicle performance and emissions when using a blend of ethanol/gasoline of up to 17 to 24 % is that fuel control is able to compensate for a high oxygen content in the fuel (Hammel-Smith et al. ethylbenzene and xylene (BTEX) may decrease compared with the use of neat gasoline in the same vehicle. emissions and automatic transmission in addition to other engine variables. 2002). Whether (and if so to what degree) these changes will be better or worse overall in terms of the air quality and health has been considered in various studies. and if so to what extent. the regulated emissions will change compared with the use of neat gasoline when switching to the use of a blend of ethanol/gasoline. especially in the USA/California. This is especially true for vehicles equipped with older types of fuel systems.e. toluene. such as . and in this report. According to the NREL these systems have been important in the evolution of the use of alcohols as automotive fuels (Hammel-Smith et al. but those of benzene.Page 47 7. fuel injection. especially vehicles using blends of ethanol in gasoline. especially of acetaldehyde.. Electronically controlled fuel injection systems have long replaced carburettors and they are more advanced today in that new functions have been incorporated. These fuels are called “clean fuels. EVALUATION OF EMISSIONS AND FUEL CONSUMPTION In a paper released in 1992 the US EPA defined “Clean Fuels” as including “alcohols. to a certain degree at least. 1992). One of the conclusions to be drawn is that it is generally not certain that a higher blend of ethanol can be used in all vehicles currently available. natural gas. as already mentioned in this report. electricity. create less pollution than do today’s gasoline. Concerning the use of a blend with a certain content of ethanol in gasoline it is quite clear. The use of electronic mapped digital systems makes it possible to control ignition. for the inevitable drop in the energy content of the fuel. that there is a risk that emissions.” A key issue today is whether newly manufactured gasoline-fuelled vehicles equipped with an efficient emission control system emit more or less harmful substances than vehicles fuelled with any of the fuels mentioned in the paper from the EPA.. Potential barriers in this respect are the age of the vehicles. In vehicles equipped with advanced engine control systems the ability to exploit the higher octane rating compensates. It can also be questioned whether any automotive fuel used today can be defined as a “clean fuel” since all types of fuels generate pollution when burned in a combustion engine. and propane” (US EPA. their technological standards and their control systems. When considering the performance and emissions from motor vehicles. It is accepted that adding an alcohol. the technological status of the vehicle should be considered. i. 2002). ethanol. because of physical or chemical properties. in gasoline will enhance the octane rate of the fuel. When considering the effect of blending ethanol with gasoline on emissions a factor that must be taken into account is that motor vehicles are sensitive to changes that affect the air/fuel ratio.

3.2 and 5. 2003). Ford Falcon AU-III. The base fuel differences are however relatively insignificant with respect to distillation and constituency when compared to the change introduced by the ethanol blending” (Orbital Engine Company. The aim of the later study. respectively) were used as base gasolines for blending with ethanol. Hyundai Accent. named 2B. as discussed in sections 5. Two types of gasoline (AEN* Summer ULP and AEN Perth ULP. Australian Energy News (AEN) . 7. is as follows: “In summary. designated ULP and PULP. 2004). there are some small but quantifiable differences to be taken into account when comparing trends over the accumulated mileage and across some of the vehicle fleet using the ULP stock. according to Orbital. This effect does not generally occur when using alcohol blended gasoline in newer models of vehicles. Newer models of vehicles equipped with closed-loop fuel injection systems. • • • • • Holden Commodore VX. Subaru Impreza WRX.Page 48 carburettors or open loop fuel injection systems. Engine oil analysis. The investigation presented in the cited report is an extension of earlier tests (Orbital Engine Company. When using alcohol blended gasoline it has been observed that NOx emissions may increase compared to the use of neat gasoline due to the leaning effect of the alcohol. 2004). The project which finally included different parts was performed as an initiative of the Department of the Environment and Heritage project “Market Barriers to the uptake of Bio fuels – Testing Petrol Containing 20 % Ethanol (E20)” (Orbital Engine Company. The difference between the two types of gasoline. Fuel consumption measurements.1. 2004): • • • * Exhaust emissions measurements. included an assessment of durability over accumulated mileage and the following measurements and analyses at specific “breakpoints” (Orbital Engine Company. When reading the tables and studying the figures it should be noted that presented data on HC emissions include components other than hydrocarbons. Toyota Camry Altise. The tests carried out included comparative measurements of emissions from engines from engines running on neat gasoline and a blend of 20 % ethanol (E 20) in gasoline in pairs of the following five vehicles. During the survey of reports presenting data and experience related to the use of ethanol blended gasoline some data from emission and fuel consumption measurements have been found. In the following sections these data and experiences are briefly described. Evaluation of Emissions in Australia In Australia a number of investigations and emission tests have been conducted during the last five to seven years in a project initiated by the Department of the Environment and Heritage entitled “Market Barriers” (2004). especially those with advanced closed-loop fuel injection systems with adaptive learning functions are less sensitive in this respect.

but the emission performance of E20 was considerably worse than that of the neat gasoline at 80 000 km. Figures 7.1 there was only a small difference in emission levels when comparing the two fuels at 6 400 km. Regulated emissions at mileages of 6 400 km and 80 000 km.3 47. which includes the US 75 test cycle.8 CO 0.123 -10. Table 7. 7.1.2. Since one of the factors could be the catalyst system.177 0.1 NOx 0. .881 -6.9 26.4 To elucidate the reasons for the observed deterioration in emissions with accumulated mileage associated with use of the blends. The emission testing included both regulated and non regulated emissions and the main results were as follows.155 0.710 1.279 0. The three phases can be seen in Figure 7. The three phases of the test cycle followed during the emission test. of which Phase 1 (the first 505 sec) is the cold start phase – according to the test procedure the vehicle is initially equilibrated to a room temperature of around 20 to 25 °C. Fuel Type Regulated Difference (%) Emission Gasoline E20 (g/km) 6 400 km 80 000 km 6 400 km 80 000 km 6 400 km 80 000 km THC 0. Figure 7.3 and 7.1.065 0.445 27 151.097 0.Page 49 • • Engine wear analysis at completion of mileage accumulation. Since the effects of using ethanol-gasoline blends on engine wear have already been considered in this report discussion here is mainly focused on the emissions. The main results were as follows As can be seen in Table 7. Fuel system analysis at completion of mileage accumulation. especially with respect to loss of catalyst efficiency. The catalyst efficiency was studied for each of the three phases of the test cycle. the cited authors studied factors that could contribute to their impact on emissions.1.665 1.122 0.173 0. detailed analyses of the individual vehicles were carried out. The emission testing included measurements of both regulated and non regulated constituents and the tests were carried out in accordance with the Australian test procedure ADR37/01 for monitoring emissions from light duty vehicles.4 show the difference in the efficiency of the catalyst found when using the 20 % ethanol blended fuel compared with the use of neat gasoline in each of the three phases.

Gasoline vs E20 120 100 80 6400 km 80 000 km % 60 40 20 0 E20 E20 E20 E20 Gasoline Gasoline Gasoline Gasoline Gasoline E20 6400 km 80 000 km E20 Holden Ford Toyota Hyundai Subaru Figure 7.Gasoline vs E20 120 100 80 % 60 40 20 0 Gasoline Gasoline Gasoline Gasoline Holden Ford Toyota Hyundai Subaru .2. Gasoline E20 E20 E20 E20 .Page 50 Phase 1 of FTP 75 Catalyst NOx Efficiency for the Vehicle Fleet at 6000 and 80000 km . Figure 7. Phase 1 NOx catalyst efficiency when using E20 compared with neat gasoline after 6 400 and 80 000km driving. Phase 1 NOx catalyst efficiency when using E20 compared with neat gasoline after 6 400 and 80 000km driving Phase 2 of FTP 75 Catalyst NOx Efficiency for the Vehicle Fleet at 6000 and 80000 km .3.

2) suggests that the ULP grade was used in the neat gasoline tests. to some degree. Furthermore. Another factor to consider when studying data from emission tests is the impact of sulphur in the fuel. but elsewhere it suggests that PULP was also used.4. Gasoline vs E20 120 100 80 6400 km 80 000 km % 60 40 20 0 E20 E20 E20 E20 Gasoline Gasoline Gasoline Gasoline Gasoline E20 Holden Ford Toyota Hyundai Subaru Figure 7. during Phase 2 than during Phase 3. For the Toyota vehicles there is very little difference in catalyst efficiency between use of E20 and use of neat gasoline. it is not clear whether the same grade of gasoline was used for the ethanol-gasoline blends as that used for the neat gasoline tests. respectively. There is reason to expect the deterioration of the vehicles tested after 80 000 km driving to be linked. The three figures show several interesting features: • • • • There is a considerable difference between the pairs of vehicles. A table taken from the report (Table 7. to sulphur in the fuel used in the tests carried out by Orbital. The catalyst efficiency was somewhat higher.Page 51 Phase 3 of FTP 75 Catalyst NOx Efficiency for the Vehicle Fleet at 6000 and 80000 km -. the efficiency was considerably lower during Phase 1. Studies carried out for the American Lung Association of Minnesota have shown that sulphur in the fuel has a considerable impact on both regulated and unregulated emissions. The Australian gasoline specifications at the time of the tests show that the upper limits for the sulphur contents in ULP and PULP were 500 ppm and 150 ppm. although it can be assumed that even a sulphur content of 150 ppm in the base fuel would have had a considerable impact on the emissions. As expected. The most important observation to note is that the deterioration of the catalyst performance was considerably worse when using E20 than when using neat gasoline. Phase 1 NOx catalyst efficiency when using E20 compared with neat gasoline after 6 400 and 80 000km driving. There is a difference in catalyst efficiency when comparing the three phases of the test cycle. at least for some vehicles. According to Orbital two grades of gasoline were used in the ethanol blends: unleaded gasoline (ULP) and Perth unleaded gasoline (PULP). .

731 3.3 Toyota Echo 2001 1.106 0.045 0. Emission data from tests with neat gasoline and 20 % ethanol-gasoline blends.084 N/A 0.3 265.8 NOx 0.6 81.5 252.671 1.6 Number of cylinders V6 3 V8 4 4 Transmission Test inertia [kg] 1590 966 2160 1136 1250 Automatic Automatic Automatic Automatic Automatic * † AENFO02 results are based on tests conducted at 8 900 km rather than 6 400 km.126 0.2.871 2.1 236.798 126.6 -2.0 -4. 15% and 20%).3 N/A 250.5 CO2 255.4 143.9 CO 0.120 0.345 0.105 0.6 CO2 256.218 51.039 0.481 265.821 48.049 0.711 0.4 163.2 -0.142 0.174 0.6 * Ford THC 0.034 0.046 0.3.162 0.051 0.288 0.40 -3.4 250.191 0. ‡ In the available edition of the report it is noted that “the report has not undergone detailed technical review by the Environmental Technology Advancement Directorate” Canada.265 0.120 0.9 NOx 0.9 30.7 258.3 and the fuel properties are shown in Table 7.800 0.60 Subaru† THC 0.3 -1.079 0.083 0.125 0.457 0.147 0.025 0.070 0.043 0.5 46.071 0. Selected data for the tested vehicles.3 166.45 1.873 0.895 92.3 -3.8 235. Emissio 6 400 km 40 000 km 80 000 km % Difference n ULP E20 ULP E20 ULP E20 ULP E20 g/km Holden THC 0.472 1.7 0.031 0.0 11. The aim of the program was to compare emissions from the vehicles when using neat gasoline and oxygenated fuel (Augin and Graham.388 0. .155 0.5 CO 0.050 0.041 0.0 104.4 122.710 1.9 CO2 168.3 Toyota THC 0.697 0.075 4.024 0.6 225.9 CO 0.0 -12.5 Honda Civic 2001 1.1 293.0 254.8 -1.208 34.8 24.7 CO 2.4.18 0.065 0.2.2 7.6 81.Page 52 Table 7.8 172.6 -5.0 150.5 248.4 235.171 0.0 NOx 0.047 105.457 0.126 0.0 427.112 0.8 255.112 24. Vehicle Model Engine year displacement [L] Pontiac Grand Am 1999 3.9 CO 0.907 18. Evaluation of Emissions in Canada A report with a limited‡ distribution from Environment Canada describes a series of comparative tests carried out on five vehicles using neat gasoline and ethanol-gasoline blends (with ethanol contents of 10%.155 0.6 NOx 0.056 0.488 0.0 -2.8 260.0 253.15 0.0 253.865 0.1 NOx 0.304 0.8 250.845 0.637 -12.132 0.6 254.023 79.134 0.551 0. 2004).081 0.090 1. AENSU05 results are based on tests conducted at 7 600 km rather than 6 400 km. Table 7.6 259.059 0.059 0.030 0.4 Honda Insight 2000 1.063 0.100 0.119 22.036 0.104 58. The vehicles used in the tests are listed in Table 7.728 0.041 0.0 166.7 Hyundai THC 0.9 95.048 N/A 0.5 CO2 247.3 256.936 N/A 1.0 Chevrolet Silverado 1999 5.027 80.6 CO2 255.7 267.5 165.

according to the authors of the report (Augin and Graham.6 13.20 0. The emission tests were carried out in accordance with the US Federal Test Procedure (FTP 75) and two repeats of each cycle were performed on each vehicle in order to provide a minimal measure of the repeatability.7541 In this section the results from tests of regulated emissions are presented in the form of figures.3 0.5 to 7.9 and Tables 7.7 5.7 ARITHMETIC MEAN OF CARBON MONOXIDE [CO] EMISSION (5 VEHICLES) 0.5 % O by mass 3.7453 0.00 0 % EtOH 10 % EtOH 15 % EtOH 20 % EtOH Figure 7.7 82.5 7. 20 % Ethanol 79. A more complete set of emission data presented in the report by Augin and Graham is given in the Appendix 1.30 0.5 to 7.5 Density [g/ml] 0.Page 53 Table 7.50 g/km 0.4. 2004).3 13.5 13.7519 1 Summer Grade Commercial baseline tests of fuel.0 % H by mass 13.7497 0.10 0. The results of the emission tests are shown as means for the five vehicles in Figures 7. Mean emissions of carbon monoxide from the five test vehicles according to the US EPA FTP 75 test procedure .40 0.60 0.5.8 81. Fuel properties SGC1 10 % 15 % Ethanol Ethanol % C by mass 86. Selected data for the fuels used in the emission tests.

0 150.035 0.030 0.020 0.040 0.010 0.0 50.6.005 0. Mean emissions of NOx from the five test vehicles according to the US EPA FTP 75 test procedure.020 0.0 100.0 75.0 125. g/km .015 0.010 0.0 0.025 0.030 0. ARITHMETIC MEAN OF OXIDES OF NITROGEN [NOx] EMISSIONS (5 VEHICLES) g/km) g/km 0.060 0.080 0.000 0 % EtOH 10 % EtOH 15 % EtOH 20 % EtOH Figure 7.0 200.050 0.0 25.8.7.040 0.0 175.070 0. A RITHMETIC MEA OF CA N RBON DIOXIDE [CO2] EMISSION (5 V EHICLES) 225.0 0 % EtOH 10 % EtOH 15 % EtOH 20 % EtOH Figure 7.050 0.000 0 % EtOH 10 % EtOH 15 % EtOH 20 % EtOH Figure 7. Mean emissions of hydrocarbons (HC) from the five test vehicles according to the US EPA FTP 75 test procedure.045 0.Page 54 ARITHMETIC MEAN OF HYDROCARBON [HC] EMISSIONS (5 VEHICLES) 0. Mean emissions of carbon dioxide from the five test vehicles according to the US EPA FTP 75 test procedure.

814 Table 7.044 0.9.472 BDL three different Ethylene Toyota Honda Echo Civic mg/km mg/km 1.099 10 % Ethanol 0. Below Detection Limit.375 1.640 1.40 0.311 0.311 0.870 0.554 0.597 Table 7.087 0.541 0.6.491 0.406 1.846 4.640 BDL 20 % Ethanol 4.298 10 % Ethanol 0.143 0.5.332 2.019 0.90 0.344 1.360 0. Mean fuel consumption of the five vehicles according to the US EPA FTP 75 test procedure.20 0. Emissions of aldehydes when using neat gasoline and three different blends of ethanol.417 4.721 15 % Ethanol 0. Emissions of specific hydrocarbons when using neat gasoline and blends of ethanol.70 0.181 0.829 1.273 0.603 0.406 1.00 0.311 0.80 0. l/10 km .578 0.385 0.BDL means below the detection limit for the instrument used Methane Ethylene Acetylene Toyota Honda Toyota Honda Toyota Honda Vehicle ⇒ Echo Civic Echo Civic Echo Civic US FTP cycle mg/km mg/km mg/km mg/km mg/km mg/km 0 % Ethanol 4.261 1.671 0.338 1.50 0.622 BDL 15 % Ethanol 4.534 0.926 20 % Ethanol 0.615 BDL* 10 % Ethanol 4.423 * BDL.553 1.665 0.10 0.572 1. Table 7.373 0.212 4.212 0.7.30 0.379 0.416 1. Formaldehyde Acetaldehyde Toyota Echo Honda Civic Toyota Echo Honda Civic Vehicle ⇒ US FTP cycle mg/km mg/km mg/km mg/km 0 % Ethanol 0.653 15 % Ethanol 0.Page 55 A RITHMETIC MEA OF FUEL CONSUMPTION [FC] FOR N (VEHICLES) 1.00 0 % EtOH 10 % EtOH 15 % EtOH 20 % EtOH Figure 7.293 0.261 0.690 0.435 20 % Ethanol 0.516 0.848 1.615 0.60 0.423 0.952 4. Emissions of aldehydes when using neat gasoline and three different blends of ethanol. Formaldehyde Acetaldehyde Honda Insight Grand Am Honda Insight Grand Am Vehicle ⇒ US FTP cycle mg/km mg/km mg/km mg/km 0 % Ethanol 0.032 0.

respectively. 2002). • 7. • According to the presented data it is not clear whether the tailpipe emissions of CO2 increase or decrease when ethanol is blended with gasoline.1 g/km and there is no clear indication whether blending ethanol in gasoline increases or decreases them. • HC emissions amount to less than 0.8. The increase found in this investigation is also quite dramatic compared to corresponding increases found in other investigations discussed in this report. For the Toyota vehicle they decrease. especially when comparing vehicles with relatively large and relatively small engines.Page 56 The following conclusions can be drawn from the comparisons of the use of ethanol blended fuel and neat gasoline: There are considerable variations in the emission levels between different blends of ethanol in gasoline and also between the different vehicles. . The emissions of the measured specific hydrocarbons may either decrease or increase when using ethanol blended gasoline. CO emissions decrease when replacing neat gasoline with ethanol blended fuel.. The five vehicles tested are listed in Table 7. UK. Vehicle Model Engine size Emission Mileage identifier (litre) Standards km 1&6 Toyota Yaris 1.0 Euro III 22 000 2 Vauxhall Omega 2. on behalf of the UK Department of Transport. The aim of the tests was to generate data to be used as emission factors for gasolinefuelled vehicles in the European context. • The presented data provide clear indications that the emissions of formaldehyde increase when using ethanol blended gasoline.2 Euro II 51 000 4 VW Golf 1.6 Euro II 117 000 The fuels used for the tests were neat gasoline and a blend of 10% ethanol in gasoline. • For all vehicles except the Toyota Echo NOx emissions increase when using a blend of ethanol in gasoline. • As expected. * AEA Technology is a British technology company. An interesting point to note is that the RVP of the neat gasoline and the blended fuel was 60 kPa 66.5 kPa. Vehicles selected for emission testing and measurement of fuel economy. Harwell. the acetaldehyde emissions increase when using ethanol blended gasoline. • As expected fuel consumption increases when using a blend of ethanol in gasoline.3.6 Euro III/IV 21 000 5 Rover 416 1. • As expected. Table 7.2 Euro III 19 000 3 Fiat Punto 1. The Toyota Yaris was tested twice. Evaluation of Emissions in the UK A series of emission tests from five vehicles fuelled with a blend of 10% ethanol in gasoline has been carried out by AEA Technology plc*.8. since significant changes in the test procedure for unregulated emissions was made after the third vehicle was tested (Reading et al.

11.10 0.Page 57 The emission tests were conducted according to the current European test cycle.52 10.95 7. .96 8.9. Arithmetic mean of five vehicles tested according to the Cold start ECE emission test cycle.00 CO THC NOX Cold EUDC gasoline Cold EUDC E10 Figure 7.5 1 0.10.98/69) 2&8 WSL Congested 3&9 WSL Urban 4 & 10 WSL Suburban 5 & 11 WSL Rural 6 & 12 WSL Motorway 90 7 & 13 WSL Motorway 113 Hot/cold start Cold Hot Hot Hot Hot Hot Hot Duration (seconds) 1180 1030 1205 480 586 306 256 Target distance (km) 11.5 2 1.5 0 CO THC NOX Cold ECE gasoline Cold ECE E10 Figure 7. The WSL-tests (results from the WSL tests are not presented here) were carried out following the standard procedure for the test laboratory.30 0. Table 7.25 0. as listed in Table 7.91 6. A more complete set of emission data presented in the report by Augin and Graham is given in Appendix 1.15 0.35 0. Arithmetic mean of emissions from five vehicles tested according to the EUDC Cold start emission test cycle.10 to 7.14.20 0. It should be noted that only results from ECE/EUDC tests are presented here. In this section the results from tests of regulated emissions are presented in Figures 7. COLD START EUDC-EMISSION g/km 0.05 0. and six of the test cycles designed by the Warren Spring Laboratory (WSL).18 The ECE/EUDC tests were carried out following the defined test procedures.14 5.01 1.9. Cycle Cycle identifie r 1 1 ECE/EUDC (Dir.5 3 2. COLD START ECE-EMISSIONS g/km 4 3. ECE/EUDC. Test cycles.

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PA RTICULA TE EMISSIONS
mg/km 10 8 6 4 2 0 Cold ECE gasoline Cold ECE E10 Cold EUDC gasoline Cold EUDC E10 n.d.

Figure 7.12. Arithmetic mean of particulate emissions in tests according to ECE and EUDC Cold start emission cycles.
CARBON DIOXIDE EMISSION [CO2] g/km 300 250 200 150 100 50 0 Cold ECE gasoline Cold ECE E10 Cold EUDC gasoline Cold EUDC E10

. Figure 7.13. Arithmetic mean of CO2 emissions in tests according to ECE and EUDC Cold start emission cycles.
FUEL CONSUMPTION g/km 100 80 60 40 20 0 Cold ECE gasoline Cold ECE E10 Cold EUDC gasoline Cold EUDC E10

Figure 7.14. Arithmetic mean of fuel consumption in tests according to ECE and EUDC Cold start emission cycles. When comparing the data from the measurements of fuel consumption and emissions of regulated consitutents, PM and CO obtained using a blend of 10 % ethanol in gasoline with those obtained using neat gasoline the following conclusions can be drawn • Fuel consumption is slightly increased. • CO- and PM-emissions are significantly reduced. • HC emissions are increased rather than decreased. • NOx-emissions are not significantly increased. • For some of the vehicles the tailpipe emissions of CO2 are decreased.

Page 59

The unregulated emissions are increased for a few components while the emissions are decreased in most cases. There are significant differences between vehicles, so for some vehicles the emissions are increased while for others they are decreased. As expected, the emission of acetaldehyde is increased in most cases. In the following table the numbers of increases (+) and decreases (-) are presented. Unfortunately, the unregulated emissions were only measured from three vehicles (plus a repeated measurement on the Toyota Yaris) and there are only four comparative measurements for benzene and nitrous oxide. As can be seen in Table 7.10, ammonia and PAH emissions were only measured from three vehicles. Table. 7.10. Numbers of increases (+) and decreases (-) of unregulated emissions found in the tests using E10 compared to the tests using neat gasoline.
Changes Methane 1,3butadiene Formaldehyde Acetaldehyde Nitrous oxide Benzene Ammonia ΣPAH

Increase Decrease

2 7

2 7

2 7

6 3

1 3

1 3

2 1

2 1

7.4.

Evaluation of Emissions in Sweden

An extensive investigation was carried out in Sweden in which the amounts of both regulated and non-regulated constituents emitted were compared when using various types of gasoline, LPG, diesel oil, different blends of methanol and a blend with 23 % ethanol in lead-free gasoline (E23) to fuel the following vehicles: five Saabs, five Volvos, one Volkswagen and one Mercedes Benz (Egebäck and Bertilsson, 1983).The tests were carried out on the following vehicles: five Saab, five Volvo, one Volkswagen and one Mercedes Benz. None of these vehicles was equipped with a catalyst. Of all the tests carried out only those involving use of E23 are of interest here. Considering both the amounts of the emissions, and their mutagenicity, the results suggest that use of E23 has both pros and cons. For example, when comparing the use of the 23% ethanol blend in gasoline with the use of neat gasoline, the emissions of ethanol and acetaldehydes increased, while emissions of polycyclic aromatic hydrocarbons (PAHs), especially benzo(a)pyrene (BaP), and NOx were somewhat lower, as were the mutagenic effects. Since the temperature in Sweden is rather low in the winter -– occasionally down to minus 20 °C in the Stockholm area and minus 30 °C to minus 40 °C in the north of Sweden – and the mean temperature over the year is around plus 7°C in the Stockholm area (around 0 °C in the north of Sweden), the influence of the outdoor temperature on the emissions generated when using blended fuel and neat gasoline has been studied in a number of projects. It is well known that the use of an alcohol as a fuel in motor vehicles will increase the cold start emissions if the vehicle is not specially designed, i.e. equipped with an engine heater to improve engine starts. In one investigation (Egebäck et al., 1984) five well-maintained and carefully-checked cars without catalytic converters and one equipped with a three-way catalyst system were used. The vehicles were tested with unchanged fuel-air ratio settings (which were set for neat gasoline) with three different fuels. The fuels used were neat gasoline, 5% ethanol mixed with unleaded gasoline (E5), and 15% methanol mixed with a refinery-produced gasoline. All fuels were tested at 22 °C and the neat gasoline and ethanol mixture were also tested at +5° and -7°C. Since nearly all light duty vehicles with spark ignition engines in Sweden today are equipped with a three-way catalyst the results of the emission testing at different temperatures are of

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interest for this report. A comparison of the emissions from the catalyst-equipped vehicle adapted for the use of alcohol in neat lead-free gasoline can be seen in Table 7.11. Table 7.11. Emissions of regulated and non regulated emissions generated when using neat gasoline and E5 at different ambient temperatures. US-73 test cycle.
Fuel Temp °C Gasoline E5 CO g/km HC g/km NOx g/km Formaldehyde mg/km Acrolein mg/km Particles mg/km Σ PAH μg/km B(a)P μg/km Fuel– cons. l/10km

22 -5 22 5 -6

2.27 3.90 2.50 3.10 2.90

0.23 0.50 0.36 0.25 0.43

0.22 0.28 0.20 0.30 0.36

6.6 2.3 6.3 4.2 1.4

<0.1 <0.1 1.2 <1´2 0.6

8.2 30.1 8.5 26.8

49 33 71

0.9 2.1 2.2

1.09 1.26 1.17 1.24 1.26

As can be seen from the figures in the above table the ambient temperature has a clear impact on the emissions, especially the particulate emissions and (thus) PAHs. Starting the engine at low temperatures is known to have a stronger effect on the emissions when using fuels with high contents of an alcohol than when using neat gasoline. Important aspects of adding an alcohol to gasoline to consider are its effect not only on the exhaust emissions, but also on the evaporative emissions and how the fuel is changed by the addition. The aim of an investigation carried out by Laveskog and Egebäck (1999) for the Swedish Transport and Communications Research Board (KFB) was to study the effect of such additions on the RVP of the fuel and the evaporative emissions by adjusting the vapour pressure of the fuel. Two types of gasoline were ordered from a refinery with vapour pressures (RPV) of 63 kPa and 70 kPa. To elucidate the strength of the effect of adding alcohol on the vapour pressure, samples were sent to a special laboratory for analysis (see “Fuel type”, Table 7.12). Both regulated and evaporative emissions were measured (the latter by the standardised SHED method. Ethanol blended fuel was compared with neat gasoline in order to determine how addition of ethanol affects the exhaust emissions and evaporative emissions compared with neat gasoline. In total, three vehicles were each tested, once, with three test fuels with two different vapour pressures, yielding a total of 18 emission tests. Of the three cars tested, two were equipped with a catalytic converter. The two older cars – a Volvo 240 GL 1985 model and a Volvo 240 DL 1987 model – represented the technology level found in most cars sold in Sweden in the years following 1987 but only the latter had a catalytic converter.. The age of the oxygen sensors and catalysts of this car corresponded to approx. 50,000 km driving in traffic and they were designed to meet the Swedish A12 emission requirements. The other vehicle, equipped with a catalytic converter, was a Saab 9000T and the engine of this car was upgraded to correspond with a 1996 model, equipped with an adaptive fuel supply system, which automatically adjusts the rate of injected fuel according to the energy content of the fuel. In addition to the emissions tests, the oldest car was also tested for evaporative emissions (SHED test) with the base gasoline (71.5 RVP), base gasoline (64 RVP) + 10% ethanol, and base gasoline (71.5 RVP) + 25% ethanol. The emission test results and the fuel consumption for the catalyst-equipped cars (Volvo DL and Saab 9000T) are presented in Tables 7.13 and 7.14.

Fuel type Density g/mL Ethanol % Energy content MJ/kg / MJ/l RVP.15 0.06 0.15 0.18 0.764 25 39.13 0.750 <0.754 10 1) 25% ethanol with gasoline 0.06 0.755 <0.17 0.21 0.12 0. Results of the measurement of exhaust emissions during an urban driving cycle (UDC) according to US standards. 10% EtOH Cat.15 1.07 0. 64 69 67 71.04 1.03 1.11 1.99 1. Base gasoline. Results of measurements of exhaust emissions during an urban driving cycle (UDC) according to US standards.791 g/mL at 18 °C according to 2) The energy content for ethanol is set to 27.12.5 76 73 1.98 0.06 1. Saab 9000 CS.05 0.3 2) 1) The density of ethanol is 0.13 1.16 0.14. kPa analysed Gasoline with lower vapour pressure (63 kPa) Unmixed gasoline 0. 25% EtOH Cat.05 0.08 Volvo DL 0% EtOH 10% EtOH 25% EtOH 0% EtOH 10% EtOH 25% EtOH Cat.11 Table 7.06 Fuel consumption l/10 km 0.04 0.06 0. Volvo 240 GL.5 kPa.71 0.06 1.23 1.13 0.08 Saab 9000 T 0% EtOH Cat.23 0.1 / 32. 64 69 67 71. Cat.1 1) 10% ethanol with gasoline 0.05 0.760 25 43.9 42. 10% EtOH Cat.82 1.15 0.05 0. Cat.5 kPa. 1996 engine and engine management system.0 2) 1) 25% ethanol with gasoline 0.8 2) 39.1 MJ/kg 71.13.17 0.00 1. Base gasoline 64 and 71.5 76 73 2.13 0.5 1) 10% ethanol with gasoline 0.17 0.30 243 240 235 243 240 238 0.14 0.6 / 30.09 1. 0% EtOH Cat.2 / 31. 64 kPa and 71.17 0. Car Amount EtOH% Exhaust System RVP kPa CO g/km HC g/km NOX g/km CO2 g/km NMHC g/km Fuel consumption l/10 km 1.19 0.03 1.04 1.759 10 42. Cat. Cat.8 / 33.16 1.05 0.13 2.10 0.Page 61 Table 7.01 1.14 0.18 0.12 242 253 250 251 244 238 .25 0.08 1.7 / 30.13 1.5 76 73 Table 7. Cat.5 43. Car Amount EtOH% Exhaust System RVP kPa CO g/km HC g/km NOX g/km CO2 g/km NMH C g/km 0. 1985 model.2 2) 64 69 67 Gasoline with higher vapour pressure (70kPa) Unmixed gasoline 0.9 / 32.06 0. Analysed and calculated values for test fuels.14 0. 25% EtOH Cat.

Page 62 The CO and HC emissions were lower for the Volvo with a catalytic converter (Table 7. NOX emissions rose from 0. Efficiency also seemed to increase for this car.14).S. 2002). However.5 RVP +10% ethanol g/test 37. The results from the tests of this car are presented in Table 7. all emissions decreased slightly with the 10% ethanol mix.15.30 g/km. In contrast to the few reports found for blends with low ethanol contents a number of studies were found concerning emissions from FFVs.13). but insignificantly with the 10% mixture. values from single measurements using fuels with 0% and 10% ethanol contents. Volvo 240 DL.15. Department of Agriculture part-funded the work. including California. Unfortunately. Evaporative losses from a car without evaporation controls. . NOX emissions were low. Evaluation of Emissions in the USA Few American studies were found in the literature survey that included measurements of emissions from commercial gasoline-based fuels with low alcohol contents suggesting that such measurements and studies have low priority in the USA. In the tests with the fuel with an RVP of 71. The emission measurements were carried out at the University of North Dakota and the U.S. 71. 1985 model. 64 RVP +10% ethanol Base gasoline.5 kPa was used. When gasoline with a vapour pressure of 71. initiated by the American Lung Association of Minnesota on the exhaust emissions from gasoline with low alcohol contents was found.5 kPa. Department of Agriculture part-funded the work. which lacked a catalyst and canister for trapping fuel vapour. With the 25% ethanol mix. NOX emissions increased significantly when the gasoline with a vapour pressure of 64 kPa was used. Despite the increase. The comparison of these two cars indicates that a car with an adaptive emission control system has better emission characteristics than a car without such a system.5. and showed a tendency to fall further as the ethanol content in the fuel increased. as the increase in fuel consumption for ethanol mixtures does not correspond to the reduced energy content of the test fuel. HC emission Base gasoline. The emission measurements were carried out at the University of North Dakota and the U.2 38.19 g/km to 0. In Minnesota a series of studies.4 Increase in emissions [%] 4. In Minnesota a series of studies was commissioned by the American Lung Association of Minnesota on the exhaust emissions from gasoline with low alcohol contents (Aulich and Allen. In the car with an adaptive fuel supply system the effect of the ethanol mixture on CO emissions appears to be small.6 14 7. 71. and the already very low level of HC emissions were almost totally unaffected (Table 7. it should be borne in mind that gasoline blended with 10% ethanol has been commonly used in many areas in the USA during the last 20 to 25 years. the tendency was the same as for the other cars – the fuel consumption was lower than expected when ethanol was added to the gasoline.9 42.5 RVP Base gasoline. Table 7. the NOx emissions were still lower than the emission standards for this car. evaporative emission tests were only carried out on the Volvo 240 GL.

2000 / Rules and Regulations the level of sulphur should be reduced. EPA Statutory Antidumping Baseline Fuel Parameters.00 300 90.0 339 In 1999 the EPA introduced more rigorous emission standards. 2000. University of North Dakota. 2006 and subsequent N/A 30. 65.6 10. November 29.9 RVP. Table 7. vol% 32. 28 / Thursday. the EPA has established new requirements for the sulphur content in gasoline. No.00 300 N/A 300 Refinery or Importer Average Corporate Pool Average Per-Gallon Cap The paper by Aulich and Allen of the Environmental Research Center.00 120. According to the Federal Register / Vol. 65. Since the sulphur content is one of the most important variables to reduce in the fuel.7 46. psi 8. See Federal Register / Vol. .7 8. which have shown that the emission rate depends considerably on the fuel used.2 vehicle emission * The purpose of the Antidumping Requirements is to ensure that conventional gasoline is not more polluting than it was in 1990. February 10. vol% 83. 230 / Wednesday. to 15-40 ppm by weight and limited to a maximum of 80 ppm by 2006. No.0 83. see Table 7.60 28.17.4 Olefins. . ppm 339 338 Average Annual 1. 2004 January 1. Minnesota gasoline is regulated under the Antidumping* Requirements introduced by the EPA and therefore it is of interest to study whether these requirements are fulfilled. Table 7. benzene and olefins contents in gasoline. February 10. released by the American Lung Association of Minnesota.8 8.16. on average. vol% 41. The Antidumping Statutory Baseline Fuel Parameters set by the US EPA are shown in Table 7. Summer Winter Benzene.7 E200. Gasoline sulphur requirements according to the Federal Register.0 E300.16.00 30.0 83.0 Sulphur. 2005 January 1. The aim of the investigation discussed here was to further study the impact on emissions of the sulphur. vol% 9.17.Page 63 Since 1999.0 50.64 Aromatics. necessitating amendments to the fuel requirements. Samples of gasoline from three different gasoline suppliers were analyzed in detail and the impact of the fuel sulphur content was evaluated by using the resulting fuel data as inputs in the EPA’s MOBILE6. the American Lung Association of Minnesota has been presenting studies on the impact on emissions of sulphur in the fuel and this issue has been discussed in a number of reports. vol% 1. reports results from an evaluation of the impact of fuel sulphur on emissions.53 1.2 11. 2000 / Rules and Regulations. Gasoline sulphur standards for the averaging period beginning: January 1.0 26.

% Benzene in Fuel. vol% Olefins.5 1.18. Holiday.19.5 1.2 24. .3 24. The estimated impact of fuel sulphur content on HC and NOx emissions.0 30.0 49 BP E10 10.19 are shown in Table 7.Page 64 modelling software (US EPA 1993). g/km Benzene.0035 6 0. The results of this part of the evaluation are summarized in Table 7. vol% Sulphur.0055 7 1.2 23.2 15.098 0. Therefore.5 9.3 7.50 167 SA 0.31 57 Amoco 0. vol% Aromatics. Holiday. ppm Holiday 0. 23 samples of fuel containing 9.9 212 SA E10 10. ppm The emission tests followed the “hot start” phase of the FTP-75 test cycle.6 8. there is a need to keep the contents of these components as low as possible in gasoline.1 90 Non-ethanol 0. Table 7.3 Butadiene. is known to have an effect on people’s health while olefins comprise a group of hydrocarbons that are known to be reactive in the atmosphere and may also cause deposits in the fuel system of the vehicle. Amoco and SA (SuperAmerica) are gasoline companies. g/km Olefins in Fuel. vol% Benzene.8 % ethanol were analyzed.0064 17 2. % In another study presented by the American Lung Association of Minnesota (2003) the five blends of fuel listed in Table 7.51 188 Two other components in the fuel that have a significant impact on the emissions are olefins and benzene.20 were studied to assess the impact of sulphur. In all. g/km Sulphur in Fuel. a single component of gasoline.095 0. Table 7.9 Amoco 0. Average Fuel Properties (American Lung Association of Minnesota. 2003).00034 0.1 N/A 103 E85 78.00050 0.19.069 0.3 SA 0.4 N/A N/A N/A 8 Ethanol. The results of the tests carried out on a dynamometer and the data evaluation for the fuels listed in Table 7. The results of the evaluation conducted by Aulich and Allen on the impact of olefins and benzene in the fuel are summarized in Table 7.18.2 to 9. The estimated impact of the fuel contents of olefins and benzene on emissions of 1. Table 7.4 1.21. Amoco and SA (SuperAmerica) are gasoline companies. Holiday 0. g/km NOx.00071 0. Benzene.3 butadiene and benzene.20. Holiday E10 10. HC.7 1.

or as fuel economy (miles/US gallons) in the USA and Canada.g.2.21. In another report Orbital Engine Company has presented results from measurements of fuel consumption according to the Highway Fuel Economy Cycle (HWFET). HC and NOx emissions were similar to those for the BP and SA fuels. This statement is consistent with findings by Laveskog and Egebäck. g/km NOx.019 49 BP 0. cold start FTP cycle.005 0. g/km Sulphur. and the estimated levels of these emissions had to be based on their respective detection limits. but the levels were higher than for the other fuels tested. according to some other sources. which had a sulphur content of just 8 ppm. However. the difference in energy content “is compensated by the fact that the combustion efficiency of the ethanolblended fuel is increased” (Canadian Renewable Fuels Association. e.056 0. 2004).108 90 Non-ethanol 0. HC.010 0. than for the other fuels. a literature review prepared by the Orbital Engine Company for Environment Australia.4) indicated that the lower energy content of the blended fuel was to a certain degree compensated by its higher combustion efficiency (Laveskog and Egebäck. 1999).072 0. The impact of fuel sulphur content on HC and NOx emissions.097 0. In a paper from the Canadian Renewable Fuels Association it is declared that although a 10 % ethanol blend contains about 3 % less energy than neat gasoline. ppm Holiday 0.Page 65 Table 7. For the BP fuel HC emissions were consistent with the predictions according to MOBILE6. 2002). The emissions of HC and NOx were much lower for E85.15 (Orbital Engine Company 2004). Fuel Consumption The consumption of fuel is either measured and presented as fuel consumption (L/10 km or L/100 km). For the non-ethanol fuel with a sulphur content of 103 ppm. since their investigation (discussed in section 7. 7.119 103 E85 0. . The measured emissions were significantly lower than the levels predicted by the EPA model.080 212 SA 0. as shown in Figure 7. Adding an alcohol such as ethanol to gasoline at up to 5 to 10% may result in a minor increase in the volumetric fuel consumption. possibly because the tests were carried out with hot cycles while the EPA predictions were based on a complete.037 8 The cited study emphasises that: • • • • HC and NOx emissions for the Holiday fuel were under the detection limits. there is a direct proportionality between fuel economy and the energy content of the ethanol-gasoline blend (Orbital Engine Company.6.

18) the fuel consumption results are presented.1. and in the following figures (7. The measurements of emission and fuel consumption were carried out on five vehicles of “newer” models and comprised tests in which both gasoline and ethanol were used in the same vehicle in order to generate comparative data. Some results of the emission measurements carried out by the Orbital Engine Company to study the efficiency of catalysts are presented in section 7.15. The EPA Highway Fuel Economy Cycle.16-7.Page 66 Figure 7. .

16.400 and 80 000 km when driving according to the city cycle Metro-Highway Average Fuel Consumption for the Vehicle Fleet over milage. Average fuel consumption of the tested vehicles at 6.18.17. Gasoline vs E20 9 8 7 6 5 4 3 2 1 0 E20 E20 E20 Gasoline Gasoline Gasoline 6400 km 80 000 km Fuel Consumption [/100 km] E20 Gasoline Gasoline Holden Ford Toyota Hyunday Subaru Figure 7. Fuel consumption of the tested vehicles at 6.400 and 80 000 km when driving according to the cycle city Highway Average Fuel Consumption for the Vehicle Fleet over milage. Gasoline E20 E20 . Average fuel consumption of the tested vehicles at 6. Gasoline vs E20 Fuel Consumption [l/100 km] 12 10 8 6 4 2 0 E20 E20 E20 E20 Gasoline Gasoline Gasoline Gasoline Gasoline E20 6400 km 80 000 km Holden Ford Toyota Hyunday Subaru Figure 7.Page 67 Fuel Consumption [L/100 km] FTP 75 Average Fuel Consumption for the Vehicle Fleet over milage. Gasoline vs E20 14 12 10 8 6 4 2 0 E20 E20 E20 Gasoline Gasoline Gasoline 6400 km 80 000 km E20 Gasoline Holden Ford Toyota Hyunday Subaru Figure 7.400 and 80 000 km when driving according to the city cycle.

MJ/10 MJ/10 Diff.22 +10.22 35.85 +0.85 1.90 53. such as changes of tyres or other parts which could have affected the results of the study.19 +14.42 34.37 -1.64 -4.70 +2.09 1.50 +3.84 2.65 +3. 2004).indicates a reduction in fuel consumption and energy use when comparing E30 with E10.00 1992 Chevrolet K1500 1. 2004). . the first of which concerned fuel consumption.51 1.73 + indicates an increase in fuel consumption or energy use when comparing E30 with E10.98 +5. A third form concerned drivability. It should be noted that the authors of the present report have not had access to appendices to the cited report.92 1997 Chevrolet K 1500 1.23 37.46 35. which was carried out to measure fuel consumption and emissions.28 1.66 31. the drivers of the cars during the field tests had to collect samples of oil for analysis and to record data concerning: • • • maintenance and performance of the vehicles.24 +12..16 1997 Chevrolet K3500 1. The drivers were asked to fill in forms. Vehicle E10 E30 % E10 E30 % l/10 l/10 Diff.06 1997 Ford Taurus 1. while a second concerned maintenance. km km km km 1996 Oldsmobile Acieva 1.69 1.93 34. The fuel consumption and energy used per unit distance in the chassis dynamometer tests were matched to the distance driven in the on-road tests.81 58.69 +11. Two blends of ethanol in gasoline. drivability complaints.14 58.78 51.01 1.01 +8. During the on-road tests the vehicles were driven by their owners (Bonnema et al.28 31. .24 34. including changes to the car. and hence have not been able to verify the interpretation of the data collected.41 1998 Ford F-250 1.22.01 +1.39 1992 Geo Metro 0.99 53.09 1.38 1990 Chevrolet C1500 1.96 33.86 +8.04 19. Oil samples were taken to analyse particles in the oil to evaluate whether accelerated wear of the engine had occurred.22.68 +9.60 -6. Consequently.42 +1.26 54.. Minnesota State University. were used during the test program.66 1994 Buick Regal 1. The vehicles were tested on a chassis dynamometer according to both the hot 505 section of the standard test cycle and on the road when driven by owners of the cars.56 48.65 1.74 57.42 20. E10 and E30.54 1997 Ford F-150 1.52 +8.Page 68 A research project has been carried out on 15 vehicles of models from different years by a group at the Minnesota Centre for Automotive Research.33 57. The results for fuel economy obtained in the Hot tests on the chassis dynamometer are summarized in Table 7. Fuel consumption and energy use when tested according to Hot 505 procedures (Bonnema et al. based on the volumetric consumption. Table 7.88 47.29 +1. fuel consumption.97 +6. and to analyse drivability characteristics.62 0.30 40. engine wear and material compatibility.06 1.09 +2.11 1998 Dodge Caravan 1.15 +3.

the table shows a decrease for three of the vehicles. the influence of using ethanol-gasoline blends with higher ethanol contents should be similar to their effect on fuel consumption. the lower energy content of the ethanol blend may be somewhat compensated by its higher octane rating. The fact that vehicle studies have found a great diversity of responses to increasing ethanol content in terms of fuel consumption can be explained in a number of ways. provided that the engines used have advanced ignition (knock control) systems according to Chandra Prakash (1988). although knowledge of these variables is essential for fully understanding the data. but as can be seen. especially during acceleration and take-off from standstill. or to uncertainties in the measurement of fuel consumption. This may be due either to these vehicles being more energy efficient. . the data in the above table indicate that there were differences between vehicles with respect to the effects of the ethanol blend in gasoline. and it is run in an area where the base fuel used has a relatively low octane number. as expected. For example: If a test compares a fuel with no ethanol and one with a 10% ethanol content. However. Fuel consumption increased on a volumetric basis when E30 was used instead of E10. and the differences varied from less than 1% to over 12 %.Page 69 However. Carburetted vehicles may be affected by lean-mix problems if adjusted to a “low fuel consumption” setting. Concerning the energy used. which was less than expected. a complicating factor is that the cited studies do not supply specific information on either the engine specifications or the fuels used for testing.

1991).1 the Reid Vapour Pressure (RVP) (measured. In contrast. which is removed to produce low RVP gasoline (Korotney.e. i. 1977. and increasingly polar as the ethanol content increases. polar solvents dissolve polar solutes and nonpolar solvents dissolve nonpolar solutes. A compound in gasoline which has a major impact on the RVP is butane (Korotney. branched and aromatic hydrocarbons). RVP. by definition. kPa 80 70 60 50 40 30 20 10 0 0 20 40 60 80 100 Volume % ethanol Figure 8. in Figure 8. Reid Vapour Pressure (at ~38 °C) shown as a function of the percentage of ethanol blended with gasoline (gFurey and Jackson. introducing polar compounds like ethanol into gasoline (which is nonpolar) makes the gasoline blend more polar than neat gasoline. The neat gasoline from 1997 (Furey and Jackson. which are nonpolar and have different boiling points. For both of the fuels shown in the figure the highest relative RVP was obtained at a percentage of ethanol in the neat gasoline of about 10%. VAPOUR PRESSURE It is known that adding ethanol to gasoline raises the vapour pressure of the fuel. The lightest chemical component of gasoline fuel in general is butane. In Figure 8. Thus.Page 70 8. with relatively low boiling points (and hence relatively high vapour pressure). The chemical explanation for this is that gasoline consists mainly of hydrocarbons (straight. since nonpolar compounds in the neat gasoline. Hence. 1996).1. This indicates that the evaporative emissions from ethanol blended gasoline consist mainly of butane. This results in the vapour pressure of the ethanol-gasoline blend rising. Decreasing the initial vapour pressure of the neat gasoline will reduce the absolute vapour pressure of a 10 percent ethanol blend. will evaporate as the gasoline blend becomes more polar. It is a well-known fact from solubility investigations that like dissolves like. 1977) had a higher initial vapour pressure than the gasoline from 2002 (Hsieh et al. 2002). there are strong indications that the maximum RVP will be obtained at a 5 to 10 percent ethanol content in gasoline.1 the largest vapour pressure increase (a approximately 10 % increase in the RVP) is observed in the 0 to 5 percent ethanol interval. .. regardless of the neat gasoline fuels used. ♦DOE. Furthermore. at 100 ºF) is shown as a function of the percentage of ethanol blended with gasoline. 1996). the ethanol molecule (CH3CH2-OH) contains a hydroxyl group (-OH) which makes it polar.

mid and premium grade gasoline containing ethanol (3. In the early 1980s Furey (GM) reported that even a low level of alcohol in gasoline could have a high impact on the vapour pressure of the fuel (Furey 1985. A report prepared for the Swedish Transport and Communications Research Board presented a limited investigation of two fuels (one vapour pressure-adjusted and the other unadjusted) used in three cars (see also section 7. a graph for converting psi to kPa and vice versa (based on a psi to kPa conversion factor of 6.5 kPa. A large number of paper and reports have focused on the fact that blending ethanol in gasoline increases the vapour pressure. In many countries. The increases in vapour pressure found after adding 10 % ethanol were 5 kPa and 4. respectively. n-pentane. 1986. An important issue in several countries related to the increase in vapour pressure caused by mixing gasoline with ethanol has been whether or not compensatory adjustments should be made to the vapour pressure of the base gasoline. in a headspace analysis in which they concluded that n-butane. RVP is commonly expressed in kPa units.71 0.Page 71 The compounds in the vapour phase from regular. To facilitate comparisons.91 0.51 0. including European countries. Graph for converting psi to kPa and kp/cm2.61 0. 1990).65 wt%) have been investigated by Harley and Coulter-Burke (2000).2. 110 100 90 80 70 60 50 40 6 8 10 psi 1.41 12 14 16 kP/cm 2 kPa Figure 8.11 1. 2-methylbutane and ethanol collectively accounted for more than 50% of the total headspace vapour mass at 38 ºC. In the EU. A commonly quoted figure for the increase in RVP when blending base gasoline available on the US market with 10% ethanol is 1 psi (a little less than 7 kPa).01 0. especially in the USA.81 0.25 to 9. Since many countries have regulations concerning RVP failing to meet the standards may even be illegal. the RVP of gasoline is regulated by the European gasoline standard (EN 228). while psi (pound per square inch) is used in the USA. . for example “Issues Associated with the Use of Higher Ethanol blends” (NREL 2002).4).895) and psi to kp/cm2 (another unit for measuring RVP used in some reports) is shown in Figure 8. see below concerning the “1 psi waiver”. and this phenomenon has been investigated in a number of studies. If it is not adjusted the RVP may increase above regulated limits and may result in increased evaporative losses.2.

Two letters from EPA staff claim that a fuel that met RFG requirements in every respect except its RVP and had an RVP of 1 psi over the limit would increase VOC emissions by about 20 % relative to a baseline gasoline. even if the gasoline is not adjusted to comply with RVP requirements (i. is that the use of ethanol blended gasoline is recommended in CO non-attainment areas. Thus. 8. such as the USA. One factor to take into account. The opinion among the rule makers within the EPA was that ethanol is cheaper than MTBE per gallon and that this cost difference could well compensate for the costs of adjusting the RVP. Documents from the California Air Resources Board (CARB) (CARB. The effect of this waiver is discussed in a study released by the EPA that provided part of the rationale for introducing reformulated gasoline (RFG). especially for the US EPA. There has been ongoing debate in the USA about whether or not this waiver should be retained. which at the time could be either MTBE or ethanol (US EPA. gasoline containing an oxygenate. However. another relevant issue is driver acceptance of the fuel. The US EPA has been arguing that the waiver for ethanol-blended gasoline can be seen as a barrier hindering the broader introduction of reformulated gasoline. adding ethanol to gasoline has provided a means to meet CO levels required by the air quality standards in many of the current. have decided to decrease the vapour pressure of the base gasoline used in alcohol blends in order to meet the existing standards/regulations. 2000). and one of the most controversial questions addressed when the RFG rule was drafted was how ethanol/gasoline blends should be treated.USA In the USA the vapour pressure of 10% ethanol-gasoline blends has been allowed to exceed the limits imposed for conventional gasoline by 1 psi (the “1 psi waiver”) Andress. In the cited paper (US EPA. and in the fuel’s ozone-forming potential. 1993) the EPA also discussed the detrimental effect on emissions of granting the waiver of 1 psi RVP. On the other hand. and hence increase VOC emissions. 1998) show that replacing gasoline with ethanol may clearly reduce CO emissions. since blending ethanol in gasoline will increase the vapour pressure of the fuel. i. since an increase in the use of ethanol. so-called CO non-attainment areas. Australia and Sweden.1.e. as a replacement for MTBE. would increase demand for ethanol. Since both VOC and NOx are important emissions in the formation of tropospheric ozone the 1psi waiver has not been applied to mixtures of ethanol in reformulated gasoline (RFG). An argument propounded in comments sent to the EPA was that ethanol would be excluded from the market without a waiver.Page 72 Since a high vapour pressure of the fuel may cause vehicle drivability problems and make hot starting impossible as a result of vapour lock. RVP . there has been pressure from the farmers producing ethanol and the Ethanol Fuel Association. the EPA had to accept that adjusting the RVP could lead to cost penalties. . It was proposed that a renewable oxygenate should be used.e. 1993). According to the literature some countries at least. The EPA argued that the base gasoline had to be adjusted to ensure that the vapour pressure met the standards. for the ethanol blended fuel. the 1 psi waiver is applied). which is primarily intended for use in ozone non-attainment areas to avoid increased formation of ozone. which are minor compared to the cost of adding oxygen via oxygenate additions. these documents also show that adding ethanol to gasoline without adjusting the RVP leads to increases in the emissions of volatile organic compounds (VOCs) and nitrogen oxides (NOx). However. inter alia.

Wilson.9 -4.1) (1. Gary Whitten.0 1.2 7.Page 73 Furthermore.8 1. Finished Gasoline RVP Approximate RVP Increase Requirement when Ethanol is Added to Make a 10% Blend 9.4) Sources: William J. Table 8. "Update of the Relative Ozone Reactivity of Reformulated Gasoline Blends.1. 1993). see Table 8.9 2.0 1.1.1. The reduction will be less if ethanol blended gasoline is used. assuming half of that at higher market shares based on analysis (US EPA. the effect of adjusting the RVP of base gasoline intended for blending with ethanol.9 1. Fuel Studies and Standards Branch. Washington. RVP effect of blending ethanol to the base gasoline. A primary feature it displays is that there is a relationship between the RVP of the base gasoline. 2002) discusses the energy losses from the gasoline pool due to removing C4 and C5 hydrocarbons from it in order to meet the RVP requirements of gasoline without the 1-psi waiver.4 7. paper presented at the National Conference on Reformulated Gasoline and Clean Air Act Implementation.” Acro Chemical Company. as can be seen in Table 8. Consequently. and considerably less if RVP-adjusted gasoline is not used as a base according to the EPA estimations.3 Base Gasoline RVP Adjustment Needed if 1 Pound Waiver Not Allowed (1.2 Table 8.7 7.1 8." June 11. inter alia. Publication 4261 The paper cited above (EIA. ** Commingling.2.2 Percentage Change from 100% N/A 28 74 87 98 MTBE Baseline * Emission percentage change input values shown are based on those calculated in the letter from Chester France to Dr. Piel. DC.3) (1. Inc. and the magnitude of the impact on the RVP when adding ethanol to the base gasoline is shown in Table 8. A paper from the US Energy Information Administration section (EIA. Losses of “In-Use” VOC Emission Control as a Result of the Ethanol Waiver for RFG* Ethanol Market Share (%) 0 8 24 30 35 % VOC Reduction Due to 11 10.2** -2.4 0. The study that the paper was based upon was initiated by discussions about the possible removal of the 1-psi waiver following a request by Senator Bingaman .0 7. the EPA argued at that time that ethanol blends with a 1 psi waiver would have an advantage over RFG and thus might dominate the market (US EPA.2 MTBE Share % VOC Reduction Due to 0 -1.4 Total % VOC Reduction 11 7. Office of Mobile Sources.6 Ethanol Share (with distillation) % VOC Due to Commingling 0 -1. 2002) of the US Department of Energy (DOE) describes. to Richard D. 1993. Machiele. The estimated reduction in VOC emissions likely to follow the introduction of RFG based on unblended gasoline is estimated to be 11 %. Director. American Petroleum Institute. 1993). Alcohols and Ethers. October 1991. Information Resources.4 -2. Memorandum 6 from Paul A.4 -2. the reduction in VOC emissions will diminish as the ethanol market share increases.1 -3. “Oxygenate Flexibility for Future Fuels.0 -3.

5% 4. especially California. refined from crude petroleum.1 psi. 2002). where the maximum RVP allowed is 7.2% 7.0 psi RVP requirement and a 7.3% 2.8% RVP A paper published by the US EPA (Korotney. called hydrocarbons.1 % increase in the energy of the gasoline pool if there is a 7.3% -0. Energy Information Administration.9% 5.8 psi to 8. while RFG is “blended to burn cleaner and reduce smog-forming and toxic pollutants” (Virginia Department of Environmental Quality 2005).0 to 7.1% 7. It is interesting to note that an adjustment of the base gasoline intended for use with ethanol blends in order to keep the RVP under the required limits may reduce the energy content of the gasoline pool to a larger degree than the energy supplied by the added ethanol (EIA. These two examples could be used as models for calculating the effect of adjusting the base gasoline for blending.2 psi. However. 2004). 2002). but also to reduce emissions . Low RVP gasoline is produced from conventional gasoline by removing butane (EPA 1996). In contrast.5% 7.5 % increase if there is a psi 9. Korotney addresses implications of the facts that the only compound removed from conventional gasoline is butane and that low RVP gasoline is produced solely to meet the RVP requirements of 6.Page 74 (Chairman of the Senate Committee on Energy and National Resources) presented in a separate paper (Office of Oil and Gas of the Energy Information.3 kPa). it should be emphasised that the components (mostly butane) removed from the base gasoline when adjusting the RVP will generally be used for other purposes and not wasted. The increase in evaporated hydrocarbon emissions that will occur if the RVP is not adjusted should be analyzed and discussed when deciding whether these polluting emissions will be unacceptably high (see table below). Not adjusting the base gasoline intended for use in 10 % ethanol blends will result in a 5.0 8.5% 7. when deciding whether it should be adjusted or not. in energy terms.8 % reduction in its energy content. Conventional gasoline is a mixture of compounds.0 RVP requirement. However. the magnitude of the reduction in energy content depends on the RVP requirement and the gasoline used for blending. “Reformulated gasoline (RFG)” and “Conventional gasoline”. adjustment of the gasoline to be used for blending with 10 % ethanol will result in a 2.8 10.2% 6. in areas of the USA where the maximum RVP is 9 psi (62. plus small amounts of a few additives (Utah Petroleum Association.8% -0. with typical values of 7. Conventional gasoline is also called “Commercial gasoline” and in certain areas of the USA will be blended with ethanol (commonly to 10 %).1% -2.0 psi (48.1 kPa) the result of adding 10 % ethanol to RVP adjusted gasoline will be a 4.0 11.Since the intentions when designing reformulated gasoline were not only to meet the RVP requirements. 1996) considers RVP-related characteristics associated with three different gasoline blends: “Low RVP gasoline”.5 % increase in the energy content. Volume and Energy Effects of Adjusting RVP Prior to Adding Ethanol Volume Change due to Adding Energy Change due to Adding Ethanol to Make a 10% Ethanol Ethanol to Make a 10% Ethanol Blend Blend Without RVP With RVP Without RVP With RVP Waiver Waiver Waiver Waiver 9. In the USA.

C.Page 75 of toxic substances. there is no tax reduction for ethanol in Brazil today. they carried out was limited. • • Another paper released by the EPA (US EPA. Today. The introduction of ethanol was due more to rural and agricultural politics than to environmental concerns. RFG. In addition. because its low production costs (reduced incrementally over the past 20 years) allow it to compete on the fuel market without any such advantages. Ethanol is regarded as an environmentally friendly fuel with low CO2 emissions. Nevertheless. 8. a number of FFVs and vehicles optimised for running on neat ethanol are being used in Brazil. all marketed gasoline is blended with approximately 20 % ethanol. 1996) represents a response to a letter from the American Petroleum Institute (API) is presented (US EPA. the EPA’s Fuels and Energy Division Director. VOC and CO.J. The Brazilians have also tried blending ethanol to different levels with gasoline since then. empirical evidence indicates that use of low RVP gasoline may actually increase the NOX emissions by 1 %. Furthermore. However. In a short answer to the API.e. and no need for further debate is recognised. the number of relevant emissions tests etc. so using low RVP gasoline should have little or no effect on NOx emissions. Exhaust emission reduction is very small or nonexistent. Low RVP gasoline will have little or no effect on NOx. notes that “The modest reductions in NOx for Phase I.Brazil Brazil introduced ethanol as a neat fuel for spark ignition engines more than 20 years ago. Low RVP gasoline will not reduce carbon monoxide (CO) emissions. on the other hand. produce less ozone) per gram than exhaust VOC. his conclusions concerning low RVP gasoline. 1996)The director of the API. mainly because of variations in the production capacity and changes in the taxation system. RVP . In a report (US EPA. 2000. and may in fact increase them slightly. C. very few tests have been done in Brazil regarding the environmental effects of using ethanol as a vehicle fuel. they will not be found in evaporative emissions. The potential problems associated with increased vapour pressure due to adding ethanol to gasoline. RFG gasoline. The primary emission benefits (VOC) of low RVP gasoline come from reductions in evaporative emissions. Hence. reducing the RVP will have less effect on its levels than using RFG. compared with conventional gasoline are inter alia that: • • • • • • Low RVP gasoline will reduce the evaporative emissions. The main argument by Krambuhl was that the low RVP gasoline is more cost-effective than the reformulated gasoline. Since nitrogen oxides (NOx) are combustion products. the Phase II complex model standards at 40 CFR 80. The use of ethanol as a vehicle fuel in Brazil has varied over the years.N. RFG. He also invited the API to a meeting with the EPA in order to clarify the latter’s position. which will have also affect NOx and CO emissions. provide a means for immediately reducing ozone without waiting for fleet turnover”. opposed statements of the EPA (Korotney) in their paper about low RVP gasoline. 1999) it is stated that “Beginning on January 1. Since ozone is formed in the atmosphere from complex reactions involving NOx. Krambuhl. will affect CO emissions since they are influenced by the oxygen content of the fuel and not the RVP. including increased . Evaporative emissions of VOC tend to be less reactive (i. Freed.2. and the more substantial reductions in NOx for Phase II.41(e) and (f) will apply to all RFG in the gasoline distribution system”.

The objectives of the project were: • • • • To clarify the effect of fuel vapour pressure on volatility and evaporative emissions from modern cars equipped with canisters. To provide a firm technical basis for debates on gasoline vapour pressure limits in relation to ethanol blending for the Fuels Directive Review. a level at which the increased vapour pressure has declined more or less back to the original RVP of the base gasoline (Alfred Szwarc. The evaporative emission components detected were ethanol. C4-C6. However. To assess the effect of ethanol blending on fuel properties and evaporative emissions (quantitative and qualitative).Europe In Europe the vapour pressure of gasoline is restricted to: • • A minimum of 45 kPa and a maximum of 60 kPa in summertime. However. In another.3. At the European level (JCR – ISPRA). * During wintertime in Finland. the total amounts of hydrocarbons (HC) that evaporated were quantified and the composition of the evaporative emissions was chemically characterized. In countries with Arctic and sub-Arctic climates.Page 76 evaporative losses. To assess the impact of the cars’ fuel system technology on the evaporative emissions (canister aging. but reduced aromatic emissions. RVP . benzene. see section 7. the RVP must be at least 45 kPa and no more than 70 kPa in summertime*. do not apply in Brazil since they use either neat ethanol (with very low RVP) or at least 20 % ethanol blended in gasoline. the vapour pressure and evaporative emissions from E85 (85 % ethanol and 15 % gasoline). Norway and Sweden the RVP ranges from 50 to 95 kPa. . Compared to the reference gasoline. mentioned earlier. The E10 mixture gave the highest HC evaporative emissions. Using a simulated Sealed Housing for Evaporative Determination (SHED) test method. one such study is described in the report. and ethanol blends (with 5 and 10 % ethanol contents) of these fuels were to be examined. In Sweden not many investigations have been carried out on the relationship between ethanol blends in gasoline. representative of the recent European fleet. Compared to gasoline. the base gasoline with a higher vapour pressure gave significantly higher C4 – C6 alkane and alkene emissions. The tests were to be carried out on two base gasolines (one vapour pressure-adjusted and one unadjusted). increased vapour pressure and increased evaporative emissions. 2004). the E10 gave elevated C4 – C6 alkanes and olefin emissions. in 2004 Eucar and Concawe carried out a joint investigation of evaporative losses and other phenomena associated with blending ethanol in gasoline. no official report from the project has been presented as yet.4). such as Sweden. 8. metal/plastic tanks). E10 and reference gasoline were studied in a project carried out by Lu-Karlsson (1999) at the MTC (Motortestcenter of Sweden). alkanes and olefins. prepared for the Swedish Transport and Communications Research Board (KFB) by Laveskog and Egebäck (1998. personal communication. toluene.

thus increasing the vapour pressure and leading to a positive deviation from Raoult’s law. (2002). However.7 % oxygen by weight instead of 3. χgas+χeth=1 Where Ptotal represents the total vapour pressure of a solution containing gasoline and ethanol.1. In Figure 8. In a paper from Environment Australia discussing this issue (Environment Australia. Ptotal = Pgas + Peth = χgasP0gas + χetP0eth . Furthermore.4. As gasoline is a mixture of chemical compounds and not a pure compound. Using these values as input data a theoretical molecular formula of C15H26 can be calculated for gasoline. based on the same primary data as used in Figure 8. consisting of ≈87 percent (w/w) carbon and ≈13 percent (w/w) hydrogen. which according to the standards should be <62 kPa in the area around Sydney. and P0gas and P0eth are the pressures of the “pure” solutions. as shown in Figure 8. 2. <67 kPa in Perth and <76 kPa in Queensland during the summer months according to Hellens (2002) of BP Australia. accordingly to Hsieh et al. only a theoretical discussion can be applied. which can be attributed to the ethanol and gasoline interactions in the blend being weaker than the interactions among the molecules as neat liquids. ethanol blends should have to meet the Reid Vapour Pressure requirements.3 a positive deviation from Raoult’s law can be seen.3 the vapour pressure of a gasoline-ethanol fuel blend is shown as a function of the ethanol mole fraction (χeth).5. The ethanol mole fraction was calculated using a “theoretical” calculated mean molecular weight of gasoline.3. The main issue addressed by the authors involved has been the percentage of ethanol that should be allowed to be blended in the fuel. while the process to set environmental standard for gasoline should allow only 7. The theoretical mole fraction of gasoline in the ethanol-gasoline blend was calculated using information on the percentage (by weight) of carbon and hydrogen in the gasoline. 2002) it is pointed out that ethanol-gasoline blends with10 % ethanol content are already available on the market.5). 8. . in Figure 8. respectively.Australia According to the literature studied there is a clear preference for mixing ethanol in gasoline in Australia. χgas and χeth are the mole fractions of gasoline and ethanol. Theoretical Discussion on Vapour Pressure Using Raoult’s Law For liquid-liquid solutions where both components – in this case gasoline (gas) and ethanol (eth) – are volatile a modified Raoult’s law applies.Page 77 8.8 % ethanol in gasoline (i.e. The estimated weight percentages used for carbon and hydrogen in gasoline are 87 and 13. respectively. Molecules in the blend have a higher tendency to reside in the gas phase. RVP .

no direct correlations between the gasoline vapour pressure and the exhaust VOC emissions from vehicles have been found.8 1 Mole fraction of ethanol Figure 8. Gasoline standards applied in the USA are designed to solve problems such as poor air quality in city centres and the formation of tropospheric ozone. However. the evaporative emissions from the vehicles are limited. Reid Vapour Pressure (gFurey and Jackson. will have a lower energy content than gasoline that is not so adjusted Increased vapour pressure of a fuel may affect the drivability of the vehicle at high ambient temperatures. The highest RVP is reached at a blending with approximately 10 % ethanol. Increasing the ethanol content above 10 % reduces the RVP. kPa 80 70 60 50 40 30 20 10 0 0 0. but no data or reports arising from it have been published to date. There is not much data from Swedish or European investigations on the effects of increased fuel vapour pressure on evaporative and tailpipe emissions. Raults law RVP.2 0. vapour lock may occur.3. the data from the USA can be mutually contradictory. since the lowest ethanol content of the Brazilian fuel blends is 20%. i. since the gasoline used in the USA is quite different from Swedish/European gasoline standards. Further increases in ethanol content will further decrease the RVP of the blend to levels below the original RVP of the gasoline used. However. It may also affect hot engine start ability. Δ gasoline RVP. . 8. X Ethanol RVP. It is difficult to apply data from USA directly to Swedish or European conditions. ♦DOE.e. Furthermore.4 0. • Findings • • • • • • When ethanol is added to gasoline the vapour pressure of the resulting blend increases.6. which are not always prioritised in Europe. 1991) as a function of the mole fraction of ethanol (χeth) blended in gasoline. but still fulfils the RVP requirements set by EN 228 specifications. There are very few data on emissions from Brazil regarding vehicles running on neat ethanol or ethanol gasoline blends. RVP-adjusted gasoline that is used for blending with ethanol.6 0. Increased RVP may increase VOC emissions. depending on the type of evaporative emission control system used. and at levels of 20 to 40 % ethanol (depending on the specification of the gasoline used) the RVP of the blend returns to the original level of the gasoline.Page 78 Vapour pressure. * gasoline/ethanol blend of ideal solution. 1977. This issue is currently being investigated in an EU project.

this potential problem can be overcome by informing local fire stations about the presence and locations of ethanol-blended gasoline filling stations. . a concern raised by the SRSA is that ethanol can adversely affect the foam used by fire fighters. Thus. If the ethanol content is increased above approximately 10 % the RVP of the gasoline/ethanol blend is lowered (Figure 8. However. Blending up to approximately 10 % ethanol in the gasoline increases the initial RVP of the neat gasoline (Figure 8. which is then an explosive chemical mixture. a critically important safety issue (McArragher. 1996). This means that use of ethanol contents higher than approximately 25 % will increase the risk that vapour will form with pressures under the upper flammability limit.1).1). thus avoiding the risk for explosion. suggesting that it should reduce the risk for a flammable mixture forming. At approximately 25 % ethanol. 2004) there is no difference between gasoline and ethanol-blended gasoline from a legal perspective in terms of the risk for flammability or explosion.Page 79 9. This means that the head space in a tank should be saturated with gasoline vapour at a greater partial pressure than the upper flammability limit for a gasoline-air mixture. However. According to the Swedish Rescue Services Agency (SRSA. although ethanol-resistant foam is available. the gasolineethanol blend has approximately the same RVP as the neat gasoline. at low RVP and low ambient temperatures there is a risk that the headspace in a tank will be saturated with gasoline vapour which is under the upper flammability limit of the gasoline-air mixture. RISK FOR EXPLOSIONS AT LOW AMBIENT TEMPERATURES McArragher (1996) discussed the minimum Reid Vapour Pressure required to ensure that the upper flammability limit of gasoline vapour is exceeded.

LCA can be used to assess and compare.Page 80 10. effects of using different vehicle fuels. largely because of small differences between them in terms of parameters such as the test vehicles (age and engine/vehicle configuration) and the test cycles used. .1. ranging from 5 to approximately 20 % ethanol. In LCA a product is followed from “cradle to grave” i. 10. with respect to issues such as whether a raw material can be replaced with a less toxic one without increasing the total environmental impact due to changes in transportation distances or modes. For example. However. from raw material acquisition. through production. The results may elucidate the “total” effects on the climate. sub-optimization can be avoided. from them. gasoline fulfilling RVP requirements even after blending with ethanol) and unadjusted gasoline (with which blends would not meet such requirements). 1997) defines it as a “technique for assessing the environmental aspects and potential impacts associated with a product”. and whether production of the new raw material (or substitution of a product with a similar one) will generate more or less toxic emissions The ISO standard for LCA (ISO 14040. use and waste disposal. Evaluating the potential impacts associated with those inputs and outputs. environment and health of replacing gasoline to varying degrees by bio ethanol. such as gasoline. Magnus Blinge of Chalmers University of Technology. in response to a request by the Swedish Alternative Fuel Committee. other unregulated contituents. LCA in the Context of This Project The main purposes of the literature study related to LCAs within the BIFF-project were to search for. in a “cradle to grave perspective”.e. Interpreting the results of the inventory and impact assessment phases in relation to the objective of the study.e. by: • • • Compiling an inventory of relevant inputs and outputs of its production system. LCAs that included assessments of as many as possible of the following: • • • The environmental and health effects of emissions from the use of neat gasoline and various ethanol-gasoline blends. One of Blinge’s main conclusions was that it was not possible to make a good comparison between these LCAs or to extract relevant average emission data concerning production. LIFE CYCLE ANALYSIS (LCA) OF GASOLINE AND ETHANOL BLENDS Life Cycle Analysis is a tool for analyzing and assessing environmental consequences of human actions. Otherwise. Emissions not only of carbon dioxide and/or other greenhouse gases. the LCA will not give reliable answers to the questions posed. and examine. but also of regulated emissions and. as far as possible. 1996) compared about 20 different LCAs related to conventional and alternative vehicle fuels. Gothenburg (Blinge. when using LCA for assessment/comparison of different situations it is important to apply the same system boundary and framework conditions consistently. Both vapour-pressure adjusted gasoline (i. vehicle use etc. originally used to address product-related environmental issues. By assessing all of the industrial processes associated with manufacturing a given product. bio ethanol and bio ethanol-blended gasoline.

LCA Studies for Ethanol in Neat Form or Blended with Gasoline USA The literature survey revealed that many LCAs have been carried out on the production and use of ethanol. Midwest Corn. US. Examples of such LCAs include: • • Fuel-Cycle Fossil Energy Use and Greenhouse Gas Emissions of Fuel Ethanol Produced from U. mostly in the USA. Changes in emissions from sensitive “emission points” from harbour/refinery to vehicle/tailpipe due to use of ethanol-gasoline blends with various ethanol contents and. carried out in the USA and other countries could provide a reasonable basis for predicting life-cycle changes in emissions that would follow the use of 5 to 20 % ethanol blends with gasoline. if possible.Page 81 • • • Potential differences in the emissions associated with various ethanol blending levels in different types of gasoline (RVP-adjusted and unadjusted). it was (and is) essential to remember that basing predictions on LCAs is likely to be difficult. environmental and health impact. C Saricks and D Santini. Effects of Fuel Ethanol Use on Fuel-Cycle Energy and Greenhouse Gas Emissions. the so-called nonattainment areas (with respect to CO or tropospheric ozone). However. Argonne National Laboratory. unless the system boundary and framework conditions are very similar.S. Argonne National Laboratory. since these LCAs were based on conditions specific for the USA there are various difficulties in using them as a basis for predictions related to Swedish and/or European conditions other than merely giving hints about likely results. . A further objective of the work was to find out if LCAs. However. 1997). 1997 (Young et al. identification of the best point in the chain for blending ethanol into gasoline.g. M Wang. and their impact (especially on the environment and health). under typical American conditions. to minimise evaporative losses. 10. LWG) or gasoline with a maximum vapour pressure and low level of specific compounds.. the gasoline quality differs between regions/states in the USA and the US authorities have established special gasoline qualities for areas with special air quality problems. reformulated gasoline (RFG). under Swedish or European conditions. Michel young. Christopher Saricks and May Wu. gasoline with a maximum level of vapour pressure (low vapour pressure gasoline. The conventional fuel used in the comparisons is generally common US gasoline. such as those mentioned above. 1999).: • • • The raw materials for the production in the USA are often corn or corn residues. and fuels for use in Otto engines. or even impossible.2.. If (and if so how) switching from the use of RVP-adjusted gasoline to unadjusted gasoline (allowing increases in vapour pressure) in gasoline-ethanol blends would affect the overall climatic. e. such as benzene and aromatics. The vehicle parameters used in the LCA calculations are generally typical for engines/vehicles sold in the USA 5 to 10 years ago. In addition. USA (Wang et al. This means gasoline qualities with a minimum level of oxygen or a minimum level of added oxygenate (MTBE or ethanol). which is not the same as European and less than that Swedish gasoline.

still seems to be one of the best. EUCAR and the EU-Commissions/Joint Research Centre. (I Carvalho et al. The University of Melbourne (Beer et al. Germany. information and technology. the Australian Greenhouse Office. in addition to being old. 1997). despite being relatively old. ExxonMobil. the LCAs that have been found mostly focused on emissions of carbon dioxide. 2002). entitled “Life Cycle Analysis of Bio Fuels for Transportation used in Fuel Cells and Conventional Technologies under European conditions”. and was published in December 2002 (ADEME. Europe For European conditions General Motors. as reported in “Well-to-Wheel Analysis of Future Automotive Fuels and Power Trains in the European Context” (Concawe 2004). and is a complement to a similar study for North American conditions published in 2001 (GM 2001). together with Argone National Laboratory.Page 82 Furthermore. This LCA. focusing on (or at least including) ethanol. 2002). This report also focuses on the emissions of greenhouse gases. but LCAs seldom consider emissions of regulated or other non-regulated constituents. of Chalmers University of Technology.. the results are primarily valid for Swedish conditions and not applicable to the rest of Europe. together with Ecobilan.. Another LCA related to European conditions was jointly undertaken by CONCAWE. 2004). ADEME. of the Institut für Energie und Umweltforschung. It also covers non-regulated emissions. published a report entitled “Well-to-Wheel Energy use and Green House Gas Emissions of Advanced Fuel/Vehicle System – A European Study” The work was carried out with BP. carried out an LCA on different alternative fuels following a request from the Swedish Transportation Research Board (Blinge et al. Sweden Several LCAs have been carried out on the production and use of alternative vehicle fuels under Swedish conditions.. In 1997. The other. as can be seen from the title this LCA-study only covers greenhouse gases and energy use. carried out by the French authority for environment and energy. PricewaterhouseCoopers and DIREM. Shell and TotalFinal Elf as active participants. One carried out by Patyk and Reinhardt. However. However. Heidelberg. Other countries Two LCAs from countries outside Europe and the US are: • • Comparison of Transport fuels carried out by Beer and co-workers. this LCA is focused solely on emissions of greenhouse gases. Gothenburg. 2002). and sometimes other greenhouse gases. However. Magnus Blinge. and not based on the latest data. Another Swedish LCA that is specifically related to Swedish conditions is Agro Ethanol’s LCA on the annual production of 50 000 m3 grain-based ethanol at the Agroetanol AB production plant outside Norrköping. Assessment of Greenhouse Gas Emissions in the Production and Use of Ethanol in Brazil. Government of the state of Sao Paulo. . (Patyk and Reinhardt. carried out by Isaias de Carvalho and coworkers. as do two other European LCAs on bio fuels/ethanol. was called “Energy and Greenhouse Gas Balances of Bio Fuels Production Chains in France.

The investigation by Blinge and coworkers. 1997) is an exception. or ethanol-gasoline blends with low alcohol contents (5 % or occasionally 10 %. In most of the LCAs carried out to date on ethanol.2. E5 or E10). Environment and Energy Life Cycle Assessment of Automobiles Fueled by Bio-ethanol Blends in China”. there is at least one example of an LCA in which different types of gasoline were examined that could be used as a procedural model for LCAs considering ethanol blends of RVP-adjusted and unadjusted gasoline. Furthermore. LCAs comparing blends with higher ethanol contents. 10.9. 2004). study by Zhiyuan Hu and coworkers of Shanghai Jiao Tong University. including China (see below). distribution and use of alternative fuels/ethanol most have mainly focused on their climatic impact. distribution and use of a vehicle fuel such as ethanol is often carried out with country-specific framework conditions such as the sources and nature of the raw material used to produce the fuel. but these have also focused mainly on emissions of greenhouse gases with clear country-specific framework conditions. For the chain from refinery to refueling of the vehicle seven stages were defined and emission factors were calculated. Portugal (Mata et al. To summarize: • • • It is difficult to find LCAs that meet the criteria sought here. It is difficult to draw general conclusions concerning specific emissions due to the production. when they were carried out. emissions of other greenhouse gases. a life cycle analysis or assessment compared the potential environmental impact of various gasoline blends that all met the same octane and vapour pressure specifications. up to 20 or 30 % for example. “neat” ethanol for FFVs. are scarce. or considered. were compared in terms of their potential environmental impact due to hydrocarbon emissions. but fulfilled standard octane number and RVP requirements. 2003). 85 % ethanol and 15 % gasoline (E85). are compared with neat gasoline. (Blinge et al. In the cited LCA. Several types of gasoline that differed in their specifications. as is the “Economics. In addition. but exclude the fuels’ use in a vehicle. and they are difficult to find.. distribution and use of ethanol as vehicle fuels from a number of different LCAs because of differences in their system boundaries and framework conditions. China (Zhiyuan et al. The study was performed by Teresa Mata and co-workers of the University of Porto. Although it is difficult to find the kind of LCA sought for and described in chapter 4. there have been few studies related to non-regulated emissions. The results of the .3.. The system boundaries were set to include the refinery process. Concerning the parameters studied in LCAs on the production. LCAs that consider regulated emissions are not common. especially emissions of carbon dioxide and. LCAs have been carried out in other parts of the world. Discussion LCAs on the production.Page 83 Both of these LCAs are concerned with emissions of greenhouse gases and energy efficiency. India and Canada. largely concerning the raw material. occasionally. of course. It is difficult to use LCAs that have been published to date to predict general conditions for situations that were not foreseen.

but they have applied more or less country-specific framework conditions with respect to the raw material used for the ethanol production and specific gasoline specifications. If possible the LCA should include some kind of evaluation concerning the extent to which different types of canisters could reduce the evaporative emissions from the vehicle and the extent to which they would reduce the total volume of emissions. relevant fuel specifications etc). 2003).4. Gasoline not fulfilling the RVP conditions. 10. Consider the emissions not only of greenhouse gases but also of regulated and other nonregulated constituents. LCAs carried out in the USA or other parts of the world probably differ too much in their framework conditions to provide a relevant basis for predictions under European/Swedish conditions. distribution and use of gasoline with blends of RVP-adjusted and unadjusted gasoline with 5 to 20 % ethanol. Such an LCA could be structured similarly to that of Mata and co-workers (Mata et al. other greenhouse gases and both regulated and non-regulated emissions should be measured. To obtain information concerning whether (and if so. some gasoline blends are less detrimental for the environment than others. Findings LCAs are difficult to find. They have also often focused (as have most LCAs on the production. as well as differing in their potential environmental impact. This implies accepting an increased RVP. but with specific Swedish framework conditions. Gasoline fulfilling RVP conditions in Europe/Sweden. from a well-to-wheel perspective. Besides carbon dioxide. Such an LCA should focus on: • • • • Ethanol blended gasoline with ethanol contents in the 5 to 20 % range. . how) evaporative emissions and tailpipe emissions might differ. Compare regulated and non-regulated emissions (tailpipe emissions and evaporative emissions) from a well-to-wheel perspective and their impact on the environment and health from the production. A number of LCA:s have been carried out (mainly but not solely in the USA).Page 84 study showed that since the blending components such as alkylate. cracked gasoline and reformate have different octane numbers and vapour pressures. worldwide or in Europe/Sweden that: • • • Have relevant framework conditions (modern engine systems. From a European or Swedish perspective. it seems necessary to carry out a new LCA. distribution and use of other alternative fuels) on the emissions of greenhouse gases.

some investigations evaluated in the present report have given contradictory results. Many authors of papers dealing with alcohol fuels claim that the main cause of reported problems of using alcohols. especially in terms of the fleet of vehicles. Therefore. especially methanol. Higher than 10 % contents of ethanol in gasoline are expected to be of more importance after the year 2010. e. There is a need to develop and update methods for sampling and analysing vehicle exhaust emissions generated from the combustion of alternative fuels. In addition. American car manufacturers have agreed to accept the use of blends with up to 10 % ethanol in gasoline in their vehicles. updated exhaust emissions (of both regulated and unregulated compounds) from neat gasoline and ethanol gasoline blends should be characterized as described in the present report in tests at both ambient temperature of 20 ºC (in accordance with current certification procedures) and lower temperatures.g.Page 85 11. Further studies of the vehicle fleet in Sweden may be needed to generate information about the implications of using gasoline blends with up to 10 % ethanol for older cars which may be less tolerant to them than newer models. Owners of such cars should refrain from using alcohol blended gasoline. without changing the warranty conditions. Investigations and evaluations conducted for the American Lung Association of Minnesota discussed in the present report have shown that the sulphur content of the fuel has a considerable impact on both regulated and unregulated emissions. A conclusion which can be drawn from the literature study is that newer models of vehicles are more tolerant to changes in the composition of fuels such as a blend of 10 % ethanol in gasoline. Many car manufacturers in Europe and Japan sell vehicles in North America. emission regulations and certain other factors. -20 ºC. data on emissions generated using fuels with relatively high sulphur contents cannot be directly applied to Swedish . the design of currently available on the European market. may allow the use of blends with at least 10 % ethanol in gasoline. It is difficult to apply data from investigations carried out in other countries directly to Swedish conditions since many variables differ from country to country. However. the fuels. The percentage of ethanol in gasoline blends evaluated should primarily be in the range of 10 % as this could be the first upper target. including Sweden. Therefore. Start ability and drivability at low ambient temperatures such as -20 ºC are important variables to investigate due to the harshness of Swedish winters. as a fuel for vehicles is that they have often been used in older cars. Methods for sampling and analysing exhaust emissions have not been adequately developed for alternative fuels in general since traditional sampling and analysis methods were developed for characterizing emissions from traditional fuels such as gasoline and diesel oil. One problem that may apply to older vehicles is that alcohol tends to react with rubber. CONCLUSIONS AND RECOMMENDATIONS Please note that conclusions from the literature study are written in regular font (Times New Roman) and recommendations by the authors of the present report are written in italic.

The chemical compound in gasoline that contributes most to the RVP is butane. emitted hydrocarbons should be analysed to generate data for use in further evaluations. since the lowest ethanol content of Brazilian fuel blends is 20%. depending on the type of evaporative emission control system used. Fuel Reid Vapour Pressure When an alcohol is blended with gasoline the vapour pressure of the blended fuel will increase (and considerably more for methanol than for ethanol). Increasing the RVP of a fuel may affect the drivability of the vehicle at high ambient temperatures. tests at low ambient temperatures (-20 °C) should also be included. since their fuel tanks will contain ethanol/gasoline blends. and at a level of 20 to 40 % ethanol (depending on the specification of the neat gasoline used) the RVP of the blend returns to the original level of the base gasoline. Very few data have been found on evaporative emissions from Brazil regarding vehicles running on neat ethanol or ethanol gasoline blends. the upper limit allowed for RVP could be exceeded.1. By decreasing or increasing the butane content in gasoline the RVP can be reduced or increased. which provide a basis for evaluating health and environmental effects. The RVP then declines with further increases in the ethanol content. Local fire stations should be informed about the presence and location of ethanol blended gasoline filling stations to ensure the use of ethanol-resistant foam in the case of fire.10 %). 11. since Swedish gasoline standards have allowed only 10 ppm sulphur since January 2005. However. A further increase in ethanol content will then reduce the RVP of the blend to levels lower than that of the gasoline used. Besides measurements obtained following standard procedures. since it may cause vapour lock and may also affect hot engine starts. Increasing RVP may increase the VOC emissions. This is also an important issue to consider if fires occur in vehicles running on these fuels. Emission factors are needed for emission inventories. With such data it will be possible to: (i) evaluate whether the evaporative emission standards are met and (ii) to evaluate whether the emitted hydrocarbons will have an impact on the environment and health in Sweden. the evaporative emissions from the vehicles are limited. respectively. There is a need for updated emission factors for both regulated and unregulated exhaust emissions from “modern” vehicles running on neat gasoline and ethanol-blended gasoline. the RVP increases most rapidly with further additions in the ethanol content interval from 0 to 5 %. and it peaks at a blending level of approximately 10 % ethanol. . comparing emissions from the use of both RVP-adjusted and non RVP-adjusted gasoline. In addition to measurements of evaporative emissions according to the standard method. There is a need for updated emission factors for evaporative emissions from “modern” vehicles running on ethanol mixed with gasoline (5 .Page 86 conditions. If a gasoline with an RVP at or close to the upper limit is mixed (commingled) with a gasoline containing ethanol. If ethanol is added.

In a paper from the Transportation Office of Energy Efficiency in Canada it is said that blending 10 % ethanol in gasoline (E10) will result in the energy content of the fuel being 3 % lower than the energy content of the base gasoline used for blending. However. This has been especially significant in the USA after the strengthening of the evaporative emission regulations. the investigations carried out by Orbital have been of great value for this project since a broad spectrum of emission data are presented in the reports and they discuss many aspects such as fuels. vehicle performance and wear. However. data obtained in tests with such vehicles were of particular interest. The ethanol contents in the blended fuels were 10. on five vehicles fuelled with a blend of 10 % ethanol in gasoline are of some interest. Data on regulated. Since this decrease in energy content will be partly compensated by “improved combustion efficiency” of the ethanol blended fuel the . Investigations and evaluations conducted for the American Lung Association of Minnesota have shown that sulphur in the fuel has a considerable impact on both regulated and unregulated emissions. Emissions of CO and PM were significantly reduced when the use of blended was compared with neat gasoline.2. since new measures had to be introduced to comply with the standards. respectively. Sweden and the USA. Beside the investigations carried out in Australia the emission tests carried out at Harwell. There is only one main drawback with the data from the extensive tests involved. Only limited data have been found concerning evaporative emissions.Page 87 11. Regulated Emissions As the energy content (MJ/l) of ethanol-gasoline blends is lower than that of neat gasoline their use will probably cause fuel consumption to increase for the average driver. Since nearly all vehicles in Sweden are equipped with a three-way catalyst exhaust gas aftertreatment system. firstly because a 10 % ethanol in gasoline blend was used. The search for literature on the effects of ethanol blends on regulated emissions showed that very few data are available on emissions measured when using a blend of 10 % ethanol in gasoline. 15 or 20 %. The Orbital Engine Company has carried out a series of investigations on vehicles fuelled with ethanol blended gasoline initiated by Environment Australia. according to available information. A report from Environment Canada compares emission data from tests on ethanol blended gasoline and neat gasoline. and secondly because the vehicles used were models that are also used in Sweden. One of these measures was to shift to the use of steel tanks for the fuel and another was to use new and more reliable tubes in the fuel lines. the fuel (gasoline) used for the tests with blended fuel and the neat gasoline had sulphur contents of up to 150 and 500 ppm. catalysts. Generally the emission levels were low and no significant differences in NOx emissions were found. Canada. in some relevant investigations it has been noticed that emissions via permeation have increased when using ethanol blended gasoline. unregulated and evaporative emissions have been gathered and presented. The emission data found and discussed in this report are from investigations in Australia. When comparing data from the different ethanol blends with data from tests on neat gasoline no dramatic differences were seen. vehicles. England. Most of these investigations have focused on a blend of 20 % ethanol in two or three grades of gasoline produced for the Australian market. England (UK). One main drawback when collecting and studying data from different investigations is that the number of vehicles tested is often limited.

substantial experience of the use of ethanol blended gasoline has been collected over a long time. especially in low temperature conditions should be carried out. In comparison. so (an) appropriate method(s) must be developed (see also the conclusion and recommendation about HC emissions discussed above). Therefore. Performance and Wear During the study of the literature no evidence of serious engine wear and/or other material problems were found when a blend of 10 % ethanol in gasoline had been used. Therefore there is an urgent need to develop an analytical method that can determine HC emissions which are not affected by other “non HC” compounds present in the exhaust. In the present report it has been emphasised that the method used for measuring hydrocarbons (HC) in the exhaust from motor vehicles using an alcohol blended fuel are not satisfactory from a legal perspective since the emissions of unburned alcohol are included in the readings of the instrument (FID). toluene. 11.Page 88 overall increase in fuel consumption when using E10 will be only 2 %. From the literature it is not clear whether there is risk that emissions of quinones from gasolinefuelled vehicles will increase as the ethanol content increases in a gasoline/ethanol blend. the limit for the ethanol content in gasoline has been set to 10 % under the warranty conditions. Due to the gasoline dilution effect of adding ethanol the emissions of benzene. and tests including evaporative emissions at low temperatures.4. to a lesser degree. The emissions of aldehydes (especially acetaldehyde and. Unregulated Emissions There is a need for updated emission factors of unregulated exhaust emissions. formaldehyde) and alcohols from vehicles running on alcohol/gasoline blends are expected to increase. 11. A blend of 10 % ethanol in gasoline has long been allowed in the USA by the car manufacturers without any serious restrictions on the warranties of their vehicles. The resulting figures could probably be used to evaluate the environmental and health effects of using ethanol blends. which is beneficial from environmental and health perspectives. It has also been noted that this level of ethanol in gasoline has been used in the USA since the end of the 1970s. . ethyl benzene and xylene from blends are lower than those from neat gasoline. It is recommended that particles emitted from vehicles fuelled with ethanol/gasoline blends should be thoroughly characterised chemically. However. There is no standard validated method for determining aldehyde and alcohol emissions from motor vehicles. it is recommended that a pilot investigation should be initiated to investigate if quinone emissions are related to the ethanol content of ethanol-gasoline blends. general interest from a health perspective in particle emissions from vehicles in the literature examined. There is clear. and this characterisation should include measurements of their sizes and numbers. For regulated emissions the recommendation is that a broader more detailed study of the emissions. The components examined should include the chemical compounds and compound classes listed in the present report. Thus. increasing the speed of the vehicle from 100 km/h to 120 km/h increases fuel consumption by 20 %.3.

0025 % by weight. The project included both laboratory tests and field trials. It has not been possible to verify whether this is linked to the fact that the sulphur content of gasoline in Australia is relatively high. but using specific Swedish framework conditions. a study conducted in Minnesota (USA). 11. . (2003). according to AMSE 1114). Furthermore. both RVP-adjusted and non RVP-adjusted gasoline should be included. distribution and use of the blends should be considered. but they are more or less based on country-specific framework conditions with respect to the production. In contrast to the experiences in Australia. regulated and other unregulated emissions should be included in it. in which two blends of ethanol in gasoline (one with 10 % and the other with 30 % ethanol) were examined. most of them focus solely on the emissions of greenhouse gases. especially at high accumulated mileages. Unfortunately. Representatives of the oil industry and car owners also favoured the 10 % limit. no emission data are available from these tests. The impact on the environment and health. Furthermore. It can be concluded from the literature survey that LCA data with relevant framework conditions for the use of bio ethanol and bio ethanol mixed gasoline in a Swedish/European perspective are limited or lacking. Furthermore. since this possibility was not considered in the reports from Australia. of the production. Life Cycle Analysis A number of LCAs have been carried out worldwide on the use of bio ethanol. In the 1970s and 1980s a quite extensive program was carried out in Sweden to study the effects of using alcohol blends in gasoline in motor vehicles. Such an LCA could be structured in a similar way to the LCA published by Mata et al.5. In the light of the findings concerning the engine wear and other observed problems associated with the use of 20 % ethanol in gasoline the Australian government has decided to limit the amount of ethanol in gasoline to 10 %. Therefore very few Swedish data are available. however. as well as greenhouse gases (carbon dioxide. A high level of sulphur in the ethanol blended fuel may affect the engine fuel system since there is a small amount of acetic acid in neat ethanol (a maximum of 0. distribution and use of alternative fuels. In Sweden the sulphur content in gasoline has been reduced to a maximum of 10 ppm. found that the ethanol caused no serious wear problems. A new LCA based on Swedish framework conditions should focus on ethanol-gasoline blends with alcohol contents ranging from 5 to 20 %. methane and nitrous oxide). No such program has been established to collect experience and data regarding the use of ethanol blended gasoline since then.Page 89 Extensive tests and studies carried out in Australia have found that using an ethanol-gasoline blend with 20 % ethanol increased the wear and other damage to the fuel system of the vehicles.

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xylene California Air Resource Board Ethanol Carbon monoxide The Oil Companies´ European Association for Environment. (3%) General Motors Global Warming Potential Hydrocarbons Initial Boiling Point The International Energy Agency GM GWP HC IBP IEA . Health and Safety in Refining and Distribution Dimethyl ether Department of Energy US Energy Information Administration Electronic Fuel Injection Ethanol European Union European Council for Automotive Research and Development Evaporative 15% conventional gasoline and 85% ethanol Final Boiling Point Flexible Fuelled Vehicle Flame Ionization Detector Gasoline A gasoline extender made from a mixture of gasoline (90%) and ethanol (10%. ABBREVIATIONS API B(a)P BRON BTEX CARB CH3CH2-OH CO CONCAWE DME DOE EIA EFI Eth EU EUCAR Evap E85 FBP FFVs FID Gas Gasohol American Petroleum Institute benzo(a)pyrene Blending Research Octane Number benzene toluene. often obtained by fermenting agricultural crops or crop wastes) or gasoline (97%) and methanol.Page 103 13. ethyl benzene.

Swedish National Board for Technical Development Evaporative Test Chamber (Sealed Housing for Evaporative Determination) Total Hydrocarbons Three Way Catalyst Unleaded petrol US Environmental Protection Agency Volatile organic compounds Volume percent Technical Research Centre of Finland .Page 104 IEA JRC KPa LPG MTBE MON NDIR NMOG NOx PAC PAH PAN PULP Psi RFA RFG RON RVP RCGWE SEKAB SPI STAB STU SHED THC TWC ULP US EPA VOC Vol % VTT International Symposium on Alcohol Fuels EU Joint Research Centre Kilo Pascal Natural gas and Motorgas/Petroleum gas Methyl Teriary Buthyl Ether Motor Octane Number Nondispersive Infrared Non Methane Organic Gases Nitrogen oxides Polycyclic Aromatic Compounds Polycyclic Aromatic Hydrocarbons Peroxy acetyl nitrate Perth unleaded petrol Pounds per square inch Renewable Fuels Association Reformulated Gasoline Research Octane Number Reid Vapour Pressure Relative Contribution to the Global Warming Effect. Svensk Etanolkemi AB Swedish Petroleum Institute Swedish Motor Fuel Technology Co.

026 0.068 0.0 175.9 161. Grand Honda Insight Silverado Echo Civic Vehicle ⇒ Am US FTP cycle CO g/km CO g/km CO g/km CO g/km CO g/km 0 % Ethanol 0. APPENDIX 1 14.740 0.068 0.050 0.205 20 % Ethanol 0. Emissions of CO2 when using neat gasoline and three different blends of ethanol.068 0.087 0.033 Table A4. Emissions of NOx when using neat gasoline and three different blends of ethanol.808 0.4 103.143 0.155 Table A2.186 0.709 0.8 176.8 162.049 0. It is particularly noteworthy that the Grand Am and Silverado show higher levels of emissions than the other vehicles Table A1.051 0.963 0.049 0. Emission tests in Canada The following five tables.740 0.218 0.273 15 % Ethanol 0.0 162.3 .1.305 10 % Ethanol 0. list emission data generated during the tests carried out in Canada and presented in section 7. Grand Honda Insight Silverado Echo Civic Vehicle ⇒ Am US FTP cycle NOx g/km NOx g/km NOx g/km NOx g/km NOx g/km 0 % Ethanol 0.068 0.087 0.1 307.2 101. Grand Honda Insight Silverado Echo Civic Vehicle ⇒ Am US FTP cycle CO2 g/km CO2 g/km CO2 g/km CO2 g/km CO2 g/km 0 % Ethanol 249.224 0. Emissions of CO when using neat gasoline and three different blends of ethanol.0 161.081 0.021 15 % Ethanol 0.024 0.068 0.242 0.2 of the main part of the report.025 10 % Ethanol 0.280 0.131 0.056 0.081 0.030 10 % Ethanol 0.027 0.068 0.5 20 % Ethanol 248.Page 105 14.118 0.6 179.017 20 % Ethanol 0.3 105.2 307.920 0.6 10 % Ethanol 244.075 0.056 0.777 0.9 303. Emissions of HC when using neat gasoline and three different blends of ethanol.938 0.261 0.021 Table A3.124 0.032 15 % Ethanol 0.027 0.0 305.033 0.124 0. A1 to A5.205 0.060 0.087 0.068 0. As can be seen there is a considerable variation in emission levels from vehicle to vehicle.050 0.024 0.039 20 % Ethanol 0.5 15 % Ethanol 247.068 0.8 176. Grand Honda Insight Silverado Echo Civic Vehicle ⇒ Am US FTP cycle HC g/km HC g/km HC g/km HC g/km HC g/km 0 % Ethanol 0.6 100.

55 35. Drive cycle CO2 CO THC NOX PM g/km g/km g/km g/km g/km Fuel cons. Drive cycle CO2 g/km CO g/km THC g/km NOX g/km PM g/km Fuel cons.701 0.Page 106 Table A5.04 Vehicle 6 Toyota (Yaris) (repeated) running on base gasoline fuel. It can also be seen that some vehicles show an increase in emissions when ethanol blended fuel is used.731 0.402 0.108 0. Emission tests in UK The following four tables.5 107.047 g/km 0.904 0.16 PM g/km 0.346 0. g/km 55.352 0.024 0.512 0.102 0.328 0. while others show a decrease.787 0. g/km Cold ECE 165.465 0.018 0.04 36.410 0. As can be seen there is considerable variation in emission levels from vehicle to vehicle.720 0.063 0. 7 0. g/km Cold ECE Cold EUDC 161. and those of unregulated emissions in Tables A7 and A8.6 109.0058 53.5 g/km 2.790 20 % Ethanol 1.764 10 % Ethanol 1.460 1.9 1.077 0. In Tables A6. 1 1. Grand Honda Insight Silverado Echo Civic Vehicle ⇒ Am US FTP cycle FC FC FC FC FC l/10 km l/10 km l/10 km l/10 km l/10 km 0 % Ethanol 1.0011 Cold ECE Cold EUDC Fuel cons.803 14. Summary of regulated emissions for all tested vehicles Vehicle 1 Toyota (Yaris) running on base gasoline fuel.038 0.0049 51.323 0.016 g/km 0.739 0.3 of the main part of the report.464 1.307 0.435 1. A7 and A8 the emission data and fuel consumption of interest are presented.293 0.0083 0. Table A6.207 0. Fuel consumption when using neat gasoline and three different blends of ethanol. the measurements of regulated emissions and fuel consumption in Table A6.2.144 0.99 34.150 Cold 110.0018 0. A6 to A9. list emission data generated during the tests carried out in England and presented in section 7.03 .035 0.027 EUDC Vehicle 1 Toyota (Yaris) running on E10 fuel CO THC NOX Drive cycle CO2 g/km 162.783 15 % Ethanol 1.0059 0.463 1.

011 0.004 0.005 g/km 0. Drive cycle CO2 CO THC NOX g/km g/km g/km g/km PM g/km Fuel cons.70 Vehicle 3 Fiat (Punto) running on base gasoline fuel.3 181.006 0.26 35. g/km Cold ECE Cold EUDC 323.159 0.157 0.18 Vehicle 4 Volkswagen (Golf) running on base gasoline fuel.422 0.6 125.190 0.2 0. Drive cycle CO2 CO THC NOX PM Fuel cons.0056 0.225 g/km 0. g/km g/km g/km g/km g/km g/km Cold ECE Cold EUDC 246.12 39.296 0.010 0.0042 106.262 0.425 0.63 Vehicle 3 Fiat (Punto) running on E10 fuel.0046 78.0034 52.983 0.Page 107 Vehicle 1 Toyota (Yaris) (repeated) running on E10 fuel.217 0.1 106. Drive cycle CO2 CO THC NOX g/km g/km g/km g/km PM g/km Fuel cons.0084 0.005 0. Drive cycle CO2 CO THC NOX PM Fuel cons.447 0.7 g/km 1.029 0.0202 0.1 1.0029 0 65.0058 0.0 110.891 0. g/km Cold ECE Cold EUDC 191.019 0.04 66.016 0.14 36.011 0.183 0.0 132.0027 g/km 123.011 0.73 .85 CO2 g/km CO g/km THC g/km NOX g/km PM g/km Fuel cons.0071 0.087 0. Cold ECE Cold EUDC Drive cycle g/km 386.00 Vehicle 2 Vauxhall (Omega) running on base gasoline fuel.132 0.9 0.1 4.0005 66.24 41.006 0.551 0.059 0.243 0 g/km 0.187 0. Drive cycle CO2 CO THC NOX g/km g/km g/km g/km PM g/km Fuel cons.004 0.16 59.7 211.2 4.211 0.402 0. g/km Cold ECE Cold EUDC 156.577 0. g/km Cold ECE Cold EUDC 200.

70 Vehicle 5 Rover (416) running on E10 fuel CO THC Drive cycle CO2 NOX g/km 0.6 147.0074 0.173 0.004 Benzene mg/km N/D* 0.896 0.014 EUDC Vehicle 4 Volkswagen (Golf) running on base gasoline fuel. g/km Cold ECE Cold EUDC 226.0008 0. Drive cycle CO2 CO THC NOX g/km g/km g/km g/km PM g/km Fuel cons.974 9.89 Vehicle 5 Rover (416) running on base gasoline fuel.509 18.347 Nitrous oxide mg/km 0.307 0.739 0.124 Benzene mg/km 10.003 0.68 46. Drive cycle CO2 CO THC NOX g/km g/km g/km g/km PM g/km Fuel cons. 5 and 6 Vehicle 6 Toyota (Yaris) (repeat)) running on base gasoline fuel.422 0.104 0.079 1.0009 Cold ECE Cold EUDC g/km 256. Drive Methane 1.3Formaldehyde Acetaldehyde Nitrous cycle butadiene oxide mg/km mg/km mg/km mg/km mg/km Cold ECE 92.450 0.246 0.5 8.3Formaldehyde Acetaldehyde Nitrous cycle butadiene oxide mg/km mg/km mg/km mg/km mg/km Cold ECE 79.0036 83.602 0. g/km Cold ECE Cold EUDC 250.302 PM g/km 0.231 0.288 1.009 0.031 1.0056 0.75 41.5 127.095 EUDC Vehicle 6 Toyota Yaris (repeat).38 Table A7.078 EUDC Benzene mg/km N/D* 3.3Formaldehyde Acetaldehyde cycle butadiene mg/km mg/km mg/km mg/km Cold ECE 13.255 0.009 1. running on E10 fuel Drive Methane 1.509 0.0011 74.841 g/km 0.604 0.8 0.198 Cold 11. g/km 88.Page 108 Vehicle 4 Volkswagen (Golf) running on E10 fuel.020 0.2 g/km 7.593 3.010 0. Drive Methane 1.003 .197 0.004 0.619 Cold 0.026 Fuel cons.039 0.092 1. Summary of FTIR emissions measurements for vehicles 4.326 0.042 0.007 0.095 0.35 48.525 0.640 0.183 0.135 0.2 146.012 0.773 0.660 Cold 13.373 0.

232 0.86* ECE+EUDC Vehicle 4 Volkswagen (Golf) running on base gasoline fuel.388 0.347 4.846 N/D* 1.408 Nitrous oxide mg/km N/D* 0.401 0.200 43.660 1.71* ECE+EUDC . Drive cycle Benzene Ammonia Formaldehyde Acetaldehyde Total PAHs mg/km mg/km mg/km mg/km µg/km Cold 0. Summary 2 of FTIR emissions measurements for vehicles 4. repeat) running on E10 fuel Drive cycle Benzene Ammonia Formaldehyde Acetaldehyde Total PAHs mg/km mg/km mg/km mg/km µg/km Cold 0. Drive cycle Benzene Ammonia Formaldehyde Acetaldehyde Total PAHs mg/km mg/km mg/km mg/km µg/km Cold 0.260 0. repeat) running on base gasoline fuel.114 0.183 0.667 0.654 44.039 EUDC * No data presented.001 Benzene mg/km N/D* N/D* Acetaldehyde Nitrous oxide mg/km mg/km 13.057 5.220 Cold 11.567 0.244 2.049 113.3Formaldehyde cycle butadiene mg/km mg/km mg/km Cold ECE 11.247 0.107 Cold 7.3Formaldehyde cycle butadiene mg/km mg/km mg/km Cold ECE 69.074 Cold 0.007 Benzene mg/km N/D* N/D* Table A8.977 1.011 0.076 0. Drive Methane 1.655 0.031 EUDC Vehicle 5 Rover (416) running on base gasoline fuel. 5 and 6 Vehicle 6 Toyota (Yaris.334 0.120 0.3Formaldehyd butadiene e mg/km mg/km mg/km Cold ECE 50.Page 109 Vehicle 4 Volkswagen (Golf) running on E10 fuel.107 0. Drive Methane 1.001 0. Acetaldehyde Nitrous oxide mg/km mg/km 4.124 4.124 EUDC Vehicle 5 Rover (416) running on E10 fuel Drive cycle Methane 1.302 4.225 N/D* Benzene mg/km N/D* N/D* Acetaldehy de mg/km 12.365 0.163 0.62* ECE+EUDC Vehicle 6 Toyota (Yaris.

493 66. Drive cycle Benzene Ammonia Formaldehyde Acetaldehyde Total PAHs mg/km mg/km mg/km mg/km µg/km Cold 0.178 30.298 1.072 0.826 1.17* ECE+EUDC * Average value for Cold ECE+EUDC and the following driving cycles: WSL Congested.818 18.532 42.755 0.22 * ECE+EUDC Vehicle 5 Rover (416) running on base gasoline fuel. WSL Urban.214 0.Page 110 Vehicle 4 Volkswagen (Golf) running on E10 fuel Drive cycle Benzene Ammonia Formaldehyde Acetaldehyde Total PAHs mg/km mg/km mg/km mg/km µg/km Cold 0.57* ECE+EUDC Vehicle 5 Rover (416) running on E10 fuel Drive cycle Benzene Ammonia Formaldehyde Acetaldehyde Total PAHs mg/km mg/km mg/km mg/km µg/km Cold 1. .056 2.788 0.357 7.

Page 111 15. Evaporation Test of Two Ethanol Blended RON 95 Summer Gasolines Separate report from AVL MTC AB. . APPENDIX 2 15.1.

Evaporation Test of Two Ethanol Blended RON 95 Summer Gasolines Magnus Henke 2005-04-29 .

...............2 Testing equipment...................................3................5 Test procedure.......................................................4 Vapour pressure analyses......1 Changes over time in Hydrocarbon levels (FID)....................................3 List of Tables .................................................................................................................................................................................................................1 Test Facilities .....2.................................................2...............................................3 Comparison of final values.......................... 11 4................................................................................................................................................................... 8 3............................................................4 Blending & Storage....................................... 20 5..........3 Purging of the VT shed....................................... Bar graphs............................... 5 3............................................................................................................................ 20 5.......................................................................................................... 20 AVL MTC Armaturvägen 1...............MTC-AA-0024 Rev...........2....2...................................... 8 3............................2 Test procedure in the VT shed.. 15 4................................4 List of Bar graphs....’............ 12 4.............1 Specifications........O.................................................................................................................................................................................. 14 4................................ 8 3.............................................2 Butane........................................................................................................................................... 19 5 Indexes ....................5........2 Changes over time for other components (MS)....................2.. 11 4..............1 Conditioning:.....................................................................5................4 Toluene and Xylene..............................................................................................................................................................................Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 2 (20) TABLE OF CONTENTS 1 2 3 Summary ............................................................................1 List of Pictures .......................................... 4 Experimental ..................................................................................5 MTBE ............................................................... 6 3........ SE-136 23 Haninge............... 9 3.......................................................... 8 3................................................................................... 10 4...3 Benzene .......6 Calibration ................................................................................................................................................ P.......................... 20 5................................... 13 4............................... 3 Introduction ..................................5............................................................................................................................................................................................................. Tel 08-500 656 00 2 ............................ Box 223.... 16 4.................. 6 3......... 10 4........................................................................... 4 Prepared Date – Rev Document ..................................... 5 3..’..........2 List of Figures and charts.................1 Ethanol........ 20 5.....................................3 Fuels.......................................................................................... 5 3..................... 9 4 Results ...............

a half-filled container prepared with an opening for the gaseous compounds to pass through was placed on its side in the shed at an ambient temperature of 45 ºC. as expected since the vapour pressure of commercially supplied gasoline is primarily adjusted to meet regulated standards by adjusting butane levels.O. Each fuel was stabilized at 0ºC at the beginning of the test and had a final temperature of about 40ºC. Total hydrocarbon (THC) emissions were monitored at appropriate intervals through the use of a Flame Ionization Detector (FID) installed in the VT Shed and a number of components of interest of the same test fuel were sampled throughout the tests with a mass spectrometer (MS). 10% and 15%) have been measured in a VT Shed. and thus showed slightly different evaporation patterns from the other components. although there was some overlap. Tel 08-500 656 00 3 . In the tests. Test results showed that the RVP rises sharply when ethanol is first added to the fuels and peaks at ethanol contents between 5 and 10% Butane was the main component that vaporized during the tests. The evaporation of ethanol was influenced both by its content in the tested blends and by the consequent changes in vapour pressure (RVP). respectively) blended with low percentages of ethanol (0%. RVPs. 4 Prepared Date – Rev Document . For reference purposes E85 (85% ethanol) was also measured in the same manner. The FID data showed that evaporated THC levels ranged from 200 ppm for the unblended gasoline with the low (63 kPa) RVP. The addition of ethanol also caused the evaporation of all the remaining components to increase by approximately the same factors as the butane Evaporation from the blends with the high RVP (70 kPa) base gasoline was stronger than the evaporation from the gasoline with the lower RVP (63 kPa). P. Box 223.MTC-AA-0024 Rev. SE-136 23 Haninge. 5%. AVL MTC Armaturvägen 1. of 63 kPa and 70 kPa.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 3 (20) 1 SUMMARY The evaporative emissions from two summer gasoline fuels (with Reid Vapour Pressures. to 340 ppm for a 10% mix of ethanol in the high RVP (70 kPa) gasoline.

RVP. and in some cases possible. to market and use these hybrid fuels. of 63 kPa and 70 kPa. This report focuses on the use of ethanol. Previous experience suggests that alcohols should be added to gasoline for this purpose.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 4 (20) 2 INTRODUCTION To meet the requirements of the European Directive designed to promote the use of biofuels (2003/30/EC) Sweden has to substantially increase the production or imports of renewable fuels. Methanol and ethanol are the main alternative fuels that have been tested on a relatively large scale. SE-136 23 Haninge. AVL MTC Armaturvägen 1. One problem related to the use of ethanol in gasoline is the increased vapour pressure caused by the alcohol when mixed in relatively low proportions with gasoline. both as blended and pure fuels.MTC-AA-0024 Rev.O. respectively) and ethanol contents of 0%. Legislation has to make it easier. P. 5%. To meet these goals in a short time steps have to be taken to ensure that the introduced fuels are usable by the current vehicle fleet. 4 Prepared Date – Rev Document . In the study reported here. the partial vapour pressures of ethanol and selected components of gasoline were measured in tests with blends of two base gasolines (with Reid Vapour Pressures. The only plausible way to reach this goal is to increase the amount of these fuels blended in today’s conventional fuels. Blends of around 10% are of particular concern today. 10% and 15%. Box 223. Tel 08-500 656 00 4 .

2 Testing equipment All tests were performed using a gas-proof test container (not the fuel container mentioned below) in which the evaporative behaviour of whole cars is normally tested. along with an Air Sense Mass Spectrometer. 4 Prepared Date – Rev Document . The AVL MTC Motor test centre is an accredited laboratory for automotive testing and has been in operation for approximately 15 years.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 5 (20) 3 3. Sweden. P. This instrument. Picture 1 – VT Shed Container with Mass Spectrometer to the left AVL MTC Armaturvägen 1.MTC-AA-0024 Rev.O. It is called a VT shed as both its volume and temperature are controlled.1 EXPERIMENTAL Test Facilities All tests were performed at AVL MTC in Haninge. Box 223. SE-136 23 Haninge. was used for the tests. 3. AVL MTC has experience of more than 10 years of testing for the Swedish Environmental Protection Agency and the Swedish National Road Administration. A standard component of this kind of equipment is a Flame Ionization Detector (FID) for measuring the total emitted hydrocarbons. in February 2005. Tel 08-500 656 00 5 .

a larger quantity of which had been removed from the 63 kPa RVP fuel. P. to ensure that the vapour pressure of the final blend does not exceed specified limis.3.3 Fuels The base fuels used were identical mixtures. Tel 08-500 656 00 6 .Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 6 (20) 3.1 Specifications Table 1. except for their contents of the Reid Vapour Pressure (RVP)-regulating compound butane.MTC-AA-0024 Rev. 3. Adjusting the RVP in this way is a standard procedure when commercially preparing gasoline that is to be blended with ethanol.O. Gasoline Certificate of Quality (RVP 63 kPa) AVL MTC Armaturvägen 1. SE-136 23 Haninge. 4 Prepared Date – Rev Document . Box 223.

Tel 08-500 656 00 7 .MTC-AA-0024 Rev. P.O. 4 Prepared Date – Rev Document . Box 223. SE-136 23 Haninge. Gasoline Certificate of Quality (RVP 70 kPa) AVL MTC Armaturvägen 1.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 7 (20) Table 2.

On average the transportation and preparation of the previously blended fuel before the tests took only 3 min. To make sure a uniform concentration was present throughout the entire volume of the VT shed. the fuel was stored in the conditioned area until just before the test. Purging the VT shed. the hole was opened and a thermocouple was plugged in to monitor the fuel temperature during the test. Box 223. Particularly close attention was paid to obtaining a uniform start temperature and making sure that no fuel was exposed to temperatures that might cause early vaporization. The test procedure in the VT shed. when the container was set on its side. P.4 Blending & Storage The test fuels were blended by personnel with a very good understanding of the test and the difficulties associated with it.5. When the desired temperature was reached the container was taken into the VT shed and the test was started.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 8 (20) 3. 4 Prepared Date – Rev Document . By the time the test was started the temperature of the gasoline had risen on average by 1. AVL MTC Armaturvägen 1. For the same reason. Therefore blending was performed in an area conditioned to a maximum of 0ºC. Conditioning: The fuel was brought down to sub-zero temperatures before being poured into the special test container and taken into the test facility.5. Tel 08-500 656 00 8 .5 Test procedure Each test consisted of three major parts: • • • 3. In the test container the temperature of the fuel was monitored continuously.2 Test procedure in the VT shed A specially prepared fuel container conditioned at 0ºC was placed in the container whilst the VT shed itself was set to maintain a steady 40ºC throughout the test.1 Conditioning the fuel and filling the test container.5ºC. 3. which was plugged until the start of the test. a small floormounted fan directed away from the fuel container acted as an “air mixer”. SE-136 23 Haninge. 3. In the fuel container a small hole was drilled.MTC-AA-0024 Rev.O.

SE-136 23 Haninge. AVL MTC Armaturvägen 1.MTC-AA-0024 Rev. Box 223. 4 Prepared Date – Rev Document .3 Purging of the VT shed To ensure that the VT shed was rid of all residual vapour before a new test was started it had to be purged. Tel 08-500 656 00 9 .Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 9 (20) 3. This is a lengthy procedure which involves taking the shed to its maximum temperature for approximately an hour. All calibration gases were delivered by Air Liquide and traceable in accordance to the standard of NIST. A graph displaying changes in temperature over time of all the tested blends is presented below (Figure 1).5. P. Temperatures of the Fuels and Shed Cell Air During the tests 50 45 40 VT Shed Cell Air Temperat re 35 Degrees Celcius 30 Air temp R63-0 25 Air temp R63-5 20 Fuel temp R63-10 Fuel temp R63-15 15 Fuel temp R70-0 Fuel temp R70-5 10 Fuel temp R70-10 Fuel temp R63-5 Air temp R63-15 Air temp R70-0 Air temp R70-5 Air temp R70-10 Air temp R70-15 Air temp R63-85 Air temp R63-10 Fuel temp R63-0 5 Start temp of Fuel = 3 deg C Fuel temp R70-15 Fuel temp R63-85 0 Time. 2 hrs Figure 1 Temperature of the Fuels and VT Shed cell Air during the tests 3.O.6 Calibration Both of the instruments used for measuring (the FID and MS) during this project were calibrated using certified pre-mixed gases to ensure quality. The rising traces represent the fuel container temperature and the steady traces the VT shed air temperature.

Tel 08-500 656 00 10 . SE-136 23 Haninge. 2 hrs Figure 2 Changes over time in Total Hydrocarbon Concentration (FID) in the VT Shed AVL MTC Armaturvägen 1.MTC-AA-0024 Rev.’ Concentration of total HC (FID analyzer) during 2 hrs of testing 400 350 R63-0 300 Concentration of tot HC. ppm R63-5 R63-10 250 R63-15 R70-0 200 R70-5 R70-10 R70-15 150 E85 RVP 70 (0-15% Eth) RVP 63 (0-15% E85 100 50 0 Time. The final concentrations at the end of the tests are also presented in bar graph format at the end of this report to facilitate comparisons.O.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 10 (20) 4 RESULTS Changes over time in the air levels of the measured constituents as the tests progressed are here presented in chart form to facilitate interpretation of the measurements. 4 Prepared Date – Rev Document .1 Changes over time in Hydrocarbon levels (FID). P. Box 223. 4.

2hrs Figure 3 Changes over time in the Ethanol Concentration in the VT Shed AVL MTC Armaturvägen 1.avg. ppm ethanol Ethanol (fl.) 70-10 C2H5OH-45 RVP63 (5-15) 12.avg.0 0.) 70-15 C2H5OH-45 Ethanol (fl. (Ethanol (fl. the relationship was not linear.) 63-10 C2H5OH-45 Ethanol (fl. This is shown here since the vapour contents (ppm) were virtually the same for both the 5% and 10% blends.0 Ethanol (fl. Two factors contribute to this pattern.) E85 10.) 70-0 C2H5OH-45 Ethanol (fl. Tel 08-500 656 00 11 .2 4. the ethanol content of the vapour proved to increase with increasing ethanol content in the test container to some extent.0 E85 6.0 Ethanol (fl.0 Ethanol (fl.avg. However.avg. however.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 11 (20) 4.) 63-0 C2H5OH-45 Ethanol (fl.) E85) 8. 4 Prepared Date – Rev Document . ethanol enhances the vapour pressure according to a relationship that is not linear and peaks at relatively low ethanol contents of around 10% in ethanol-gasoline blends. while those of both the 0% and the E85 blends were considerably lower. In addition. Naturally.avg.O. the vapour pressure is positively correlated to the ethanol content of the blend in the container.0 4.) 63-15 C2H5OH-45 RVP70 (5-15) 16. SE-136 23 Haninge.2.0 Concentration.0 18. Ethanol Unsurprisingly.0 Poly.0 Ethanol (fl. RVP70-0 2. P.) 70-5 C2H5OH-45 14.avg.) 63-5 C2H5OH-45 20.avg. Box 223.avg.1 Changes over time for other components (MS).0 RVP63-0.avg.0 Time. Concentration of Ethanol in Shed during 2 hrs of testing 22.MTC-AA-0024 Rev.avg.

avg.avg.) 70-5 Butane (fl.) 70-0 Butane (fl.avg.0 Concentration of buthane.2 Butane Butane is the main compound used to regulate the vapour pressure of gasoline. (Butane (fl.0 Time. (Butane (fl. 2 hrs Figure 4 Changes over time in the Butane Concentration in the VT Shed AVL MTC Armaturvägen 1.) 63-0 Butane (fl.0 E85 0.) 63-0) 40. as shown below.0 Butane (fl. the butane vapour pressure-enhancing effect of the ethanol blended in the base gasolines was probably maximal at contents between 5 and 10%. P.) E85) Poly.O.avg.0 20.) 70-10 80.avg.) 63-15 RVP 70-5% RVP 70-10% RVP 70-15% RVP 70-0% RVP 63-5% RVP 63-10% RVP 63-15% RVP 63-0% 100. The gasoline with the higher Reid Vapour Pressure (RVP) index was therefore expected to have a higher content of vaporizing butane.0 Poly.avg.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 12 (20) 4. SE-136 23 Haninge.avg.) 70-15 Butane (fl.avg.’? Concentration of Butane in Shed during 2hrs of testing 140. which is used in higher ambient temperature ranges.) 63-10 Butane (fl.) 63-5 120.0 Butane (fl. 4 Prepared Date – Rev Document .avg. This expectation was confirmed in the tests.avg.MTC-AA-0024 Rev.) E85 60. for instance in summer gasoline.avg.2. Tel 08-500 656 00 12 . It is removed to reduce the vapour pressure when required. In addition.0 Butane (fl. Box 223. ppm Butane (fl.

05 0. P.50 Concentration of Benzene.avg.avg. are widely used to substitute lead as an anti-knock compound in gasoline.40 0.25 0. Box 223. 20% (with E5)’. SE-136 23 Haninge.55 0.45 0.60 0. Tel 08-500 656 00 13 .avg. Benzene is also created during the combustion process in engines.) 63-15 C6H6-78 Benzene (fl. 4 Prepared Date – Rev Document .MTC-AA-0024 Rev.avg.10 Benzene (fl.) 63-0 C6H6-78 0.avg.30 0.2. Aromatics.15 0.) 70-5 C6H6-78 Benzene (fl. AVL MTC Armaturvägen 1.65 Benzene (fl.) 63-10 C6H6-78 Benzene (fl.) 63-5 C6H6-78 Benzene (fl. Concentration of Benzene in Shed during 2hrs of testing Approximately a 20% maximum concentration increase.70 0.avg.3 Benzene Benzene is an aromatic hydrocarbon with both ozone formation and carcinogenic potential. (E5) 0.) 70-15 C6H6-78 Benzene (fl.00 Time. ppm Benzene (fl. however.) E85) E85 0.) 70-0 C6H6-78 RVP 70-5 (max) RVP 70-0 RVP 63-5 RVP 63-0 0.) 70-10 C6H6-78 Benzene (fl.35 0. 2hrs Figure 5 Changes over Time in the Benzene Concentration in the VT Shed Max concentration increase compared to base levels: approx.) E85 Poly. so its emission levels are strictly restricted. (Benzene (fl.avg.avg.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 13 (20) 4.20 0.avg.avg.O.

) 70-10 o-C8H10-106 Xylene (fl.4 0. ppm 2.avg.avg.2. 2hrs Figure 6 Changes over Time in the Toluene Concentration in the VT Shed Concentration of Xylene in Shed during 2hrs of testing 1.) 63-5 o-C8H10-106 Xylene (fl.0 Time.0 Toluene (fl.) 70-5 C7H8-92 Concentration of Toluene.) 70-5 o-C8H10-106 0. Tel 08-500 656 00 14 .avg.avg. Box 223.0 Concentration of Xylene.avg.) E85) 0.0 Toluene (fl.avg. (Xylene (fl.) 63-10 C7H8-92 Toluene (fl.4 Toluene and Xylene Concentration of Toluene in Shed during 2hrs of testing Approximately a 20% maximum concentration increase.avg.5 0.) E85 Poly.) 63-0 C7H8-92 Toluene (fl.) 63-10 o-C8H10-106 1.avg. ppm Xylene (fl.8 Xylene (fl.0 0. (E5) 3. SE-136 23 Haninge.) 63-0 o-C8H10-106 Xylene (fl.5 1.avg.) 70-0 C7H8-92 Toluene (fl.avg.0 Time.avg.6 Poly.MTC-AA-0024 Rev.) 63-5 C7H8-92 2. (Toluene (fl.avg.avg.) 63-15 o-C8H10-106 Xylene (fl.) E85 0. 4 Prepared Date – Rev Document . P.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 14 (20) 4. 2hrs Figure 7 Changes over Time in the Xylene Concentration in the VT Shed Max concentration increase compared to base levels: approx.) 70-0 o-C8H10-106 Xylene (fl.avg.avg.avg.) 70-15 o-C8H10-106 Xylene (fl.) 70-15 C7H8-92 Toluene (fl.avg.5 Toluene (fl.avg.) E85) 1.avg.2 0.) 63-15 C7H8-92 Toluene (fl.O.avg.2 Xylene (fl.) 70-10 C7H8-92 Toluene (fl. 20% (with E5) AVL MTC Armaturvägen 1.

) 70-0 MTBE 0.) 70-15 MTBE 0.avg.MTC-AA-0024 Rev. Box 223.) 63-10 MTBE 0. Tel 08-500 656 00 15 .2.) 70-10 MTBE MTBE (fl. (MTBE (fl.15 0.30 Concentration of MTBE.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 15 (20) 4.00 Time. P.avg.25 MTBE (fl.) E85 Poly.avg. 4 Prepared Date – Rev Document . ppm MTBE (fl.20 MTBE (fl.) 63-0 MTBE MTBE (fl.35 MTBE (fl. SE-136 23 Haninge.) 70-5 MTBE MTBE (fl.avg.avg.10 0.05 0.avg.avg.O.avg.40 0.avg.5 MTBE Concentration of MTBE in Shed during 2hrs of testing 0.) 63-5 MTBE MTBE (fl.) E85) 0. 20% (with E5)’ AVL MTC Armaturvägen 1.avg. 2 hrs Figure 8 Changes over Time in the MTBE Concentration in the VT Shed Max concentration increase compared to base levels: approx.) 63-15 MTBE MTBE (fl.

3 Comparison of final values. 4 Prepared Date – Rev Document . Bar graphs The concentrations of the measured emissions from E85 are included as a separate series since we have no information on the vapour pressure of the base gasoline used for blending. P. it probably has a relatively high RVP since this level of ethanol lowers the Reid Vapour Pressure of the final mix.MTC-AA-0024 Rev.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 16 (20) 4.O. Butane concentration at the end of the test (ppm) AVL MTC Armaturvägen 1. SE-136 23 Haninge. Box 223. Tel 08-500 656 00 16 . However. Ethanol Concentration at the end of the test 25 20 15 10 5 0 0% 5% 10% Blend of Ethanol 15% E85 Ethanol RVP63 Ethanol RVP70 Ethanol E85 Bar graph 1. Ethanol concentration at the end of the test (ppm) Butane Concentration at the end of the test 140 120 100 80 60 40 20 0 0% 5% 10% Blend of Ethanol 15% E85 Butane RVP63 Butane RVP70 Butane E85 Bar graph 2.

Box 223.5 2 1.MTC-AA-0024 Rev. SE-136 23 Haninge.5 0 0% 5% 10% Blend of Ethanol 15% E85 Toluene RVP63 Toluene RVP70 Toluene E85 Bar graph 4.7 0.3 0.4 0.5 0. P. Toluene concentration at the end of the test (ppm) AVL MTC Armaturvägen 1.O.2 0. Tel 08-500 656 00 17 . Benzene concentration at the end of the test (ppm)** Toluene Concentration at the end of the test 3 2.5 1 0.1 0 0% 5% 10% Blend of Ethanol 15% E85 Benzene RVP63 Benzene RVP70 Benzene E85 Bar graph 3.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 17 (20) Benzene Concentration at the end of the test 0.6 0. 4 Prepared Date – Rev Document .

Tel 08-500 656 00 18 .2 1 0.4 0.05 0 0% 5% 10% Blend of Ethanol 15% E85 MTBE RVP63 MTBE RVP70 MTBE E85 Bar graph 6.25 0.MTC-AA-0024 Rev. Box 223. Xylene concentration at the end of the test (ppm) MTBE Concentration at the end of the test 0.4 1.2 0.6 Xylene RVP63 0.4 0.8 0. SE-136 23 Haninge.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 18 (20) Xylene Concentration at the end of the test 1. 4 Prepared Date – Rev Document .35 0.2 0 0% 5% 10% Blend of Ethanol 15% E85 Xylene RVP70 Xylene E85 Bar graph 5.1 0. MTBE concentration at the end of the test (ppm) AVL MTC Armaturvägen 1.15 0.3 0.O. P.

The results are shown in Bar graph 7. to prevent any components escaping and thus changing the properties of the sample before analysis. Results from the Reid Vapour Pressure analyses by Saybolt RVP 63 RVP 70 E85 AVL MTC Armaturvägen 1. provided by the company. Tel 08-500 656 00 19 . The samples were packed in gas-proof containers. SE-136 23 Haninge. Box 223.O.4 Vapour pressure analyses A small amount of each of the gasoline and ethanol blends was sampled and sent for analysis to Saybolt Co. Vapour pressure as analysed by Saybolt Reid Vapor Pressure (RVP). 4 Prepared Date – Rev Document .MTC-AA-0024 Rev. kPa 100 90 80 70 60 50 40 30 20 10 0 0% 5% 10% 15% E85 Bar graph 7. P.Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 19 (20) 4.

................ MTBE concentration at the end of the test (ppm) ...................................................................... 14 Figure 7 Changes over Time in the Xylene Concentration in the VT Shed .......................... 17 Bar graph 5....................... Gasoline Certificate of Quality (RVP 70 kPa) .... Box 223............................ 6 Table 2....... 4 Prepared Date – Rev Document ........................... 11 Figure 4 Changes over time in the Butane Concentration in the VT Shed ............ Ethanol concentration at the end of the test (ppm) ... Toluene concentration at the end of the test (ppm) .......................................... Results from the Reid Vapour Pressure analyses by Saybolt .. 17 Bar graph 4....................................... 14 Figure 8 Changes over Time in the MTBE Concentration in the VT Shed .................................. 19 AVL MTC Armaturvägen 1...2 List of Figures and charts Figure 1 Temperature of the Fuels and VT Shed cell Air during the tests........3 List of Tables Table 1...................................MTC-AA-0024 Rev..... Gasoline Certificate of Quality (RVP 63 kPa) ...................... 18 Bar graph 6......................... 7 5.................. 5 5...........4 List of Bar graphs Bar graph 1............................................. Xylene concentration at the end of the test (ppm)........................ Benzene concentration at the end of the test (ppm)**.................. 9 Figure 2 Changes over time in Total Hydrocarbon Concentration (FID) in the VT Shed ...................................... 18 Bar graph 7........................................ 16 Bar graph 3................ Tel 08-500 656 00 20 .............................................................O................................................. 15 5..Ref Page Magnus Henke 2004-07-13 Report <2005-05-30> <1> 20 (20) 5 5.. SE-136 23 Haninge....... Butane concentration at the end of the test (ppm) ................... P....... 12 Figure 5 Changes over Time in the Benzene Concentration in the VT Shed...................... 13 Figure 6 Changes over Time in the Toluene Concentration in the VT Shed ............................. 16 Bar graph 2.............. 10 Figure 3 Changes over time in the Ethanol Concentration in the VT Shed .............................1 INDEXES List of Pictures Picture 1 – VT Shed Container with Mass Spectrometer to the left....................................................

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