FORMULATIONS OF FUELS

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FORMULATIONS OF FUELS

Laboratoire des Matériaux, Surfaces
Ecole Européenne
Chimie Polymères Matériaux et Procédés pour la
Catalyse
François GARIN Directeur de Recherche CNRS
European Laboratory for Catalysis and Surface
Sciences
Workshop Clean I.C. engines and fuels
Thursday April 7th, 2005 Louvain la Neuve
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INTRODUCTION
From K.P. de Jong, in Environmental Catalysis,
Edited by F.J.J.G. Janssen and R.A. van Santen,
Imperial College Press, 1999 page 57
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INTRODUCTION
From K.P. de Jong, in Environmental Catalysis,
Edited by F.J.J.G. Janssen and R.A. van Santen,
Imperial College Press, 1999 page 57
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New formulations, matching engines and fuels
INTRODUCTION

• We are confronted with the growth of the number
  of cars and of the energy yield.
• Moreover we have to take into account
• the environment and the energy sources.
• Formulation of fuels that significantly reduce
  deposit formation in the combustion chamber and
  on injectors valves and reduce engine-generated
  noise, odors and emissions better energy yield.
• Several criteria are involved in this
  optimization.
• Getting maximum of performances (yield, power,
  ),
• Exhaust gases must be minimized,
• The best pleasure for driving has to be realized,
• All these qualities have to be kept versus time.
• Diversification of the Energy sources

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INTRODUCTIONWorld energy consumption

• Today, the energy repartition is
• 36 on petroleum ( 46 in 1973)
• 24 on coal
• 24 on gas (15 in 1973)
• 13 in nuclear power
• 3 in hydraulic
• 84 are fossil resources
• We have to use renewable energy
• The amount of energy produced by means of
  renewable wind, sun and biomass is estimated to
  be 10 of the total energy use in 2020.
• Ref Déclaration du gouvernement sur lénergie,
  27 avril 2004, M.-F. Beaufils

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Fuels, energy consumption and pollution control
INTRODUCTION

• Since about one century huge amount of
  ingeniousness has been developed to produce
  Good cars with high performances, great comfort
  and which are very safe.
• Now we are faced to severe objectives
• Decrease of pollutant emissions via the quality
  of the fuels
• Decrease of CO2 emissions
• Diversify energy supply
• Develop alternative fuels
• Draft of this presentation

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Years
Evolution of the automotive pollution rules in
Europe (Light cars)
Amounts of pollutants
From J.-C. Guibet, Carburants et Moteurs, 1997
Editions Technip
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Decrease of the pollutant emissions via the fuels

• If exhaust catalysts can reduce the gas pollutant
  emitted by a factor of 90, the effect of the
  improvement of the fuel quality can be around 10
  to 30.
• Parameters examined vol. of aromatics, olefins
  and MTBE, T90, as well as concentration of S,
  vol. of ethanol and ETBE.
• In fine there is the reformulated fuel in USA or,
  in Europe, the new formulations for Eurosuper.
• temperature at which 90 is evaporated

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Decrease of the pollutant emissions via the
fuelsThe Eurosuper for gasoline
Ref J.-C. Guibet, Caburants et moteurs, Editions
Technip, Vol 2, 1997, page 541
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Decrease of the pollutant emissions via the
fuelsfor Diesel fuel
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Decrease of the pollutant emissions via the
fuelsfor Diesel fuel

• To continue to improve the quality of the Diesel
  fuel versus the pollutant emissions one tendency
  is to incorporate oxygen compounds to facilitate
  the combustion in the zones rich in fuel.
• Influence of diglyme or dimethyldiglycol
• CH3-O-CH2-CH2-O-CH2-CH2-O-CH3
• Dihexylether
• Or the biofuel rape methyl ester (Colza )

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!
The motor tuning is standard or severe
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Decrease of the pollutant emissions via the
fuelsReformulated Diesel fuel
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ECE Economic Commission for Europe (1) EUDC
Extra-Urban Driving Cycle FTP Federal Test
Procedure (2) (1) and (2) Driving cycle
normalized
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Conclusion of this first part the Global
Warming Potential GWP

• Green house effect values in 1995 for 100
  years
• Gas CO2 Coef. 1(relative values versus CO2 )
• CH4 11 to 27
• N2O 270 to 310
• Gasoline and Diesel fuel Comparison of the
  emissions.
• Taking into account the upstream (oil refinery,
  transportation and distribution) and the engine
  combustion. The figures are in grams of CO2 per
  km exhaust upstream
• Gasoline
• Urban Cycle (15 km/h) 310 46
• Extra Urban Cycle (75 km/h) 206 31
• Diesel fuel
• Urban Cycle (15 km/h) 251 29
• Extra Urban Cycle (75 km/h) 158 18
• Conclusions
• The Diesel engines are less pollutant by around
  20
• We have to decrease the CO2 emissions,
• Energy supplies must be diversified.

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ALTERNATIVE FUELS

• ALTERNATIVE FUELS Other fuels than the
  traditional ones.
• From Liquefied Petroleum Gas LPG, Natural Gas for
  Vehicle NGV, Diesel Fischer Tropsch, ..
• Agricultural resources/ Ethanol from alcoholic
  fermentation, esters derived from vegetal oils,
  .
• These fuels can be used alone in dedicated
  engines (Natural Gas, hydrogen, Dimethylether
  DME, or as improving components, in small
  quantities, to the conventional fuels, and are
  used in classical engines (ethanol, biofuels,
  GTL Gas to Liquid, )
• The second approach can be used in the middle
  course.

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ALTERNATIVE FUELS- I - To GASOLINELPG
(Liquefied Petroleum Gas)

• Petrol cut C3-C4,
• Octane Number (MON) 89, S lt 200 ppm
• of vehicles equipped with LPG in 1995
• 8.7 in The Netherlands
• 4.4 in Italy
• 0.1 in France
• 0.4 in USA
• 0.7 in Japan
• 7.6 in South Korea

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ALTERNATIVE FUELS- I - To GASOLINE
Gains during LPG motor running
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ALTERNATIVE FUELS- I - To GASOLINENGV (Natural
Gas for Vehicle)

• Huge natural resources
• 2.109 TOE in 1995
• (1000 m3 0.85 TOE)
• Production evaluated in 2020
• NGV 2.6. 109 TOE
• Crude oil 3.5. 109 TOE
• The words oil and natural gas reserves are
  equivalent (about 150. 109 TOE) but the gas is
  more uniformly distributed all around the world.
• Composition 85 of C1 and around 5 of C2 O.N.
  130 for CH4 alone

Upstream consumption in energy
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Decrease of pollutant emissions from a car by the
use of Natural Gas. (ECE) Economic Commission
for Europe - Extra Urban Driving Cycle (EUDC)
Stoechiometric control
Without catalyst
With catalyst
Reduction, in , obtained versus the gasoline
channel
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Comparison between gasoline, diesel oil and NGV
for exhaust of green house gases. Values
expressed in gCO2/km
upstream
exhaust
PRG GWP Global Warming Potential
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ALTERNATIVE FUELS - METHANOL and MTBEToday all
the methanol used as fuel is previously
transformed in MTBE (methyl tertiobutyl ether)
For reformulated gasoline
TBA Tertio Butyl Alcohol, ETBE Ethyl
TertioButyl Ether, TAME Tertio Amyl Methyl Ether
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ALTERNATIVE FUELS - METHANOL and MTBE

• Amounts in vol. of these oxygenated compounds
  European Directive 85/536/EEC
• Methanol 3
• Ethanol 5
• Alcohols between 5 to 7( isopropyl,
  tertiobutyl, isobutyl)
• Ether 10 (with at least 5 C)
• The global oxygen concentration is 3.7 wt
• The use of methanol
• Problem with water traces demixtion which is
  unacceptable. A co-solvant is added Tertiobutyl
  alcohol (TBA).
• With methanol an increase of the volatility can
  be observed azeotrope formation, and also
  corrosion of organic materials.
• Due to these problems this solution is little or
  none used.
• The only good point is its octane number.
• Addition of MTBE
• No demixtion, no azeotrope and good octane number
• With 15 of MTBE decrease of 11.1 and 5.5 of CO
  and HC emissions respectively
• MTBE is the good candidate for the reformulated
  gasoline

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ALTERNATIVE FUELS BIOFUELSEuropean Directive
2003/30/EC minimal of 5.75 for biofuels

• For Gasoline engines
• Ethanol from fermentation
• One advantage good octane number
• Problems volatility, incompatibility with water
  and soots up.
• EthylTertioButyl Ether ETBE
• Isobutene Ethanol
• Has only advantages compared to ethanol
• The vapor pressure of the mix is maintained or is
  lowered.
• Better octane numbers, for the same quantity of
  ethanol introduced. Addition of 11 of ETBE 5
  of ethanol, and the increase for MON is 1.4
  instead of 0.7 if we add only ethanol.
• Perfect tolerance to water.
• Now is added 5v/v of ETBE in gasoline.

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ALTERNATIVE FUELS BIOFUELS

• For Diesel engine
• Ethanol can be used as triethyleneglycol
  pro-cetane additive NO2-O-(CH2-CH2-O)3-NO2.
• Biodiesel methylic or ethylic esters from
  vegetable oils as methylic ester of colza (MEC)
• In Europe the market is in 2004
• MEC 1. 106 Tons/year
• Diesel fuel 130. 106 Tons/year
• Biodiesel can be used at 5v/v (B5) or 30 v/v
  (B30)
• Other fuels from Biomass
• Biomass to Liquids (BtL) Syngas formation then
  Fischer-Tropsch Sunfuels, Biotrol, or H2, or
  methanol, or DME

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Alternative fuels - Comparison
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Perspectives for alternative fuels in Europe
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• Potential benefits of biofuels
• Reductions in oil imports and improved energy
  security
• Reduced air pollution
• Improved vehicle performances
• Agricultural/rural income, jobs
• Reduction in solid wastes (biomass, )
• Potential costs of biofuels
• Higher fuel production costs
• Vehicle/fuel system modifications
• Increases in some pollutant emissions
• Higher crop and crop product prices
• Other environmental impacts (fertilizers, )

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Conclusions I

• In France by the year 2007
• The petroleum market is estimated, for
  gasoline, to 10.106 Tons, in regular decrease,
  and for diesel to 34. 106 Tons, in regular
  increase.
• Ethanol or ETBE will be added (5 v/v) to
  gasoline but the market for gasoline cars will
  continuously decrease.
• Increase of the production of colza from 390 000
  Tons to
• 1 150 000 Tons for diesel cars.
• Ethanol ester from vegetable oil
  CH3-(CH2)16-COOC2H5. With this ester will be
  added 114 000 Tons of ethanol.
• ethanol ether ETBE. With this ether will be
  added 185 000 Tons of ethanol.
• By the year 2007, 300 000 Tons of ethanol will be
  added in the fuels
• Ethanol ester 1 150 000 Tons will be mixed to
  Diesel fuel
• From UFIP Union Française des Industries
  Pétrolières, Décembre 2004

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Conclusions II

• We must find the best compromise in terms of fuel
  (and/or additives) specifications to achieve the
  broadest Homogeneous Charge Compression Ignition
  (HCCI) operating range combustion.
• This HCCI solution is attractive with near zero
  NOx and PM (particle matter) emissions from the
  combustion.
• But such a combustion process can be achieved
  only by an appropriate control strategy of air
  and fuel mixing.
• Development of more appropriate fuel formulations
  may help to improve the benefits of HCCI engine
  operation.
• My colleagues will now discuss about formation of
  pollutants and combustion.