Fuels and lubricants chemistry - - PowerPoint PPT Presentation

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• Wrocław University of Technology

Marek Kułayski

Fuels and lubricants chemistry

Place for presentation max: 30 pages

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Place for presentation max: 30 pages

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Changes in gasoline properties and composition can help reduce vehicle emissions. Certain gasoline modifications are very effective in enabling vehicle emissions control systems to perform at their optimum levels. But other gasoline modifications are not nearly as effective at reducing emissions compared to the use of the vehicle emission control systems. The explanations here apply chiefly to vehicles built since 1985. Sulphur

Sulphur oxides in the exhaust gases, becomes poison the

three-way catalyst.

Reducing sulphur content in gasoline increases converter

efficiency and decreases VOC, CO, NOx, and toxics emissions.

Reducing the sulphur content also reduces the direct

emission of sulphur dioxide — a criteria pollutant.

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Vapor Pressure Decreasing the vapor pressure of gasoline reduces evaporative VOC emissions and to a lesser extent can reduce exhaust VOC and CO.

Oxygenates

CO is the result of incomplete combustion and its

formation is very dependent on the Air/Fuel. In

• lder cars, adding oxygenates to gasoline has the

same effect as increasing the amount of combustion air. It adds more oxygen to the combustion chamber, makes combustion more complete, and reduces formation of carbon monoxide.

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The emissions benefit of oxygenates was greatest in pre-1990

vehicles with less effective A/F control systems. The closed- loop A/F control systems in newer vehicles have become progressively better and better over time.

By adjusting intake A/F based on the oxygen content of the

exhaust, these systems decrease intake air to compensate for

• xygen in the fuel, negating most of the emissions benefit

associated with having oxygenate in the gasoline. The addition

• f adaptive learning systems has improved A/F control even

more.

Consequently, oxygenates seem to have little effect on

exhaust emissions from these newer vehicles, so long as they are operating in closed-loop mode.

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Typical Diesel Fuel Properties

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Gravity Flash Point Colour Viscosity Cloud Point Pour Point Sulphur Distillation Carbon Residue Corrosion Ash Cetane Number Aromatics Aniline Point

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Diesel Fuel specific gravity and NOx emissions relationship

Properties of fuels

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7 18 82

0.508 44.1 Propane

7 34.7

Oxygen, wt.%

100 25 13.1 33-16 12-15

Hydrogen, wt.%

75 52.2 84-87 85-88

Carbon, wt.% Composition, 0.07 0.424 0.796 0.81 - 0.89 0.72 - 0.78 Specific gravity, 15.5oC 2.02 16.04 46.07 105~200 100~105 Molecular Weight H2 CNG Ethanol Diesel fuel Gasoline Properties

Properties of fuels

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EUROPE:

For passenger cars and light duty vehicles: Directive 70/220/EEC with review 98/69/EC (Euro 3 i 4) For heavy duty vehicles and buses: Directive 88/77/EEC with review 2001/27/EC (Euro 4 i 5)

USA:

For passenger cars and light duty vehicles: EPA Tier 2 California Standards Tier 1/LEV II For heavy duty vehicles and buses: EPA Emission Standards for MY 2004 - 06 Greenhouse gases

Kyoto Protocol since 16th February 2005 ACEA Declaration, CO2 emission – 14.0 g/km in 2008 – 2012 period

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0.08 1.0 2008

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0.10 1.0

• 01. 2005
• 0.15

0.20 2.30

• 01. 2000
• 0.5
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• 01. 1996
• 0.97
• 2.72
• 07. 1992

Gasoline

Euro 1 Euro 2 Euro 3 Euro 4 Euro 5

0.005 - 0.015 0.08- 0.20 0.50 2008

Euro 5

0.025 0.30 0.25

• 0.50
• 01. 2005

Euro 4

0.05 0.56 0.50

• 0.64
• 01. 2000

Euro 3

0.10 0.9

• 1.0
• 01. 1996

Euro 2, DI

0.08 0.7

• 1.0
• 01. 1996

Euro 2, IDI

0.14 0.97

• 2.72
• 07. 1992

Euro 1

Diesel PM HC + NOx NOx HC CO Date of introduction NAME

/&4& 895*:

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2013

Euro VI

0.5 0.02 2.0 0.46 1.5 2008

Euro V

0.5 0.02 3.5 0.46 1.5

• 10. 2005

Euro IV

0.8 0.10 5.0 0.66 2.1 10.2000 0.15 0.02 2.0 0.25 1.5

• 10. 1999 EEVs

Euro III

• 0.15

7.0 1.1 4.0

• 10. 1998
• 0.25

7.0 1.1 4.0

• 10. 1996

Euro II

• 0.36

8.0 1.1 4.5 >85 kW, 1992

• 0.612

8.0 1.1 4.5 <85 kW, 1992

Euro I Smoke PM NOx HC CO

Date of introduction NAME

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Pb elimination Sulphur reduction (SO2, HC, PM) benzene reduction total aromatics reduction (CO, HC, benzene, deposits)

• lefins reduction (deposits)

vapour pressure optimization (HC, CO) T90 reduction (HC, deposits)

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10 50 10 150 500 1000 mg/kg Sulphur cont. 40

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35 min 1993 13 000

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max 40

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35 min 1999 13 000

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max mg/l % % % % % kPa Units 3 5 10 7 10 15 10 3 5 10 7 10 15 10 Methanol Ethanol Isopropanol t-butanol Isobutanol ethers C 5

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5 50 Pb cont. 18,0 35,0 21,0 42,0 Olefins cont. Aromatics cont. 1,0 1,0 Benzene content 2,7 2,7 Oxygen cont. 71

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75

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• Boiling range

V100 V150 V180 60 45 60 45

Vapour press.(summer)

max max min max min 2008 2005 2000 Properties

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Boiling range, T95

845 820 845 820 kg/m3

Density, 15CC

51.0 51,0

Cetane number max max min max min 2009 2005 2000 Units

Properties

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500 1000 1500 2000 1998 2000 2002 2003 2004 Germany France Italy Others EU-25 Total EU

Source: Cargill Refined Oils Europe

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Natural gas is a mixture of hydrocarbons (mainly methane — CH4) and is produced either from gas wells or in conjunction with crude oil production. Chemical Properties: The main constituent of natural gas is methane, which is a relatively unreactive hydrocarbon. Natural gas as delivered through the pipeline system also contains hydrocarbons such as ethane and propane; and other gases such as nitrogen, helium, carbon dioxide, hydrogen sulphide and water vapor.

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B 100 – 100 % FAME (EN 14214) B 5 – 5 % FAME in diesel fuel (EN 590:2004)

B 20, B 30

• poor stability
• filter blocking deposits
• poor water tolerance
• microbiological contamination
• poorer properties in low temperature

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different chemical structure – compatibility problems alternative, renewable resources necessity of engine and cars adaptations for biofuels lower CO2 emission in cycle of live Different performance properties, lack of testing methods

free of S and aromatics

Necessity of separate distribution systems Higher price, poorer availability contain oxygen, lower emission of CO, PM

Negatives Positives

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Diesel

EN-590

Gasoline EN-228 Methanol Ethanol FAME B 30 FAME B 100 EN-14214 FAEE 100 and FAEE5 Alcohol and alcohol derivatives in diesel fuels Diesel emulsion Synthetic Fischer Tropsch Diesel E 10 E 15 M 85 Methanol for blending Ethanol for blending E 85 E 95

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Normalized products Standard under elaboration For normalization during 5 years period For normalization during 5-10 years period For normalization during 10 - 20 years period

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LPG EN 589

Natural gas Biogas

CNG LNG EN 1160

Hydrogen

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Classification of Lubricants

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(<Synthetic lubricants do not break down easily and do not

produce coke or other deposits)

Lubricating Oil Properties

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Gravity Flash Point Viscosity Cloud Point Pour Point Carbon-Residue Test Ash Test Precipitation Number Corrosion and

Neutralization Number

Oiliness Extreme-Pressure

(Hypoid) Lubricants

Chemical and Physical

Stability

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Cloud Point

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Pour Point

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Carbon-Residue Test

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Ash Test

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Precipitation Number

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Thank you for attention

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