Handbook of Fuels E-Book

• Herausgeber: Wiley-VCH GmbH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 1015

Veröffentlichungsjahr: 2021

Beschreibung

A guide to industrially relevant products and processes for transportation fuels

The Handbook of Fuels offers a comprehensive review of the wide variety of fuels used to power vehicles, aircraft and ships and examines the processes to produce these fuels. The updated second edition reflects the growing importance of fuels and fuel additives from renewable sources. New chapters include information on current production technology and use of bioethanol, biomethanol and biomass-to-liquid fuels. The book also reviews novel additives and performanace enhancers for conventional engines and fuels for novel bybrid engines.

This comprehensive resource contains critical information on the legal, safety, and environmental issues associated with the production and use of fuels as well as reviewing important secondary aspects of the use and production of fuels. This authoritative guide includes contributions from authors who are long-standing contributors to the Ullmann's Encyclopedia, the world's most trusted reference for industrial chemistry. This important guide:

• Contains an updated edition of the authoritative resource to the production and use of fuels used for transportation
• Includes information that has been selected to reflect only commercially relevant products and processes
• Presents contributions from a team of noted experts in the field
• Offers the most recent developments in fuels and additives from renewable sources 

Written for professionals in the fields of fossil and renewable fuels, engine design, and transportation, Handbook of Fuels is the comprehensive resource that has been revised to reflect the recent developments in fuels used for transportation.

Leseprobe

Table of Contents

Cover

Title Page

Copyright

Preface to the Second Edition

Preface to the First Edition

1 Introduction

1.1 History of the Spark Ignited “Otto” Engine and of Gasoline

1.2 History of the Diesel Engine and of Diesel Fuel

1.3 History of Alternative Fuels

1.4 Emission Regulations Worldwide

1.5 Well‐to‐Wheel Analysis of Alternative Fuels

References

Notes

Part I: Automotive Fuels

2 Engine Technology

2.1 Otto Engines

2.2 Diesel Engines

References

3 Fuel Composition and Engine Efficiency

3.1 Fuel Composition and Engine Efficiency

References

4 Fuel Components: Petroleum‐derived Fuels

4.1 Petroleum‐derived Fuels

References

5 Liquefied Petroleum Gas

5.1 Introduction

5.2 Properties

5.3 Production and Processing

5.4 Purification

5.5 Storage and Transportation

5.6 Uses

5.7 Safety Aspects

References

Notes

6 Natural Gas

6.1 Occurrence

6.2 Composition

6.3 Processing

1

6.4 Transport/Distribution/Local Blending

6.5 Properties and Specifications

6.6 Natural Gas as Automotive Fuel [1]

6.7 Safety Aspects

6.8 Biomethane

References

Notes

7 Synthetic Diesel Fuels

7.1 XTL Fuels

7.2 DME (Dimethyl Ether) and OME Fuels

7.3 Well‐to‐Wheel (WTW) Analysis for XTL and DME Fuels

7.4 Well‐to‐Wheel Analysis for XTL and DME

References

Notes

8 Synthetic Gasoline Fuels

8.1 GTL Naphtha

8.2 Methanol to Gasoline Process (MTG)

8.3 Production Process

8.4 Fuel Properties

References

Note

9 Ethanol

9.1 Production

9.2 Feedstock

9.3 Land Use

9.4 Nitrogen Oxide Emissions

9.5 Water Foot Print and Impact on Water Table

9.6 Other Environmental Effects

9.7 Bioethanol Made from Lignocellulose

9.8 Fuel Standards

9.9 Fuel Properties

9.10 Well‐to‐Wheels Analysis for Fuel Ethanol and Ethanol Gasoline Blends

9.11 WTT Analysis for Bioethanol

9.12 WTW Analysis

References

Notes

10 Methanol

10.1 Introduction

10.2 Physical and Chemical Properties

10.3 Production of Methanol

10.4 Methanol as Fuel

10.5 Methanol‐based Derivatives as Fuels and Fuel Additives

10.6 Economic Aspects

10.7 Outlook

References

Notes

11 2,5‐Dimethylfuran (DMF) and 2‐Methylfuran (MF)

11.1 Synthesis of Dimethylfuran

11.2 Properties of 2,5‐Dimethylfuran and Methylfuran

11.3 Combustion and Emissions

References

Notes

12 Alternative Biofuel Options – Diesel

12.1 Biomass‐to‐Liquids (BTL)

12.2 Biodiesel (FAME)

12.3 Vegetable Oils (VO)

12.4 Hydrotreated Vegetable Oils

12.5 Well‐to‐Wheel Analysis of FAME and HVO Fuels [86, 87]

References

Notes

13 Hydrogen

13.1 Introduction

13.2 Life Cycle Analysis

13.3 Hydrogen Production

13.4 Historical Overview of Hydrogen Engine: Research and Development

13.5 Properties of Hydrogen which Influence Engine Combustion

13.6 Undesirable Combustion Phenomena

13.7 Design Criteria for Hydrogen Engines

13.8 Hydrogen‐fueled Wankel Engine

13.9 Performance Characteristic of a Hydrogen‐fueled SI Engine

13.10 Exhaust Emissions

13.11 Combustion Characteristics

13.12 Hydrogen Use in CI Engines

13.13 Hydrogen‐CNG Blend

13.14 Safety Criteria for Hydrogen Engines

13.15 Hydrogen Detection

13.16 Storage of Hydrogen

13.17 Hydrogen Transportation and Distribution

13.18 Hydrogen Vehicles based on Internal Combustion Engine

13.19 Conclusion

References

14 Octane Enhancers

*

14.1 Introduction

14.2 Technical Information

14.3 Types of Octane Enhancers

14.4 Metal‐containing Additives

14.5 Ashless Octane Enhancers

References

Further Reading

Note

15 Hybrid and Electrified Powertrains

15.1 Introduction

15.2 Classification

15.3 Functionalities

15.4 Battery

15.5 Energy Management

15.6 Market Situation and Outlook

References

16 Fuel Cells

16.1 Transportation Applications

16.2 Fundamentals

16.3 Costs, Durability, and Reliability

16.4 Cold and Freeze Start

16.5 Efficiency

16.6 Summary

References

Part II: Automobile Exhaust Control

17 Introduction

*

Reference

Notes

18 Pollutant Formation and Limitation

*

18.1 Carbon Monoxide

18.2 Hydrocarbons

18.3 Oxides of Nitrogen (NOx)

18.4 Particulate Emissions

18.5 Carbon Dioxide (CO2)

18.6 Sulfur Compounds

Reference

Notes

19 Catalytic Exhaust Aftertreatment, General Concepts

*

19.1 The Physical Design of the Catalytic Converter

19.2 The Washcoat

19.3 The Catalytic Material

19.4 Production of Catalysts

References

Note

20 Catalytic Aftertreatment of Stoichiometric Exhaust Gas

*

20.1 Three‐way Catalysts

20.2 Oxygen Storage in Three‐way Catalysts

20.3 Precious Metals in Three‐way Catalysis

References

Note

21 Exhaust Aftertreatment for Diesel Vehicles

*

21.1 The Diesel Oxidation Catalyst

21.2 The Particulate Filter

21.3 NOx Treatment of Oxygen‐rich Exhaust

Notes

22 Exhaust Aftertreatment for Lean‐burn Gasoline Engines*

Note

23 Conclusion and Outlook*

Notes

Part III: Aviation Fuels

24 Aviation Turbine Fuels

*

24.1 History

References

Further Reading

Notes

25 Aviation Gasoline (Avgas)

*

25.1 History

25.2 Avgas Grades

Reference

Further Reading

Notes

Part IV: Marine Fuels

26 Marine Fuels

26.1 History

26.2 Specifications

26.3 Composition

26.4 Properties

Reference

Notes

Index

End User License Agreement

List of Tables

Chapter 1

Table 1.1 Engine fuel, a highly complex mixture of various components pro...

Table 1.2 Distribution of MY2015 gasoline turbochargers [5].

Table 1.3 Leading biodiesel producers in 2017.

Table 1.4 EPA Tier 1 emission standards for passenger cars and light‐du...

Table 1.5 Tier 2 Emission standards, FTP 75, g/mile.

Table 1.6 Tier 3 fleet average NMOG + NO

x

SFTP standards (mg/mile).

Table 1.7 LEV emission standards for light‐duty vehicles; FTP‐75, g/mil...

Table 1.8 LEV II emission standards for passenger cars and LDVs < 8500 ...

Table 1.9 LEV III particulate matter emission standards, FTP‐75.

Table 1.10 California fleet average GHG emission standards.

Table 1.11 Japanese emission standards for diesel passenger cars, g/km.

Table 1.12 Emission standards for four stroke gasoline passenger vehicl...

Table 1.13 Timeline for nationwide implementation of light duty emissio...

Table 1.14 Overview of alternative fuel options and pathways considered...

Table 1.15 Overview of automotive fuels and vehicle combinations.

Chapter 3

Table 3.1 Summary of effects of gasoline properties on emissions in non...

Table 3.2 Summary of ffects of gasoline properties on emissions in cata...

Table 3.3 Summary of effects of diesel fuel properties on emissions in ...

Table 3.4 Summary of effects of diesel fuel properties on emissions in ...

Chapter 4

Table 4.1 Important properties of various gasoline components (approxim...

Table 4.2 Approximate composition of various fuel components (in volume...

Table 4.3 Properties of various hydrocarbon groups with regard to their...

Table 4.4 Properties of diesel fuel components.

Chapter 5

Table 5.1 Physical properties of the main LPG components.

Table 5.2 The LPG specifications of the US Gas Processors Association.

Chapter 6

Table 6.1 Natural gas compositions from different sources.

Table 6.2 German national standard for natural gas (technical regulatio...

Table 6.3 Properties of CNG in comparison with other fuels.

Table 6.4 DIN 51624, Issued 2008, CNG for the use as automotive fuel, r...

Table 6.5 Combustion characteristics of CNG, gasoline, and diesel.

Table 6.6 Feedstock forecast for 2030.

Table 6.7 Biomethane production pathways.

Table 6.8 Comparison of biomethane upgrading technologies.

Table 6.9 Swedish standard for biomethane used as vehicle fuel.

Table 6.10 European biomethane transport fuel requirements.

Chapter 7

Table 7.1 Summary of production capacities of GTL plants worldwide.

Table 7.2 Requirements of EN15940 and test methods.

Table 7.3 Key GTL fuel properties.

Table 7.4 Emission benefits of GTL in heavy‐duty application.

Table 7.5 Emission benefits of GTL in light duty application.

Table 7.6 Comparison of ASTM and ISO standard.

Table 7.7 Contaminant levels of ISO 17196.

Table 7.8 Comparison of DME fuel with methane, propane, methanol, and d...

Chapter 8

Table 8.1 Selected MTG properties.

Chapter 9

Table 9.1 Raw materials used for bioethanol production.

Table 9.2 Land use change emissions (LUC) emissions.

Table 9.3 N

2

O contribution to GHG emissions for selected biofuel feedst...

Table 9.4 Overview on selected fuel ethanol and ethanol‐gasoline blend ...

Table 9.5 ASTM fuel ethanol specifications.

Table 9.6 European fuel ethanol specification.

Table 9.7 Selected fuel properties of ethanol, gasoline, and E85.

Chapter 10

Table 10.1 Main physical properties of pure methanol.

Table 10.2 Important properties of methanol as fuel in comparison with ...

Table 10.3 Various mixing ratios with conventional petroleum products.

Table 10.4 Methanol fuel blend matrix.

Table 10.5 FCA emission test results of 95 RON against M15 for a Fiat/C...

Table 10.6 MTG gasoline vs. US conventional refinery gasoline[76–78]

Table 10.7 Selected properties of MTBE.

Table 10.8 Physical properties and characteristics of DME.

Table 10.9 Properties of OME‐1 to ‐6 in comparison with diesel fuel.

Table 10.10 Properties of DMC and MF.

Table 10.11 Cost reduction potential of key process steps of electricity ba...

Table 10.12 Cost of RE methanol production for various scenarios.

Table 10.13 Methanol fuel can be cost‐competitive.

Chapter 11

Table 11.1 Properties of 2,5‐dimethylfuran and methylfuran compared with etha...

Chapter 12

Table 12.1 Feedstocks for biodiesel esters.

Table 12.2 General trends of selected fuel parameters – impact of feedstock.

Table 12.3 Oil content of microalgae and oil yield based on crop type.

Table 12.4 Comparison of ASTM and EN standards.

Table 12.5 Extract from CONCAWE guideline for FAME.

Table 12.6 Cetane numbers of selected fatty acid esters.

Table 12.7 Cold temperature properties of different FAMEs.

Table 12.8 Material compatibilities with FAME (B100).

Table 12.9 Properties of vegetable oils (diesel as reference value).

Table 12.10 Typical properties of HVO, European EN 590:2004 diesel fuel and ...

Chapter 13

Table 13.1 Thermodynamic properties of hydrogen, methane, and gasoline (gener...

Table 13.2 Combustion properties of hydrogen, methane, and gasoline (generall...

Table 13.3 Fuel induction techniques.

Chapter 14

Table 14.1 Approximate average composition of the US and Western Europe...

Table 14.2 Oxygenates suitable for fuel blending.

Table 14.3 Physical and blending properties of ethers.

Table 14.4 Physical and blending properties of alcohols.

Table 14.5 Octane numbers of C

5

hydrocarbons and TAME.

Table 14.6 Selected properties for different high‐performance gasoline ...

Chapter 16

Table 16.1 Overview of compressor types implemented in FCEVs according ...

Table 16.2 DOE technical targets for fuel cell systems and stacks [34–3...

Table 16.3 DOE technical targets for cold and freeze start [35].

Chapter 17

Table 17.1 Emission regulation in Europe for passenger cars.

Chapter 24

Table 24.1 Major civil jet fuel grades and their specifications.

Table 24.2 Major fuel specifications for civil jet A‐1‐type fuel.

Table 24.3 National standard aviation fuel test methods.

Table 24.4 Typical nonspecification properties [18].

Table 24.5 Alteration of boiling range.

Chapter 25

Table 25.1 Specifications of aviation gasolines.

List of Illustrations

Chapter 1

Figure 1.1 Technical data: air‐cooled single‐cylinder four‐stroke engine, ...

Figure 1.2 TheDaimler single‐cylinder engine, patented in 1885.

Figure 1.3 Daimlers “small, lightweight, high‐speed engine” powering the f...

Figure 1.4 The “Gasoline Factory Rhenania” at Düsseldorf, Germany, in 1903...

Figure 1.5 Pump room and filling of cans and drums with gasoline at the “G...

Figure 1.6 The chemical laboratory of the Rhenania gasoline works near Ham...

Figure 1.7 1924 Shell began a “modern” service station network in Germany....

Figure 1.8 Historic overview on gasoline injection technology.

Figure 1.9 The first Diesel engine from MAN, a single cylinder of 19.6 l c...

Figure 1.10 Lenoir engine.

Figure 1.11 Historical development and future targets for CO

2

emission lev...

Figure 1.12 Fuel consumption trends for different scenarios from [44].

Figure 1.13 Steps of the WTW and TTW analysis.

Figure 1.14 Summary of TTW simulation Results for NEDC for 2010 and 2020+ ...

Figure 1.15 Energy use and GHG emissions for non‐hydrogen pathways (2020+ ...

Figure 1.16 Energy use and GHG emissions for hydrogen pathways.

Chapter 2

Figure 2.1 Combustion in the Otto engine (a) without ignition; (b) normal ...

Figure 2.2 Combustion in the diesel engine (a) noisy combustion; (b) norma...

Chapter 3

Figure 3.1 Significance of gasoline distillation properties for engine per...

Chapter 4

Figure 4.1 Typical properties of gas‐oil components (a) synthetic middle d...

Chapter 5

Figure 5.1 Oil–gas recovery scheme: (a) gas and gas condensate; (b) oil an...

Figure 5.2 Sources of LPG in the refinery: (a) crude oil fraction; (b) cat...

Figure 5.3 Schematic of an LPG plant: (a) feed gas – gas heat exchanger; (...

Figure 5.4 Tank‐to‐Wheel GHG emissions for selected fuels.

Figure 5.5 GHG emissions for compact vehicles by drivetrain from

Chapter 6

Figure 6.1 Largest proven natural gas reserve holders.

Figure 6.2 Slow‐fill CNG refueling scheme.

Figure 6.3 Fast‐fill CNG refueling scheme.

Figure 6.4 2014 CNG vehicle market.

Figure 6.5 Systematic outline fuel supply system bi‐fuel vehicle.

Figure 6.6 Fuel supply, engine combustion system, and exhaust gas treatmen...

Figure 6.7 Biomethane production and biomethane use as vehicle fuel in cou...

Figure 6.8 European biomethane plants 2011–2015 (a) and production by feed...

Figure 6.16 WTT GHG balance for CBG pathways.

Figure 6.10 WTW total expended energy expended and GHG emissions for conve...

Figure 6.11 WTW total expended energy expended and GHG emissions for LPG (...

Chapter 7

Figure 7.1 Schematic outline of XTL process.

Figure 7.2 Example product slate.

Figure 7.3 Interdependancy of cetane number and cold flow properties (CP/C...

Figure 7.4 Impact of GTL blend content on NO

x

emissions in Euro IV and E...

Figure 7.5 Vapor pressure and liquid density of DME – temperature dependen...

Figure 7.6 Schematic outline of DME pressure balanced vehicle filling syst...

Figure 7.7 Synthetic diesel fuel pathways.

Figure 7.8 WTT total expended energy balance for synthetic diesel pathways...

Figure 7.9 WTT GHG emissions for synthetic diesel pathways.

Figure 7.10 DME fuel pathways.

Figure 7.11 WTT GHG emissions balance for DME pathways.

Figure 7.12 WTW energy requirements and GHG emissions for synthetic diesel...

Chapter 8

Figure 8.1 Hydrocarbon types in MTG (https://www.globalsyngas.org/uploads/...

Chapter 9

Figure 9.1 Development of bioethanol sales in Germany.

Figure 9.2 Fuel ethanol production in 2018.

Figure 9.3 Global ethanol production by feedstock.

Figure 9.4 Effect of ethanol addition on ASTM D 86 distillation curve.

Figure 9.5 Sugar beet to ethanol pathways.

Figure 9.6 Wheat to ethanol pathways.

Figure 9.7 Wheat straw to ethanol pathway.

Figure 9.8 Sugarcane to ethanol pathway.

Figure 9.9 WTT total expended energy for sugar beet and wheat to ethanol p...

Figure 9.10 WTT total expended energy for other ethanol pathways.

Figure 9.11 WTW expended fossil energy and GHG of selected ethanol pathway...

Figure 9.12 WTW expended fossil energy and GHG emissions savings for ethan...

Chapter 10

Figure 10.1 Methanol – one of the most important commodities in chemical i...

Figure 10.2 Worldwide consumption of methanol and expected increase.

Figure 10.3 Worldwide methanol demand by application in 2015.

Figure 10.4 Principle ways to generate synthesis gas.

Figure 10.5 Molar ratios of Hydrogen and CO in various synthesis gas gener...

Figure 10.6 ATR reactor.

Figure 10.7 Flow sheet of a prereformer and ATR unit.

Figure 10.8 The equilibrium constants for the three main reactions of the ...

Figure 10.9 The equilibrium compositions for the methanol synthesis depend...

Figure 10.10 Lurgi combined reactor system.

Figure 10.11 Principal options to produce renewable methanol.

Figure 10.12 Lurgi process with an adiabatic and an isothermal reactor....

Figure 10.13 Flow sheet of the “G.A. Olah Plant”.

Figure 10.14 Operating costs for various energy carriers.

Figure 10.15 Road distance made good per MJ for different fuels.

Figure 10.16 Alternative fuels or fuel additives derived from methanol....

Figure 10.17 MTG reaction pathways.

Figure 10.18 Simplified flowsheet of MTG Process.

Figure 10.19 Evonik catalytic distillation MTBE process.

Figure 10.20 Process flow scheme for Lurgi's MegaDME® process.

Figure 10.21 Positive effects of DME to improve the exhaust of truck diese...

Figure 10.22 Principle routes for the production of OMEs.

Figure 10.23 Principle overall process route to OME‐3 to ‐5.

Figure 10.24 Contents of PN of various blends of diesel fuel with OME‐1....

Figure 10.25 The trade‐off between PN and NO

x

formation.

Figure 10.26 A “cradle‐to‐grave” analysis of the impact on NO

x

‐ and PM‐emi...

Figure 10.27 Cost of OME production based on methanol cost.

Figure 10.28 Flow diagram of the oxidative carbonylation to produce DMC....

Figure 10.29 China methanol consumption in fuel products

Figure 10.30 Cost breakdown for methanol synthesis from natural gas in the...

Figure 10.31 Correlation of the methanol production cost to the natural ga...

Figure 10.32 Cost breakdown of a methanol synthesis from coal in China (pr...

Figure 10.33 Cost breakdown for methanol production from biomass (wood cos...

Figure 10.34 Global methanol pricing comparison.

Figure 10.35 Chinese methanol and derivatives prices.

Figure 10.36 Gasoline production cost from renewable power.

Figure 10.37 Substantial cost reduction potential taking into account pote...

Chapter 11

Figure 11.1 The rationale for converting carbohydrates to DMF and related ...

Figure 11.2 Regulated emissions (NO

x

, total hydrocarbons HC and carbon m...

Chapter 12

Figure 12.1 Biodiesel sales in Germany [1].

Figure 12.2 FAME production process – the transesterification reaction.

Figure 12.3 Composition of fatty acids in various biodiesel feedstocks. Link...

Figure 12.4 Mean iodine values of different vegetable oils, (viscosity incre...

Figure 12.5 Basic chemistry of HVO.

Figure 12.6 WTT total expended energy for different FAME pathways. For compa...

Figure 12.7 WTT GHG emissions. For comparison, the fossil diesel balance inc...

Figure 12.8 WTW fossil energy expended and GHG emissions for selected biodie...

Figure 12.9 WTW expended fossil energy and GHG emissions of B7 compared with...

Figure 12.10 WTT total energy expanded for HVO pathways – compared to corres...

Figure 12.11 WTT GHG emissions for selected HVO pathways. Key to pathway cod...

Figure 12.12 WTW fossil energy expended and GHG emission savings for selecte...

Chapter 13

Figure 13.1 An integrated hydrogen energy system.

Figure 13.2 Production routes of hydrogen from several sources.

Figure 13.3 Major application areas of hydrogen energy: transport and powe...

Figure 13.4 Minimum ignition energy of hydrogen and methane.

Figure 13.5 Flammability range of hydrogen as compared to other fuels.

Figure 13.6 Range of equivalence ratio for stable combustion in engines.

Figure 13.7 Variation of brake thermal efficiency with equivalence ratio....

Figure 13.8 Variation of oxides of nitrogen with equivalence ratio measure...

Figure 13.9 Pressure crank angle diagram of a hydrogen engine.

Figure 13.10 Effect of various charge diluents on the performance characte...

Figure 13.11 Effect of flame on hydrogen vehicle as compared to gasoline v...

Figure 13.12 Transport of hydrogen from production to end use application....

Figure 13.13 Hydrogen‐fueled minibus.

Figure 13.14 Hydrogen–fueled three‐wheeler.

Figure 13.15 Hydrogen fueling to the three wheelers.

Figure 13.16 NO

x

emissions in mass concentration level.

Chapter 14

Figure 14.1 EU gasoline sales in 2015 RON, Research octane number.

Figure 14.2 Pressure profile versus crank angle during combustion. (a) Nor...

Figure 14.3 Comparison of RON for different C

6

hydrocarbons.

Figure 14.4 Effect of paraffin structure and molecular mass on RON.

Figure 14.5 Graphic interpretation of blend formula.

Figure 14.6 Antiknock effectiveness of various organometallic compounds re...

Figure 14.7 Historical trend in lead consumption in gasoline in the United...

Figure 14.8 Historical trend of lead content (g/l) in Italian gasoline.

Figure 14.9 Worldwide evolution of leaded gasolines.

Figure 14.10 Effect of TEL (a) and TML (b) on gasoline front octane number...

Figure 14.11 Octane numbers for blends of TEL in isooctane. (1 US gallon ≈...

Figure 14.12 Effect of TEL on different base fuels. (a) Olefin‐rich fuel; ...

Figure 14.13 Number of days in which US cities exceeded emission limits....

Figure 14.14 Historical trend of fuel ethanol production in the United Sta...

Figure 14.15 Emissions standards evolution for new light‐duty vehicles in ...

Figure 14.16 Local methanol gasoline standards in China in 2016.

Figure 14.17 Blending RON of MTBE in different base gasolines. (a) Gasolin...

Figure 14.18 Correlation between RON of MTBE and octane level of base stoc...

Figure 14.19 Antiknock effect of MTBE and TML on different base gasolines....

Figure 14.20 Effect of oxygenates concentration on vapor pressure of gasolin...

Figure 14.21 World production of ethanol.

Figure 14.22 Worldwide MTBE plant locations.

Chapter 15

Figure 15.1 Schematic visualization of a hybrid electric powertrain.

Figure 15.2 Passenger car powertrain type forecast for 2030 in million uni...

Figure 15.3 Overview of possible hybrid powertrain topologies.

Figure 15.4 Example for a serial hybrid range extender concept by Rheinmet...

Figure 15.5 Possible arrangements of parallel hybrid powertrains depending...

Figure 15.6 Schematic of the Toyota power‐split hybrid.

Figure 15.7 Overview of the degree of hybridization for different hybrid c...

Figure 15.8 Estimation of fuel consumption reduction potential by regenera...

Figure 15.9 Exemplary load point shifts to improve the engine's efficiency...

Figure 15.10 Exemplary torque curves in boosting mode by combination of el...

Figure 15.11 Comparison of specific power and energy for different types o...

Figure 15.12 Simplified visualization of the reactions in a lithium‐ion‐ba...

Chapter 16

Figure 16.1 Chevrolet Electrovan. Image source and photo courtesy of the G...

Figure 16.2 Recent FCEVs of Honda, Hyundai, Mercedes‐Benz, and Toyota. Ima...

Figure 16.3 Fuel cell range extender (BREEZE!).

Figure 16.4 Structure of a stack with two single cells.

Figure 16.5 Polarization curve of a fuel cell.

Figure 16.6 Scatter bands of stack and system efficiencies.

Figure 16.7 Exemplary automotive fuel cell system topology.

Figure 16.8 Selected trend scenarios of PGM loadings per vehicle for inter...

Figure 16.9 Comparison of well‐to‐wheel efficiencies.

Chapter 19

Figure 19.1 Aftertreatment concepts for lean‐burn and stoichiometric engines.

Figure 19.2 Various designs of emission control catalysts (beads, ceramic mono...

Figure 19.3 Design principle of a ceramic monolithic‐based converter for after...

Figure 19.4 Close‐up view of a washcoated ceramic monolith.

Figure 19.5 Transmission electron micrograph of PGMs on a washcoat particl...

Figure 19.6 Principle of catalyst production processes. PM, precious metal...

Chapter 20

Figure 20.1 Processes for catalytic automotive‐exhaust purification. (a) Singl...

Figure 20.2 Range of

λ

values in which various catalytic aftertreatme...

Chapter 21

Figure 21.1 Wall‐flow monolith particulate filter.

Figure 21.2 NO

x

storage cycle.

Figure 21.3 A typical system for NO

x

control by area onboard SCR.

Chapter 22

Figure 22.1 Aftertreatment system for a gasoline direct‐injection engine.

Chapter 24

Figure 24.1 Typical viscosities vs. temperature [18].

Figure 24.2 True vapor pressures [18].

Guide

Cover Page

Title Page

Copyright

Preface to the Second Edition

Preface to the First Edition

Table of Contents

Begin Reading

Index

WILEY END USER LICENSE AGREEMENT

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Handbook of Fuels

Energy Sources for Transportation

Edited by

Barbara Elvers and Andrea Schütze

Second, Completely Revised, and Updated Edition

Editors

Dr. Barbara Elvers

Hennebergstr 15

22393 Hamburg

Germany

Dr. Andrea Schütze

Wacholderweg 13

22335 Hamburg

Germany

Cover Images: © RonFullHD/iStock.com

All books published by WILEY‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.:

applied for

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A catalogue record for this book is available from the British Library.

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The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2022 WILEY‐VCH GmbH, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN: 978‐3‐527‐33385‐1

ePDF ISBN: 978‐3‐527‐81348‐3

ePub ISBN: 978‐3‐527‐81347‐6

oBook ISBN: 978‐3‐527‐81349‐0

Preface to the Second Edition

Looking back at the first edition of the Handbook of Fuels, published 14 years ago, you ask yourself what has changed in the meantime. Certainly not the finding that petroleum‐based products, ranging from propane/butane mixtures to bottom‐of‐the barrel residual fuel oils still make up the vast majority of fuels used in automobile, aviation, and marine propulsion. However, with growing awareness of the environmental impact of mobility and transportation, the share and diversity of alternative fuels used in the engines of passenger cars, trucks, aviation turbines, and piston engines as well as marine propulsion are rising constantly.

To take this into account, the individuals chapters devoted to natural gas, bioethanol, fatty acid esters, Fischer–Tropsch derived fuels, and bioethanol have been extended considerably in the new edition. Furthermore, in contrast to the first edition methanol and methanol‐derived fuels (ranging from ethers to methanol‐to‐gasoline) are described, methanol not only as fuel in fuel cells, but also in four‐stroke passenger car engines. Methanol‐derived ethers play a major role as octane enhancers, such as methyl tert‐butyl ether and tert‐amyl methyl ether. New sections describe 2,5‐dimethylfuran and 2‐methylfuran as potential fuels in spark‐ignition engines. Hydrogen will grow in importance both as fuel in internal combustion engines and in fuel cells and its applications will be treated in both chapters.

Production of the different alternative fuels is described in the corresponding chapters, while a description of the refinery process for production of the “classical” fuels is omitted.

Growing environmental concerns as regards to toxic emissions of sulfur and nitrogen oxides, particulates, and the greenhouse effect of carbon dioxide not only stimulated the development of alternative fuels, but also led to stringent emission limit in all sectors of transportation. The chapter on automotive exhaust control describes the current emission limits worldwide.

Propulsion units going beyond internal combustion engines are described in the chapters about hybrid powertrains and fuel cells. Whereas hybrid powertrains use both electric energy (provided by batteries) and the energy of internal combustion, in fuel cells the energy needed to drive an electric motor is provided by the reaction in the fuel cell. Electric cars using only batteries to power the electric motor will not be described in this handbook.

In the future electric powertrains will certainly gain enormously in importance, but will this lead to the end of internal combustion engines? The future will tell.

Hamburg, June 2021

Barbara Elvers

Preface to the First Edition

We are living in an era relying on mobility and transportation. We are used to – and expect – fast transport of all kinds of goods even to remote locations, and personal mobility became a key issue in everyday life of many people, at least in industrialized countries. However, transportation is not possible without usage of energy. When looking back in history, oats were grown to feed the horses, which had to carry riders and coaches, steam had to be produced from coal and water to drive steam engines, and movement of ships and boats required wind and sails or a rowing crew.

Today's means of transportation mainly rely on fuels that are combusted in an engine or turbine. The vast majority of fuels are still petroleum‐based products, utilizing the entire product slate of oil refining, reaching from propane/butane for automotive fuels over gasoline, diesel fuel and kerosene, used in automobile engines and aviation, to bottom‐of‐the‐barrel residual fuels combusted in marine diesel engines. To gain deeper insight into the complexity of a refinery and fuels production, this handbook will start with a chapter on oil refining, providing the basis for the chapters on automotive, aviation turbine, and marine fuels.

However, in a time facing dwindling oil reserves and growing environmental concerns new alternative fuels and means of transportation have to be sought and exploited. To give an overview on current research and development in this area, two separate chapters are devoted to hydrogen fuel and fuel cells, while the alternative fuels bioethanol, natural gas, fatty acid methyl ester, synthetic fuels (coal/biomass/gas to liquids), and liquefied petroleum gas are treated in the chapter on automotive fuels. Application of methanol in fuel cells is described in the corresponding chapter, while description of the use of methanol as carburetor fuel has been omitted intentionally. The automobile industry is more than reluctant to develop engines utilizing this toxic liquid, which, in order to guarantee supply, has to be at disposal at gasoline stations.

The combustion of fossil fuels results in emission of sulfur and nitrogen oxides, unburned hydrocarbons, particulates, and gas carbon dioxide. Measures to lower emission values are described in the chapters on automotive exhaust control and fuel cells. Also combustion of bioethanol, fatty acid methyl esters, and hydrogen is anticipated to result in a reduction of CO2 emissions and dealt with in the corresponding chapters. Hybrid concepts, consisting of a combination of a fuel and a non‐fuel – the battery – will not be described in this handbook.

As long as no decisive breakthrough has been achieved with one of the alternative fuels, we will certainly have to live with a fuel mix, exploiting the advantages of the different types of fuel on the one hand and minimizing their drawbacks on the other.

Hamburg, July 2007

Barbara Elvers

1Introduction

Klaus Reders and Andrea Schütze

Hamburg, Germany

The history and development of the automotive fuels, gasoline and diesel together with their corresponding engines began more than 100 years ago and is still ongoing. During this entire period, engine and fuel technologies were mutually dependent on each other. However, with subsequent engine development, the fuel requirements changed and likewise, improvements in engine technologies were often only possible through specific progress in fuel technologies.

In the early days of both the spark‐igniting Otto and the self‐igniting diesel engines, the mere starting and running of the engines, i.e. the preparation of a combustible air–fuel mixture, were the main problems. The most important quality criterion for gasoline was that it had to evaporate easily: a finger dipped into the fuel had to dry rapidly in the open air.

Diesel fuel had to ignite, with little delay, at the end of the compression stroke of the engine, as a result of increases in heat and pressure. In contrast to gasoline volatility, the ignition quality of a fuel was much more difficult to determine and it took Rudolf Diesel and other inventors considerable time and experimental effort to establish that lamp kerosene and gas oil were the most suitable fuels.

Even after the initial breakthrough, both engines suffered from fuel‐related problems, the spark‐ignited engine from uncontrolled early “self‐combustion” of the air–fuel mixture, which caused engine damage and severely reduced engine efficiency, and the diesel engine from the problem of exact metering of the small amounts of fuel at high pressure and high speed, as is required for fuel‐injection systems.

It was about 50 years after the invention of the spark‐ignited engine that a gasoline additive (tetraethyllead [TEL]) was found that reduced the uncontrolled combustion, known as engine knock, and thus allowed the construction of engines with much improved efficiency.

Small engines suitable for use in trucks became available about 30 years after the invention of the diesel engine, when high‐pressure fuel‐injection pumps had been developed, but it took another 10 years before Mercedes Benz installed the first diesel engine in a passenger car (PC).

Subsequently, prolonging engine life and safe operability under all climatic and driving conditions and increasing the yield of engine fuels from a given amount of crude oil by new refinery processes became important targets for fuel development until end of the twentieth century.

Since the 1980s the reduction of emissions during the production, transportation, storage and, of course, use of fuels in engines has become increasingly important. The primary objective for engine and fuel development was the reduction of air pollutants like NOx, HC, and CO. In the last two decades concerns on global warming and global energy demand have added a new aspect, centering on fuel consumption and CO2 emissions. The idea of fuel efficiency itself was not new; it can be traced back to the oil crises in the 1970s – a time where the search for alternative fuels also started. Some of the concepts, like methanol, have in the meantime gained only minor importance, whereas others like ethanol or biodiesel have been implemented commercially successfully as blending component with conventional fuels.

Engine fuels meanwhile have been optimized to a complex mixture of a large number of components meeting international standards and quality criteria. They guarantee maximum possible safety in the complete chain from production to their final usage, optimum engine operation over the whole engine lifetime, and, at the same time, minimum possible effects on the environment (Table 1.1).

To date a variety of engine fuels does exist, each having advantages and disadvantages. Some of them implemented in the market, some still at the beginning of their commercial life cycle and some still options on the shelf. The new edition of the Handbook of Fuels provides an overview on the available new, alternative fuel technologies as well as on developments of classical diesel and gasoline fuel to date. Moreover a comprehensive review and outlook of engine and exhaust control technology are presented, including hybrid and fuel cell concepts. Future mobility is one of the key challenges of our century and will continue to inspire innovation in automotive engine and fuel development – remaining a process that can be most efficiently undertaken in a joint approach in order to achieve maximum engine and fuel efficiency.

Table 1.1 Engine fuel, a highly complex mixture of various components produced to international standards, meeting engine, customer and environmental requirement.

Raw materials

Targets for fuel properties

Engine requirements

Crude oil – aromatics, olefins, paraffins, naphthenes (alcohols, ethers)

High energy content

Efficient engine performance

Excellent combustion properties

Low fuel consumption

Additives based on organic chemistry

Low tailpipe emissions, incl. CO

2

Optimum drivability

Alternative fuels – natural gas biomass/ethanol vegetable oils or esters

Safe fuel handling

Long engine and exhaust gas aftertreatment life

No deposits or corrosion in engine or fuel supply system

Solar energy/electricity

Acceptable environmental properties and toxicity

Low emissions

1.1 History of the Spark Ignited “Otto” Engine and of Gasoline

In 1876 Nikolaus August Otto developed a stationary, single‐cylinder, four‐stroke engine that ran on coal gas. This invention, which was later named after him, set a development in motion that substantially shaped the industrial age and has not yet come to a halt [1–5].

The development of motorized road transport was triggered by his dissatisfaction with the performance of the gas engines built in his factory in Deutz, near Cologne, which was founded in 1872. These heavy stationary engines used town gas as a fuel and operated at atmospheric pressure. They worked reliable and sold well in the beginning. However, all efforts to improve the incredibly low efficiency of these engines (3 horsepowers [hp] could be gained from an engine 4 m in height) failed, because a combustion process without compression was applied.

Nikolaus Otto therefore restarted tests that had been abandoned in 1862, that is, to develop a piston engine which combusts a gas–air mixture produced outside the engine after compression by the piston. This process would lead to much higher pressures in the combustion chamber and consequently to higher engine performance. This time he succeeded. In autumn of 1876 the first four‐stroke engine was being operated and a year later the German “Reichspatent” 532 was issued. Overnight all previous gas engines were outdated because of the new “high‐efficiency” engine.

The initial Otto four‐stroke engine consisted of a single horizontal cylinder with a bore and stroke of 161 by 300 mm, resulting in a compression ratio of only 2.5. It used slide valves, reminiscent of the steam engine, and employed a flame for ignition. When operated on illuminating gas, it developed 2.2 kW, operating at 180 rpm. Its thermal efficiency of 14% seems low to the readers of today, but was two to three times that of a comparable steam engine. However, it was still monstrous, weighed 6.8 t, and was still fueled by town gas.

The technical director of the “Gas Engine Factory Deutz AG,” Gottlieb Daimler, was not satisfied with the new engine. He envisaged a small high‐speed four‐stroke engine that could be built into a vehicle powered by a fuel, which could be transported at ambient pressure. The Deutz factory was not interested in this concept and consequently Daimler left the company and moved to Bad Cannstatt near Stuttgart, where he began his own studies, together with engineer Wilhelm Maybach. Right from the beginning Daimler intended to use a light mineral oil fraction, known as “ligroin,” as the fuel, which up to that point had predominantly been used as a cleaning agent.

Within a very short period Daimler and the ingenious designer Maybach developed patentable basic technologies enabling their small four‐stroke engine to run on a light gasoline fraction:

The “uncontrolled glow tube ignition,” a heated platinum tube pointing into the combustion chamber between the valves to ignite the compressed air–fuel mixture.

The “curve groove steering” to open and close the exhaust valve.

The “float carburetor” as a further development of the surface carburetor in which the intake air was sucked in through the “ligroin” (the light gasoline fraction).

The light gasoline, which had a density of well below 0.700 g/ml and a final boiling point of 85 °C, was sufficiently volatile to produce an ignitable air–fuel mixture in these early and simple carburetors [3]. The float carburetor had a considerable size as it was also used as a fuel reservoir, nevertheless it operated reliably. In 1885 the first vehicle from the workshop of Daimler and Maybach, the “Petroleum Reitwagen” (riding car) motorcycle (Figure 1.1), was on its “maiden trip” from Bad Cannstatt to Stuttgart‐Untertürkheim. It can be considered as the prototype of the modern internal combustion engine (ICE), using a vertical cylinder and injecting gasoline through a carburetor (patented in 1887). A year later the gas engine manufacturer Carl Benz surprised the public with a three‐wheeled “patented motor vehicle” (Figure 1.2) and in the same year Daimler installed his “small, lightweight, high‐speed engine” in a four‐wheeled motor carriage (Figure 1.3).

Meanwhile, four‐cylinder in‐line engines had been constructed and in 1893 Maybach developed the first spray‐nozzle carburetor, which replaced the large float carburetor. However, at that time it was not realized that this novel carburetor could also prepare ignitable air–fuel mixtures with gasolines of higher density and higher final boiling point and also of lower volatility. Therefore, the low‐density light gasoline used up till then remained the preferred fuel for many years to come.

Figure 1.1 Technical data: air‐cooled single‐cylinder four‐stroke engine, bore 58 mm, stroke 100 mm, swept volume 0.264 l, maximum output 0.5 hp., engine speed 600 rpm, weight 90 kg, vehicle speed 12 km/h.

Source: Ref. [6].

Figure 1.2 TheDaimler single‐cylinder engine, patented in 1885.

Figure 1.3 Daimlers “small, lightweight, high‐speed engine” powering the first four‐wheeled passenger car, “the motor carriage” from 1886; a boat (1886); a fair train (1887); a truck (1889).

The invention of the spark ignition engine offered a variety of advantages for the early motorists over the steam car of the day. Among them were the almost instantaneous starting characteristics (a steam car needed up to 30 to 40 minutes in order to build up the necessary operational pressure) and its operation radius. This was three to four times longer than that of a steam powered vehicle – the driving factor being the need for water refill, because steam cars were not equipped with a condenser at the time. The major disadvantage of the combustion engine in its early days was the noise associated with each exhaust event, which could frighten passengers or people passing by. The add‐on of mufflers to reduce the noise was therefore much appreciated by the public. An additional discomfort of the ICE was its need to be started by means of a hand crank. It could be an exhausting experience and engine backfire, a consequence of incorrect spark timing, lead to accidents involving broken arms or jaws. The invention of the electric starter in 1911 by Charles Coleman and Charles Kettering made engine starting a much smoother and more pleasant experience for the driver.

The first recorded gasoline specification known to us originates from 1907. The US Navy specified a “high‐grade refined gasoline, free from all impurities” with a Baumé density of 80°Be (about 0.673 g/ml). Motorists bought their gasoline at the pharmacy (the only place where it was available) and usually checked the density with a hydrometer.

When it was recognized that engines with spray‐nozzle carburetors could also use heavier distillate gasolines, the fuel density was no longer the main specification parameter. It was discovered that the boiling characteristics of a gasoline was by far a better measure of its evaporation properties and hence new specifications were based on distillation properties.

Gasolines with a wider distillation range were also important from the supply point of view. With the rapidly increasing number of vehicles – in 1913 more than one million motor cars were registered worldwide – it became more and more difficult for the existing refineries to meet the demand for gasoline with the necessary quality (Figures 1.4, 1.5, 1.6, 1.7). In the United States, for example, the required amount of gasoline was higher than the available quantity of distillates (straight‐run products even by 1912). It was therefore imperative to produce more gasoline suitable for motor vehicles from the available crude oils, independent of their natural composition. This was even more important for Europe than for the United States, which at that time had nearly unlimited crude oil resources.

Figure 1.4 The “Gasoline Factory Rhenania” at Düsseldorf, Germany, in 1903. This was the first refinery of the Royal Dutch Petroleum Maatschappij, which merged with the Shell Transport and Trading Co. in 1907 to become the Royal Dutch/Shell group.

Figure 1.5 Pump room and filling of cans and drums with gasoline at the “Gasoline Factory Rhenania” in 1905.

To solve the supply problem, a new refinery technology, thermal cracking, known in principle since 1869, was used from 1913 onwards to increase the production of gasoline from a given amount of crude oil. This technology rapidly increased in significance. However, unfortunately, it produced not only suitable light gasoline components from heavy crude oil constituents but also unstable olefins, which led to oxidation problems (gum formation and deposits). Hence oxidation inhibitors became the first implied gasoline additives.

Figure 1.6 The chemical laboratory of the Rhenania gasoline works near Hamburg, Germany, founded in 1910.

The spray‐nozzle carburetor and gasolines of suitable volatility ensured more precise mixture preparation and solved the early starting and running problems. However, the desire to increase the power output for a given engine size required higher cylinder pressures, which could be effected, for example, by increasing the compression ratio. This led to a new problem called engine knock. Although the phenomenon was not understood for some time, the results of the pinking combustion noise were obvious: overheating of pistons and valves causing severe engine damage.

Sir Harry Ricardo investigated the knock phenomenon and in 1910 he had discovered that addition of benzene prevented knock and engine damage. In his further studies he investigated the knock performance of gasolines with different compositions, their components and also that of specific hydrocarbons, alcohols, and other oxygenates. In general he found that branched and cyclic hydrocarbons, and also straight‐chain hydrocarbons with olefinic double‐bonds, produced less knock and would allow higher engine compression ratios than the straight‐chain n‐paraffins, which were predominantly present in distillate straight‐run gasoline. These results were another reason for the development of refinery conversion technologies.

As the engine knock problem could not be solved at that time by selection of gasoline components and refinery technology, research was directed toward antiknock additives. In 1918, it was found that aniline had antiknock performance and by 1921 the General Motors researchers Midgley and Boyd, after testing a large number of substances, found that tetraethyl lead (TEL) had a very strong antiknock effect. This highly toxic material and its derivatives were used for about half a century as gasoline additives. Rising environmental concerns and the introduction of exhaust gas catalyst after‐treatment systems eventually required unleaded gasolines to be introduced.

Figure 1.7 1924 Shell began a “modern” service station network in Germany. A gasoline pump at the road side in Landau, in the upper Rhine area.

In the following decades, new refinery processes to increase the gasoline output and to raise the antiknock performance (octane quality) were developed:

Catalytic cracking

(1935) had, compared with thermal cracking, the advantage of produce less unstable olefins.

Isomerization and

alkylation

(1938) increased the yield of branched paraffinic hydrocarbons with better octane quality.

Cyclization

(with simultaneous dehydrogenation) (reformate 1939, platformate 1949) produced aromatics with high octane quality (modern catalytic reformers can minimize the benzene concentration).

With new refineries and the new upgrading processes, it was possible to meet the worldwide increasing demand for gasoline in both quantity and quality. However, owing to political and other reasons, there were local differences. Germany, for instance, had little access to crude oil, but a large coal production. During World War I, a gasoline consisting of 70% benzene, produced as byproduct of coal coking, and 30% ethanol from biomass was developed. In the 1920s, blends of either gasoline or benzene with alcohols were used and also gasoline–benzene mixtures.

By order of the German government, from 1930 onwards gasolines had to contain 2.5% ethanol. Under pressure from farmers, this fraction was increased to 10% in 1932. However, as a result of the increasing motorization, the necessary amounts of ethanol could not be supplied, and therefore from 1936 onwards mixtures of ethanol–methanol were also used increasingly. It is interesting that even at that time, problems of corrosion of aluminum alloys and zinc‐coated iron, caused by methanol were being reported.

In spite of the significant substitution, a considerable amount of crude oil/gasoline had to be imported. During this period the first coal liquefaction plants were erected. The first unit working according to the Bergius–Pier coal hydrogenation method went on stream in 1936. The plant produced a gasoline with an octane quality (research octane number [RON]) of about 70. In comparison, the Fischer–Tropsch hydrocarbon synthesis supplied fuel with an RON of only 50 to 58. Therefore, it was still necessary to use alcohols and benzene to achieve an acceptable octane quality.

To control the gasoline quality problems in Germany at that time, in 1938 the motor industry was advised to limit the octane requirement of the engines to 74 RON. In May 1939 it was decided to add TEL to gasoline. The maximum concentration was 0.42 g/l and during World War II the minimum octane number of German gasoline was 74 RON.

At the end of the Second World War, nearly all refineries and units for the gasoline production in Germany had been destroyed. An office for mineral oil, founded shortly before the war, continued to work after the war to organize the short‐term supply of oil products. After this office was closed in 1951 and international oil companies had built new refineries according to modern and international standards, the gasoline quality in Germany improved and reached that of the remainder of the western world in about 1960. The requirements of motorists and the motor industry, together with strong competition between the oil companies, led to an ever‐increasing gasoline quality, which was achieved through new components and with gasoline additives. The aim was perfect engine operation under all climatic conditions, a long engine life, high power output, and high fuel economy. Milestones in the additive development were, apart from alkyl lead compounds and antioxidants, anti‐icing additives to prevent carburetor icing, phosphorus‐containing additives to reduce spark plug fouling brought about by highly leaded gasoline and various generations of detergents to keep carburetors, and later the complete inlet system, including the fuel injection nozzles, free from deposits.

When it was recognized that the increasing use of leaded gasoline caused worldwide lead contamination of air, water, and soil and that lead found its way into plants, animals, and humans, it was decided to reduce the maximum lead concentration in gasoline stepwise and to compensate the loss in octane quality by the addition of refinery components, however, not by benzene this time! In Germany the maximum lead concentration was reduced to 0.4 g/l in 1972 and to 0.15 g/l in 1976. The introduction of unleaded regular grade (research octane number, RON 91) in Germany in 1985 allowed the motor industry to introduce vehicles with a catalytic system for treating exhaust gas. At that time unleaded regular grade was the most commonly used unleaded gasoline in the United States. A year later the unleaded so‐called Euro premium (RON 95), a new grade, followed. The octane quality of 95, agreed between the oil and the motor industries, did not require investment in the refineries, because the composition was similar to that of leaded premium (RON 98), but of course without the lead. In 1989 the unleaded Super plus (RON 98) was introduced in small quantities. One of the components used as a lead replacement in this grade was methyl tert‐butyl ether (MTBE). Vehicles without a catalyst could only use unleaded gasoline when their engines were equipped with sufficiently hard exhaust valve seats. The motor industry supplied the relevant information and the oil industry installed telephone hot lines to inform their customers accordingly.

The sale of leaded regular gasoline stopped in 1988 and of leaded premium in 1996. Long before that date the motor industry had equipped all new engines with hardened exhaust valve seats and the oil industry had developed additives (e.g. potassium based) to protect the exhaust valve seats of old engines so that leaded gasolines were no longer required.

Whereas pivotal engine parameters, like spark ignition timing or mixture preparation had originally been manually controlled, this had now changed to a high degree of automatization, making use of mechanics, pneumatics, and hydraulics. Today's engines with their sophisticated on‐board computer and engine control functions are increasingly controlled electronically. These developments in engine technology have fostered a mutual dependency with the quality and development of gasoline to fire the engine.

From 1950 on, increasing attention was given to the further improvement of gasoline by the addition of small quantities of highly active additives.

Since 1970, measures for improving the environmental compatibility of automotive fuels have become increasingly important worldwide. The first step was the successive reduction in the lead additive content of gasolines. Later, completely unleaded gasolines were developed, which were a prerequisite for the introduction of catalytic converters.

In the mid‐1980s homogeneous‐charge spark‐ignition gasoline engines (using carburetion, throttle‐body‐, or port‐fuel‐injection) were the dominant automotive engines. One of the key concerns of that time addressed the presence of deposits in various parts of the engine, e.g. carburetor, inlet valves, or fuel injectors, and understanding their impact on engine performance and engine‐out emissions. These issues could be overcome by the invention and employment of suitable fuel performance additives. Each engine technology required new and tailored additives in order to overcome its specific deposit problematic(s). This is a continuous process and is still ongoing.

The 1970s also saw the early developments of exhaust gas recirculation (EGR), a technique deployed in order to reduce the engine‐out NOx emission. Reduction of hydrocarbon and carbon monoxide emissions could be realized by the implementation of simple computers to control engine and combustion as well as the development of so‐called oxygen sensors, which were able to improve the efficiency of the three‐way catalyst via improved control of the air/fuel ration. A further decrease in engine emissions was effected by moving from carburetor to fuel injection technology (MPI = multi point injection). This enabled precise control of the amount of fuel delivered to the cylinder as well as further optimizations of combustion chamber design and the increase of the compression ratio. In 1980 6% of vehicles were equipped with fuel injection technology – in 1990 carburetors had seized to exist [4] (see Figure 1.8).

Figure 1.8 Historic overview on gasoline injection technology.

Source: Ref. [8]. © 1996, Institution of Mechanical Engineers.

In the mid‐1990s the first commercial vehicles were equipped with gasoline direct injection (GDI