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Fuels and

Lubricants
Handbook:
Technology,
Properties,
Performance,
and Testing
George E. Totten, Editor
Section Editors
Steven R. Westbrook
Rajesh J. Shah

ASTM Manual Series: MNL37WCD

ASTM International
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Library of Congress Cataloging-in-Publication Data

Fuels and lubricants handbook: technology, properties,


performance, and testing/George E. Totten, editor;
section editors, Steven R. Westbrook, Rajesh J. Shah,
p. cm.(ASTM manual series; MNL 37)
Includes bibliographical references and index.
ISBN 0-8031-2096-6
1. FuelTestingMethodology. 2. FuelAnalysis.
3. Lubrication and lubricantsAnalysis. I. Totten,
George E. II. Westbrook, Steven R., 1956-III. Shah,
Rajesh J., 1969-IV. Series.
TP321.F84 2003
662',6dc21

2003049604

Copyright 2003 ASTM International, West Conshohocken,


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Printed in Glen Bumie, MD


June 2003

Foreword
This publication, Fuels and Lubricants Handbook: Technology, Properties, Performance,
and Testing, was sponsored by ASTM Committee D02 on Petroleum Fuels and Lubricants and edited by George E. Totten, G. E. Totten & Associates, LLC, Seattle, Washington. The section editors were Steven R. Westbrook, Southwest Research Institute,
San Antonio, Texas; and Rajesh J. Shah, Koehler Instrument Company, Bohemia, New
York. This publication is Manual 37 of ASTM's manual series.

Contents
PrefaceGeorge E. Totten, Steven R. Westbropk, and Rajesh J. Shah

ix

I. PETROLEUM REFINING PROCESSES FOR FUELS


AND LUBRICANT BASESTOCKS^o/esfe / . Shah, Section Editor
Chapter 1Petroleum Oil Refining
Marvin S. Rakow

II. FUELS: PROPERTIES AND PERFORMANCE


Steven R. Westbrook, Section Editor
Chapter 2Liquefied Petroleiun Gas
Roberts. Falkiner

31

Chapter 3Motor Gasoline


B. Hamilton and Robert J. Falkiner

61

Chapter 4Aviation Fuels


Kurt H. Strauss

89

Chapter 5^Automotive Diesel and Non-Aviation Gas Turbine Fuels


Steven R. Westbrook and Richard he Cren

115

Chapter 6Introduction to Marine Petroleum Fuels


Matthew F. Winkler

145

III. HYDROCARBONS AND SYNTHETIC LUBRICANTS:


PROPERTIES AND PERFORMANCE/?a;es/i/. Shah, Section Editor
Chapter 7Hydrocarbon Base Oil Chemistry
Arthur J. Stipanovic

169

Chapter 8Hydrocarbons for Chemical and Specialty Uses


Dennis W. Brunett, George E. Totten, and Paul M. Matlock

185

Chapter 9Additives and Additive Chemistry


Syed Q. A. Rizvi

199

Chapter 10Synthetic Lubricants: Nonaqueous


Thomas F. Buenemann, Steve Boyde, Steve Randies,
and Ian Thompson

249

Chapter 11Environmentally Friendly Oils


Hubertus Murrenhoff and Andreas

267
Remmelmann

Chapter 12Turbine Lubricating Oils and Hydraulic Fluids


W. David Phillips

297

vi

CONTENTS
Chapter 13Hydraulic Fliiids
Willie A. Givens and Paul W. Michael

353

Chapter 14Compressor Lubricants


Desh Garg, George E. Totten, and Glenn M. Webster

383

Chapter 15Refrigeration LubricantsProperties and Applications


H. Harvey Michels and Tobias H. Sienel

413

Chapter 16Gear Lubricants


Vasudevan Bala

431

Chapter 17Automotive Lubricants


Shirley E. Schwartz, Simon C. Tung, and Michael L. McMillan

465

Chapter 18Metalworking and Machining Fluids


Syed Q. A. Rizvi

497

Chapter 19Petroleum Waxes


G. Ali Mansoori, H. Lindsey Barnes, and Glenn M. Webster

525

Chapter 20Lubricating Greases


Thomas M. Verdura, Glen Brunette, and Rajesh Shah

557

Chapter 21Mineral Oil Heat Transfer Fluids


John Fuhr, Jim Oetinger, George E. Totten, and Glenn M. Webster

573

Chapter 22Non-Lubricating Process Fluids: Steel


Quenching Technology
Bozidar Liscic, Hans M. Tensi, George E. Totten,
and Glenn M. Webster

587

rv. PERFORMANCE/PROPERTY TESTING PROCEDURES


Steven R. Westbrook and Rajesh J. Shah, Section Editors
Chapter 23Static Petroleum Measurement
Lee Oppenheim

635

Chapter 24Hydrocarbon Analysis


James C. Fitch and Mark Barnes

649

Chapter 25Volatility
Rey G. Montemayor

675

Chapter 26Elemental Analysis


R. Kishore Nadkami

707

Chapter 27Diesel Fuel Combustion Characteristics


Thomas W. Ryan HI

717

Chapter 28Engineering Sciences of Aerospace Fuels


Eric M. Goodger

729

Chapter 29Properties of Fuels, Petroleum Pitch, Petroleum Coke,


and Carbon Materials
Semih Eser and John M. Andresen

757

CONTENTS
Chapter 30Oxidation of Lubricants and Fuels
Gerald J. Cochrac and Syed Q. A. Rizvi

787

Chapter 31Corrosion
Maureen E. Hunter and Robert F. Baker

825

Chapter 32Flow Properties and Shear StabiUty


Robert E. Manning and M. Richard Hoover

833

Chapter 33Cold Flow Properties


Robert E. Manning and M. Richard

879
Hoover

Chapter 34Environmental Characteristics of Fuels


and Lubricants
Mark L. Hinman

885

Chapter 35Lubrication and Tribology Fundamentals


Hong Liang, George E. Totten, and Glenn M. Webster

909

Chapter 36Bench Test Modeling


Lavem D. Wedeven

963

Chapter 37Lubricant Friction and Wear Testing


Michael Anderson and Frederick E. Schmidt

1017

Chapter 38Statistical Quality Assurance of Measurement Processes


for Petroleiun and Petroleum Products
Alex T. C. Lau

1043

Index

1061

vii

Preface
There are many books on various aspects of fuels and lubricant chemistry, applications,
and testing. However, few focus on testing and none provide extensive, in-depth coverage on fluid properties and testing methodologies together. And while there are numerous national and international standards that deal with specific testing procedures
appropriate for fuels and lubricants, it is generally beyond the scope of these procedures to provide an extensive discussion of the principles behind the tests and their relationship to the properties themselves. Therefore, there is a strong need to address
these informational shortcomings in the Fuels and Lubricants industry, which is one of
the most significant tasks undertaken in this work.
The ASTM Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing is an extensive, in-depth, well-referenced handbook that provides
a detailed overview of various testing methodologies and also provides a thorough
overview of the applications-related properties being tested. Since this manual provides
an overview of all of the ASTM and important non-ASTM test procedures relating to the
application areas addressed, it is an excellent companion text to the Annual Book of
ASTM Book of Standards, or it is an invaluable reference manual on its own.
The organization of the ASTM Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing is based approximately on the committee structure
of the ASTM D.02 Petroleum Fuels and Lubricants Committee and the standards for
which each committee is responsible. The information in this text is subdivided into
four sections: I-Petroleum Refining Processes for Fuels and Lubricant Basestocks;
II-Fuels; Ill-Hydrocarbons and Synthetic Lubricants; and IV-Performance/Property
Testing Procedures.
This manual contains thirty-eight chapters covering the following topics:
An overview of petroleum oil refining processes
Liquified petroleum gas (LPG)
Aviation, automotive diesel, non-aviation gas turbine, and marine fuels
Gasoline and oxygenated fuel blends
Petroleum hydrocarbon base oil chemistry
Synthetic hydrocarbons
Environmentally friendly fluids including those formulated from vegetable oil and
synthetic ester basestocks
Lubricating oils for turbines, compressors (industrial and refrigeration), gears, and
automotive applications
Metalworking fluids
Petroleum waxes
Lubricating greases
Oils used in non-lubricating applications: heat transfer fluids and metal quenchants
Detailed discussion on: static petroleum measurement, volatility, elemental analysis,
fuel combustion characteristics, oxidation, corrosion and viscosity
Properties of coke, petroleum pitch, and carbon materials
Hydrocarbon structural analysis procedures
An extensive discussion of lubrication and wear
Environmental and toxicity testing
Statistical quality assurance testing procedures
Essentially, all of the numerous important applications and test methods involved
in the Fuels and Lubricants industry are discussed and referenced here. We strongly
believe that this book will be an invaluable resource for anyone working in this
industry, especially since this information is not available in any other single source.
ix

PREFACE
The preparation of a text of this scope was an enormous task involving many people.
The editors are deeply indebted to the authors for their h a r d work and incredible patience. Specicd thanks go to Monica Siperko and Kathy Demoga at ASTM for their continued support and encouragement throughout the development of this text. The editors are especially indebted to their families for many evenings and weekends lost to
this project. We Eilso acknowledge the vital support of Southwest Research Institute and
the Koehler Instrument Corporation.
George E. Totten
General Editor
G.E. Totten & Associates, LLC.
Seattle, WA, USA
Steven R. Westbrook
Section Editor-Fuels
Southwest Research Institute
San Antonio, TX, USA
Rajesh J. Shah
Section Editor-Lubricants
Koehler Instrument Company
Bohemia, NY, USA

Section I: Petroleum Refining Processes for Fuels and


Lubricant Basestocks
Rajesh J. Shah, Section Editor

MNL37-EB/Jun. 2003

Petroleum Oil Refining


Marvin S. Rakow^

THIS CHAPTER PRESENTS AN OVERVIEW of t h e m o d e m , integrated

oil refinery, a n d how it separates a n d processes crude oil and


other hydrocarbon feedstocks into the required array of liquid fuels a n d other products. A description of an overall, simplified refinery flow plan serves to introduce the subject and
terminology unique to the industry.
I m p o r t a n t crude oil properties a n d test methods, along
with a perspective on past, current, a n d likely future fuel
product quality and demand, is presented. Each important
refinery process is described in sufficient detail to appreciate
its purpose, operating characteristics, yield a n d quality parameters, a n d current and future utilization in light of anticipated fuels product trends.

GENERIC REFINERY FLOW PLAN


Figure 1 is a simplified block flow diagram of a fully integrated refinery utilizing the major process options in genereJ
use. Each actual plant will incorporate those options that
meet crude throughput and quality, as well as product dem a n d and quality, while striving for m i n i m u m capital and
operating cost. Since most refineries reach their current configuration by periodic revamp and expansion, it is both likely
and economically feasible for two refineries with similar feed
and product slates to have a different mix of processes to satisfy all technical a n d economic parameters.
Crude oil first undergoes physical separation by distillation
(ASTM Test Method for Distillation of Petroleum Products,
D 86-99a) to yield various boiling range streams as dictated by
the chemical processing to follow (Table 1). The atmospheric
distillation unit usually separates about one-half of the crude
oil into the indicated cuts ranging from the low boiling gases
through a gas oil. The final boiling point of the atmospheric
gas oil can range from as low as 340C t o as high as 410C.
Vacuum distillation of the atmospheric distillation unit bottoms (ASTM Test Method for Distillation of Petroleum Products at Reduced Pressure, D 1160-95) usually separates another 30% of the crude oil as vacuum gas oils having a fined
boiling point ranging from 500-575C.
Selection of downstream processing units is greatly dictated by demand and specifications of the different products,
and, particularly, increasing sulfur removal requirements.
One of the key considerations is gasoline demand. For exam-

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pie, in the United States, one hundred volumes of crude oil


are converted into about fifty volumes of gasoline (the ratio
is about 42% o n a weight basis). Yet, crude oil typically has
only 15 to 20% of its hydrocarbons in the gasoline boiling
ramge. The fluid cataljrtic cracking unit (FCCU) is the main
process that provides the additional "gasoline" and is thus a
key process unit in the U.S. refinery flowsheet. The gasoline
to crude oil ratio is substantially lower in all other parts of the
world; thus FCCU, while in place worldwide, plays a significantly lesser role in non-U.S. refineries. Similar comparisons
are summarized for other refinery processes in Table 2.
In order of increasing boiling range, description and utilization of the distillation fractions are as follows:
CI to C4 gasesThe crude oil gases, along with gases created by the downstream process chemistry, cu^e separated
by carbon n u m b e r and hydrocarbon type in one o r more
light ends plants (also called vapor recovery units, o r "sats"
and "unsats" gas plants). Impurities, the main one being
H2S, a r e removed, with final separation providing t h e
product disposition shown in Table 3.
LSRThe light (straight run) gasolines, in most refineries,
are blended directly t o t h e gasoline pool. If a refiner is
squeezed for octane number, o r if LSR octane quality diminishes d u e t o refiner response to changing gasoline
specifications, the octane n u m b e r of this stream cem be increased by the isomerization process.
HSRThe heavy (straight r u n ) naphtha, whether from
crude oil or other process units, is too low in octane number to be economically blended in gasoline. Thus, all HSR
is processed through the catalytic reforming unit (CRU)
wherein the hydrocarbon composition is changed or "reformed" to a higher octane n u m b e r stream.
KerosineThis fraction, after appropriate cleanup (treating), is directly sold to the kerosine and jet fuel markets
and is also used as a blending component for the lighter
fuel oils and diesel fuels. Since the jet fuel market now exceeds the kerosine market in parts of the world, many refiners now label this stream the "jet" cut.
Atmospheric Gas Oil (AGO)The gas oils are generally
those distillable streams heavier than kerosine. The name
was derived in the early industry days when these oils were
thermcJly cracked to produce olefin-containing "illuminating" gases for street lighting, for example. Depending on
the final boiling point of the AGO a n d the downstream process options, t h e atmospheric distillation unit m a y jdeld
one AGO c u t o r two. The lighter portion m a y b e hydrotreated to produce low sulfur diesel, while the heavier
cut, hytrotreated or not, is typically processed in the FCCU.

www.astm.org

MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

C, + C,
GASES

REF. FUEL

PROPANE

LPG
ALKYLATE
-MTBE
GASOLINE

LPG

BUTANES

CRUDE

LSR

A
T
M
D
I

S
T

ATM V

ISOMERIZATION

-GASOLINE

NAPH

HYDROTREATING

KERO

HYDROTREATING

GAS OIL

CAT
REFORMING

JET FUEL

HYDROTREATING

GASES

RESID

No. 2 FO/DIESEL

MTBE
ALKYLATION

L
V
A
C
D
I

GASOLINE

GASOLINE

GASOLINE
FLUID

LVGO

LCO

No. 2 FO

CATALYTIC
HCO
CRACKING

HVGO

DO

No. 6 FO
CARBON BLACK
H, PLANT

HYDROCRACKING

No. 6 FO
ASPHALT
VAC RESID

REFORMER FEED
JET FUEL

VISBREAKING
DEASPHALTING
COKING
HYDROCRACKING

FIG. 1Refinery block flow diagram.

Vacuum Gas Oils (LVGO and HVGO)i:\iese cuts are usually processed in the FCCU. They can be processed in a hydrocracking unit (HCU) wherein they can be converted
into catalytic reformer feed, jet and diesel fuel, and for production of lubricating oil base stocks.
Vacuum ResidThe residuum portion of crude oil is the
non-distillable cut, boiling above, say, 575C. It cannot be
distilled without causing substantial thermEd destruction
of its hydrocarbons. This cut is sold to the asphalt and
heavy fuel oil markets, or processed by the options shown
in Fig. 1.

The need for sulfur removal is on an ever-increasing path


as average crude oil sulfur content continues to increase and
product sulfur is forced to lower levels by environmental legislation. Sulfur removal, today, is accomplished in "hydroprocessing" units. Hydrotreating, wherein the goal is to
remove sulfur (and other heteroatoms) with minimum conversion of the hydrocarbon feed stream to lower boiling
molecules, is the most widely utilized. Alternatively, hydrocracking is utilized to remove heteroatoms and concurrently
convert varying amounts of "high boilers" to lower boiling
streams.

CHAPTER 1: PETROLEUM
TABLE 1Crude section cuts.
Carbon
Number
Name/Other Names
Gases
Light straight run gasohne
light n a p h t h a
LSR
gas condensate
Heavy straight run naphtha
Heavy naphtha
Naphtha
Reformer feed
Kerosine or kerosine
jet
Light atmospheric gas oil
furnace oil
diesel
Heavy atmospheric gas oil
AGO
gas oil
Light and heavy vacuum gas oils
LVGO and HVGO
Vacuum resid"
vacuum bottoms
short resid
vacuum reduced crude
asphalt

C1-C4
C5-C6

Approximate
Boiling Range, "C
-160-0
25-90

C6-C10

85-190

C9-C15

160-275

C13-C18

250-340

C16-C25

315^10

C22-C45

370-575

C40+

500+-565 +

"The corresponding bottoms from the Atmospheric Crude Tower is called:


Atmospheric Resid
Reduced Crude
Atmospheric Bottoms
Topped Crude
Long Resid

OIL REFINING

the maximum possible hydrogen. To compUcate matters, in


crude oil some carbon atoms are also bonded to sulfur, nitrogen, oxygen and metals, as well as trace amounts of other
elements.
The four hydrocarbon types, based on the above characteristics, are:
Name
Paraffin
Olefin
Naphthene
Aromatic

Chain/Ring

Saturated/Unsaturated

Example

Chain
Chain
Ring
Ring

Saturated
Unsaturated
Saturated
Unsaturated

Hexane
Hexene
Cyclohexane
Benzene

The four types are listed in the order shown after chemical analysis, and are usually referred to by the term PONA
analysis (ASTM Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption, D 1319-98). In chain hydrocarbons, all carbon atoms
can be linked in a straight row; these are the "normal" versions, such as the example of a six-carbon hydrocarbon,
normal hexane (n-hexane). "Isomers" of n-hexane exist as
branched-chain versions; as a group, these are labeled
isoparaffins, for example i-hexanes. They are commonly
connotated as nC6 and iC6s. When a hydrocarbon type
analysis is made that includes a normal/isoparaffin split, the
normals keep the letter P, the isos take the letter I, and the
olefin/aromatic order is reversed, resulting in the acronym
PIANO. This same split is not attempted for the normal and
branched-chain olefins because of the greater number of
potential olefin structures and the lesser impact on refinery
process options.

HYDROCARBON TERMINOLOGY
There cire four basic tjrpes of hydrocarbon chemical structures. Their differences relate to the bonding between carbon
atoms and whether the carbon bonds create a chain- or ringshaped molecule. The number of electrons in the outer shell
of a carbon atom requires each atom to have four bonds to be
stable. This four-bond requirement can be peirtially met by a
carbon atom forming single or multiple bonds with adjacent
carbon atoms. Nearly all hydrocarbon molecules encountered in refining chemistry consist of all singly bonded carbons, or contain pairs of doubly bonded adjacent carbons;
the remaining bonds cu-e satisfied with hydrogen. When eill
carbon-carbon bonds in a molecule are single, it is called saturated, because it contains the maximum possible amount of
bonded hydrogen. When there cire double bonds present, the
hydrocarbon is labeled unsaturated, since it holds less than

Region
Asia/Pacific
Western Europe
Eastern Europe/FSU
Middle East
Africa
North America
So. America/Caribbean

TABLE 3Disposition of refinery C1-C4 gases.


Carbon
Number

Chemical
Name

CI
C2

Methane
Ethane
Ethylene
Propane
Propylene

C3
C4

End Uses

n-Butane
i-Butane
Butylenes

Refinery Fuel Gas (RFG)


RFG
RFG, PetrochemicEils
Liquefied Petroleum Gas (LPG)
Petrochemicals, Alkylation Unit,
Polygas or Dimerization Unit
LPG, Isomerization Unit, Gasoline
Blending
Alkylation Unit
Alkylation Unit, MTBE, Polygas or
Dimerization Unit, Petrochemicals,
Isooctane Unit

TABLE 2^Worldwide refining capacity as percent of crude.


Weight Percent on Crude Capacity
Crude Oil
Distillation,
Vacuum
Hyd retreating
Million mt/year
Distillation
FCCU
CRU
+ Hydrocracking

1020
740
540
300
160
1010
340

23
36
35
34
15
46
43

4110
Source: Oil & Gas Journal Worldwide Refining Report for January, 2001.

13
15
8
5
6
33
19

9
13
12
9
11
19
5

41
58
38
37
25
68
29

Coke

0.4
0.5
0.8
0.3
0.2
4.5
1.8

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

By chemical naming convention, all saturated hydrocarbons, the paraffins and naphthenes, end in the letters "ane,"
while all unsaturated hydrocEirbons, the olefins and aromatics, end in the letters "ene." Each of the four species has different properties and reactivity, and this plays a major role in
refinery unit selection and operation. The amount of the various heteroatoms and the m a n n e r in which they are bound to
carbon also is critical to refinery operation. These factors will
be apparent throughout the remainder of this chapter as well
as in other parts of this manual.

C R U D E OIL

almost always less dense than water, which has a specific


gravity of 1.0. Worldwide, average API Gravity is about 31
(sp. gr. = 0.87) and ranges from a high of about 45 for "light"
crudes to a low of 8-15 for the "heavy" crudes, tar sand oils,
and the like. Aromatics are the densest of the hydrocarbon
types and are therefore lowest in API, while peiraffins Eire generally highest in API gravity. As boiling point of the crude oil
increases, a r o m a t i c s content increases. Thus, high API
crudes likely have lower concentrations of high boilers and
most likely less aromatics, while low API crudes are generally
higher in aromatics and in high boilers.
Sulfur

Hydrocarbon Composition
Crude oil is composed of aromatic, paraffin and naphthene
hydrocarbons. Minor amounts of olefins may be present. Average aromatics content is about 50%; however, it can range
from as low as 2 5 % in light paraffinic crudes to as m u c h as
75% in heavy oils, such as those recovered from Canadian tar
sands. The paraffin/naphthene ratio is widely ranging and is
qualitatively identified via the labeling of many crudes as
"paraffinic" or "naphthenic." Hydrocarbon composition affects many considerations in selecting processing options, or
meeting product specifications, as shown by the following examples:

Worldwide, weight average crude oil sulfur content is about


1.25% with commercial production ranging from 0.1-6%.
Crudes low in sulfur are labeled "sweet" while those higher in
sulfur ure designated "sour." The terms derive mainly from
the foul, or sour, odor of one of the sulfur species, the mercaptans, as well as the corrosiveness of hydrogen sulfide and
the mercaptans. The split between sweet and sour was at
0.5% when average sulfur was m u c h lower than today; now,
the crossover is more likely in the 0.5-1.5% range and is usually designated by each refinery depending on its history and
capability to process higher sulfur crudes. Barring the discovery of major low sulfur crude oil pools, it is expected that
average sulfur will continue to modestly increase.

Aromatics
Because of their inherent molecular stability, they are the
bane of refining. Aromatics are the most difficult compounds
to thermally crack, hydrogenate, and desulfurize. They are
increasingly "unwanted" species in fuel products because
they are the hardest to completely combust, thus contributing more to pollution and equipment maintenance. As product aromatics content is regulated to lower levels, refinery
process severity and costs will increase. Aromatics do have
value in the refinery flow plan as a high-octane gasoline
blending component from the catalytic reforming unit and in
the recovery of chemical grade aromatic feedstocks for the
petrochemical industry.
Paraffins

and

Naphthenes

These constituents are more readily processed in the refinery.


Each offers "positive" and "negative" features, but the effects
of these species are not as severe as for the aromatics. As an
example, paraffins crack cleanly and thus yield m i n i m u m
coke, but, in fuel blends, they raise pour point and are more
difficult to octane-upgrade in the CRU.
Density
The density of chemiceJ compounds is expressed as specific
gravity (sp. gr.). In the petroleum industry, this weight/volu m e relation is expressed worldwide as "API (American
Petroleum Institute), or commonly as "API Gravity", per the
formula "API = (141.5/sp.gr.) - 131.5 (ASTM Test Method
for API Gravity of Crude Petroleum and Petroleum Products,
D287-92). The formula was adapted from the Baume density
equation used for sulfuric acid. Its value is the creation of a
whole n u m b e r scale to more readily discern one crude oil
from another, rather than using decimals, since crude oils are

Nitrogen
Generally, nitrogen content is about 5-20% of sulfur content
in most crudes. This is a helpful circumstance because nitrogen removal requires greater process severity than sulfur removal since nitrogen is mostly bound in ring form while a
greater percent of sulfur is bound in chain form. Heteroatom
removal from rings is more difficult than from chains. Many
California crude oils are high in nitrogen content, often
equaling sulfur content, and thus require greater process
severity than other crudes of equal sulfur content.
Metals
Organometallic compounds are predomineintly found in the
vacuum resid. Important metals are nickel, vanadium, copper and iron, with nickel (Ni) and vanadium (V) usually in
highest concentration. Ni + V levels in resid range from a few
p p m to as m u c h as 1000 ppm. The metals, particularly Ni,
have an adverse effect on catalyst performance and have
specified maximum limits in products such as heavy fuel oil
and petroleum coke. This can affect crude selection options
for many refinery process configurations and product slates,
as well as in process selection for future refinery revamp/expansion projects.
Oxygen
Acids, particularly naphthenic acids, and phenols constitute
the main organic oxygen compounds in crude oil. A substantial portion are in the naphtha, kerosine, and gas oil boiling
ranges. These compounds are readily eliminated via hydrogenation, and will pose less concern as more hydrotreating is

CHAPTER
added to the flow plan to achieve greater sulfur removal. If
these streams are not hydrotreated, the acids are usucJly removed by many variations of caustic treating.

PRODUCTS
The main refinery products, except for the gas streams shown
in Table 3, are automotive gasoline, kerosine/jet fuel. No. 2
and No. 6 fuel oils, and No. 2 diesel fuel. Changes to the refinery flow plan have mainly been driven by changes in crude
oil quality, and in specifications and demand for these products. It should be noted that all industry fuels and lubricants
are presented in this manual including a complete presentation and discussion of test methodology and properties.
Gasoline
The first meaningful specifications evolved in the 1920s.
From this beginning until 1990, the two key control properties have been "octane number" and "volatility." Octcine number, the measure of the engine to resist the rapid "pinging"
noise, called "knock," due to improper combustion, steadily
increased as engines became larger and more powerful, peaking in the eeirly 1970s. The refinery met the required octane
appetite of the car population by instcJling processes that
produce high octane streams, such as the FCCU, CRU, and
alkylation and isomerization. In addition, organolead compounds, mainly tetraethyllead (TEL), were used to add about
eight octane numbers to the gasoline pool.
Two laboratory octane n u m b e r test methods are used to
measure and control this gasoline quality parameter, the Research Octane N u m b e r (RON) and Motor Octane N u m b e r
(MON), per ASTM Test Methods for Research Octane Numb e r a n d Motor Octane N u m b e r of Spark-Ignition Engine
Fuel, D 2699-97a and 2700-97, respectively. Their different
operating conditions, detailed in this manual, act to delineate
and bracket the potential for knock in the automobile population. In most of the world, RON is the value the consumer
sees at the "pump," while in the United States and Canada,
the average of both the RON and MON is the guiding specification.
The first significant response to pollution from vehicular
emissions came with the passage of the U.S. Clean Air Act in
1973. This legislation stipulated that the m a i n pollutants
emitted from the automobile tailpipe; namely, u n b u m e d hydrocarbons, carbon monoxide and nitrogen oxides, had to be
reduced by 90%. The automotive industry chose to use a catalyst to comply with this regulation. This "catalytic converter" requires platinum, or other noble metal such as palladium, to effect the desired emissions reduction chemistry.
Platinum's activity, however, is adversely affected by lead. As
a result the oil industry had to remove lead from gasoline and
would have lost the eight octane numbers from the addition
of TEL. The Act also required an increase in fuel economy
from 12.5 mpg (5.35km/l) to 27.5 mpg (11.77km/l). This led
to a reduction in vehicle weight and power, which in turn reduced octane appetite by about four numbers. Thus, the net
effect on the U.S. oil industry from 1974 through the mideighties was to add about four octane numbers to the base
gasoline pool. This was achieved mainly by the addition of

1: PETROLEUM

OIL REFINING

process technology such as catalytic reforming and alkylation. However, the industry also introduced organic oxygenates to gasoline blends, initially alcohols and then ethers,
since such compounds have high octane quality (Table 4).
Of the three utilized alcohols, the only surviving member is
ethanol, which is used in the U.S. through the help of government price subsidy. Concern for water solubility, corrosion, and emissions problems from the alcohols, verified or
not, drove the U.S. refining industry to the ethers. The first,
a n d still dominant, ether was methyl tertiarybutyl ether
(MTBE), which was initially provided by ARCO Chemical
converting tertiarybutyl alcohol, a by-product from their
propylene oxide process, to the isobutylene feed needed to
make the ether.
Volatility requirements can be described as the control of
the boiling range of the gasoline to assure that the automobile operates properly during startup, warm-up, and hot operation. Gasoline specifications assure that there is a proper
balance among the C5 through C l l hydrocarbons that constitute the gasoline boiling reuige, and that the final boiling
point is limited. Volatility control also includes the need to
add liquefied n-butane to provide sufficient vapor pressure
(ASTM Test Method for Vapor Pressure of Petroleum Products (Reid Method), D 323-99a) to ensure cold engine startup.
This results in "seasonal" volatility grades wherein butane
content and boiling range Eire varied to match expected ambient temperature.
As industry used the oxygenates to meet octane number requirements, data showed oxygenates can reduce pollutants
such as carbon monoxide (CO) and nitrogen oxides (NO^).
And, as analysis of the effect of various gasoline constituents
on tailpipe emissions became better defined, it became apparent that other compositional changes would be beneficial.
This was addressed by passage of the U.S. Clean Air Act
Amendments in 1990. This legislation, and subsequent regulations such as those enacted in Ccdifomia, has substantively
changed the entire composition of gasoline (Table 5), per
ASTM Specification for Automotive Spark-Ignition Engine
Fuel, D 4814-99. As a result, the refinery has undergone continuous change to meet the cleaner fuel product requirements. These changes, initiated in the U.S., are being adopted
throughout most of the world; in some instances, legislation
in other locales is resulting in even more severe specifications
(Table 6).

TABLE 4The oxygenates.


Blending
Actual
RVP, kPa RON MON

Source

Name

Alcohols
Methanol
Natural Gas
Ethanol
Crops
t-butyl alcohol Propylene Oxide By-Product
Alcohol
Ethers
MTBE
TAME
ETBE
TAEE
DIPE

133
130
109

99
96
93

54
27
17
6

118
111
118

100
98
102

Olefin

Methanol
Isobutylene
Methanol
Isoamylene
Ethanol
Isobutylene
Ethanol
Isoamylene
(Propylene + Water)

"Average of RON and MON.

32
16
12

104"

8 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


Jet Fuel

TABLE 5History of U.S. gasoline specifications.


Pre-1974
Regular Grade
RON
MON
Pb, g/1
Premium Grade
RON
MON
PB, g/1
RVP, kPa
Oxygen, %w
Benzene, %w, max
90% Dist., C, max
Aromatics, %w
Olefins, %w
Sulfur, p p m w

94
86
0.8
100
90
0.9
62-103
0

1992-1994

1974-1991
Remove Pb,
Increase Fuel
Economy

91
83
0.1

"

98
88
0.1

1995+
91
83
0
98
88
0
50-90
2.0-2.7*
0.8-1.0
165-180
20-35
4-10
30-150

2.7*

0.3-1.0"

185-190
30-45
8-15
300-500

'^Optional use for octane number improvement.


'Mandatory in locales requiring "oxy fuel" or reformulated gasoline.

TABLE 6Gasoline specifications in U.S. and Europe.


California

United States
1998-2000
2004

Locale Year
Oxygen, %w
MTBE, %w
Benzene, %w
Sulfur, p p m w
Aromatics, %v
Olefins, %v

2.0-2.7
11.0-14.8
0.95-1.0
150-350
25-32
6-12

0.0-2.7
Unknown
0.8-1.0
30-150
20-30
4-9

Europe

1996

2000

2005

2.0
11.0"
0.8-1.0
30
25
4-6

2.7
14.8
1.0
150
35
14

2.7
14.8
1.0
10-30
30-35
12-14

''MTBE banned by 2003, but enforcement is currently on hold.

Today's military and commercial aircraft use jet fuels that are
produced almost exclusively from the kerosine fraction of
crude oil or similar boiling range cuts from certain refineiy
processes (Table 7). Key requirements focus on sulfur and
aromatics contents, clean burning characteristics, and storage stability (ASTM Specification for Aviation Turbine Fuels,
D 1655-99). Increasingly, refineries use hydrotreating technology, as well as crude slate selection, to meet specifications
and aircraft power demand. Legislative reduction in sulfur
and aromatics is not currently anticipated.
F u e l Oil
The various fuel oil grades are shown in Table 8 (ASTM
Specification for Fuel Oils, D 396-98). The major products
are No. 2 and No. 6 fuel oils. No. 2 fuel oil, commonly called
furnace oil or home heating oil, is the fuel used for residential and small commercial oil heating systems. No. 6 fuel oil
is commonly called industrial or heavy industrial fuel oil
when used by utilities for electricity and steam generation.
It is called Bunker, or Bunker C, fuel when used by the marine industry for those ships powered by "furnaces." Nos. 1,
4, and 5 are specialty products. For example, No. 1, also
known as stove oil, is a kerosine-type blend for small stovelike non-atomizing b u r n e r s a n d some farm equipment,
while Nos. 4 and 5 are lower viscosity industrial fuel oils for
smaller commercial furnaces such as those used by schools
and hospitcds.
Sulfur content is an important quality parameter. While
most No. 2 fuel oil is specified at 0.5%, maximum, (ASTM
Test Methods for Sulfur in Petroleum Products, D 129-95,
D 1266-98, and D 2622-98, for example) m u c h product has
considerably lower sulfur because of the n e w low sulfur
diesel requirement. Many refiners have found that the added
cost to desulfurize No. 2 fuel oil to match diesel specifications may be offset by reducing the n u m b e r of separate products, providing increased product blending options and reducing storage and distribution costs. No. 6 fuel oil sulfur
ranges from 0.25-3.5% depending on end use and locale. It is
anticipated that average "six-oil" sulfur content will decrease
over time.

TABLE 7Jet fuel specifications.


775-840
Density, kg/m^
204
10% Dist, C, max
Final Boiling Point, C, max
288-300
Flash Point, C, min
38-60
Aromatics, %v, max
20-25
Sulfur, %w, max
0.3-0.4
MercaptEin Sulfur, %w, max
0.002
Freeze Point C, max
- 4 0 to -47

TABLE 8Fuel oil specifications.


Grade
Uses
Density, kg/m^, max
90% Dist, C, max
Flash Point, C, min
Pour Point, C, max
Sulfur, %w, max
Viscosity
mm^/s @ 40C
min
max
mm^/s @ 100C
min
max

No. 1
Stove
and Farm

No. 2
Home
Heating

850
288
38
-18
0.3-0.5

876
338
38-55
-6
0.3-0.5

1.3
2.1

1.9
3.4

No. 4

No. 5

No. 6

Light
Industrial

Medium
Industrial

Heavy Ind'l
& Marine

55
-6

55

60
0.25-3.5

5.5
24.0
5-9
9-15

15
50

CHAPTER
TABLE 9Diesel fuel specifications.
No. 1

No. 2

No. 4

Uses

Farm,
City Bus

Automobile
Truck,
Railroad

Railroad,
Marine,
Stationary Engine

90% Dist, C, max


Sulfur, ppmw, max
Cetane No., m i n
Flash Point, C, min
Aromatics, %w, max

288
10-5000
40-55
38-55
10-35

338
10-5000
40-55
52-55
10-35

20 000
30
55

Grades

Diesel Fuel
Key diesel fuel specifications and major uses eire shown in
Table 9 (ASTM Specification for Diesel Fuel Oils, D975-98b).
The U.S. Clean Air Act Amendments also required the reduction of sulfur to 0.05% (500 ppmw), maximum, for over-theroad usage; namely, buses, trucks, and automobiles. The legislation did not require lower sulfur for other use such as the
railroad and marine industry. Again, as with the fuel oils,
m u c h No. 1 and 2 diesel is made "low sulfur" for all markets
to minimize product distribution costs. Driven initially by
European and California legislation, diesel fuel sulfur is being further reduced toward 10-50 ppmw, requiring more severe hydrotreating.
While the U.S. law did not substantially constrain aromatics content, California law did, requiring reduction of aromatics to as low as 10%. Worldwide adoption of this level of
dearomatization will be difficult to achieve near-term, but a
trend toward lower aromatic content diesel is occurring. This
is being affected in part by requiring higher Cetane N u m b e r
diesel fuel (ASTM Test Method for Cetzuie Number of Diesel
Fuel Oils, D613-95). Aromatics decrease "cetane rating."
P o u r point (ASTM Test Method for Pour Point of
Petroleum Products, D97-96a) and cloud point (ASTM Test
Method for Cloud Point of Petroleum Products, D5771-95)
are importctnt parameters to assure proper flow of fuel oils
and diesel fuels under all anticipated ambient temperatures.
Pour point must be low enough to prevent solidification of
the entire fuel while cloud point must be low enough to assure that normal paraffins will not solidify and block fuel
flow in piping or through nozzles.

CRUDE OIL PREPARATION


AND SEPARATION
A refinery may process just one crude oil or u p to as many as
a few dozen, depending on factors such as captive crude supply, access to ocean and river delivery, and pipeline supply logistics. At a refinery handling multiple crudes, individucil
crude oils are usually fed sequentially over variable lengths of
time. Some of the crude oils may first be blended in intermediate crude storage tanks to reduce the effects of substcintial
changes in crude oil quality on the process units.
In almost all refineries, the crude oil slate is processed as in
Fig. 2. Crude oil is first "descJted" to reduce entrained and
dissolved salts, mainly sodium, m a g n e s i u m and calcium
chlorides, to a n acceptable level a n d to remove "debris" such
as mineral matter resulting from transportation. The crude
oil is then physiccJly separated by distillation in atmospheric

1: PETROLEUM

OIL REFINING

a n d v a c u u m towers/columns/crude u n i t s to provide the


streams in Table 1. Many refineries incorporate a preflash
column before the atmospheric tower to remove a portion of
the lower boiling components. This improves subsequent cut
point control and flexibility in the atmospheric tower, and
can increase m a i n c o l u m n capacity. A complex heat exchange network is used to warm the crude to desalter temperature and then to furnace inlet temperature.
Desalting is accomplished by mixing 100 parts of crude oil
with about 3-10 parts of water at about 120-140C. Emulsifier or demulsifier additives may be used to aid either the
mixing of crude and water or separation of the two after mixing. Electrically charged plates may also be used to coalesce
water to aid in separation. The desalted water is then sent to
wastewater treatment and, if necessary, for stripping of undesired contaminants such as benzene.
After further heat exchange, usually to 210-240C, the
crude is sent through multi-pass furnaces to attain atmospheric column inlet temperature in the range of 340-410C.
Then, by control of top column reflux a m o u n t and temperature, reboil, and p u m p a r o u n d / p u m p d o w n parameters, the
desired cuts are obtained.
Atmospheric column bottoms are usually sent to the vacu u m tower to recover the vacuum gas oils to a final boiling
point (FBP) as high as 575C, although 540-565C may be
more common. The ability to reach desired FBP depends on
m a x i m u m furnace outlet temperature a n d its concomitant
coke laydown on the furnace coils vs. economic run length,
and attainable vacuum. Vacuums in the range of 7-25mm Hg
absolute are usually achieved using steam ejector systems or
vacuum p u m p s .

PROCESSES FOR GASOLINE AND


DISTILLATE YIELD A N D QUALITY
Fluid Catalytic Cracking
This is the predominant process for converting high boiling
gas oils a n d resid into lower boiling streams, mostly gases, a
gasoline blending component and a light gas oil for No. 2 fuel
oil blending, fts place in the refinery is mainly driven by the
yields and compositions of the product components, the ability of the process to vary product yield/composition, a n d
lower capital investment cind operating costs compared to alternative process options.
Figure 3 depicts the process operating principles. Many
equipment configurations and catalysts are employed, but
the essence of the process is reactor and regenerator "vessels," vapor phase fluidization of the catalyst in each vessel,
flow of catalyst between the two vessels, thermal cracking of
the feed in the reactor and removal of coke from the catalyst
in the regenerator. Much of the design variations cire related
to engineering improvements and the increased processing
of poorer quality feed, which in t u r n has been enabled by
greatly increased activity of today's catalysts.
Fresh feed and, if desired, heavy product recycle, are introduced into the reactor. The feed vaporizes and thermally
cracks in about 1-3 s at about 525-550C, to yield a potential
variety of product s t r e a m s exemplified in Table 10. Coke
forms in the reactor section due to rapid polymerization of
olefins a n d aromatics as cracking chemistry occurs. This

10 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
Condenser

0iS^SI I

Atmospheric
Distillation

*'Wet Gas
*LPG

Reflux

Light
"B-' Water
r'stabifeation'l Straight Run
-*
and.
^
L.SpJtttinjtJ_*

xr

~ ) P Stripper

Naphth:
Kerosene

Crude

Stripper
Steam

-Water

* Diesel

Preheat
Desaiteri
"Gas Oil

Steam

Brim
Preheat L f i j J
Preflash
Drum

Vacuum
Distillation

Furnace^i=J
-Topped Crude

Steam

Non-condensat)les
and steam

PreCondenser
High Pressure
Steam
NonC.W. condensables
O

QHot Wbll Accumulator [)


^ Heavy
Gas Oil

Naphtha

Sour Water

Topped
Crude
Q Ejectors

Coil
Steam

Stripping
> Vacuum Resid
Steam
FIG. 2Atmospheric and vacuum distillation units.

coke "lays down on" the fluidized catcJyst particles, diminishing their activity. The "coked-up" catalyst is continuously
removed from the reactor section and transported with air to
the regenerator wherein controlled combustion converts the
coke into a "flue gas" consisting mainly of carbon monoxide
(CO), carbon dioxide (CO2), water (H2O), and sulfur and nitrogen oxides (SOx and NOx) resulting from the presence of
sulfur and nitrogen in the feed. This combustion raises the
catalyst temperature to 680-760C which, in turn, supplies
most or all of the heat to raise fresh feed to its reactor temperature as the "hot" regenerated catalyst is continuously removed from the regenerator and re-mixed with fresh feed. In
fact, many FCC units operate in heat balance, meaning that
all heat to raise the feed to reactor temperature is supplied by
the regenerated catalyst.

CO, a pollutant, must be removed from the regenerator flue


gas. Even if CO emissions were not an issue, economics of
maximizing heat recovery would dictate oxidation of CO to
CO2. This is accomplished by the use of combustion additives
in the regenerator, improved regenerator design and operation, and external secondary combustion in a CO or waste
heat boiler. SOx and NOx pollutants face refinery emission
limits. Acceptable levels in the flue gas can be achieved with
regenerator additives, various flue gas scrubbing processes,
or by installing "cat feed hydrotreaters" to reduce the sulfur
and nitrogen content in the FCCU feed.
Run length between scheduled turnarounds for inspection
and maintenance is 3-5 years. Longer runs have resulted
from ongoing improvements to the overall design that include multistage regeneration, improved cyclones and feed

CHAPTER
nozzles, and taking advantage of favorable FCCU process
economics. Factors favoring economics include the ability to
produce high yields of high-value gas and gasoline from low
value feed, substantial yield flexibility resulting from catalyst
selection and variable operating parameters, operation at essentially atmospheric pressure, and no addition of hydrogen
as is required in the hydrcracking process.
The cyclone systems in both the reactor and regenerator are
mechanical devices to collect the catalyst carried out of the
dense phase fluidized beds by the respective cracked product
and flue gas vapors. Although thousands of tons of catalyst
circulate each day, cyclone efficiency is so close to 100% that
losses are kept in the 1-10 ton-per-day range. The losses from
the reactor are returned via the downstream product recovery
train. Losses from the regenerator are collected and then disposed, thus creating the need for daily catalyst replacement.
Early catalysts were silica-alumina "clays" incapable of
processing resid and limited in activity. Today's catalysts
contain various highly active zeolites, combined with appropriate silica-alumina bases, which permit the processing of
heavier, dirtier feed, as well as provide increased yields of

Reactor Vapor

Reactor

Reactor Riso'

Regenerator
/

Spent-Catalyst
Stripper

Combustor
Riser
Catalyst
Cooler
(Future)
Combustor

Spent-Catalyst
Standpipe

RecirculatedCatalyst
Standpipe

RegeneratedCatalyst
Standpipe

CooledCataiyst
Standpipe
(Future)

Chargestock

t
Combustion Air
UitGas
FIG. 3Fluid catalytic cracking unit.

1: PETROLEUM

OIL REFINING

11

TABLE 10FCCU yields.


Operating Mode

Gasoline

Gas

Distillate

Reactor Products, %w
C1-C2
C3s
C4s
Gasoline
Light Cycle Oil
Heavy Cycle Oil
Coke on Catalyst

3
6
11-12
46-52
15-19
7-8
6

6
22
20
27
12
5
8

2
4
8
38
35
9
4

light products without the overproduction of coke. Catalyst


formulations can be chosen to maximize gasoline yield and
octane number, gas yield and olefin content; tolerate resid
metals; and resist higher regenerator temperature resulting
from additional coke p r o d u c t i o n from the higher carbon
residue level in the resid portion of the feed.
Reactor effluent is taken to the "cat main fractionator"
wherein the main separation occurs to yield the olefin containing gases, gasoline blending streams, a light gas (cycle) oil,
and a heavy gas (cycle) oil. If the heavy gas oil has the right
properties, it, or a heavier portion of it, may be sold as feed to
produce carbon black for the manufacture of tires and printing inks. If so, it will be labeled carbon black oil, decant oil,
slurry oil, or clarified oil. It is the heavy gas oil that is used as
the "washing" stream at the b o t t o m of the fractionator to remove the catalyst to the settler and then back to the reactor.
The gases undergo further absorption and distillation to
achieve the desired separation for various end uses. Some refiners select feed, catalyst and operating conditions to maximize olefin gas yield at the expense of gasoline and/or light
cycle oil yield. This has been done to meet growing demand
for propylene as a petrochemical feedstock and to provide
butylenes for MTBE and alkylation feed.
The "cat" gasoline, a major gasoline blending component
used throughout the world, is treated for mercaptan sulfer removal prior to product blending for odor and corrosion control. Removal of other sulfer compounds, or just the sulfur
atoms themselves, will be required to meet future demand for
low sulfer gasoline. While desulfurization via hydrotreating
will r e m a i n a d o m i n a n t technology for some time, other
sulfer removal technologies, for example utilizing extraction
or oxidation, are in various stages of commercicdization.
The light cycle oil is mainly blended to No. 2 fuel oil. As
feeds to the "cat" unit get dirtier, and as demand for cleaner
fuels grows, the refiner will be faced with an increasing need
to reduce the sulfur, nitrogen, and aromatics content of this
stream, if for n o other reason than to provide blending flexibility into the diesel fuel markets. Heavy cycle oil yield is very
low in today's operation; most refiners blend this cut to No. 6
fuel oil, while some recycle it to extinction in the reactor. It
was this recycle of the FCCU gas oil in the early days of this
process that gave rise to labeling them light and heavy cycle
oil in addition to light and heavy gas oil.
Key fluid catalytic cracking process variables include:
Catalyst circulation rate, commonly called the "cat-to-oil
ratio"
Reactor temperature
Catalyst activity
Feed residence time

12

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

The cat to oil ratio, in the weight range of 4 to 15, can be


varied within the Umits of maintaining the necessary pressure balances and vessel vapor velocities so that catalyst flow
and bed fluidization are properly maintained. Reactor temperature will vary with cat-to-oil ratio, regenerator temperature and catcdyst cooling, and from feed preheat for those
units having feed furnaces. Process severity is mainly defined
in terms of conversion of the heavy feed into gas and gasoline, and is expressed as 100 minus the product streams boiling above gasoline. Conversion typically ranges from
50-85%. Lower conversion is desired to meiximize light cycle
oil yield for blending No. 2 fuel oil during the oil heating season, while higher conversion is set to meet gasoline a n d
olefin gas deniEmd.
Catalytic R e f o r m i n g
This process is an essential part of every refinery that desires
to use the heavy straight run naphtha fraction from crude, or
similar boiling range material from a n o t h e r process unit
such as the hydrocracker, as a gasoline component. The feed,
usually a C6-C10 cut, is too low in octane n u m b e r to be economiccdly blended to the gasoline pool. The "cat reformer"
converts low octane n u m b e r peiraffins and naphthenes in the
feed into "high octane" aromatics in the product. Typical feed
unleaded RON is 40-65 while product is 94-103.
There Eire three main reactor configurations, two of which
are shown in Fig. 4; all accomplish essentially the same
chemistry.
SemiregenerativeFixed bed reactors, all operating in series.
CyclicFixed bed reactors in series; one out of service on
rotating basis for catalyst regeneration.
ContinuousMoving bed reactors in series with "continuous" catalyst regeneration.
The evolution from the original semiregenerative reformer
to today's continuous unit was driven by "competing chemistry" within the process and by the need for higher octane
n u m b e r product to help replace the lost octanes from lead.
Hydrogen must be added with the naphtha feed to minimize
coke formation and laydown on the catcdyst and achieve economic run length, since catalyst performance is readily diminished by coke. Higher operating pressure aids in reducing coke formation chemistry. However, the goal is to
maximize the conversion of naphthenes to aromatics since
higher eiromatics content translates into higher octane number reformate. Lower operating pressure increases aromatics
yield since it makes it easier for hydrogen to "escape" from
the naphthene. The continuous process is thus able to operate at lower pressure because the resulting higher coke make
can be removed "continuously." In actuality, a catalyst particle tcikes about five days to migrate from the top of the first
reactor to the bottom of the last; such r u n length in the fixed
bed "semi-regen" reformer would be unacceptable.
The original catalyst that enabled this chemistry consisted
of an alumina base promoted with 0.25-0.75% platinum. Today's catalysts may contain just the platinum promoter; may
be bi- or tri-metallic using additional metals such as rhenium
and tin; may have the alumina base converted to the more
acidic chloride form by treatment with chlorine or chloroform, for example; or may utilize appropriate zeolites. In any

case, the sensitivity of the catalysts to coke, and to deactivation from heteroatoms such as sulfur and nitrogen, requires
that the naphthas first be hydrotreated.
Fresh hydrotreated naphtha feed plus recycle hydrogen is
heated to reactor temperature of about 500-530C in a furnace and fed to the first reactor. The over-riding chemistry is
endothermic dehydrogenation of naphthenes to aromatics.
Thus, as the feed progresses down through the catalyst, as
m u c h as 60C cooling occurs from top to bottom in the first
reactor, reducing activity and hence aromatics yield. The net
effect is that octane n u m b e r gcdn in one reactor is not enough
to make the process attractive. Therefore, the reactor effluent
is reheated in a second furnace, or in a second coil within the
same furnace, back to 500-530C and fed to a second reactor,
and so on, until desired octane product is attained. Cat reformers usually consist of three reactors although as many as
five are utilized.
Typical yields at two product RON levels are shown in
Table 11. The net hydrogen produced from aromatics formation is the m a i n source of hydrogen in the refinery for its
desulfurization and related needs. Refineries are in "hydrogen balance" if all such hydrogen can be provided by the reformers. If not, refiners purchase hydrogen or build their
own hydrogen plants.
Figure 5 depicts the main process parameters of catalytic
reforming; namely, the "yield-octane" relationship. Higher
octane n u m b e r d e m a n d requires higher reactor temperature
and/or longer residence time. Both will cause more of the
naphtha feed to crack into gas and thus reduce gasoline 3rield.
"Reformer severity" is uniquely defined as the unleaded RON
of the C5 + liquid product, the second major gasoline blending component. In fact, the gasoline streams from the fluid
cat cracker emd cat reformer make u p about two-thirds of the
world's gasoline.
Significant changes in feed composition to the reformer
a n d in downstream utilization of the reformate are occurring, related to the move toward cleEmer fuels. The major
source of benzene in gasoline is catal3^ic reformate. The
trend is to reduce benzene to a m a x i m u m of 1%, with the potential for even lower limits being legislated in parts of the
world. When the p u s h for lower benzene content began,
worldwide benzene levels ranged from as low as 1.6% in the
U.S. to as high as 5% in pEirts of Europe and Asia. Refiners
can reduce benzene concentration as follows:
1. Remove benzene precursors from the feed. This is accomplished by increasing the initial boiling point of the heavy
naphtha feed, or, in essence, raising the cut point between
light and heavy straight run naphtha. This results in less
feed available to the reformer and lower octane quality in
the resultant higher boiling range light straight r u n
stream.
2. Leave the benzene precursors in the feed. In this case, refiners can then distill the C6 cut from the reformate. Benzene can be extracted from this cut for chemical sale, or the
benzene can be reacted with olefins to produce alkylbenzenes. The C6 cut can also be hydrotreated to convert benzene to cyclohexEine with a resultant loss in octane number.
Clcciner gasoline also mcindates lower final boiling point
and lower total aromatics. This requires the refiner to eliminate a substantial portion of high boiling fraction from the
naphtha feed and, in some cases, to r u n the reformer at lower

CHAPTER 1: PETROLEUM OIL REFINING


Semiregenerative Catalytic
Reforming Unit
Net hydrogen
Compressor

Recycle hydrogen

Off Gas

^^-^c^O

Heavy
Naphtha

C3s&C4s

Separator

Reformate

Continuous Catalytic
Reforming Unit

Spent Catalysi
Product
'Separatiofi
Naphtha &
Recycle Gas

FIG. ASemiregenerative and continuous catalytic reforming units.

13

14 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

severity to yield less total aromatics. Beside the loss of octane


number and yield, these changes likely yield less by-product
hydrogen, a costly ingredient needed for desulfurization
chemistry.
Catalytic reformate also plays an important role in the
petrochemical industry by being a major source of benzene,
para-xylene, ortho-xylene, and toluene primary feedstocks.
The recovery of these aromatics is illustrated in Fig. 6. Total
reformate, or a narrower C6-C8 cut, is fed to a liquid-liquid
extraction column where it is contacted countercurrently
with a solvent with known selective solubility for aromatics.
The main solvents are sulfolane or di- to tetra-ethylene glycols. The aromatics, called the extract, are then distilled from
the reusable solvent. The rejected paraffins and naphthenes,
called raffinate, must find a new home which can include the
solvent/spirits market or as feed to ethylene plants running
on naphtha; recycling the raffinate to a high severity catalytic
reformer is usually not economically attractive. The "pure"
aromatics in the extract are then separated in a series of distillation columns, except for meta- and para-xylene, which
have virtually identical boiling points. Their separation is accomplished either by crystallization, which takes advantage
TABLE 11Catalytic reforming unit yields.
Reformer Severity

102

94

Yield, %w
Hydrogen
CI + C2
C3
iC4
nC4
C5+ Reformate

3.0
3.7
3.5
1.8
2.5
85.5

1.7
1.0
1.8
1.4
2.1
92.0

of their widely different freeze points, or by adsorption with


molecular sieves, which takes advantage of their different
molecular diameters.
Isomerization
This process mainly converts normal paraffins into isoparaffins. The technology is employed to increase the octane quality of light straight run gasoline/naphtha by converting npentane and n-hexane into mixed C5-C6 isoparaffins. The
process is also used to convert n-butane into isobutane to either provide feed to the alkylation process or as a step in the
process to make MTBE when isobutylene is not available.
A simplified process flow diagram is shown in Fig. 7. Fresh
feed, along with recycle hydrogen, is heated to reactor temperature of 180-260C by heat exchange or a furnace. The
feed then flows down through a fixed bed of catalyst that is
similar to reforming catalyst. Operation may be oncethrough, or with peirtial or total recycle of unconverted nparaffin. The recycle can be recovered using distillation to
separate lower boiling isoparaffin product from the normals,
or adsorption with molecular sieves to separate smaller diameter n-paraffins from isoparaffins. Recycle yields a greater
octane number increase at the expense of higher capital investment and operating cost. Octane improvement generally
ranges from 5-25 numbers depending on feed composition
and process configuration.
Because of the low reactor temperature, thermal cracking
of the feed is very low, in the order of 1-2% compared to
12-20% in the CRU. However, the sensitivity of the catalyst to
coke laydown still requires the presence of hydrogen to minimize coke formation and hence provide satisfactory activity
and run length.

96

High Aromatics Feed

2
g>

Low Aromatics Feed

76
94

96

98

100

RON without Pb
FIG. 5CRU yield/octane relationship.

102

104

CHAPTER

1: PETROLEUM

OIL REFINING

15

'^Raffinue

Bxtfictio
^Tnadngind
Fnctiamtioii
Feed

LSGBflD
EEXTRACTOR
S'STRlPfCR
RC - RECOVERY COLUMN
SR - SOLVB^TREOENERATOR
FIG. 6Solvent extraction unit for btx recovery.

Alkylation
The reaction of an olefin with an aromatic or isoparaffin is labeled alkylation. Benzene is alkylated with ethylene to eventually produce styrene, and with propylene to eventually produce phenol. These "petrochemical" technologies are found
in some refineries. But the "alky" process that is part of the
typical refinery flow plan (Fig. 1) is the reaction of C3-C5
olefins with the paraffin isobutane.
The process requires that the paraffin be branched to provide a reactive tertiary carbon atom, bonded to only one hydrogen. Normal paraffins, having only primary or secondary
carbon atoms, are not sufficiently reactive. Isopentane could
be used, but it is already a clean, high-octane liquid contained in the C5 part of the gasoline pool. Thus, the gas isobutane becomes the obvious choice since it is reactive, not part
of the gasoline pool, and reasonably available in the refinery
as a crude oil component, as well as in the C4 product from
processes s u c h as the FCCU, CRU, a n d hydroprocessing
units.
The chemistry can be accomplished with any olefin. Ethylene is not used because it is expensive to recover, operating
pressure would have to be considerable since the process is
carried out in the liquid phase, and the resulting alkylate octane quality is poor compared to processing higher molecular weight olefins. Propylene is a n "alky" feed in many units,
but its use competes against its value as a petrochemical feed
for polypropylene, propylene oxide, and linear alpha olefins.
The butylenes are the predominant alky feed because of their

availability, cost t o separate into chemical grade components, and high octane quality of the alkylate. However, as
the light olefin content of gasoline diminishes due to evolving
legislation, refiners may also find it economically attractive
to use amylenes as alky feed, instead of converting them to
lower octane pentanes in a hydrotreater.
In many refineries, there is insufficient isobutane to match
the availability of olefins from the FCCU and cokers. The
missing iC4 can be produced by isomerizing available nC4,
by purchase from the natural gas condensate pool, or from
nearby refineries lacking an alky plant.
The catalysts that are commercially employed are 98-99%
sulfuric acid (H2SO4), or concentrated hydrofluoric acid
(HF) because the chemistry requires a very strong acid. Commercialization of solid-type catalyst is in progress. The process in concept is simple: pressurize the system to liquefy the
hydrocarbon feeds, mix them with the strong liquid acid, and
separate the alkylate from the catalyst. The process in reality
is complex because of acid carryover into the alkylate; formation of acid-hydrocarbon molecules; significant exothermic heat of reaction; the need for substantial excess isobutane to suppress olefin polymerization; high catalyst
consumption and utility cost in the case of H2SO4; and safety
considerations, especially with hydrofluoric acid.
Sulfuric acid alkylation m u s t r u n at low temperature,
namely, about 5-10C, in order to minimize olefin polymerization, acid consumption, and by-product yield. This requires refrigeration of the catalyst and feed, and substantial

16 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK

4Mafenp
Hydiogra

[ ^

ri
c:^

X
.J^

iall:^^

OM

sr

LEGEMD
D-DRYER
R-REACrOR
ST STABILIZER

C5-C

booMnli
FIG. 7Isomerization unit.

mixing energy because of the acid's high viscosity. Most alky


units used sulfuric acid from the commercialization of the
process in the 1940s until the 1970s, the period when energy
cost was low. In addition, H2SO4 consumption is substantial
at about 0.1 kg per kg alkylate. Since the early 1970s, most
new units have been H F alky plants to counteract higher energy cost. H F alkylation operates at about 25-50C negating
refrigeration, acid viscosity is so much closer to that of the
hydrocarbons that designs can accomplish the chemistry in
piping or in simpler mixing vessels, and acid consumption is
only about 0.001 kg per kg alkylate. However, the use of H F
poses a more serious safety concern than H2SO4 in the event
of a n acid release. A sulfuric acid spill will cause soil and
g r o u n d w a t e r contamination; however, hydrofluoric acid,
which boils at 20C, will release a vapor cloud of H F as it escapes emd depressurizes. Releases of H F at a n u m b e r of U.S.
refineries in the 1980s led to significant re-engineering to assure process safety and "save" the process from legislative extinction.
A simplified flow diagram is shown in Fig. 8 for an H F alkylation unit. Key highlights include separation of the acid from

alkylate, cooling of recycle acid, recovery and recycle of isobutane, cleanup of alkylate, and separation of products. Typical
product yields, quality, and disposition are shown in Table 12.
MTBE
Oxygenates were introduced into the gasoline pool in the
1970s to help replace the lost octanes from lead additives.
Their use has now been mandated in many parts of the world
based on data showing their ability to reduce harmful vehicle
emissions. The majority of worldwide use of MTBE is by
commodity chemical p u r c h a s e . However, a substantial
a m o u n t is made within the refinery gate, in particular in the
United States. Typically, the MTBE unit is installed in front
of a n alkylation unit. The C4 cut from the FCCU is first fed to
the MTBE unit where the isobutylene is reacted with purchased methanol. The effluent C4 paraffin and olefin stream,
minus isobutylene, is then sent to the alky plant.
MTBE has helped the refiner meet gasoline d e m a n d and
octane, and is being adapted for blending worldwide. In fact,
during the 1980s and much of the 1990s, it was the fastest

CHAPTER 1: PETROLEUM OIL REFINING


FEED
PRElKEATMEm-

REACTION
SECTION

BOSIRIFFER

DEFKOPANIZER

17

HFSnUFPER

Mixed
Batane*

OUfin
Feed
"j

DiyingAnd
Diokfin
Saianlioa

FIG. 8HP alkylation unit.


TABLE 12HF alkylation unit yield and quality.
Olefin Feed

C3 + C4

C4

Yields, %w
4-10
Propane
n-Butane
2-5
3-6
80-93
Alkylate
76-90
Alky Bottoms"
3-8
3-8
1
Alky Tar*
1
Alkylate Dist, C
Initial BP
40
40
75
10%
70
100
30%
90
105
100
50%
110
70%
105
125
90%
120
195
Final BP
190
96
RON, without Lead
93
MON, without Lead
92
94
^Too high boiling for gasoline. Usually blended to diesel and fuel
oil.
' A "waste" stream of high molecular weight. May be processed in
cracking units, burned as fuel, or disposed.

growing "chemical," with usage now surpassing 20 million


mt per year. However, the use of this ether and perhaps other
ethers could be reduced or banned because of concern for
contamination of drinking water from gasoline storage tank
leakage, as detected in parts of the U.S. Should this happen,
refiners will again have to find substitute streams to replace
lost octane and "barrels." This issue could become economically critical to the refiner and consumer as the industry simultaneously reduces gasoline and diesel fuel sulfur, as well
as gasoline aromatics and olefins.
TAME, the ether produced by reacting isoamylene with
methanol, has entered the refinery picture because it can provide an opportunity to reduce the C5 olefin content of gasoline. A number of MTBE plants have been revamped to handle the higher boiling olefins. However, if MTBE use is

banned, it is likely that TAME will suffer the same fate.


Ethanol continues to be used, particularly in the United
States and Canada, and some refiners are substituting
ethanol for the ethers.
Other technologies utilizing isobutylene, beside alkylation,
are being added to the refinery flowsheet. One example is the
dimerization of isobutylene to isooctene, followed by its conversion to isooctane via hydrogenation.

PROCESSES FOR HETEROATOM REMOVAL


AND AROMATIC/OLEFIN SATURATION
The main technology for removing unwanted heteroatoms
such as sulfur and nitrogen, and for reducing aromatics euid
olefin concentration in refinery liquid streams, is by contacting the stream with hydrogen in the presence of a catalyst,
and at appropriate temperature and pressure. The vocabuIciry to identify the numerous applications is extensive and
not universally consistent. The most common generic name
is hydroprocessing. This has been further divided into three
categories; hydrotreating, hydrorefining, and hydrocracking,
to delineate process severity for desired product cleanliness,
as well as feed and product boiling range. Currently, hydrotreating and hydrocracking are the two most widely used
names for this technology, with the trend to place hydrorefining within the hydrotreating category.
Process severity, with respect to the above vocabulary, is defined by percent conversion (Table 13), or how much of the
feed is thermcdly cracked into lower molecular weight, lower
boiling product. Conversion is usually defined as 100 minus
the amount of product in the same boiling range as the feed.
The vocabulary also expands to include the word desulfurization, since sulfur reduction has been and remains the key need
for hydroprocessing, in addition to denitrogenation and
dearomatization. Some of the myriad names and abbrevia-

18

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

TABLE 13Hydroprocessing terminology.


Conversion, %w
Hydrotreating (HT)
Hydrorefining (HR)

"0"
As little as possible

Hydrocracking (HC)
Additional Terminology
HDS
HDT
HDN
HDA

25 +

NHT
DDS
MHC
ARDS
VRDS

Objectives
Cleanup without conversion
Cleanup of higher boiling streams
with minimum conversion
Cleanup + Conversion

Hydrodesulfurization
Hydrotreating
Hydrodenitrogenation
Hydrodearomatization

(HDA is also used for Hydrodealkylation


of Toluene to Benzene)

Naphtha Hydrotreater
Distillate Desulfurizer
Mild Hydrocracking
Atmospheric Resid Desulfurization
Vacuum Resid Desulfurization

tions for this technology are also listed in Table 13. The refinery streams that can/must undergo hydroprocessing, and the
reasons for the process selection are summarized in Table 14.
An example of a simplified process flow diagram is shown
in Fig. 9. Fresh feed, with hydrogen recycle and make-up hydrogen for the a m o u n t c o n s u m e d by the hydrogenation
chemistry, are heated to reaction temperature in a furnace
and then fed downflow through one or more fixed catalyst
bed reactors in series. After the desired reactions have occurred, the remainder of the process involves the recovery of
a high purity hydrogen recycle stream, separation of any
cracked hydrocarbon gases from the desulfurized liquid
product, as well as distillation of the liquid into appropriate
cuts. Start-of-run r e a c t o r t e m p e r a t u r e ranges from 2 8 5 400C a n d pressure from 900-20 000 kPa; generally, the
higher the boiling range axid "dirtiness" of the feed and the
greater the desired cracking severity and dearomatization,
the greater is the required temperature, pressure and n u m b e r
of reactors, as well as chemical hydrogen consumption. Excess hydrogen via the recycle is needed to minimize coke formation and laydown on the catalyst; this recycle is about 3-5
times the expected hydrogen consumption.

cess of hydrogen to minimize coke production, this runaway


can increase reactor temperature by u p to 60C per minute,
creating an unsafe operating condition. Refineries therefore
usually cap furnace outlet temperature at about 435-440C.
Thus, processing heavier, dirtier feed at higher severity,
which requires higher start-of-run temperature, results in
shorter r u n length and/or multiple reactors.
The metal promoters on the alumina base end up in their
oxide form from the drying of the finished catalyst. After being in the reactor for a short time the metal oxides will convert to sulfides from the hydrogen reducing atmosphere,
combined with the production of hydrogen sulfide. The oxide
form is overactive and can cause temperature excursion, increased coking, and partial catalyst deactivation from
changes in the alumina and metal promoter structure. Thus,
cobalt-moly and nickel-moly catalysts must be "presulfided"
or "presulfurized" prior to the start-of-run. This can be done
in-situ by adding compounds such as dimethyldisulfide to a
feed to condition the catalyst, for about one to two days, or it
can be done ex-situ wherein the catalyst is pretreated by the
manufacturer, and then shipped and loaded to assure that
the metals remain in the sulfide form.

The catalysts comprise the widest selection among all the refinery processes because this technology is used to "clean" all
refinery streams from light straight r u n gasoline through vacu u m resid. The two most common formulations consist of
combinations of cobalt and molybdenum or nickel and molybd e n u m promoters on an alumina base. The "cobalt-moly" catalyst, as it is typically called, is preferred for sulfur removal
while the "nickel-moly" combination is active for nitrogen removal and some aromatics saturation. Some catalysts also utilize nickel-tungsten. Noble metal catalysts such as platinum as
well as zeolites are now employed, in particular for deep
deciromatization. Cobalt-moly and nickel-moly catalysts contain in the range of 3-25% promoter metals depending on feed
properties and planned hydroprocessing severity.
Hydroprocessing is exothermic and increases with hydrogenation severity. Reactor outlet temperature in a fixed bed
reactor can be as m u c h as 35C greater than inlet temperature when processing vacuum gas oils and resid. Further, as
the run proceeds, slow b u t inevitable loss of catalyst activity
due to coke and metals laydown occurs and is compensated
by raising furnace outlet temperature. Hydrogenation reaction rate increases with temperature and at about 470C, can
result in a "runaway" reaction. Since there is always an ex-

At the end of a run, burning the coke off can regenerate the
"coked up" catalyst. This also is accomplished in-situ or exsitu. Ex-situ removal more efficiently removes the coke, but
at increased cost. If performed in-situ, the catalyst will usually remain in the reactor for 2-4 runs, after which refiners
will d u m p the spent catalyst and replace it with fresh material. Spent catalyst is usually then taken to hazardous waste
disposal. If the catalyst has been used to process resid, it may
be sent for nickel and vanadium recovery or to a process that
can remove enough of the feed metals to reactivate the catalyst and allow its reuse.
Hydrogen consumption and throughput rate, often called
"space velocity," are two of the key process and economic
variables. As the boiling range of the feed, and thus its heteroatom and aromatics content, increases, it can be expected
that hydrogen consumption will increase a n d throughput
will need to decrease to increase residence time. A similar response occurs for a given feed as conversion increases. Examples of yield, hydrogen consumption and residence time
for different feeds are shown in Table 15.
Hydroprocessing will continue to play a n ever-increasing
role in worldwide refining. The factors driving this conclusion are:

CHAPTER 1: PETROLEUM OIL REFINING

19

TABLE 14Hydroprocessing options.


Stream
Lt Str Run Gasoline
Hvy Str Run Naphtha
Coker Naphtha

B.P.

Sulfur

For the Reduction of


Nitrog.
Arom.

Diolef.

Acids
X
X

FCCU GasoHne
Catalytic Reformate
Kerosine/Jet
Lt Attn Gas Oil
Atm Gas Oil
Coker Gas Oil

Vac Gas Oil


Vac Gas Oil

Resid

End Use
Isomerization Unit Feed
Cat Reformer Feed
Gasoline Blending, Cat
Reformer Feed
Low Sulfur Gasoline
Low Benzene Gasoline
Jet Fuel, Low Sulfur Diesel
Low Sulfur Diesel
Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel
FCCU Feed
Gasoline Blending, Cat
Reformer Feed, Jet Fuel,
Diesel Fuel, Lube Oil
Base Stocks
Cat Reformer Feed,
Jet Fuel, Diesel Fuel,
FCCU Feed, Coker Feed,
No. 6 Fuel Oil

"Boiling Point Range


HEATER IffTSTQ. REACTOR

lEAlER 9 0 STTO. REACTOR

STABIUZER HlACnONATOR
LightEmli

FIG. 9Fixed bed hydroprocessing unit.


The sulfur content of crude oil has been increasing over
the years and is expected to continue that trend, barring
major discoveries of low sulfur crudes.
The sulfur content of fuel products, as we know them today, has been decreasing and this trend is expected to accelerate as the world seeks cleaner fuels.

3. The aromatics content of fuel products has been decreasing and this trend should continue and expand worldwide.
The technology and catalysts to achieve these results are
available; the only missing ingredient is money. If gasoline,
jet fuel, and diesel fuel continue as the major sources of
transportation fuels, then the industry will be forced to uti-

20 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


TABLE 15Hydroprocessing unit yields.
Feed
Density, kg/m^
Sulfur, p p m w
Nitrogen, p p m w
Initial Boiling Ft., C
50% Distilled
Final Boiling Ft.
Products
Naphtha
Yield, %w
Density
Sulfur
Nitrogen
Jet/Diesel
Yield
Density
Sulfur
Nitrogen
Atm Gas Oil
Yield
Density
Sulfur
Nitrogen
Hydrogen Consumption,
%w of Feed

FCCU LCO +
Coker Gas Oil

FCCU
LCO

Crude
VGO

940
22 400
940
220
275
375

935
28 000
1 000
365
470
575

980
8600

24
730
<1
<1

27
770
<1

35
810
<20
1

68
865
<20

94"
900
500
120

215
280
385

38
825
<20
<2
1.4

2.8

3.1

"Includes AGO

lize hydroprocessing for virtually every such product, worldwide.

PROCESSES FOR RESID CONVERSION AND


UPGRADING
Processing of resid has its unique pEirameters and constraints
because of its composition. It, among the crude oil cuts, is:
the highest in carbon residue resulting in high rates of coke
production or laydown on catalyst.
the highest in sulfur, contaminEtnt metals, aromatics and
usually nitrogen, resulting in high operating severity
and/or hydrogen consumption.
The easiest way for the refiner to handle resid is to sell it.
Its two m a i n markets Eire asphalt for road paving, roofing,
and the like, and No. 6 fuel oil for utility and marine energy.
To a lesser extent, resid is used by some refiners as a feed for
the production of hydrogen. The asphalt market is finite, and
the "six oil" market is limited to the a m o u n t that can be sold
economically to compete with other fuels such as cocJ and
gas. The net result is that the average refiner cannot dispose
of Eill of its resid via the above scenarios. In addition, the concern for air pollution is driving the world toward the use of
lighter, cleaner fuels. In response, a group of technologies
have established their place in the refineiy flowsheet to clean
resid and convert it into lower boiling streams. These processes yield products of a higher hydrogen to carbon ratio
than that of the resid feed, essentially the result of the cracking and/or saturation of its aromatics, which have the lowest
hydrogen to carbon ratio among the hydrocairbon types cind
crude oil fractions. The industry has categorized these technologies as accomplishing this desired chemistry by carbon
rejection or by hydrogen addition. There Eire dozens of resid

upgrading processes in commercicd operation; however, six


have established a prominent position, as follows:
Carbon Rejection
Hydrogen Addition
Visbreaking
Fixed Bed Hydrocracking
Solvent Deasphalting
Fluidized Bed Hydrocracking
Delayed Coking
Fluid Coking/Flexicoking
Table 16 shows a regional s u m m a r y of the worldwide installations for these technologies.
Visbreaking
This is a thermEtl cracking process using heat alone to partially crack the resid feed to lower boiling products. Most
commercial units operate in the 20-30% conversion range,
thus, 70-80% of the product r e m a i n s in the resid boiling
range. The attractiveness of the process is alluded to in its
name; although most of the product is in the same boiling
reinge as the feed, this material is significantly lower in viscosity than the feed. Hence, the heat treatment reduces or
"breciks" the viscosity of the remaining resid, leading to the
process name. The value of visbreciking is in utilizing the unconverted resid to blend No. 6 fuel oil. This product is made
by blending lower boiling, higher VEJUC streams, commonly
named cutter stocks, to reduce or cut the high viscosity of the
resid in order to meet product specifications. By lowering
resid viscosity, less cutter stock is required.
There are very few visbreakers in North America since this
area has substantial gas production and is oriented toward
lighter fuels. The opposite pattern exists in Europe, for example, where there are over 60 million metric tons of visbreaking capacity to meet that region's greater utilization of
heavier fuels, in general. Furthermore, until recently, Europe
has been a gas-poor region.
There are two m a i n vEtriations t o the visbreaking flowsheet:
one is the soEiker coil visbreaker, the other the soaker drum
visbreaker, as in Fig. 10. Both subject the resid feed to heating in a furnace; in the soaker coil unit, all thermal cracking
tcikes place in the furnace coil, while in the soaker d r u m unit,
the feed is partially cracked in the furnace at about 30C
lower temperature and the cracking is completed by providing increased residence time in the drum, as follows:
Residence Time, min.
Soaker Coil
Soaker Drum

Temperature, "C
465^85
435^55

1-2
4-8

The original driving force for the sociker drum process was
to minimize coking in the furnace coil and thus increase run
length. However, improvements in furnace design have narrowed the differences in process severity so that either process may be selected.
TABLE 16Resid process capacity.
Capacity, Million mt/year
Process

Worldwide

North
America

Western
Europe

AsiaPacific

Visbreaking
Delayed Coking
Fluid Coking
Fixed and Fluid Bed
Hydrocracking

159
155
24

11
96
8

62
13
1

21
16
3

110

35

10

48

CHAPTER 1: PETROLEUM
FRACTIONATION
TOWER
HEATER

START

^>-4vvv1-

ftd

I i

QUENCH

f
RESID

FRACTIONATION
TOWER

X-

SOAKER

HEATER

START

TT

()--^^-^

QUENCH

RESID

FIG. 10Visbreaking unit.

TABLE 17Visbreaking unit yields.


Feed
Initial Boiling Pt., C
Yield, %w
Density, kg/m^
Sulfur, %w
Viscosity, m^/s @ SOX

345
970
4.1
720

Resid
Product
345
78
990
4.3
250

Feed
540

Resid
Product

1015

540
72
1035

100 000

45 000

Typical product yields are shown in Table 17. The thermally cracked gases contain olefins, but less than FCCU
gases, and provide an added source of petrochemiccd and
alkylation unit feeds. Visbroken light naphtha can be blended
into gasoline after removal of diolefins and mercaptan sulfur,
and the heavy naphtha can be sent to the cat reformer hydrotreater (often called the naphtha hydrotreater) for olefin
saturation and sulfur/nitrogen removal, followed by octane
number upgrading in the reformer. The visbroken gas oils
will usually be blended to the fuel oil pool, but can be hydrocracked for diesel and jet fuel blending, or hydrotreated to
yield additional FCCU feed.
Solvent Deasphalting
This is the only process of the six in which no chemical
changes to the molecules occur. The process is based on the
low solubility of asphaltene-type residuum oil molecules in
low molecular weight paraffins. Asphaltenes are highly aromatic, difficult to crack, and contain the majority of the sulfur, nitrogen, and metals heteroatoms that are found in resid.
In the deasphalting process, feedstock, usually vacuum resid,
is mixed with a paraffin solvent, either propane, butane or

OIL REFINING

21

pentane. The "cleaner" resid components dissolve in the


paraffin while the dirtier asphaltenic ones do not. Thus the
process yields "clean resid feed" that can be economically
processed in another unit, typically the FCCU. In fact, the
process is oft-times defined as being used to provide incrementally clean "cat feed."
As the molecular weight of the paraffin increases, more of
the resid dissolves in the solvent. The part that dissolves in
the solvent is most commonly labeled deasphalted oil (DAO)
since the solvent has rejected the asphaltenes. The reject raffinate, mostly asphaltenic, is labeled pitch, tar, or simply asphaltenes. Figure 11 depicts the typical separation of heteroatoms between the DAO and pitch. The effect is usually
most pronounced for the metals, with lesser benefit for nitrogen and less yet for sulfur. Percentages of recovered DAO
for the chosen paraffin solvents are:
Solvent

Percent DAO

C3
C4
C5

25-40
50-65
80-95

The process consists of a mixing vessel or column running


at sufficient pressure to liquefy the solvent and dissolve the
DAO, separation of the DAO/solvent from the pitch, and recovery of the recyclable solvent from the DAO by distillation
and stripping. The process can also be designed with two
contact vessels operating at different temperatures to yield a
third, intermediate-cleanliness cut, usually labeled resin.
This may be done to give the refinery a more flexible scheme
for selling and further upgrading the various resid cuts. An
engineering feature that has played a role in reducing solvent
recovery cost sets the solvent recovery at temperature and
pressure such that the solvent is at or near its critical conditions. This significantly reduces solvent heat of vaporization
as well as its solubility in the DAO.
Today's fluid cataljrtic cracking cateJysts, if chosen for high
metals tolerance, can accept cat feed with as much as 30 ppm
Ni 4- V. A resid at 300 ppm metals permits the addition of
10% resid as incremental cat fee, ignoring the effects of carbon residue, nitrogen, and sulfur. However, based on typical
data (Fig. 11), the deasphalter can yield up to 75% "cleaner"
resid feed, at least from the constraint of metals that could
poison the catalyst. It is such performance that leads to the
incorporation of the deasphalting process into the refinery
flowsheet.

Delayed Coking
This is the dominant resid upgrading process in the U.S. and
is showing growth in Europe and, in particular. South America. Like visbreaking, this is also a thermal cracking process.
Unlike visbreaking, this process runs at essentially 100% conversion; all of the resid feed is converted into other products;
namely, cracked gases, coker naphthas and gas oils, and
coke. While the cracked gases and liquids are assumed to
have higher market value than the resid feed, it is the market
utilization and pricing of some of the coke that further helps
to drive favorable economics.
A schematic of the process is shown in Fig. 12. The cracking chemistry takes place in pairs of "drums." Cracked gases
and liquids leave the top of each drum, while the product

22 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

100

80

o
<

60

40

/y

o
20

^C

f. I

i^^^A

C^C^^ ,

^'^^""
40

20

60

80

100

DEASPHALTED-OIL YIELD, WT. %


FIG. 11Resid solvent deasphalting unit: DAO quality.

Quench

XZ

^r^^ (nh
L5^

I
Coke Drums

Fumace Steam

'Gasoline

Stripper
Steam
* Light Gas Oil
Heavy Gas Oil

Rc
\

'Gas

Fresh Feed

Main
Column
^^ ~ ^''^^'^ recycle

FIG. 12Delayed coking unit.

CHAPTER
coke r e m a i n s in the d r u m s . At start-up, both d r u m s are
empty. The resid is fed to one d r u m for u p to a day while the
other drum remains idle. On the second day, feed is cracked
in the other d r u m while the coke that has filled the first d r u m
is removed (decoked). This back and forth coke removal creates the continuous process. Drums have t3rpically been sized
to hold 24 h of coke make, since it required that amount of
time to decoke early units. Improvements to the decoking operation have enabled many units to r u n in 12-18 h cycles.
This has led to increased capacity revamps in existing units
or the opportunity to build smaller drums in new plants.
In a typical design, the resid fresh feed enters the bottom
section of the coker product m a i n fractionator. This provides
for heat balance in the distillation column bottom, the picku p of coke fines carried from the drums with the cracked
products, and the removal of a heavy coker gas oil product
for recycle to improve lighter product yield. Some fractionator designs also recover a lower boiling gas oil recycle. The
feed/recycle is then heated to cracking temperature, about
490-510C, in the coker furnace. Steam is usually added to
the feed to increase furnace coil velocity and thus minimize
coke laydown on the furnace tubes as the feed reaches cracking conditions. The purpose is to delay coking as much as
possible until the feed enters the bottom of the drum, hence
the process name.
The time-temperature parameters in the drum cause complete conversion of the resid. As coke is produced, steirting at
the bottom, the feed, which is part vapor-part liquid, continues to crack. As coke forms, it provides surface-induced
cracking as the feed passes through it. This operation succeeds because most of the coke that is produced is amorphous and spongy and is actually named sponge coke; thus,
the fresh feed is able to pass through.
The cracked p r o d u c t s are recovered and separated in
equipment similar to other processes. An example of 5rields
and quality is shown in Table 18. Unlike the FCCU, changes
in operating parameters, in this case temperature, pressure
and recycle ratio, have only a minor effect on product yields,
to the point that yields can be approximated based solely on
resid feed properties, in particular aromatics content, by using either carbon residue (ASTM Test Method for Conradson
Carbon Residue of Petroleum Products, D189-97) or API
gravity as the predictor. Coker n a p h t h a has lower octane
quality compared to cat gasoline. In addition, it must be selectively hydrogenated because non-catalytic cracked naphtha has a m u c h higher diolefin content, making it thermally

TABLE 18Delayed coking unit yields.


Density,
kg/m'

Resid Feed
Products
H2S

C1-C4
Naphtha
Atm Gas Oil
Vac Gas Oil
Coke

1025

Sulfur,
%w

Nitrogen,
ppmw

2.9

3000

0.5
0.95
1.9
3.7

70
600
2200

Carbon
Residue,
%w

22

Ni + V ,
ppmw

250

Yield,
%w

1.1
11.1
10.4
32.4
12.0
33.0

740
850
960

2.5

2
750

1: PETROLEUM

OIL REFINING

23

unstable and subject to polymerization and gum formation


even during storage at ambient conditions. Because of its inherent instability, it is often call wild naphtha. The coker gas
oils may be blended to fuel oil or hydrotreated for unsaturates and sulfur reduction.
Removal of the sponge coke from a full drum involves the
following steps:
Switch and Steam-outFeed
flow is switched from one
d r u m to the other. The coke is then stripped with steam to
remove entrained vapor and liquid product. The stripping
steam-hydrocarbon mix is also fed to the main fractionator. The coke typically contains 4-10% liquids after stripping. This "green" or raw coke may require further "drying" to below 0.5% liquids, via calcining, to meet market
needs.
CoolingThe d r u m is next filled with water to cool the
coke to about 90-95C. This is required to prevent spontaneous combustion of hot coke and allow for safe handling
when the drum is opened. The resultant steam production
is recovered either in the main fractionator when hot, or in
a unit called a blowdown system when it is at lower temperature.
Coke RemovalIn most designs, the d r u m heads are removed, a hole is drilled through the center of the coke, and
then high pressure water jets are used to break up the coke.
The drilling/jet equipment in most existing units operates
from drilling rigs placed on top of the drums. Large capacity coker drums can be as much as 8 m in diameter and
30-38 m in height. The drilling equipment would add Einother 38 m to the elevation, making this unit easily recognized. In early units, the coke was dumped into railroad
hopper cars directly below the elevated drums. In today's
units, coke is dumped into pits and the coke is then moved
by front-end loader or conveyor system to the transport
cars. Most of the engineering improvements in today's designs focus on reducing the time and complexity in this
step of the process.
ReheadThe heads are rebolted to the drum, the system is
pressure tested, and then hot gas such as cracked product
vapors from the operating drum, or flue gas from the coker
furnace, is passed through the empty d r u m to warm the
steel shell sufficiently to avoid thermal shock when fresh
hot feed is reintroduced.
Three types of coke can be m a d e . In usual operation,
80-98% of the coke will be sponge coke. The others are shot
coke and needle coke. Shot coke, which is hard and pelletlike, has no value other than as fuel and its yield must be minimized. Needle coke, which consists mainly of crystalline
elongated "needles," is highly valued and some cokers can be
run, if given the proper resid feed properties and unit operating parameters, to produce mostly needle coke.
About one-third of delayed coker sponge coke, after calcining, is sold to the aluminum industry to form the "carbon"
anode to produce the pure metal from aluminum oxide by
electrolysis. Depending on its electrical conductivity,
strength, and contaminant levels of sulfur and resid metals
(Ni + V), calcined sponge coke c o m m a n d s a selling price
about 2-5 times its fuel value. Needle coke may be sold to the
steel industry for operation in arc furnaces to yield high quality metallurgical steels. This coke may sell for as m u c h as
5-12 times its fuel value.

24

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Fluid Coking/Flexicoking
These technologies also convert all of the resid feed into
cracked products and coke. The chemistry takes place, however, in a reactor containing vapor phase fluidized coke particles. The heated feed is sprayed onto the coke through feed
nozzles around the reactor circumference. The product coke
deposits on the fluidized coke, which is continuously removed from the reactor. In the fluid coking process, sufficient coke is burned in a separate "burner" vessel to raise its
temperature so that this hot coke will maintain heat balance
upon its recirculation to the reactor. In the Flexicoking process, essentially all of the coke is converted to a low heat content gas in a third "gasifier" vessel, the hot gas then reheats
the circulating coke via heat transfer in what was the fluid
coker burner vessel. As an example, if the chemistry yields
30% coke in the reactor, net coke from the fluid coker will be
a b o u t 20-24%, b u t will only be a b o u t 0.5%, as a p u r g e
stream, from the Flexicoker.
The net coke from the fluid coker is in the form of shot coke
and can only be used as fuel. Because the delayed coking process yields a higher average value of coke, it accounts for
about 85% of worldwide coking capacity. The Flexicoking
process provides the refiner the option of generating a fuel
gas that can be scrubbed of H2S, instead of coke laden with
sulfur, nitrogen and metals. Because the gasifier operates on
steam and air, rather than steam and oxygen, the resulting
gas heat content is in the range of 3000 to 4500 kJ/m^.
Cracked gas and liquids yields from the fluid coking process are similar to yields from the delayed coking process. A
washing section is installed above the reactor to prevent carryover of coke fines to the coker main fractionator, produce
a coker gas oil recycle and, as a result, control coker gas oil
final boiling point.

an equilibrium catalyst activity can be maintained. This eliminates the need to raise feed inlet temperature as run length
progresses, as required in fixed bed units. In addition, the
a m o u n t of recirculating liquid product required for proper
catalyst bed operation is usually sufficient to provide a complete heat sink for the exothermic heat of reaction; thus, the
reactor essentially operates isothermally. This permits startof-run temperature as high as 435C, which is not technically
or economically feasible in fixed bed reactors. This temperature, in turn, provides enough thermal energy to substantially
crack vacuum resid, and, from the presence of hydrogen at
high pressure, typically 15000-18000 kPa, enough hydrogenation reactivity to yield substantially desulfurized lower
boiling products.

TABLE 19ARDS unit yields.


Products
Feed Naphtha
Boiling Range, C 405 + 30-175
Yield, %w
1.1
Density, kg/m^
990
740
Sulfur, ppmw
44 000
200
Nitrogen, ppmw
2800
20
Viscosity,
105
m2/s @ 100C

LGO
175-345
8.8
865
300
200

HGO
345-550
52.7
910
1300
400
10

Vac
Resid
550-134.i
980
11000
2800
2700

Fixed Bed Hydrocracking


Any boiling range material from crude oil can be hydrogenated. As the boiling range increases, required operating
severity increases. In order to desulfurize, dearomatize, and
crack resid-containing feed, multiple fixed bed reactors in series are required. Commercial installations have utilized
from 2-6 reactors to attain desired process severity. However, most commercial units are usually designed to operate
on feeds no dirtier than atmospheric resid, based on capital
investment and operating cost, since running on v a c u u m
resid substantially increases severity. Existing atmospheric
resid hydrocrackers, oft times labeled ARDS units (Table 13),
produce clean products as exemplified in Table 19.
Fluidized B e d Hydrocracking
This is a liquid phase, fluidized catalyst bed process and is
more commonly called expanded or ebullated bed hydrocracking. In this process, depicted in Fig. 13, fresh resid feed,
along with hydrogen, is introduced into the bottom of the reactor. Liquid product is also recycled to the reactor bottom to
provide needed hydraulic lift to expand the catalyst bed by
about one-third. When this occurs, the catalyst goes into random motion to create fluid bed behavior. This allows "spent"
catalyst to be withdrawn from the reactor each day and replaced with fresh material. Therefore, unlike fixed bed units.

Recycle Oil

FIG. 13Fluidized bed resid hydrocracking reactor.

CHAPTER 1: PETROLEUM OIL REFINING

25

TABLE 20Fluidized bed resid hydrocracking unit yields.


Products @ 66% Conversion
Boiling Range, C
Yield, %w
Density, kg/m'
Sulfur, p p m w
Nitrogen, p p m w

Products @ 80% Conversion

Feed

Naph

LGO

HGO

Vac Res

Naph

LGO

HGO

Vac Res

565 +

C5-175
9
710
300
85

175-345
18
860
800
480

345-565
32
920
2500
1900

565 +
34
1010
12 400
5200

C5-175
12
710
900

175-345
23
860
2700
630

345-565
38
930
11800
2500

565 +
20
1060
27 800
7000

1037
54 000
4000

Conversion levels of 50-90% have been commercially attained. And, the unit can process any quality feed, recognizing that heavier, dirtier feeds will require lower throughput
rate (space velocity), and increased hydrogen consumption
and catalyst replacement rate. Examples of yields and quality
for a representative resid feed are shown in Table 20.

PROCESSES FOR LUBE OIL BASE


STOCK PRODUCTION
Lubricating oil base stocks are produced from the vacuum
gas oils. While lube oil quality requirements are extensive,
process requirements are mainly driven by base oil viscosity
index, "cleanliness," and pour point. With respect to hydrocarbon composition, the overall requirements are that finished base stocks cannot contain aromatics, and are limited
in normal paraffin content. Aromatics must be removed or
converted to naphthenes because of their adverse effect on
oxidation stability and hot lube performance. Viscosity index
(VI) is the measure of the change in viscosity with temperature. High VI, which equates to the least change of viscosity,
is most desired. Normal paraffins provide the highest VI
among the hydrocarbon types. However, n-paraffins are also
highest in pour point; hence, their concentration in finished
lubes must be limited to avoid solidification.
There are two main process routes to produce the base oils.
The original, and still predominant, scheme incorporates
three process steps: first, aromatics are removed by solvent
extraction; secondly, normeJ paraffin content is reduced via
crystallization (dewaxing), and, thirdly, the remaining isoparaffins and naphthenes are hydrotreated to remove other
components such as organic acids, sulfur compounds and
the like that would adversely affect long term "cleanliness."
A newer process utilizes one-step high severity hydrocracking at about 18000 kPa. Under such high pressure, and with
the proper catalyst, the aromatics are completely saturated to
naphthenes, the other heteroatom-containing components
are hydrotreated as above, and a reasonable amount of the
normal paraffins are isomerized to isoparaffins, via the ability of the catalyst to effect isomerization activity as well as hydrogenation chemistry, to meet pour point requirements. If
the refiner is running a highly paraffinic crude slate, it may
still be necessary to dewax the hydrocracked product.
Aromatic extraction of vacuum gas oil is similar in concept
to extraction of catcJytic reformate, except the solvents are
different. The most widely used solvent had been phenol, but
it has been banned because of its carcinogenicity. Solvents
used today include furfural and n-methylpjrrolidone.
Dewaxing is accomplished by chilling the gas oil until the
n-paraffins solidify. The process name derives from the end

use of the n-paraffins as wax product. The two largest markets for this wax are the maJcing of candles and the coating of
cardboard cartons for the preservation of fruits and vegetables from farm to table. Separation of the solid paraffin crystals from the mother liquor is aided by solvents such as
methyl ethyl ketone and urea.
The refiner usually supplies some 4 to 9 lube base oils, that
vary mainly in viscosity, to lube plants that blend, package,
and ship finished product. The largest single market for lube
oil base stocks is for the production of motor oils. Hundreds
of other products, including greases, are also prepared for a
myriad of industrial needs. Overall, this is still a specialty
area of refining, accounting for only 1% of crude oil capacity.

OTHER REFINERY PROCESSES


while the refinery cannot run without the processes included
in this section, they are usually placed in the "other" category
since they do not contribute directly to the production of hydrocarbon streams for fuel product blending.
Hydrogen Production
Petroleum refineries, industry wide, long ago lost their ability to satisfy the need for hydrogen via recovery from the catalytic reforming process. The hydrogen shortfall can be satisfied either by buying hydrogen "across the fence," or by
building a refiner-owned plant inside the gate. Worldwide,
refinery hydrogen plant capacity has surpassed 300 million
m^/day.
There are two process routes to hydrogen: the catalytic reaction of low molecular weight hydrocarbons with steam,
and the non-catalytic gasification of heavier hydrocarbons
with oxygen. The former is known as steam reforming or
steam-methane reforming, while the latter is oft-times called
partial oxidation.
Steam Reforming
This process basically utilizes two-step or three-step chemistry, depending on when the plant was built. Older units typically involve three separate catalytic reactions, while process
innovation has reduced many of today's flowsheets to two
catalytic steps, followed by physical separation of product
components.
The first reaction, which gives rise to the process name,
"reforms" the hydrocarbon feed into a hydrogen-rich synthesis gas, per the following theoreticeJ equation:
CH4 + H2O = 3H2 + CO
The reforming takes place at about 800C over a nickel catalyst placed inside tubes within a furnace. This design is re-

26 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


quired due to the high endothermicity of the reaction. The
high temperature also results in coke formation, but the coke
reacts with excess steam to yield additional synthesis gas.
With methane as the feed, the coke usucJly reacts as fast as it
forms to keep the catalyst and tubes clean. Heavier feedstocks such as LPG, refinery fuel gas particularly containing
C3 +, or light naphtha, can cause coke buildup and limit r u n
length. A n a p h t h a hydrocarbon feed may also require hydro treating to remove heteroatoms, such as sulfur and chlorine, to protect the reforming catalyst.
The second reaction, called "water gas shift," catalytically
converts or shifts the CO to CO2, per the following equation:

Partial Oxidation

CO + H2O = CO2 + H2
This exothermic reaction takes place at about 350C over a
fixed bed of iron oxide catalyst. Some plants employ a lower
temperature second catalytic shift using a copper-zinc catalyst to convert any remaining CO. The product gas is then
treated for CO2 removed; the carbon dioxide is then vented or
recovered.
Unfortunately, the hydrogen product gas may still contain
u p to 1-3% CO/CO2 which will adversely affect catalyst in a
hydrotreater. Thus, a third reaction, called methanation, may
be employed to reduce impurities to acceptable levels. This
step is carried out in a fixed bed using a nickel catalyst and
uses a small amount of the product hydrogen, per the following chemistry:

Sulfur Recovery
Hydrogen sulfide is removed from refinery gas and liquid
streams via contact with liquid or solid absorbents and adsorbents. Among the dozen or so choices, the ones most
widely used in refineries are the ethanolamine liquid absorbents. As a result, this step on the sulfur recovery flowsheet is commonly ccilled "amine treating." After the H2S has
been separated from the hydrocarbons, it is converted into elemental sulfur in the sulfur recovery unit (SRU) by the Claus
process and its m3rriad variations. Recovery of sulfur from refineries and from natural gas production now accounts for
the majority of sulfur supply to its end users.
The most commonly used amine treating absorbents, or
solvents as they are normally called, are the primary amine,
monoethanolamine (MEA); the secondary amine, diethanolamine (DEA), and the tertiary amine, methyldiethanolamine
(MDEA). Selection is based on concentration of H2S in the
hydrocarbon gas stream, a m o u n t of other acid gas components such as carbonyl sulfide and carbon dioxide, and the
relative solvent activity compared with useable concentration of amine in water.
The hydrocarbon feed stream is contacted countercurrent
to a "lean" solvent, free of H2S, in absorbers (Fig 14). The sol-

CO/CO2 + H2 = CH4 + H2O


Most of the newer steam reformers substitute adsorption
for third-step chemistry to remove impurities from the hydrogen. The gases from the shift reactor pass through beds of
molecular sieve that alternately adsorb and desorb unconverted CO and the CO2, as well as other impurities such as nitrogen and methEine, but not the hydrogen. The product hydrogen gas usually exits the beds at 99.9% purity. The beds
are most commonly desorbed by reducing pressure; hence,
the process name pressure swing adsorption. The desorbed
material is usueilly then blended as part of the fuel required
for the reformer furnace. Other sieve beds can be used to separate CO2 for product sale.

Sweet Gas
Lean
Amine

-^MQ-J'

(POX)

The advantage of this process is that the chemistry requires no


catalyst, and zmy hydrocarbon can be used as feed including
heavy gas oils, resid, coke and coal. Its disadvantages are the
need for oxygen, high reactor temperature, and more complex
gas cleaning. On balance, most hydrogen plants are steam reformers; partial oxidation will be chosen when there is no access to natural gas or other low moleculeir weight feeds, or
when sale or utilization of high molecular weight refinery
streams Eind coke is not feasible or economically attractive.
The POX process reacts hydrocarbon and oxygen at about
1300-1550C to yield a H2/CO synthesis gas. The oxygen is
usually p u r c h a s e d over-the-fence. The "syngas" is next
treated for removal of sulfur compounds, which will include
carbonyl sulfide in addition to H2S. The scrubbed syngas is
then sent to catalytic shift conversion and hydrogen purification in similar manner to steam reforming.

^Ll

Mal<eup
-Water

Amine
Stripper
Sour Gas

Amine
Contactor

Flash
tank

Rich Amine

CKl

Lean Amine
FIG. 14^Amine treating unit.

Acid
'Gas

CHAPTER 1: PETROLEUM OIL REFINING


vent picks u p the acid gases and exits the absorber as a "rich"
solvent. This stream is then sent to a regenerator where solvent reboil provides the heat to strip the H2S from the solvent. The solvent is t h e n cleaned a n d recycled to the absorber. The solvent may be filtered at one or more places in
the flowsheet to remove impurities, such as iron sulfides, that
can cause equipment fouling and loss of solvent efficiency in
the absorber.
The conversion of H2S to sulfur involves two chemical reactions; namely:

27

chemical. Other outlets include its use as a cross linking


agent for the manufacture of tires via the vulcanization process for synthetic rubber, and as a blending component in the
manufacture of road asphalt. However, the increasing production of sulfur from refinery hydrotreating and from the
cleanup of natural gas has helped depress sulfur prices and
not every refinery is able to sell all of its production.

REFINERY POLLUTION CONTROL

H2S + 3/2O2 = SO2 + H2O


2H2S + SO2 = 3S + 2H2O
Thus, Claus plants consist of a b u r n e r to convert about
one-third of the H2S to SO2, followed by multiple fixed bed
catalytic reactors to react the SO2 with the remaining hydrogen sulfide to produce elemental sulfur, as in Fig. 15. Older
Claus plants leave enough H2S in the vent gas that a second
catalytic process is needed to convert this dilute H2S stream.
This added step is commonly labeled "tail gas cleanup."
Some of the newer Claus plant catalysts and designs claim no
need for this last cleanup step.
The Claus plant sulfur is a vapor as it leaves the reactors. It
is cooled to produce liquid or molten sulfur and can be taken
to market in that form via tank trucks or railroad cars, or it is
further cooled to yield a solid yellow powder. This powder
can be sold or stored in this form, or converted to prills or
into blocks, depending on end use.
Sulfur has many markets; the largest is for the production
of sulfuric acid, which in turn is the world's largest selling

AIR
COMPRESSOR

THERMAL
REACTOR

Many parts of the world have imposed very strict control on


refinery pollutants. The three categories are air, wastewater,
and particulates. Air pollution has mainly concentrated on
sulfur oxides and nitrogen oxides and refineries will have a
limit on allowable emission levels, established over some time
frame, with higher levels cJlowed for short periods due to unit
upsets. Three of the key emissions "points" during normal operations are furnaces, boilers, and the FCCU; flare systems become part of the formula when unit upsets take process gases
and liquids to flare from the opening of relief valves.
Wastewater treatment involves many process steps and
parts of its complexity are related to refinery unit selection
and operations. Many waste streams will first be sent to settling ponds and API separators to allow solids and various hydrocarbon liquids to be separated from the water. The water
will then undergo some n u m b e r of biological treatment steps
until "clean" water is produced. Some of the wastewaters are
recycled back to parts of the refinery while the rest is sent to
disposal via deep wells, for example.

SULFUR
SULFUR
CONVERTER CONDENSER REHEATERS

Rcycle HydfOKWi SIMMB CM

AeUQu
Fran Ajidiit
RMNnnlioQ

AddOM
From Sour Water Stripper

Com.
FIG. 15Claus unit.

28

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Particulate emissions can result from improper operation


of the catalyst recovery section on the cat cracker regenerator. This Ccin occur from loss of cyclone efficiency that in turn
will overload the flue gas solids removal system, or from malfunction in the solids removal system itself. Obviously, any
furnaces and boilers running on coke or coal require control
of particulate emissions.

COGENERATION
Refineries continue to add "cogen" plants to the flow sheet.
They offer the opportunity to convert various low value fuels
or blend components into electricity. The electricity, in turn,
can be used to supply part or all of the refinery's needs, or the
plant can be large enough to permit the refiner to sell electricity to nearby utilities. With the advent of utility supply
and price deregulation, this option can take on added attractiveness. Cogen feeds range from gases to heavy fuel oils to
delayed and Quid coke.

PRODUCT BLENDING
Blending equations have been developed over the decades to
allow the refiner to optimally blend the fuel products with a
high degree of accuracy. The equations may be relatively simple for properties such as viscosity, or relatively complex for
predicting blended gasoline octane number. These equations
have been built into the refinery computer models with the
goal that each batch of product will be blended correctly and
will meet specifications at m i n i m u m cost. While the computer models and test methods continue to improve, most
product is still blended by mixing the computer-indicated
components in a product storage tank, sampling the tank,
and then waiting for appropriate laboratory data to certify
that the blend meets specifications. Some refineries do online product blending, meaning that components are mixed
directly into a product pipeline, for example, with key tests
being performed using on-line instrumental analysis. On-line
octane analyzers are being used for gasoline blending, and
newer test methods such as near and mid-infrared are beginning to replace m o r e complex or time-consuming older
methods.

REFINING OPTIONS FOR THE FUTURE


The key issues facing the refiner will be mainly driven by:
Crude oil quality
Clean fuels legislation
Product demand and mix
Alternative transportation options
Crude oil and product pricing
Crude oil quality is expected to slowly worsen. The most
critical parameter continues to be sulfur, but any increase in
the percentage of resid from increased use of heavier crude
oils will also play an important role as the world moves towEird a lighter fuel product mix. The rate of change is obviously related to the crude oil assay quality of new discoveries.

Based on historic data and recent findings, it is not likely that


enough sweet, light crudes can be b r o u g h t to market to
counter the expected declining trend. Another factor is crude
pricing. When higher prices, say, $145/metric ton ($20/barrel) and above, prevail, the economics of producing heavier,
higher sulfur crude obviously improves and, if sufficient
price spread between heavy and light crude results, then the
refiner has a greater economic incentive to process poorer
qucJity crude. In addition, as the industry adds desulfurization capacity to meet future low sulfur fuels demand, some of
this process capacity can be designed or revamped to handle
dirtier crude. If the demand for today's fuel products continues to increase, then more and more refiners will have no
choice but to process poorer quality crude oils.
Gasoline and No. 2 diesel will be the products that face the
near term drive to cleaner fuels. The key changes to gasoline
specifications, and their impact on refining, are:
Boiling PointContinuing reduction to the E50, E70, E80
and E90, (the maximum temperature when 50, 70, 80, or
90% of the gasoline has evaporated by distillation), for example, will diminish product supply at existing refinery
crude capacity and flow sheet configuration. To meet gasoline demand, refining capacity and/or cracking units will
have to be expanded just to replace the higher boiling cuts
being removed from the blending pool.
AromaticsReduction
in total aromatics and, in particular, the higher boiling aromatics, can only effectively come
from removal of the heavy portion of straight r u n naphtha
feed to catalytic reformers, and from lower severity reformer operation. Incorporation of b o t h options m a y
maintain gasoline yield, but will result in less hydrogen byproduct. Dearomatization of heavy reformate is not expected to be economically attractive.
Benzene^Among the benzene reduction options presented
earlier, it is expected that extraction for petrochemical Scile
or removal of the C6 cut from reformer feed will prevail.
The latter will increasingly require isomerization of the
deeper-cut, lower octane number, light straight run gasoline.
OlefinsThe olefins in the C5-C6 fraction of cat gasoline
will be reduced. Likely process options are to install "light
cat gasoline" hydrotreaters, which will reduce octane number followed by isom units to octane-upgrade, to take at
least the C5 cut to alkylation units, or to convert the
isoamylenes to TAME, provided ethers are not banned.
SulfurCat gasoline provides 85-100% of gasoline sulfur
and most of this sulfur is concentrated in the higher boiling fraction. Refiners will have the choice of hydrotreating
some portion or all of the cat gasoline, or deeply desulfurizing cat feed. Process selection will eJso depend on final
realized gasoline sulfur specifications. Capitcd and operating costs to remove sulfur from "cat feed" are so m u c h
higher that, on the surface, the only apparent choice is to
treat the cat gasoline. However, cat gasoline hydrotreating
reduces octane while cat feed h5ftrotreating can improve
FCCU conversion without increasing coke on catalyst. Catalyst manufacturers and petroleum refiners continue to develop improved catalysts that will desulfurize cat gasoline
with m i n i m u m octane loss. The overall effect is that either
process option, or both, may be selected, based in part on

CHAPTER
the refinery's crude slate and overall fuel product demand
balance. It is also euiticipated that some of the new sulfur
removal processes will gain substantial commercial acceptance, offering a n opportunity to meet future gasoline sulfur specifications with p e r h a p s less octane n u m b e r loss
and less hydrogen consumption.
OxygenatesAs worldwide legislation for cleaner fuels
spreads, every region or country appears to be requiring
the use of oxygenates for pollution abatement, with the
concomitant octane benefit. It is not possible to know if the
expected b a n on MTBE in California and the consideration
of a countrywide ban by the U.S. Congress will cause a similar worldwide response. Removal of MTBE will likely
place a b a n on TAME, increase interest in ethanol, require
an increase in cat reforming, cat cracking and edkylation
capacity, increase the need for isomerization of light
straight r u n gasoline and introduce the chemical conversion of isobutylene to isooctane.
The quality of No. 2 diesel fuel will mainly focus on sulfur
and aromatics. As the world likely adopts a m a x i m u m sulfur
specification in the 10-50 p p m w range and some reduction
in aromatics concentration, refiners will in turn install or revamp middle distillate hydrotreaters that have the flexibility
to achieve deeper aromatics saturation with perhaps only the
need for a catalyst changeout.
Future product demand may be virtually impossible to predict. For example, in the U.S., the rapid acceptance of the van
and sport utility vehicle in place of the standard car led to a
decrease in overEiU vehicle fuel economy because of lack of
regulation for such vehicle tjrpes. This is in the process of being corrected but, meanwhile, gasoline demand in the U.S. is
increasing at rates exceeding earlier estimates.
Alternative sources of vehicle power create a long-term
uncertainty for the refiner. Natural gas and LPG are available in varying degree in m a n y parts of the world; LPG is a
readily available automotive fuel in European countries, for
example. Ignoring availability, the main detriment to rapid
expansion of these fuels is the needed supply and distribution infrastructure. Electricity-driven vehicles, via the battery, are not likely to play any substantive role unless a major b r e a k t h r o u g h in energy efficiency is found. Vehicles
powered o n externally-supplied hydrogen have little hope of
p e n e t r a t i n g the marketplace because of high p r o d u c t i o n
cost, delivery infrastructure, and safety. However, hybrid
battery/gasoline powered vehicles will be available shortly.
The fuel cell may have an impact on future refineries. This
would be intriguing if it becomes technically and economically feasible t o produce a hydrogen/CO synthesis gas by
steam reforming of naphtha "under the hood," since this liquid can take the place of gasoline or diesel fuel without any
changes at the "pump." Should this occur, octane n u m b e r
becomes a non-issue, the value of catalj^ic reforming, fluid
catalytic cracking and, hence, alkylation would diminish,
and hydrotreating and hydrocracking to supply additional
"clean" n a p h t h a would increase, also requiring a major increase in refinery hydrogen.
Crude a n d product pricing has become a substantive unknown for the refiner. On the crude oil side, the difficulty
has been unexpected changes in price, as well as the inability to predict future prices or the price spread between

1: PETROLEUM

OIL REFINING

29

sweet/light crudes and sour/heavy crudes. On the product


side, refiners have not always been able to obtain a reasonable return on investment for the legislated changes in fuels
specifications. The net effect in the late 1990s resulted in low
refining margins. This, in turn, has led to a sustained period
of unusually high refinery utilization rates^where 80-90%
had been considered the norm, rates have recently ranged
between 93-98%. Thus, refineries have opted for longer r u n
length, which, in turn, has pushed many of the process units
to their limit. It is expected that this mode of operation will
continue until the cleaner fuels program is in place, refinery
capacity is in better balance with demand, and crude prices
stabilize.

ASTM STANDARDS
Number

Title

D 86-99a
D 1160-95

Method for Distillation, of Petroleum Products


Method for Distillation of Petroleum Products
at Reduced Pressure
D 1319-98
Method for H y d r o c a r b o n Types in liquid
Petroleum Products by FIA
D 287-92
Method for API Gravity of Crude Petroleum
and Petroleum Products
D 2699-97a Method for Research Octane Number
D 2700-97
Method for Motor Octane Number
D 323-99a
Method for Vapor Pressure of Petroleum Products (Reid Method)
D 4814-99
Specification for Automotive Spark-Ignition
Engine Fuel
D1655-99
Specification for Aviation Turbine Fuels
D 396-98
Specification for Fuel Oils
D 975-98b
Specification for Diesel Fuel Oils
D 129-95
1
D 1266-98
f Methods for Sulfur in Petroleum Products
D 2622-98
J
D 613-95
Method for Cetane Number of Diesel Fuel Oils
D 97-96a
Method for Pour Point of Petroleum Products
D 5771-95
Method for Cloud Point of Petroleum Products
D 189-97
Method for Conradson Carbon Residue of
Petroleum Products
NOTE: The above are listed in order of appearance in text.

BIBLIOGRAPHY
[1] Wauquier, J.-P., Crude Oil. Petroleum Products. Process Flowsheets, 1st edition. Editions Technip, Paris, 1995.
[2] Wauquier, J.-P., Separation Processes, 1st edition, Editions Technip, Paris, 2000.
[3] Leprince, P., Conversion Processes, 1st edition. Editions Technip, Paris, 2000.
[4] Gary, J. H. and Handwerk, G. E., Petroleum Refining Technology
and Economics, 4th Edition, Marcel Dekker, Inc., NY, 2001.
[5] Kaes, G. L., Refinery Process Modeling, 1st edition, The Athens
Printing Co., Athens, GA, 2000.
[6] Meyers, R. A., Ed., Handbook of Petroleum Refining Processes,
1st and 2nd editions, McGraw-Hill Book Co., NY, 1986 and 1997,
respectively.

30 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[7] Maples, R. E., Petroleum Refinery Process Economics, 2nd edition, PennWell Books, Tulsa, OK, 2000.
[8] Chang, T., "Worldwide Refining Report," Oil & Gas Journal, Vol.
98.51, December 2000, pp. 56-120.
[9] "Refining Processes 2000," Hydrocarbon Processing, Vol. 79, No.
11, November 2000, pp. 85-142.
[10] Tromeur, P., Guibard, I., Harle, V., and Pike, M., "Hydroprocessing Atmospheric and Vacuum Residues," Petroleum Technology Quarterly, Vol. 5, No. 1, Spring 2000, pp. 21-27.
[11] Shorey, S. W., Lomas, D. A., and Keesom, W. H., "Use FCC Feed

Pretreating Methods to Remove Sulfur," Hydrocarbon Processing, Vol. 78, No. 11, November 1999, pp. 43-51.
[12] Swaty, T. E., Nocca, J. L., and Ross, J., "What are the Options to
Meet Tier 11 Sulfur Requirements?," Hydrocarbon
Processing,
Vol. 80, No. 2, February 2001, pp. 62-70.
[13] Law, D. v . , "Hydrocracking: Past, Present and Future,"
Petroleum Technology Quarterly, Vol. 5, No. 4, Winter 2000/2001,
pp. 55-63.
[14] Chang, T., "Worldwide Catalyst Report," Oil & Gas Journal, Vol.
97, No. 39, September 1999, pp. 45-68.

Section II: Fuels: Properties and Performance


Steven R. Westbrook, Section Editor

MNL37-EB/Jun. 2003

Liquefied Petroleum Gas


Robert J. Falkiner^

utilize the butane. Temperate climates with large seasonal


temperature changes could use propane in the winter and BP mixtures in the summer. However, the logistics of seasonal
distribution and air/fuel calibration changes, coupled with a
more than adequate propane supply, generally favors the use
of propane throughout the year.
The same properties that make LPG so useful contribute to
some of the unique challenges in using it safely. Water/ice/hydrate properties are unique. Pressurized systems are more
prone to leaks, even when the equipment is idle. The heavier
than air vapor density allows accumulation in low points and
cavities in the absence of ventilating air flow. When mixed
with air in the right ratio in the narrow range, it has the
potential for high destructive power in the event of a n
ignition source that results in an explosion or fire. Consequently, persons handling LPG and installing equipment are
tjrpically required to be trained and licensed. A variety of
safety devices and procedures are used, and LPG is odorized
to help detect potentially dangerous leaks.

LIQUEFIED PETROLEUM GAS ( L P G ) IS A GENERIC TERM FOR

ETHANE (C2) TO BUTANE (C4) h y d r o c a r b o n mixtures t h a t


can exist as liquids u n d e r modest pressures at a m b i e n t
temperatures.
Methane (CI, natural gas) must be refrigerated to less
than 259F to be condensed by compression to Liquefied
N a t u r a l Gas (LNG). Pentane a n d heavier hydrocarbons
(C5 + , condensate) are liquids at ambient temperature and
pressure, and are used in the manufacture of gasoline,
n a p h t h a fuels, and solvents. Ethame, propane, and butane
are gases at standard temperature and pressure, but can be
liquefied by compression and condensation of the vapor at
ambient temperature. Propane (C3), Butane (C4), and butane/propane mixtures (C3/C4 or B-P mix) have ideal properties for a fuel, widely used throughout the world in an
amazing variety of applications. They are stable, high-energy content, relatively low sulfur, clean burning fuels that
can be transported economically as a liquid, and be used either as a liquid or a gas. Pure component properties are
given in Figs. 1-4. Propane can be used from about -40C
to 45C, and butane from 0C to about l l O X (about 0-250
psig vapor pressure) or higher depending upon equipment
pressure ratings. The LPG tank is always under pressure at
normal operating temperatures above the normal boiling
point of about 42C, so there is no need for a fuel p u m p
or electrical components for most applications. This maJses
LPG ideally suited to a wide variety of portable, mobile or
remote applications, using mechanically reliable and simple
equipment. Propane applications tend to be robust and reliable as a result.

HISTORY
The LPG industry did not start until about 1904, more than
40 years after the start of North American crude oil and natural gas production a r o u n d 1860. Natural gas (methane)
cooking and lighting appliances were commonplace by 1900,
but it was difficult to make the gaseous fuel portable. It was
not feasible to transport and store compressed natural gas
(CNG) in the bulky pressure vessels of the day.
LPG is the ideal fuel for mobile and remote gas applications. It is a high BTU content liquid at typical ambient temperatures and modest (<250 psig) pressures, that is practical
for storage and transportation. It can be used like natural gas
once vaporized, in natural gas appliances adapted to gaseous
LPG mixtures with small adjustment for air/fuel ratio.
The early years of the industry were cheiracterized by the
need to solve the immediate problems of the day, without any
standardization or regulatory controls. LPG was one of the
first c o n s u m e r goods transported and sold in pressure
vessels. There were many economic and technical challenges
to produce, transport, and t h e n sell it to the public. The
industry was at the forefront of many areas of research and
development, ranging from processes, equipment and
appliances for m a n u f a c t u r e and use, to analytical test
methods for composition a n d properties. The results (in
retrospect) were predicable, a n d excesses abounded. However, in a short n u m b e r of years, the emerging industry was
compelled by marketing a n d regulatory forces to develop

This chapter deals mostly with ASTM D1835 "Commercial


Propane" and "Special Duty Propane" grades. The same distribution equipment, rail/truck tanks and storage vessels can
be used for propane or B-P mixtures so it is not outwardly
apparent what grade of LPG is being used in any region or
application. The t e r m s "propane," "LPG," and "HD5" are
c o m m o n l y used interchangeably (although this is not
technically correct). ASTM D 1835 and GPA 2140 specifications exist for "Commercial B-P Mixtures," but this is rarely
used for consumer applications in North America. There is
n o current Canadian (CGSB) specification for B-P Mixtures,
as the winter temperatures are too cold, and winter butane
d e m a n d is high for winter gasoline production. Polar
climates must use propane year round for low temperature
operability. Tropical climates (no winter temperatures, no
w i n t e r gasoline) tend to use B-P mixtures year r o u n d to
' Imperial Oil Ltd., Quality Assurance Operations and Development,
Toronto, Ontario M5W 1K3, Canada.

31
Copyright'

2003 by A S I M International

www.astm.org

32

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

10.000.0
1

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'

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Temperature, F
FIG. 1High temperature vapor pressures for light hydrocarbons. Reprinted with permission from the Gas Processors
Association.

products and practices that were acceptable to the pubhc.


Most of the standards and regulations that were developed in
the early years endure today.
History of t h e LPG Industry
LPG was originally derived from both natural gas or crude oil
production, so the industry has two related historical roots.
Refining a n d various petroleum conversion processes
became additional sources later.
The Chinese first transported natural gas, as well as brine
and oil, during the Shu Han dynasty (AD 221) from shallow
wells and seepages, through simple pipelines made of hollowed b a m b o o logs [1]. The m a i n sources of early North
American gas were from numerous surface "seeps" and "gas
springs" in Ontario, Pennsylvania and Southern California.
The "burning spring" at Niagara Falls, below the cataract,
was described early in the 1800s, and was due to a flow of gas
from the Niagara shales, which underlie the limestone of the
Falls [2]. The first small scale commercial distribution in
North America was probably in Fredonia, New York in 1820
using small bore lead pipe distributing gas from a purposebuilt shallow well. There are records of oilfield gas being
supplied to several Pennsylvania towns by 1872. The first

large scale commercial application was the piping of gas to


Pittsburgh in 1883, about 20 yeEirs after the discovery of oil in
Pennsylvania. By the early 1900s, a 20 in. pipeline 165 miles
long, was being used for natural gas production [3], and
longer pipelines soon followed.
The use of petroleum pitch from surface "seeps" date back
to recorded time [4], and these were the first source of North
American crude production around the Lake Erie basin, at
Enniskillen township in Southern Ontario a n d Titusville,
Pennsylvania in 1859/60. Early cable "drilling" consisted of
"punching a hole in the earth by repeatedly lifting and dropping a heavy cutting tool hung from the end of a cable," and
collecting the crude in a wooden crib [5]. It produced virtually no associated gas or LPG, these having weathered off
from the shallow formation. Advances in drilling technology
quickly allowed deeper wells that hit shallow high-pressure
oil and gas bearing formations, at first with near disastrous
consequences. The first "gusher," in the spring 1862, "spewed
oil above the treetops and covered 50 acres with oil 1-3 feet
deep, and p o u r e d enough oil into Black Creek to blacken
Lake St. Clair"[6]. The flow disappeared after several months
as suddenly as it began, after m o r e t h a n a n estimated 5
million barrels "floated off the waters of Black Creek"[7].
Additional discoveries were made in rapid succession all over

CHAPTER 2: LIQUEFIED PETROLEUM

N^''^55^
il'
S^ s\

\ ? %*Ji-

s
=

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sS ^-^

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33

10000

100

300

200

400

500

600

n-Butane
Rsfsrenes Stales:

T / G

H(sat liqO'100 Btu/lb # T(trp)


S<aat. Iq.) c0Btu/lb'F@T(lrp)

700
10000

7'o^

:41000

1000

(0

100

(0

CD

10

Enthalpy, Btu/lb
FIG. 3n-Butane P-H diagram. Reprinted with permission from the Gas Processors Association.
100

10000

200

300

400

m/

Propane
Rstorence Slates:
H(sat. llq.HOO Btu/lb T(trp)
S(sat. l i q . ) ' 0 Btu/lb'T O T(trp)

^1

500

600

700
10000

-^*- -

1000

1000

<0

'co

a..
100

100

3
CO
CO

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Enthalpy, Btu/lb
FIG. 4Propan P-H diagram. Reprinted with permission from the Gas Processors Association.

34

CHAPTER 2: LIQUEFIED PETROLEUM


the United States, in virtually every state from the Appalacha
to the Pacific. The industry remained regionalized around
these local sources, until the legendary Spindletop East
Texas, Panhandle and Oklahoma discoveries, and the post1900 development of crude oil and gas pipelines.
The discovery of large oil and gas fields in the early 1900s
resulted in an immediate excess production of LPG and light
naphtha hydrocarbons, far beyond the capability of developing markets to consume them. The ratio of gas to liquid
and the quality of production varied widely between different
production formations. At one extreme was low sulfur
content "dry" or "non-associated" gas, essentially pure
methane with little or no condensable liquid in the underground formation. This was ideal for distribution by gas
pipeline, especially in areas such as southern California and
the central United States where the gas wells were close to
cities, and the terrain allowed easy pipeline excavation. At the
other extreme was "sour" and "wet" gas that contained both
high sulfur and high propane and heavier content that condensed to a hydrocarbon liquid with even modest compression. "Wet" gas was generally "associated" with an underlying
crude reservoir, either as a gas cap or dissolved in the crude
at high underground temperature and pressure. Wet gas
from either crude or gas wells produced a liquid condensate
(NGL, natural gas liquid) when the gas was compressed for
distribution. Condensate had few uses, and for more than
50 years was burned or vented as a byproduct of crude and
natural gas production.
The wasteful practice of flaring enormous quantities of gas
from oil wells was eventually realized to be extremely detrimental to the amount of oil that could be recovered (see retrograde condensation). The gas pressure in a formation
helped force the oil to the surface. Excessive venting and depressurization left large portions of the crude unrecovered.
Moreover, the practices of one gas or crude producer affected
the yield of others in the same formation, since the crude and
gas could flow underground between producers whose
ownership rights were determined by surface surveys. This
resulted in several decades of litigation and regulatory development to establish fair and equitable means to balance the
often-conflicting social and economic goals [8].
The regulated recovery of liquids from ever increasing gas
and crude production resulted in a steadily increasing NGL
and LPG production, without adequate markets to consume
them. This was aggravated by increasing production of
deeper and higher pressure crude and gas reservoirs with
higher liquid condensable content. Whole industries appeared (and disappeared) based on the chronically depressed
price of LPGs and NGLs, and seasonal demand of natural
gasoline. Gas liquids were transported long distances to
find new outlets, with even some marine exports in large
drums from California. In the 1930s almost all of the world's
carbon black was manufactured from cheap Texas panhandle gas and gas liquids (eventually replaced by various
"coking" processes).
Hundreds of butane/air, propane/air, and LP-gas distribution plants were built to distribute gas to smaller towns and
cities. Most were gradually replaced by expansion of natural
gas pipeline distribution system, but a few remain in isolated
or remote areas of North America. This is commonplace in
some areas of the world with low domestic natural gas pro-

GAS

35

duction, where imported LPG is vaporized centrally, and


distributed locally in gas pipelines.
A balanced North American C3/C4 supply and demand was
achieved about 1950. This was mostly due to increased industrial or "chemicals" demand rather than the more modest
growth of consumer fuels markets. The alkylation process
converted C3/C4 into gasoline, and large-scale seasonal storage in underground salt caverns, natural formations and
large storage spheres balanced out the seasonal swings in
heating demand. Later, LPG became a preferred feedstock
for gas cracking and plastics manufacturing.
The LPG fuels industry has always been in excess supply.
The "chemicals" market is now more than twice the size of the
LPG fuels market. This tends to make LPG fuels economically
attractive in a wide variety of niche markets, wherever the
properties of LPG offer an advantage, and/or the economic return is higher than alternate BTU or chemicals value.
History of LPG
The first uses of LPG mixtures were for heating, cooking, and
lighting in remote or mobile applications that could not be
serviced by natural gas or manufactured gases (town gas,
coal gas, water gas, etc.). Natural gas distribution was limited
to mainly urban markets, that were supplied by relatively
short low pressure pipelines from regional gas wells or "town
gas" plants. Mobile applications included railway coach
lighting and heating, where high BTU liquid storage was a
great advantage over compressed gas (Pinsch gas) or carbide
gas (acetylene). Remote applications included smaller cities
and suburban areas, where underground pipelines were not
economically or technically feasible. In fact, "Rockgas" was
an early reference to the alternative to pipeline gas in areas
where buried pipelines were not feasible due to bedrock or
rocky terrain [9].
The earliest consumer use of LPG was "Blaugas" in Germany about 1904. Several plants were established in the
United States afterward [10]. This was a foul mixture obtained
by thermal cracking of hydrocarbon fuel oils, similar to town
gas production, but at lower temperatures that favored
greater condensable liquid yield. Composition was essentially
uncontrolled, and the mixture contained a large amount of
dissolved hydrogen, methane, LPG, gasoline range hydrocarbons and heavy ends, with a vapor pressure of up to 750-1800
psi at ambient temperature [11]. The first steel tanks imported
from Germany were called "bottles," a term still used today in
the "bottle gas" market. The early high-pressure cylinders
were bulky and extremely heavy. Up to 7 lbs. of steel was
transported for every pound of relatively low BTU fuel.
The earliest "Blaugas" sets used in United States had two
replaceable liquid cylinders and a third permanent gas cylinder that fed the appliance through a low-pressure gas regulator. The sets were expensive, since three "bottles," valves and
regulators were required instead of one. Liquid flowed via a
dip tube in the liquid cylinders through a valve or a "wet"
pressure regulator, where it vaporized into the third cylinder.
This maintained a relatively constant composition of gas and
avoided the problems associated with "weathering" or multicomponent distillation with the broad cut liquid being used
(although this process was not well understood at the time).
It was common in 1912 for such sets to lose many pounds of

36

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

gas daily. Stoves leaked too [12]. Even so, the industry was
modestly successful. Some "Blaugas" plants remained in operation into the 1920s b u t were all gradually displaced by
LPG recovered from crude/natural gas production a n d
refining. Small regional businesses were built up around individual supply sources and different gas mixtures and gas
sets. While the sets were relatively successful, they did experience problems from residues and ice causing regulators to
malfunction. Gasoline and heavier hydrocarbons collected in
the gas bottle, and had to be periodically drained out. Success
depended more on the ability of the equipment to tolerate the
mixture than anything else. There were no specifications to
control dryness, icing, residues, or composition.
The first commercial use of LPG produced from crude oil
or natural gas was in 1912, indirectly as result of a burgeoning demand for gasoline due to mass production of automobiles after 1908. Condensable liquids were reported as early
as 1893 in natural gas (methane) cryogenic drying processes
for natural gas distribution. There are indications of a lowpressure condensate from crude oil p r o d u c t i o n being
distributed in wooden barrels in the 1900-04 era, but it was
the automobile that changed everything. Automotive gasoline had to be liquid in atmospherically vented tanks, but
volatile enough to evaporate when mixed with air in a carburetor. The automobile created an i m m e d i a t e d e m a n d for
naphtha from crude oil as well as condensate from natural
gas or crude p r o d u c t i o n . Customers w h o b o u g h t a quart
of l a m p oil now w a n t e d gallons of gasoline. The liquid
condensate from gas production, called "casinghead gasoline," became a preferred product for sale to early refiners for
blending into gasoline, and a new industry was b o m . LPG
was displaced in importance by the frantic scramble to produce casinghead gasoline, which was m o r e profitable, at
least in the wintertime, when there was a strong demand. Initicdly, a high-pressure condensate was allowed to "weather"
in standing tanks, until enough boiled off that it was "acceptable" for use in gasoline. The limits of acceptability were only
loosely defined at the time, but these fundamental requirements eventually led to the "weathering test" and "vapor
tension" specification requirements many years later.
Propane a n d b u t a n e continued to be problematic byproducts from both crude and gas production. Propane was
too volatile to be a significant portion of gasoline, and not
volatile enough for even moderately pressurized natural gas
distribution networks pipelines. It was essentially worthless,
so there was a large economic incentive for producers to include as m u c h of the volatile propane/butane as possible into
casinghead gasoline. While m a n y of the blends provided
good fuels for the engines of the day, "a frantic scramble to
meet demands, coupled with not a little ignorance, began to
create significant problems" [13]. Many serious incidents occurred due to excessive volatility and evaporative losses that
sometimes exceeded 40%, and from boiling and over pressuring rail cEirs. In 1915, a rail car explosion killed 47 persons, injured more than 500, and virtually destroyed the town
of Ardmore, Oklahoma. Casinghead gasoline was almost universally condemned, and developed such a poor reputation
that one major refiner stopped using it in gasoline a n d
advertised it as a consumer benefit. By 1919, the last major
refiner announced that it was n o longer in the market for casinghead gasoline, and declared, "specifications were urgently

needed" [14]. As late as 1921, there were more than 100 different specifications for casinghead gasoline, most of them
meaningless and many based on what a producer may have
been producing on a particular day [15].
In April 1921, representatives from 31 companies formed
the Association of Natural Gasoline Manufacturers (ANGM),
following upon two previous efforts to organize gas processors. This Association later became the Natural Gasoline Association of America (NGAA), and now the Gas Processors
Association (GPA). Its purpose was to impose both business
a n d technical controls on the unruly new industry. They
created a new, m o r e acceptable product, called "natural
gasoline" to replace "casinghead gasoline." The ANGM
moved quickly to develop technical standards and related tariff agreements, a n d to improve operations. Within three
months, the first specifications were written for seven grades
of natural gasoline A-G, and four grades of blended natural
gasoline m o t o r fuel. The Natural Gasoline specifications
were based on density (API gravity) and percent recovered
(by evaporation). The lower gravity grades were preferred for
gasoline blending a n d c o m m a n d e d a higher price. The
blended gasoline grades were defined by a wider set of specifications, including gravity, end point, initial boiling point,
vapor tension, color, and an important new concept, percent
recovery in a standard distillation test. Boiling point criteria
and the distillation test marked significant advances in the
development of m o d e r n specifications [16]. The blended
gasoline specifications were intended to eliminate practices
such as "dumbbell" blending of kerosene with "wild" casinghead gas to give a blend with a naphtha range gravity that did
not work well in automobiles. The blended gasoline specifications were eliminated two years later, deferring to specifications developed elsewhere by the refining industry. The
natural gasoline specifications were modified several times
both for definition for the grades and for test methods as they
were developed, and are still published today by the GPA.
In 1910, a Pittsburgh motorcar owner walked into U.S. Bureau of Mines chemist Dr. Walter Snelling's office, complaining that the gallon of gasoline he had purchased was only half
a gallon by the time he got home. He thought the government
should look into why consumers were being cheated because
the gasoline was evaporating at a rapid and costly rate. Dr.
Snelling took u p the challenge and discovered that the evaporating gases were propane, butane, and other hydrocarbons.
Using coils from an old hot water heater and other miscellaneous pieces of laboratory equipment. Dr. Snelling built a
still that could separate natural gasoline into its liquid and
gaseous components [17]. This resulted in a 1913 patent for
a continuous process "to obtain the most volatile ingredient
or mixture in the form of a liquid gas under pressure" by fractional condensation of compressed heated vapors of natural
gasoline [18,19]. This virtually eliminated b o t h excessive
pressure and residue problems, and became the keystone of
the m o d e m LPG industry. The first m o d e m LP business venture, American Gasol Co., was founded by Snelling, and three
prominant "gas men" of the time, Frank Peterson and two
cousins, C. L. a n d A. N. Kerr. The products were called
"Gasol" (propane) a n d "Gasolite" (butane). The company
failed for lack of markets and the burden of cylinder and distribution costs, and was sold two years later. Snelling went
back to the U.S. Bureau of Mines explosives research, and the

CHAPTER
three "gas men" went into the casinghead gasohne business,
which was more profitable at the time.
The three "gas men" returned to the LPG business after
WWI. A. N. Kerr became president of the Casinghead Gasohne Association about 1915, one of the failed predecessors of
the ANGM (GPA). The Kerrs founded the Rockgas Products
Co. in Pittsburgh, and in 1925 the Imperial Gas Company in
Los Angeles. They tried to develop other markets for the light
ends, such as LP-gas/air town gas distribution plants and for
cutting steel. In 1932, the Kerrs authored the first chapter of
the Handbook of Butane Propane Gases on "A Chronology of
Liquid Gas Development"[20].
In 1912, F r a n k Peterson of the Bessemer Gas Engine
Company p u r c h a s e d rights to a 1909 patent to inject
naphtha gasoline into hot compressed natural gas to absorb
casinghead gasoline. He later patented a multistage compression/liquefaction process in 1912 [21]. These "hot blending" and "compression" processes were licensed to customers
using Bessemer compressors and gas engines. In 1914 he
patented "a liquefied fraction of n a t u r a l gas containing
ethane, propane and butane, substantially free of heavier hydrocarbons and from methane"[22]. He also developed one of
the first tests to estimate the "wetness" of a gas sample based
on absorbing/desorbing the sample in a mineral seal oil. Details of the test were held closely by the Bessemer Company,
which ran the test for $5 per sample. The fee was returned to
any prospective producer who purchased Bessemer equipment [23]. The close association of the liquids producers and
equipment suppliers has endured and evolved into today's
GPA and GPSA (Gas Processor Suppliers Association).
The LPG industry grew very slowly prior to 1932. In the
early years, it was inhibited by a shortage of tanks and materials due to WWI, by the wide variety of LPG mixtures and
equipment, and by competition from the casinghead and natural gasoline business. The entire infrastructure for LPG was
new, and there were many technical problems (and costs) associated with production, transportation, equipment, and
appliances. E q u i p m e n t a n d transportation costs were of
p a r a m o u n t importance, since the cost of the fuel itself was so
low. During this period there was litigation on several patents
associated with the production (and therefore the use) of
LPGs of various compositions. Most notable were the Saybolt
patent for absorbtion, held by Standard Oil, and the "stabilization" patent, held by the Carbon and Carbide Company
(now Union Carbide). Both patents were eventually held to be
invalid. In addition, the first significant regulations on tanks,
rail cars, equipment, tariffs, production limits, etc., were
p u t in place, t h r o u g h Government agencies such as the
B u r e a u of Explosives, Interstate Transport Commission,
Texas Railroad Commission, National Fire Protection
Association, and others.
Many now-familiar company and brand names appeared,
including Blaugas, Phillips (Philgas), Rockgas, Carbide (Pyrofax), Skelly (Skelgas), Shell (Shellane), and S t a n d a r d
(Flamo). Phillips and Carbide were two of the founding members of the ANGM (NGAA, GPA), and are generally credited
with developing the m o d e m LPG business. Frank Phillips,
founder of Phillips Petroleum, purchased the Snelling patent
rights, and marketed "Philgas" in the mid 1920s. Phillips
established an active research department, and did much of
the early laboratory research on liquefied gas. George G.

2: LIQUEFIED

PETROLEUM

GAS

37

Oberfell and Richard C. Alden, co-authors of the then classic


reference book "Natural Gasoline," were recruited by Phillips
to defend against the Carbide patent infringement litigation
on the pipestill "stabilization" process. The company also
benefited from the close proximity and association with the
USBM research station in Bartlesville, OK. Prior to 1920,
Oberfell had studied hydrocarbon behavior at the USBM in
Pittsburgh, and after early association with Frank Petersen,
spent five years pioneering development of low pressure absorber systems for a leading producer of natural gasoline
[24]. The Phillips research group grew to include K. H.
Hachmuth, (dryness, CoBr test), T. W. Legatski (author of the
original GPA LPG specification) and D. L. Katz (hydrocarbon
phase behavior, hydrates). The company was instrumental
in developing acceptable rail cars, freight rates equivalent
to gasoline, a n d large consolidated facilities that made
production more cost efficient.
The NGAA (GPA) developed additional specifications for
commercial propane and butane after the expiration and/or
settlement of the composition and processing patents. These
were first reported in the Proceedings of the 11th annual
Convention 1932 [25], and later published as the forerunner
of GPA 2140-Liquefied Petroleum Gas Specifications. However, there were no test methods attached to the first specifications. These were added over the years as the technology
was developed.
At the same time, the California producers and marketers
were active in related technical Eireas. The California Natural
Gasoline Association formed in 1925 as a technical society of
individuals, rather than a trade association of corporate members [26], and provided high caliber technical leadership to
the emerging industry. Western Gas published many technical articles in Butane-Propane News [27], Eind the first edition
of the "Handbook Butane-Propane Gases" in 1932. While not
a standard or specification, the handbook contained a large
amount of technical information on LPG production, distribution and use. It was an important reference book for the entire industry, including the "downstream" distribution and
marketing segments not covered by the GPA. These handbooks were maintained into the 1980s. They are no longer in
print, but are still widely available in technical libraries. Additioneil information may be available from other gas industry associations that have been active over the years, such as
the National Bottled Gas Association (now NPGA [28]), Compressed Gas Association (CGA [29]), or other regional gas
marketing associations such as the Pacific Gas Marketers Associations, Pacific Gas Association, and others. These were involved in development of related areas, such as equipment,
pressure vessel, appliance, installation and transportation
codes, standards and regulations. However, they do not appear to have been active in development of either product
standards or test methods for consumer LPG products that today is under the jurisdiction of ASTM.

HistoryLPG Properties a n d Thermodynamics


Many people consider the work conducted in this area during
the 1920s and 30s to be synonymous with the development of
Chemical Engineering as a separate discipline.
High pressure crude, condensates, and LP gases have physical properties and a commercial importance that made them

38 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

the principle target of early research in thermodynamics and


chemical processing. LPG and NGL were probably the first
commercially important, large volume materials that were
handled and processed near or above the critical temperature
of components or mixtures.
Critical phenomena had been observed in single components as early as 1823. In 1861, Thomas Andrews observed
the similar phenomena when he found that carbon dioxide
could not be liquefied at any pressure at temperatures higher
than 31C. He hypothesized that such a state existed for all
fluids and called it the "critical point" [30]. Andrews's
experiments were first made public in the 1863 edition of W.
A. Miller's textbook entitled "Elements of Chemistry" [31].
The phenomena of isothermally condensing a gas mixture to
form liquid by reducing pressure and isobarically heating a
gas-liquid mixture to form a single-phase liquid were first observed by J. D. Kuenen in 1892 when he was studying the
phase behavior of the binary system (carbon dioxide +
chloromethane). He called these phenomena "retrograde
condensation" of the first kind and the second kind,
respectively [32].
In the mid 1920s Dr. Walter Podbielniak developed the
first practical low temperature fractional distillation test
that allowed the composition of NGL mixtures to be accurately determined [33]. The "Pod" column was quickly
adopted by the industry and improved over the years both
in accuracy and automated operation. It was the industry
standard until it was eventually replaced by gas chromatographic analysis in the mid 1950s. "Downhole" samples
from high pressure formations taken at underground temperature and pressure were found to contain substantial
amounts of dissolved "liquid" methane. This violated the
then accepted principle within the industry that no material
could be a liquid above its critical temperature. The theories
on retrograde condensation in gas processing by Dr. Lacy
in a 1932 API paper were greeted with a great deal of
skepticism by the gas processing industry [34], but it certainly put technology development into high gear. This
caused quite a stir at the time, as retrograde condensation
was, as the name implies, the exact opposite of what was expected. This created a great need to understand the phase
behavior of high-pressure and supercritical mixtures, both
for crude oil reservoir pressure management and for production of high-pressure condensate. Within a decade of intensive research and development, cycling plants for
methane re-injection, liquefaction (refrigerated liquid natural gas), LPG dehydration, and sweetening processes were
all commercialized.
A large amount of technical data generated in this era is
still used today. For example, the tables and graphs in the last
published edition of the "Handbook Butane-Propane Gases"
were essentially unchanged from the first edition, published
in 1932. Similarly, the GPSA Engineering Data Book has
been in continuous publication, and the 11th edition is now
available in U.S. engineering or metric versions, and on CDROM. Tables of information for installers that are derived
from this data is still in use today in publications such as
NFPA 58 and CAN/CSA-B 149.2 (the respective United States
and CDN "propane installation codes"). There is a large
amount of related work on other vapor-liquid equilibria for
the LPG gases, their mixtures, and other materials that are

commercially important for manufacture and use of LPG.


This includes water [35], H2S, C02, COS, N2, mercaptan,
and others [36].
Development of Thermodynamic Equation of State (EOS)
methods now allows calculation of most properties of even
complex mixtures directly from composition [37]. In most
cases, properties such as vapor pressures, enthalpies, bubble
points, dew points, adiabatic flash compositions and the like,
can be calculated about as accurately as they can be measured
directly. This includes LPG mixtures around their critical
points, and "retrograde" condensation, and more recently
temiaiy solid/liquid/vapor and hydrate systems [38].

LPG S P E C I F I C A T I O N S
History of ASTM LPG Standards
Virtually all of the technical developments relating to ASTM
standards were done through GPA/GPSA member companies, and Government/Industry sponsored Research at organizations such as the USBM, Institute of Gas Technology
(IGT) and Gas Research Institute (GRI). The GPA research
reports and standards and the GPSA Engineering Data Book
have been a primeiry source of technical information for the
industry. These are available on a commercial basis, both to
GPA members and non-members [39].
The GPA maintained the LPG and NGL standards from
first publications in 1921-32 until 1960. By this time, LPG
had become an important consumer fuel, widely available
and with an ever increasing diversity of applications. National Standards were needed to ensure universal acceptance
throughout the downstream industry, and to address
potential regulatory and liability issues inherent to producer
only-specifications. In 1961, ASTM published D1835 specifications for commercial propane and butane that were technically identical to the GPA specifications, including GPA test
methods. In 1964, ASTM published D2154 Special Duty
Propane, which was similar to GPA HD-5, but later incorporated this grade into D1835 in 1975, adding butane-propane
mixtures. The GPA 2140 specifications are still maintained
by the GPA, and remain technically equivalent to ASTM
D1835. ASTM test methods adapted from the original GPA
methods are now used in both standards.
Specifications and many test methods for LPG/NGL products not covered in D1835 are still maintained by the GPA.
This includes GPA 3132, which is the current version of the
original 1932 Natural Gasoline specification, and a variety of
other NGL products, chemical feedstocks, sampling methods, and test methods. The GPA 2140 LPG specification is
widely used for contractual purposes within the upstream
gas and fractionation segments of the industry. The products
covered under ASTM D1835 and GPA 2140 specifications are
often referred to as "spec" products. All of the others tend to
be called NGL's, such as C2+ ("see-two plus," meaning
ethane and heavier), fC4 (field butane), etc. For example,
"spec butane" means that it conforms to one of the consumer
products in D1835 or GPA 2140, or another industry specification or purchase/sale contract. The composition of "NGL
Mix," or "C2-I-" or "condensate "can vary over wide ranges,
and are not manufactured to strict composition limits.

CHAPTER 2: LIQUEFIED PETROLEUM GAS


NGL mixes and other "non-spec" products are not sold to
the pubUc. They are intermediate products, suitable for
transport and storage, but intended for further processing.
They are manufactured and sold between companies with the
technical resources to define and control the quality within
the available processing capabilities at the time. They usually
have additional test methods and limits for both purity and
trace components that may be deleterious in downstream
processing [40]. This can vary over wide limits under
contract terms.
The sampling and test methods are still important for
"non-spec" products, but not for the same reasons as for the
"spec" products in D1835. For example, the market value of
an NGL mixture is determined by the composition, since
once fractionated, the ethane, propane, iso-butane, butane
and C5-I- condensate fractions each have their own market
value. The market value of an NGL mix is therefore dependent on the accuracy of the analysis, but the composition
may vary over wide limits as agreed to by the purchaser and
seller. As a result, no ASTM product specifications are necessary for these materials, but many ASTM/GPA sampling and
test methods are used. The accuracy and precision of these
methods are still very important to the industry.
ASTM D1835 specifications for "commercial propane" and
"butane-propane mix" do allow the purchaser and seller to
agree on composition limits for propane/propylene and
butane/propane. These grades could be used as specialty consumer fuels, such as brazing gas (or higher BTU heating fuels, or aerosol propellants), and are therefore included in the
ASTM standard. The ASTM standards are rarely used for
commercial contracts such petrochemical feedstocks and the
like, as even nominally similar processing units can have
different feedstock requirements. Processing contractual
agreements tend to be less restrictive on composition, and
more restrictive on trace contaminants, depending upon the
capability and tolerance of the intended processing unit.
In North America, propane is the only widely available LPG
fuel for consumer use. Ethane and butane are used in other
fuels and chemicals applications. Ethane is converted to ethylene and used predominately in the manufacture of plastics
and chemicals. Butane is used predominately as a blending
component in winter gasoline, an alkylation feedstock to
make high octane unleaded gasoline, gas cracker feedstock
for chemicals production, or as a refinery fuel gas when the
price for butane drops below the industrial price of natural
gas. Propane is sometimes referred to as "butane" in the North
American retail market, and several companies still use "butane" in their corporate name. The reason has its roots in history [41 ], as butane was more prevalent in the early years, but
has since been replaced by propane. Similarly, "HD5"
propane is inherently a reference to GPA 2140 grade HD5
(Heavy Duty, 5% max propylene). HD5 grade was developed
to limit minimum octane number for engine applications, and
similar grades are found in all international specifications
(See AutoPropane). The ASTM D 1835 "special duty" propane,
and CGSB 3.14 "Type 1" propane are generally taken to be
functionally equivalent to GPA 2140 "HD5" propane, differing
only in some sampling and test method options. Even when
contracts are written around specifications that make no reference to "HD5," the designation "HD5" tends to be used in
conversation, because it is more recognized.

39

The ASTM and GPA LPG specifications have withstood the


test of time remarkably well. They have undergone numerous
revisions in response to improved technology and/or industry
needs [42]. The vast majority of these have been associated
with sampling procedures and test methods, and only occasionally with minor changes to the limiting values [43]. The
actual composition and properties of LPG produced in 1932
is essentially unchanged from LPG produced today.
The ASTM D 1835 standard has formed the basis for many
international standards, including ISO 9162, and at this time
is the framework for virtually all the world-wide commerce in
LPG [44].
Sampling
There are three sampling methods commonly referenced in
North America: ASTM D 3700 (floating piston cyhnder), D
1265 (80% fill "open" cyhnder), and GPA 2174 (floating
piston cylinder and on-line composite sampler).
None of the sampling procedures are guaranteed to obtain a representative sample for all specifications or test
methods, under all conditions. For example, a floating piston cylinder is capable of taking a liquid sample with no
vapor generation that can deplete light ends and dissolved
gases. However, machined interior metal surfaces can make
this unreliable for trace levels of corrosive materials that
can react with the interior surfaces, especially for longer
term storage or transport. An 80% fill cylinder can have an
interior coating to make it less prone to loss of trace corrosive molecules. However, the composition is slightly
changed by venting liquid to establish the 20% vapor space
that is necessary to protect against over pressure from thermal expansion of the liquid.
ASTM and CGSB are addressing this by allowing the use of
coated D 1265 cylinders for routine use for "specification"
products, where the small but predictable loss of light ends is
not significant. Laboratory measurements and Equation of
State calculations confirm that the vapor pressure reduction
between using D 3700 and D 1265 is less than 1.6 psi at the
208 psig specification limit. This is not significant with respect to the reproducibility of the vapor pressure test
method, and would only be of concern at or near the
specification limit, at high (7-8%) ethane contents [45,46].
The D 2163 hydrocarbon composition by gas chromatograph (GC) method is being revised to allow D 1265 "for composition," with a recommendation that D 3700 floating piston
cylinder method be used for highly accurate results or when
trace gas analysis is required. ASTM D 3700 is currently
being revised to limit the scope to ASTM D 1835 "spec" products. This avoids the complications from sampling high pressure NGL's that may contain separated phases, inert gases,
and corrosive materials (for example, from production prior
to processing). A new appendix documents the various problems that must be addressed for sampling "non-spec" products. GPA 2174 (Obtaining liquid hydrocarbon samples for
GC) will be recommended for sampling "non-spec" NGLs and
related materials. This also facilitates revision of D 2163
(composition by GC) to include options for using Flame Ionization Detectors (FID) for specification products. FIDs are
very linear detectors for hydrocarbons, but do not detect "inerts" (N2, Ar, CO2, etc.) that do not combust in a hydrogen

40

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

flame. These are not normally present in "spec" products, except at very low p p m levels t h a t are not significant for
intended use (see Composition below).

Composition and Calculated Properties (Octane,


Density, Vapor Pressure)
D 1835 products composition limits are set at levels that are
stringent enough to satisfy the vapor pressure, octane
(olefin), a n d volatility/residue r e q u i r e m e n t s of the vast
majority of existing applications and equipment. Small composition differences within the bounds of the specification
are generally not significant, a n d do not affect either the
value or the end use. For example, propane containing 1-2
ethane has the same value and uses as propane with 5-6%
ethane. Similarly, propane containing 1% propylene has the
same commercial value a n d uses as 5% propylene. As a
result, "Specification" products in D 1835 are relatively noncritical for hydrocarbon composition.
The D 1835 products are relatively simple mixtures of a
small n u m b e r of components. This makes it feasible to estimate several properties that tend to blend linearly by simple
linear sum calculations. Calculation based on weighted linear s u m of component values per D 2598 can be used as an
alternate to D 1267 Reid vapor pressure, density and octane.
Similarly linear sum of C4+ (butane and heavier) can be used
as an alternate to D 1837 volatile residue.
C o m p o s i t i o n b y GC
Very little history was found on ASTM D 2163, Method for
Analysis of Liquefied Petroleum (LP) Gases a n d Propane
Concentrates by Gas Chromatography
The D 2163 GC method was originally based on u p to four
different packed columns and thermal conductivity detectors
using calibrant gas calibration procedures. Two of the colu m n packings were discontinued due to toxicity. The method
was expanded to allow other capilliary/PLOT^ columns and
alternate detectors, but retained the original calibration
procedures and precision statement. The method is currently
being u p d a t e d to allow columns based on resolution
performance, as well as FID detectors using response factors
referenced to methane, or other detectors of equivalent performance using calibrant gas procedures. D 3700 will be the
recommended sampling procedure, but D 1265 will be allowed for routine use, except where highly accurate results
are required for trace gases (see sampling above).
Octane

Propylene has a low pure component octane value, and requires individual control (5% max) because it can be varied
widely in commercial grade. Traces of the other olefins are
effectively controlled by the m a x i m u m vapor pressure
(ethylene) a n d m a x i m u m C4-t- content (butanes, butylenes
and heavier).
The defining specification for ASTM D1835 "Special Duty"
propane (GPA 2140 HD5) is the m a x i m u m 5 vol% propylene
content, intended to control the m i n i m u m octane n u m b e r for
severe service engine applications (HD5 is "Heavy Duty, 5%
maximum propylene"). Propane meeting the special grade
(HD5) specification would have a n octane rating of 95 or
greater by the D 2623 LP-method (if it were run). Commercial
grade with higher propylene content can still be used for
lower severity engine applications. The true HD5 (propane
optimized engines) market has yet to materialize.
This has resulted in decades of debate for the need for actual octane n u m b e r determination versus a linear sum calculation. Gasoline and LPG blending is known to be non-linear,
but the LPG calculation method has prevailed This is probably more because the composition limits of "HD5" propane
are restrictive enough that non-linear blending effects are too
small to be significant. The same cannot be expected for
blends of significantly broader composition [47], or for optimized engine applications that are more optimized for the
fuel. In addition, there are some discrepancies in the pure
component octane values used in ASTM D 2598, EN 589 and
the original ASTM Motor LP Knock Test Method Development as documented in SAE 670055. These differences are
relatively small, generally within 1 octane number. However,
it may be necessary in the future to optimize either the calculation or the engine determined octane number, or as more
recently suggested, by methane number.
The methane n u m b e r of a gaseous fuel is a knock engine test
using conditions similar to D2699 MON, but using methane
and hydrogen as the primary reference fuels. The method has
not been standardized to date. The advantage of the methane
n u m b e r is that the test can be extended to include all gaseous
fuels, including hydrogen, natural gas, LPGs cuid their mixtures, inert diluent gases such as N2 and CO2, and potentially
other combustible gases such as CO and HH3. In principle, it
is possible to relate methane n u m b e r to octane number, but
there are several difficulties in practice. The octane scale, with
iso-octane having a value of 100, is extended to 120 with the
addition of about 6 mL/usg tetraethyl lead. This tends to make
the test increasingly insensitive to non-linear fuel effects in
the high range, and the use of TEL even in the lab is problematic. Similarly, the methane n u m b e r does not respond well to
fuel effects at the low end of its range. Even so, a reasonably
good correlation has been found to exist [48,49].

ASTM D 2623, Test Method for Knock Characteristics of Liquefied Petroleum (LP) Gases by the Motor (LP) Method was
originally used to rate octane n u m b e r of LPG mixtures. This
used a standard CRC knock engine fitted with an LP-gas carburetor. It was withdrawn because the octane n u m b e r of
these simple mixtures could be accurately estimated by linear
blending of component octanes based o n GC analysis per D
2598.

Methane n u m b e r also appears to lend itself reasonably well


to calculation based on composition. If so, then the calculation method would be preferred for routine operations,
similar to D 2598 for LPG today.
This is a potential area of future research and standardization.

^ PLOT: Porous Layer Open Tubular (usually KCl deactivated


alumina for LPG analysis).

Some recent publications indicate that the olefin content of


propane relate to cleanliness, stability or tailpipe emissions

Olefins

CHAPTER
in a similzir m a n n e r to gasoline [50,51]. However, there are
some significant differences, and there is no consensus at this
time. Propane tanks are not atmospherically vented, so there
is no oxidative stability concerns for propane, as there is for
gasoline and other fuels. LPG carburetor vaporizer deposits
are associated with non-volatile residues, and not oxidative
gums from fuel olefins, thiophenes and other trace reactive
c o m p o n e n t s of gasoline. However, developers of m o d e r n
LPG electronic fuel injection (EFI) systems have experienced
significant difficulties with both inorganic and organic deposits that interfere with the proper operation of injectors.
Propane derived from crude oil and natural gas contains essentially n o olefins. Propane from refinery cracking processes
contain olefins, which may can either processed further (alkylation, polygas), separated for propylene sales, or blended into
propane u p to specification or contractual limits. Refinery
propane usucJly requires removal of propylene to meet the
ASTM "Special Duty" or GPA HD5 specification.
A recent study and review sponsored by the California Air
Resources Board (CARB) r e c o m m e n d e d relaxation of the
propylene a n d volatile residue specifications for a u t o
propane, citing that a 10% propylene/5% butane fuel gave the
best equivalent emissions performance [52]. The Board also
recommended a new limit of 0.5% m a x i m u m butenes, pentanes, and heavier. These changes were proposed to preserve
and enhance the current supply of auto propane fuel in California, while maintaining adequate emissions performance.
About half the propane produced in California is a byproduct
of refining processes [53].
This is a possible area of future research and standardization
Vapor Pressure
Historically, vapor pressure was the most critical LPG specification, being responsible for most of the serious problems
in the early days of the industry (see History of LPG). Vapor
pressure is invEiriably tied to pressure vessel and safety valve
certification and transportation regulations, so it is generally
viewed to be critical for regulatory compliance. However,
m o d e m pressure vessel standards as well as LPG production
e q u i p m e n t a n d analyzers have all b u t eliminated vapor
pressure as a significant operational problem.
Certification standards vary by jurisdiction, but typically, a
large safety margin is built into the system. For example, a
typical consumer cylinder pressure rated for 250 psig "working pressure" would be pressure tested after manufacture to
twice this (500 psig) and equipped with a "pressure relief
valve" (pressure safety valve or vent) 250-500 psig, 50-100%
of the test pressure. Propane, at the maximum specification
pressure, would have to be heated to over 140F to even reach
the opening ("cracking") pressure of the safety relief valve. In
addition, the actual burst pressure is controlled to typically at
least three times the working pressure (manufacturers are required to pressure test 1 cylinder out of each lot to destruction as a quality control procedure for the quality of steel and
welds). It is common practice for the manufacturer to "overbuild" cylinders to eliminate any uncertainty in the costly
certification process. For example, sample cylinders rated for
1800 psig working pressure are often tested at about 5000
psig, a n d have burst pressures far in excess of m i n i m u m

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three times the working pressure, often in the 12-15 000 psig
range. Finally, all consumer cylinders, storage vessels, trucks,
and rail cars require periodic inspection and recertification.
These considerations have essentially eliminated LPG vapor
pressure (VP), per se, as a significant problem.
The LPG VP specifications indirectly control the maximum
concentration of light ends, principally ethane in propane
and propane in butane. The manual "Reid" VP test method
was developed in a competition in the 1920s to improve upon
the original U.S. Bureau of Mines "vapor tension" method
(essentially a pressure gage on a length of 2 in. pipe). The
competition was won by Dr. Reid (D323 Reid method), and
an adaptation of this is used in D 1267 for higher VP (>26
psi) LPGs. The test has changed little over the years. Many
laboratories are no longer equipped to r u n the LPG Reid
Method. It is now much more common to calculate VP from
composition by D 2163 using calculations in D 2598 than it is
to run a manned D 1267 Reid VP. However, D 2598 method
has no component VP data for m e t h a n e (if it is present),
which may force the use of the manual method in some circumstances. In addition, D 2598 VP calculation is known to
be biased high (e.g., conservative) at high ethane contents,
due to use of a component VP extrapolated from above the
critical point of ethane.
By historical convention, the VP of LPG is reported in
"gage" or "gauge" pressure in pounds per square inch relative
to atmospheric pressure (psig). The pressure gauge used in
the D 1267 LPG Reid method reads zero at the start of the
test, but unlike D 323 or D 4953 the apparatus starts out liquid filled, and no air is introduced into the test apparatus
during the test. The test result is essentially the partial pressure of the LPG relative to atmosphere, a n d the absolute
pressure is higher by the barometric pressure at the time of
the test. This has caused significant confusion over the years
when using pressure transducers calibrated in psia units, or
when reporting in metric units (kPa), which by definition
would be interpreted as being an absolute pressure. As a result, the specifications require reporting in kPa (gage), which
is not a true SI unit. Also, this difference is sometimes confused with the high bias at high ethane contents when using
D 2598 calculation.
ASTM is currently developing a s t a n d a r d test m e t h o d
based on newer instrumentation similar to D 5191 and D
6378 for gasoline. This method uses an absolute pressure
transducer, so this requires that atmospheric pressure be
subtracted from the result to report a VP (gage) final result.
There is no universally accepted criteria for setting the maximum VP specification for propane, and this is an area for future research and international standardization. The first
GPA VP specification was 225 psig at 105F set to meet the insulated rail tank car requirements of Interstate Commerce
Commission (ICC). In 1955, the specification was revised to
215 psig at 100F, mainly to use a single water bath for both
natural gasoline and propane. Still later in 1955, the VP was
lowered to 210 psig at 100F to meet United States DOT safety
standards for rail tank cars [54]. A variety of other regulatory
limits also exist. This includes DOT 173.301 (f) (2), which limits VP in cyhnders to 300 psig at 1 SOT, Section 170.314 (c) 225
psig at 105F, and Section 173.315 (c) (1) cargo and portable
tanks at 250 psig at 115F [55]. Other regulatory requirements
would be expected in different jurisdictions. The origined HD5

42

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VP specification was 200 psig to promote heavy-duty engine


applications, but was reset to the current 208 psig limit when
this market failed to develop as expected.
Higher vapor pressure specifications allow slightly more
ethane to be included in the blend, which increases supply
slightly, and is potentially beneficial for very low (<-35C)
temperature operations. However, higher ethane content in
the gas phase can cause overly lean air/mixtures for some appliance applications with first vapor withdrawal from a full
tank, and rich operation from essentially pure propane when
the tank is near empty. This wide swing in air/fuel ratio and
the attendant problems of calibrating the air/fuel ratio in
vapor withdrawal service also prompted the industry to
reduce the VP from 215 to 210 psig in 1955.
Current ISO 9162 specifications have a maximum VP of
1550 kPa at 40C, compared to 208 psig (1435 kPa) at 100F
for ASTM, GPA, and CGSB. This difference is larger than the
difference in VP due to the small difference in test temperature. Equation of state calculations indicate that the ISO
standard would correspond to about 213 psig at 100F, making the ASTM standard more conservative by about 5 psig.
This difference is generally not significant in day-to-day
operations
The practical maximum for a universal multi-use fuel
probably lies somewhere between the current ASTM limits of
208 and the estimated ISO hmit of 213 psig at 100F.
This is a possible area of future research and standardization
Volatility Residue ("Weathering")
Most consumer propane applications withdraw vapor from
the storage tank (vapor withdrawal) utilizing ambient air
temperature to provide the latent heat of vaporization. This
works well down to about 35C or lower, until the VP with
auto-refrigeration of propane is not sufficient to satisfy appliance demand. Even thermal radiation to a black night sky
can take away several degrees of operating temperature,
which can be important when arctic nights can be up to six
months long.
The Volatility of Liquefied Petroleum (LP) Gas test (ASTM
D 1837) is an indicator of the nonvolatile materials present in
LP gas [56], and is intended to ensure that most of the LPG is
available for use, and that low volatility components do not
accumulate with repetitive tank fills. The tank will lose all
pressure and "suck a vacuum" below the normal boiling
point of the remaining components, requiring supplemental
heating, pumps and/or external vaporizers. If, for example,
excessive butane were collected in a tank after repetitive fills,
the user could experience low pressure when the level indicator showed plenty of "propane" (actually butane) still left in
the tank. This is aggravated by the strong temperature dependence of the "k" factor, or enrichment of the propane in
the vapor relative to butane. The selective vaporization of the
lighter components and retention of heavier components becomes more efficient as the temperature decreases, making
this an increasing concern in colder climates.
The original weathering test was called the Mercury Freeze
Test, but was commonly called the weathering test, or the
"tinkle and thud" test. The mercury was used as a temperature indicator, since no thermometers were then available for

-40C. One hundred milliliters of pre-cooled liquid propane


was allowed to boil off ("weather") in a glass tube with a large
drop of liquid mercury. Initially, the liquid propane temperature would be at or below the normal boiling point of
propane (42C), and the mercury would be a solid (melting
point = 39C), and then maJce a "tinkle" sound in the glass
when shaken. The temperature of the remaining liquid would
increase as the lighter components boiled off. If a sufficient
quantity of butane or heavier components were present, the
mercury would melt as the temperature of the remaining liquid rose above -39C, and "go thud" (a colloquialism for
"failure" in some circles). The pass/fail criterion was that no
more than 2 ml of liquid (mainly butane and heavier)
remained when the mercury melted.
One artifact of the test was that propane near the specification limit could pass at high altitude (low barometric
pressure), but could fail at low altitude (higher barometric
pressure). The boiling point of the mixture changed with
pressure, but the melting point of mercury did not. The test
was modified when suitable low temperature alcohol thermometers became available. The 1960 version of the method
reported the temperature when 5 ml of liquid remained, corrected for barometric pressure. The original pass/fail limit of
+ 36F was retained for butane and b-p mixtures, and a new
limit of -37F (-38.3C) was set for propane. The advent and
wide use of the chromatograph permitted addition of a quantitative limit of 2.5 vol% C4+ in propane and 2.0 vol% C5-Ifor butanes, based on GPA tests showing equivalence with
the weathering test. The weathering test was at one time going to be withdrawn, but it is still widely used as a field check,
and it was retained.
These limits are known to be conservative, even for cold
weather operations, confirmed by GPA tests at the University
of North Dakota in the winter of 1977-78 using 5-15 vol% butane. However, there has never been any compelling technical or economic justification to change this specification
[57], and the current limits are essentially unchanged from
the original intent in 1932.
Dryness of Propane
Consumers need reliable operations when it is cold, but this
is when icing is most prone to occur. As a result, "dryness" of
propane is probably the most critical of all specification for
downstream marketers and users. However, "dryness" is a
difficult property to quantify in the LPG world.
The "dryness" of propane is determined by specification
performance tests that indicate the suitability of use of the
LPG, but do not quantitatively measure water content. The
dryness criteria are so stringent that "on-spec" propane generally avoids the free water, ice, and hydrate formation regions under the conditions of most end use applications.
However, some applications, such as an inadequately heated
liquid vaporizer, may require even lower water contents,
and/or use of cryostatic de-icers such as methanol to avoid icing with propane that meets the specification "dryness"
criteria.
Propane and propane-butane mixtures are the only consumer fuels with a "dryness" specification that requires the
water content to be well below the equilibrium saturation
level. It is not adequate to use visual rating criteria, such as D

CHAPTER

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43

4176 "Clear and Bright," or "visually free of undissolved water" that is used for butane (and other fuels). It takes about
20-40 p p m of free water in a fuel to visually detect a haze
with the unaided eye. In essence, visual ratings only require
t h a t the fuel does not contain a n excessive a m o u n t of
undissolved ("free") water.
The butane test relies on visual detection of water collected
in the bottom of the sample cylinder, and not a haze rating.
The less stringent criteria is because auto-refrigeration of butane does not cause temperatures low enough to cause ice/hyd r a t e formation. As a result the same criteria applies to
b u t a n e as for other fuels.
Simple tank draining, which leaves the remaining propane
saturated with water, is not nearly enough to meet the LPG
"dryness" criteria. The presence of free water at any time in a
propane system is sufficient to put the product severely off
spec and unusable without dehydration or the addition of
methanol (see cautions below). This is critical for proper operation of LPG handling equipment and appliances. Ice accumulation can block vapor or liquid fuel lines, Eind disrupt
proper operation of mechanical equipment, such as pumps,
meters, filters, VEJVCS (fuel lock-offs), and especially regulators (vaporizor/regulators). Icing can occur very quickly, and
can be difficult to diagnose.
"Wet" propane is anything that does not pass the "dryness"
criteria, including the approximately 30-100% saturation
range, even when there is no free water. For example, a storage tank of LPG that is deemed to be "wet" may or may not
have any free water at the bottom of the tank. Water saturated LPG (but n o free water) fails all of the dryness criteria
by a wide margin. The presence of any free water amounts to
"gross" contamination.
"Wet" propane that does not contain free water responds
extremely well to low levels of methanol. Unlike ethanol, IPA,
and higher moleculetr weight alcohols, methanol does not increase the solubility of water in propane (or any other fuel).
It is a popular misconception that methanol is an effective
de-icer because it increases the solubility of water in the fuel.
Methanol decreases the solubility of water in fuels, and causes
phase separation when it is injected into water-saturated fuel.
The phase-separated liquid is non-freezing, so it will not cause
ice/hydrate blockage. When the LPG is sub-saturated with
water, the methanol remains dissolved in the propane along
with the soluble water. It phase separates along with the water whenever the temperature gets cold enough, and prevents
the separated water/methanol mixture from freezing. If the
m e t h a n o l concentration is high enough in the separated
phase, it wiU not freeze at temperatures down to the normal
boiling point of propane of 43C (i.e., nominal 50/50 vol%
methanol/water mixtures Eire commonly used as windshield
de-icing fluid good down to 40C).

in LPG service, mostly because they lack the volatility to


provide icing protection in the vapor space.
The meaningfulness of the valve freeze test becomes questionable when the LPG contains anti-icing agents. The ASTM
D 2713 method is stated to be "non-applicable" when antiicing agents are present. The current ISO and ASTM wording
of the "not applicable" footnotes are currently different, and
subject to interpretation. This is Ein area of never ending controversy, a n d is probably the highest priority area for
research and standardization.
None of the current LPG dryness methods (valve freeze,
CoBr, Dew Point) have valid precision statements. The
pass/fail criteria Eire set at levels that historically have been
shown and are known to be suitable for most end uses. The
most c o m m o n test for LPG dryness (D2713) is based on a
"valve freeze" criteria, where flow is restricted by ice/hydrate
formation in a restrictive orifice in a standard valve. The
pass/fail criterion is intended as an indicator, to prevent a
broader range of problems, and not just freezing of a small
orifice valve flashing liquid p r o p a n e at 42C. The other
common test methods are based on the color of the hydrate
of Cobalt Bromide exposed to equilibrium vapor, and the water dew p o i n t of the equilibrium vapor. Similarly, the
pass/fail criteria are set at a stringent enough level to avoid a
broad range of problems based on field experience.

Methanol is very effective in LPG systems at preventing


freezing of separated phases, but if mis-handled can aggravate the a m o u n t of separated phase that can accumulate at
tank b o t t o m s , and can propagate phase separated phases
through the distribution system.
Other alcohols or glycols form "glass" phases with water,
becoming increasingly viscous on t e m p e r a t u r e drop, b u t
without freezing in the traditional sense. They are often described as forming "slushy ice" that is very resistant to accumulation or blockage. However, these are reirely if ever used

It is initially counter-intuitive that the concentration of water


in equilibrium propane vapor, withdrawn from the vapor
space of a storage tank, increases as the t e m p e r a t u r e decreases. This is the key point of understanding water phase
behavior in propane, and the related problems of dryness of
propane.
Water has a low solubility in LPG, similar to other "pure"
parafins such as pentane, isomerate or alkylate. Since so little water is present, it is often confusing why dr3rness is so important for propane, much more so than for other fuels that

It is relatively easy to meet the dryness criteria for propane


with m o d e m production processes. However, the occasional
process failure of individual producers can affect m a n y
others in pipeline gathering systems. Seasonal brine cavern
storage, field dehydration facilities, steam/air cleaning of
storage tanks, hydrostatic testing, a n d use of c o m m o n
marine, pipeline, rail and truck facilities at EJI stages of distribution provide many opportunities for sporadic water contamination.
In the occurrence of an off-spec dryness event, the technical difficulties of sampling and analysis can be enormous, and
never certain. It is easy to show that propane is "on-spec," because the requirement is so stringent. However, when you are
trying to figure out why the fuel is "off-spec," the "dryness" of
propane quickly becomes the most exasperating specification, even if it is not the most critical [58].
There is a general correlation between water content and
the "drjmess" criteria, but even this is not certain due to nonlinearity of water solubility in propane with temperature,
relative linearity of the K ratio with temperature, and the possible presence of alcohol (especiEilly methanol), ice, and hydrates. There are additional factors that mEike the dryness of
LPG nvuch m o r e complicated t h a n simple solubility and
freezing for the other fuels. These are discussed below.
Phase Behavior

of Dissolved

Water in

Propane

44

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

contain more water. This section assumes no hydrate formation, similar to other fuels. Hydrates will be considered
immediately following.
The formation of "free" or undissolved water from a drop
in temperature is similar to other fuels, except that it occurs
at a lower concentration level due to lower solubility. The solubility of water in fuels increases with the temperature and
aromatics content of the fuel, ranging from about 100 p p m w
in low aromatics parafinic fuels to over 500 weight p p m in
high aromatics content gasoline or diesel fuels at 70F [59], A
drop in temperature of water-saturated fuel causes the phase
separation of a bulk (undissolved or "free") water phase to
form as a "haze" of small water droplets. These tend to coalesce into larger droplets and gravity settles them to the bottom of the storage tank. Pure water ice (not hydrate) will only
freeze if the temperature is below freezing. Since the solubility of water in propane is already low, there is m u c h less
water available to phase separate with a drop in temperature.
As a result, classical "fuel line freezing" is not very prevalent
in liquid propane systems, and most problems are associated
with smaller, m o r e easily plugged orifices in valves a n d
regulators than in m u c h larger diameter fuel lines.
If free w a t e r is present (e.g., grossly c o n t a m i n a t e d
propane), dispersed droplets can "super-cool" below freezing
in cold gases or liquids, including propane. This can result in
rapid ice accumulation that tends to be most severe in the - 4
to 10C range, very similar to automotive carburetor icing
and aircraft wing or propeller icing ("rime" icing). As each super-cooled droplet impinges on a surface, a portion of the water spontaneously freezes, adding to the surface ice deposit at
the impingement point. The remaining liquid water droplet is
heated to 0C by the heat of fusion, but is rapidly cooled again
by the surrounding cold fuel. This causes the remaining water to either freeze, or to form another smaller super-cooled
liquid droplet, which can repeat the process to extinction.
Flow patterns can create a small impingement point, and filter/screen surface area that is already plugged diverts flow to
unobstructed areas. This can result in a very fast and efficient
plugging mechanism. Ice accumulation in pipe elbows, meters, filters and screens is often associated with "snap" cooling to just below freezing, a condition that favors formation
of super-cooled water hazes and "rime icing." Ice accumulated under these conditions often looks like a translucent
"milky white" thick coating t h a t appears to have been
"painted" on. These conditions are more commonly found in
production facilities, prior to final drying, but can occur during downstream distribution if water has gotten into the system. Methanol is very effective at eliminating rime icing,
since only a very small concentration of methanol in the separated phase is required to reduce the freezing point to less
than about -10C.
Propane fuel systems are sealed under pressure, and not
vented to the atmosphere. Tanks in the distribution system
are never allowed to be totally liquid filled for safety reasons.
An equilibrium vapor phase is therefore always present in
downstream distribution (but not necessarily in production
facilities). Most end use applications draw equilibrium vapor
from the top of the tank, and large tanks always have a Pressure Relief Valve (Pressure Safety Valve or vent in other jurisdictions). These are safety devices that vent vapor in the
event of an overpressure situation. As a result, the water con-

tent a n d freezing behavior of the vapor phase is just as


important as the liquid phase.
A c o m m o n phrase in the literature is that propane vapor
has a much higher capacity for water than propane liquid.
This is true, but doesn't provide much clarity. Water, with a
molecular weight of 18, would have physical properties
closer to niethane (mw 16) and Neon (mw 20) if it were not
for hydrogen bonding. Hydrogen bonding results in a very
dense, high boiling liquid water phase instead of a light low
molecular weight gas. However, when water is dissolved in
propane at low p p m levels, there is little hydrogen bonding
between the water molecules, a n d it behaves like a low
molecular weight dissolved gas. Dissolved water in propane
is much more volatile t h a n propane, and becomes enriched in
the vapor phase.
The "K" ratio, or ratio of water concentration in the equilibrium propane vapor vs. the water concentration in the
liquid propane decreases with increase in temperature, ranging from over 20 (mole/mole) at low temperatures down to
about 5 at high ambient temperatures. Essentially the VP of
propane increases faster with increasing temperature than
water, in essence "diluting" the water vapor at higher temperatures. Unfortunately, this makes the propane vapor in
the tank more h u m i d when it is cold t h a n when it is hot,
making propane vapor more prone to icing.
Several operational artifacts come as result of this phase
behavior that are not intuitively obvious. For example, this
also tends to moderate the absolute a m o u n t of water per unit
volume in the vapor phase over a wide temperature range.
Propane vapor tends to be more prone to water condensation/freezing than p r o p a n e liquid. "Wet" off-spec propane
can be brought on-spec by venting equilibrium vapor, essentially distilling the water out [60], and this process will be
more efficient at cool or cold temperatures. Large sample
sizes are needed to do a valve freeze or CoBr test, because the
sample changes water content as you withdraw equilibrium
vapor during the test. The CoBr and Dew Point tests are more
stringent at cold storage tank temperatures than hot. The
valve freeze test (on the liquid) is not affected when the tank
is full, but could be affected when the tank is nearly empty
(large vapor space = large volume to enrich water in vapor,
depleting or drying out the remaining small volume of liquid). Under some circumstances, it is very difficult to obtain
a representative sample. Simply exasperating!
LPG Gas

Hydrates

It is not widely appreciated how prevalent hydrates can be in


LPG systems. Few people outside of research laboratories
have ever seen a gas hydrate, even though thermodynamically they are the most stable form of solid ("ice") in propane
systems. In fact, pure water ice is unlikely to form in liquid
propane systems at all, unless the water content is very high,
and free water is present in the propane liquid, either on the
tank bottom or as a dispersed haze in the liquid.
Gas hydrates are a class of ice-like clathrate solids formed
from water and low molecular weight C1-C5 hydrocarbons,
including propane [61]. They consist of water "cages" that surround or "enclathrate" the hydrocarbon molecules. Hydrate
formation can be a significant problem for cold weather operations for gas and gas liquids production and processing, especially prior to dehydration. They can form in LPG process-

CHAPTER
ing equipment, pipelines, and even under deep-sea conditions
due to gas seepage into cold ocean water (with the potential of
becoming a significant "new" energy resource) [62,63]. Hydrate blockages in pipes can be very hazardous. Depressurizing one side of the line can result in the hydrate blockage becoming a ballistic projectile, with the capability of causing
considerable damage. The propane-water and methane-water
systems have been studied in great detail due to their commercial importance. Several GPA and other research reports
are available detailing the phase behavior of hydrates [64].
The c o m m o n industry "rule of t h u m b " is that hydrate formation requires free water to be present, and that it cannot
occur with sub-saturated, on-spec propane. Technically, this
is not true, but it is good enough for most applications, with
some caveats to cover high dissolved water contents and high
pressures. Technically, free water does not have to be present
for propane hydrate to form, but in such cases, there is so little soluble water available for hydrate formation that it is
rarely a problem, or at least is not a more severe problem
t h a n if only water ice were formed. The presence of free
w a t e r in the hydrate formation t e m p e r a t u r e range can
cause severe problems because m u c h larger quantities of
hydrate can form. Below freezing, there is no practical reason
to differentiate between hydrates and water ice in most
applications.
Propane hydrates are stable above the freezing point of
water. The higher the pressure, the higher the temperatures
at which they are stable. They can form at any temperature
below about 5.5C (42F) in propane at its saturated VP. No
externally applied pressure (for example, a pump) is required
for propane hydrates to form. Externally, the symptoms of
having ice or hydrates in LPG systems are virtually identical.
They both form only when it's cold, they both accumulate
and plug lines and orifices, and they both are "melted" by
methanol, leaving the same a m o u n t of liquid methanol/water
mixture at the bottom of the tank. The problems are the
same, the fix is the same, and the result is the same. Most of
t h e time, it doesn't matter, a n d there is n o need to
differentiate between water ice and propane hydrate.
Gas hydrates are the "phantoms" of the LPG world, and are
notoriously difficult to "diagnose" when they do occur. They
decompose (sublime) to water and hydrocarbon gas at ambient pressures very quickly, since they are essentially solids
with a VP of about 80 psi. The sublimation rate can be high
enough to support a burning flame [65]. Often they are gone
by the time the e q u i p m e n t is depressurized and opened
for inspection.
It is always uncertain whether hydrate, pure water ice, or
both are involved when icing occurs in LPG systems. The
biggest difference is that "icing" can occur between 0 and
about 4.5C in LPG systems, due to hydrate formation. It is
r a r e for the t e m p e r a t u r e to be stable in this range long
enough during a n icing episode to make it obvious that hydrate and not water ice is the cause. The day/night temperature difference is generally m u c h larger than this. However,
even w h e n this occurs, people will generally first tend to
think that the thermometer is off by a couple of degrees, or
that there is some auto-refrigeration somewhere, rather than
a hydrate event occurring above 0C.
Hydrates can form both in the liquid and vapor phases, but
there are some differences in behaviors that can be important

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in some situations. Firstly, hydrates tend to form at free-water surfaces. This is because propane type II hydrate has a
composition of a b o u t 17.1:1 mole ratio of waterrpropane,
which greatly exceeds the propane solubility in water. As a result, when a tank containing free water is cooled towards
zero, it will tend to form a thin layer of hydrate on the water
surface, like the first thin skin of ice on a pond, puddle, or ice
cube tray. The hydrate layer becomes a barrier for propane
diffusion, effectively limiting the rate of further hydrate formation. As the t e m p e r a t u r e drops further below 0C, the
underlying "metastable" water can freeze to water ice.
Thermodynamically, the hydrate and water ice should not
exist together; they are only there due to a kinetic rate limitation. Under thermodynamic equilibrium conditions, water
ice would not form until all of the propane is consumed first
forming hydrate, leaving water or water ice in equilibrium
with hydrate, and no propane liquid. As a result, mixing and
turbulence are invariably factors in hydrate formation from
propane liquid.
Secondly, hydrates can form very quickly on tank surfaces
exposed to the vapor space by deposition from the vapor (i.e.,
the opposite of sublimation). The equilibrium concentration
of water is always higher in the vapor phase, which favors hydrate formation from the vapor. This can be a very fast and
"efficient" process, as there is no kinetic barrier, and the water
vapor and propane are already mixed. Only the rate of diffusion and convection of the water vapor limit the rate of hydrate formation. Hydrate formation from saturated equilibrium vapor depletes water from the vapor phase, essentially
dehydrating it. Additional water will vaporize from the liquid,
and contribute to additional hydrate formation. If liquid water were in the tank bottom, and one waited long enough, all
of the water would eventually form hydrate at the tank bottom, or dissolve into the liquid propane, vaporize, and form
hydrate on the vessel walls that are exposed to the vapor. This
process would continue until all the free water was consumed,
leaving only hydrate on the tank bottom and vapor walls. The
liquid propane in equilibrium with the hydrate can still be "off
spec" near the high end of the hydrate formation range. The
real fun begins when the tank gets emptied out and re-filled
with dry or warmer propane, which immediately goes "offspec" for no apparent reason, or the temperature changes
rapidly, and slugs of water or chunks of "ice" show up.
This can result in some truly exasperating situations when
investigating water related problems in cold LPG systems.
You are never sure if free water is present, or if the liquid or
vapor is in equilibrium, or if any sample is representative.
The basic concept of obtaining representative samples is
s o m e w h a t uncertain. You generally don't have a b o t t o m
drain, and you can't see inside of the tank liquid or vapor
space. When you open it up, it's all gone. This, plus the inherent difficulties of sampling/measuring low p p m levels of
water and methanol in LPG makes reliable quantitative measurement of water virtually impossible in cool/cold weather,
without extraordinary attention to sampling and analytical
detail. Throw in a couple of different test methods with no
precision statements, no calibrants, no reference standards,
no QCs and uncertain correlation, and "exasperating" is an
understatement.
It is left to the reader's imagination the many hours of stimulating conversation possible between the lab, the process

46

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

engineer, the plant manager, and the receipt terminal. This is


a potential area of future reseetrch and standcirdization.
Fortunately, the high VP of methanol makes it a very effective means to eliminate ice or hydrate formation in both the
liquid a n d vapor phase. Methanol, the lowest molecular
weight alcohol, partitions between liquid and vapor phases
closest to water, a n d tends to protect b o t h phases from
freezing.
Unfortunately, the specifications are silent on the use of
methanol, the test methods are inconsistent in response to
methanol, and there is no consensus between the upstream
and downstream industries on the intent and extent of use of
methanol in LPG. This is a potential Eirea of future research
and standardization.
Recently, some non-cryoscopic kinetic "hydrate inhibitor"
additives have been commercialized for processing/pipelining applications, but these are not applicable to specification
products [66].
Auto-refrigeration
Like any gas (except hydrogen) near ambient temperature,
p r o p a n e vapor will undergo Joule-Thomson (JT) cooling
when depressurized (flashed) across a veJve, orifice, pressure
regulator, or other device. The cooling effect is dependent on
the process, whether it is adiabatic (a valve) or isentropic
(turbo-expander) or polytropic (something in between). The
JT cooling effect is not very large, about 0.25F per psi drop in
the 30--40F range for propane, but this can be significant under certain conditions. In small regulators, the JT cooling is
offset by heat gained from the environment, tending to be
isothermcd at low flow rates (high heating from ambient air,
low JT cooling from low flow). However, as the appliance dem a n d and gas flow increases, there may not be enough convective heating to overcome the JT cooling, and the system
tends toweird adiabatic conditions. If the inlet propane vapor
is near water saturation (off-spec) and only slightly above the
freezing point, the cooling effect can be sufficient to cause
phase separation and ice formation at the expansion point.
Similarly, if the valve or regulator body is cooled below freezing, then the high-pressure propane vapor at the regulator
inlet could be cooled below freezing by the cold valve body.
This results in inlet freezing, upstream of the point of
vaporization, where the actual cooling occurs. A commercial
technical bulletin (LP-24) is available from a regulator manufacturer dealing with vapor regulator inlet line freezing from
these effects [67]. Ice will tend to accumulate over time in a
flowing system, until a blockage is eventually formed. If the
propane liquid is substantially sub-saturated (i.e., on-spec),
the cooling from expansion of equilibrium vapor is generally
not enough to cool the vapor to the water saturation temperature (dew point), and no ice/water is formed (one reason why
HD5 and functionally equivalent specs are where they are).
When liquid propane is depressurized or "flashed," a fraction of the liquid will vaporize, cooling the entire mixture
down to the boiling point and dew point of the liquid/vapor
mixture (they are the same if the mixture is in equilibrium).
This cooling effect is large, for example resulting in liquid
and gaseous propane at about 42C at atmospheric pressure. MoUier diagrams (pressure-entropy), pressure enthalpy
diagrams, or tables of thermodynamic properties can be used
to quantify temperatures, pressures, enthalpies and entropies

for a variety of conditions. Flashing liquid propane into even


moderate vacuums can attain temperatures below 80C.
The vapor pressure and solubility of water in propane below
42C is extremely low, so essentially all the dissolved water
that was present is converted to hydrate/ice. Liquid propane
vaporization systems almost always require external heating,
b o t h to convert all of the liquid to vapor, and to prevent
eventual freeze u p from ice. Transient conditions, for
example startup of automobile vaporizer/regulators in very
cold weather, t e n d to be p r o n e to icing, until the engine
coolant gets w a r m enough to keep the vaporizer above
hydrate/freezing temperatures.
The methanol addition rates t h a t are r e c o m m e n d e d in
various codes and standcirds for new tanks or for when moisture is present) are intended to remove the free water in the
tank, and leave only a small a m o u n t of methanol/water mixture prior to putting into service. They are not intended to
provide protection where gross water contamination has occurred or to allow weak water/methanol mixtures with high
freezing points to remain in the tank. For this reason, the
standards generally require inspection and removal of free
methanol/water prior to putting the tank into service.
Methanol is effective at preventing freeze-ups to very low
temperatures, but there is no universally accepted criteria for
how much methanol to add to propane during downstream
distribution as a preventative m e a s u r e . Many companies
have optimized methanol addition rates based on actual temp e r a t u r e s and/or dryness test results. These are effective
strategies with a relatively sound technical basis (see phase
behavior of m e t h a n o l ) . This is a potential area of future
research and standardization.
Butane, with a normal boiling point of neetr 0C is not capable of creating ice freezing conditions by auto-refrigeration
u n d e r normeJ conditions of use, and is treated as in other fuels with only a "visually cleeir" requirement. However, if butane is used below ambient pressure, the same precautions
may have to be used, as the boiling point at reduced pressure
is below the freezing point of water, a n d ice/hydrate cam form.
Butane, propane and their mixtures are widely used as the
working fluid in large industrial and chemical process refrigeration applications, such as industrial chillers, gas processing, refinery gas processing, or reactor cooling in alkylation
processes. These are usucJly integrated into the production
processes themselves, so they are n o t very "visible," even
though they are very large and very commonplace. All generally require some provision for w a t e r removal and icing
protection.
Phase Behavior

of Methanol

in

Propane

Methanol is a unique material in the LPG world. It is the only


alcohol with a lower molecular weight (31) than propane, and
the only one to be concentrated into the vapor (like water). As
a result, it tends to partition and "travel" with the water, making it very effective in preventing freeze-up in both the liquid,
vapor, and condensed vapor phases. The freezing point depression properties of methanol in water are very good, providing protection down to -40C [68] and below. Methanol,
being a small molecule, has a high diffusion coefficient and is
very effective at dissolving water and hydrates. No other alcohol has this broad range of beneficial properties, so methanol
is the only alcohol that is commonly used in LPG systems.

CHAPTER
The use of methanol is mandated under certain codes and
standards to minimize free water from tanks prior to putting
t h e m into service or if water is reasonably expected to be
present [69].
Methanol works by creating either a second non-freezing
separated phase in the liquid, in the vapor (hydrate), or the vapor if re-condensed. Methanol/water mixtures will not freeze,
but will gravity settle, and tend to collect at tank bottoms,
where it can be difficult to remove. This can promote other
problems such as corrosion and resulting sediment and filter
plugging, which is undesirable in the downstream applications. As a result, there is a general consensus that propane
should be manufactured as dry as necessary for "normal" operations, and that methanol should be used as needed for new
tank commissioning, and cold weather operations in downstream (post refining) distribution and use.
Methanol is equally difficult to detect as water at low p p m
levels, especially in the field. As a result, the actual amounts
of water or methanol present are rarely measured directly. It
is also recognized that methanol interferes with some of the
c o m m o n "dryness" test methods once it has been added to
propeme. D2713 "valve freeze" test is quite explicit in stating
that the test does not apply to LPG containing antifreezing
agents (although it is commonly used for this purpose in
spite of this caveat). The CoBr test is believed to be relatively
i m m u n e to methanol, but this test is not widely used. The
chilled mirror dew point test is affected by methanol, since it
phase separates with water. Electronic hygrometers (dew
point meters) m a y or may not be affected by m e t h a n o l
depending upon the principle of operation.
In colder climates, it is common for methanol to be added
to bulk storage during distribution as a preventative measure. Long-term field experience indicates that this is a n effective strategy to minimize regulator freeze-up problems, so
long as addition is controlled to the m i n i m u m required. Different companies have applied mzmy different criteria, in the
absence of reliable field tests that can be used to monitor and
control water/methanol. This is an area of r e c o m m e n d e d
focus for future research and standcirdization
A 50 wt% methzmol/water mixture (common windshield
wiper Emti-freeze in cold climates) will not freeze down to
below 40C. Therefore, as long as any separated
methanol/water phase is at least this concentrated, no freezeu p is possible under typical conditions of LPG use. Methanol
is more soluble in propane than water, so more remains in
the propane phase in equilibrium with the methanol/water
separated phase. Limited low temperature solubility data indicates that the methanol solubility in propane in contact
with a 50 wt% methanol/water solution at -40C is about
400-800 p p m w [70]. This indicates that it would take about
400-800 p p m w methanol to prevent freezing down to about
40C at ambient pressures for w a t e r saturated p r o p a n e
(about 100 p p m w at 70F). This is smaller than the solubility
of methanol in propane at ambient temperature, so methanol
use tends to be "robust" so long as gross overdoses are
avoided (and a dry grade of methanol is used). Slightly lower
treat rates would be expected for lower water contents, or if
freezing protection was only required to a higher temperature. The lower limit to eliminate all solid formation at -40C
would be expected to correspond to the 400-800 p p m w solubility of methanol in propane u n d e r these conditions. The ab-

2: LIQUEFIED

PETROLEUM

GAS

47

solute values of water/methanol solubility in LPG below the


saturation levels and at varying olefin levels are not accurately known. This is a suggested area of research a n d
standardization.
Ethanol and iso-propanol have a higher solubility and lower
vapor pressure than methanol in liquid propane. They require
a significantly higher treat rate per p p m w of water present to
prevent formation of solids at 40C in both the liquid and
equilibrium vapor. To date, methanol is technically and economically the best de-icer for propane.
In general, over-addition of methanol should be avoided, as
drops in temperature or contact with water can result in most
of the methanol phase separating in distribution and storage
and causing problems. For example, if w a r m propane containing 1% methanol either cooled down to 20C or were
contacted with water, then more than half of it will phase
separate and settle to the bottom of the storage tank as a
non-freezing water/methanol mixture. This would amount to
500-1OOOL for a large rail car. This large volume of
methanol/water mixture has the potentieJ to accumulate in
downstream storage, to the point where individual small
deliveries could contain gross quantities of water/methanol.
It is generally accepted that methanol should not be used
as an alternative to proper dehydration during production,
and that periodic use should be minimized. For the producer,
the answer is to consistently make LPG very dry, and avoid
periodic "slugs" of water. For the marketer, who is subject to
the downstream sources of water, the answer is to monitor,
and only use methanol when required during cold weather.
This is also an area of r e c o m m e n d e d research a n d
standardization.
Sources

of

Water

Water can be introduced into propane distribution systems


from a vairiety of sources. Faulty production can leave excess
dissolved water or free water in the LPG due to inadequate
dehydration. Water is used for hydrostatic pressure testing of
large pressure vessels including tanks, trucks, and rail cars.
Steam is used to clean and "inert" tanks for maintenance and
change of service. Water can become trapped in tanks from
previous wet loads due to internal "dead volume" at the
bottom of tanks due to valves or piping that is recessed for
physical protection, a c o m m o n requirement of safety codes.
Exposure of tanks to the atmosphere can result in moist air
condensing water on inside surfaces, where it becomes
trapped, and accumulates with each diurnal heat/cool cycle.
Free water in trucks or rail czirs tends to be persistent because
of the low water solubility of water in p r o p a n e . A small
a m o u n t of water in a truck or rail car can render m a n y
subsequent loads "off-spec."
Recent changes to rail car pressure vessel certification requirements provide another opportunity to further reduce
the use and occurrence of steam cleeming and hydrotesting of
large pressure vessels (truck/rail). Work is ongoing in this
cirea and several programs are planned. This is a suggested
area of research and standardization.
Measurement

of Water in LPG

There has cJways been a desire in the LPG industry to have better test methods for "dryness," especially for production and
terminal bulk receipts, which are the two main control points

48

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

(See "dryness" sections above). This has been an elusive goal


for many years, due the technical difficulties involved.
The criteria for pass/fail on the CoBr test are as follows [71]:
Color

Per Cent Humidity^

Green
Blue
Lavender
Pink

Very Dry
From nearly 0% to 30%
From 30% to 52%
From 52% to 100%

Pass (rcirely seen)


Pass
Fail
Fail

It is generally accepted that a 60 s valve freeze pass is about


equivalent to a CoBr pass, or a 26C dew point and less than
about 35 p p m w water in the LPG liquid phase. However,
these are not exact relationships, and there are several complicating factors due to differences in phase behavior with
temperature and composition. Different people have made
different assumptions in estimating equivalence between water content, the liquid propane phase, and the CoBr test results. During the CoBr test, the equilibrium vapor sample is
preconditioned with an ice bath to 32F and 50 psig, slightly
below the saturation vapor pressure at 32F. Most people
assume the humidity values in the table to apply at 32F in
doing the equivalence calculations. The a u t h o r noted that
"the values in this table were determined by series of tests on
propane vapor containing various amounts of water over a
temperature range of from 35-70F. The percents at which
the changes of color take place seem to be somewhat affected
by t e m p e r a t u r e . However, the determinations were not
accurate enough to assign closer values in the table."
In the test, the actual humidity of the sample is determined
by the bulk tank or bulk sample temperature, not the 32F
test t e m p e r a t u r e . The humidity of the equilibrium vapor
varies inversely with temperature at constant liquid water
content, due to the change in the "K" ratio. Therefore, there
is no single p p m water level of water in liquid propane that
corresponds to a CoBr (or Dew Point) pass/fail level. The
equivalence level is inherently temperature dependent.
Both the CoBr and Dew Point test methods are most severe
(conservative) at the lower temperature ranges. One can estimate the amount of water in liquid propane that is required
to pass the test on the known dependence of "K" ratio and
water dew point (vapor pressure) in gases. This depends on
what assumptions are made about the humidity level for failure condition (32% or 40%) and to what temperature the humidity shown in the table applies (32F versus 60F). A
propane sample taken at 32F has variously been estimated to
require less than 10-20 p p m w water in the liquid to obtain a
passing result. A sample taken at 100F has been estimated to
require less than 20-35 p p m w in the liquid to obtain a passing result. This temperature dependence is not recognized in
the test methods. However, the pass/fail criteria are severe
enough that propane obtaining a passing result is considered
suitable for use regardless of the temperature of the sample.

^ The humidity of the equilibrium vapor is dependent on temperature, since the wt. "K ratio varies from about 10 at 60F to about 15
at 32F. As a result, both the CoBr and Dew Point test methods are
more severe (conservative) at 32F than at 60F (or higher). This temperature dependence is not considered in the test methods, and the
same pass/fail criteria is applied regardless of the temperature of the
storage tank and equilibrium vapor.

Similarly, the CoBr sind Dew Point tests would be expected


to be somewhat influenced by gas composition, and especially by olefin content. Olefins have a higher affinity for water, and a correspondingly lower "K" ratio. Directionally,
higher propylene content would make the test less severe, requiring higher liquid water contents to obtain a test failure.
This difference has not been quantified, and is generally not
considered to be significant for commercial propane.
There are a n u m b e r of other anal3^ical techniques that can
be used for the anedytical determination of water in LPG.
Some methods, such as the Karl Fisher, can be used but are
difficult to apply to LPG, because of the physical properties.
Others, such as vapor phase determinations, can be influenced by sample size due to the very high "K" ratio of dissolved
water in propane. The cobalt bromide test, for example, recommends at least 15 gallons of LPG sample if the test cannot
be done at the storage tank with the equilibrium vapor. In
other cases, such as terminals supplied from underground
cavern storage, there is n o source of equilibrium vapor available on-site, because all the vessels are liquid filled.
Electronic hygrometers and "dew point" meters [72,73]
have been successfully used, and while they have the necessary sensitivity, and are widely used in the natural gas industry [74], they are not currently recognized in the LPG
standard. Care must be taken with their use, especially for
calibration a n d QC procedures to ensure that results are
valid. Several new ASTM procedures are now available that
allow adoption of on-line analytical techniques to product
certifications, and LPG "dryness" is a prime candidate for
these new methods. Many companies have installed solid
state electrometric probes at production facilities to monitor
drying operations, and there is emerging interest in having
these included as an alternate test method in the standard.
This is a recommended area of research and standardization.
Sampling and sample introduction also needs special care
and attention. Formation of hydrates can metke the storage
time prior to analysis a factor. At high temperatures and humidity levels, the air in the lab can contain 20 000-40 000
ppmv water vapor, and there can be more water adsorbed on
sample lines a n d cylinders t h a n is in an on-spec sample.
More than one analyst has falsely reported the humidity level
of a plastic sample transfer line as an off spec LPG result.
Recently, a new stain tube was developed for use as a field
test in natural gas pipelines that has a lower sensitivity to trace
glycol used in natural gas dehydrating systems [75]. These
stain tubes still have an interference from methanol, but may
still have some application as a field test, for example on terminal receipts prior to the addition of methanol. These calibrated in the range 2-10 Ib/MMscft (traditional units for natural gas), which is equivalent to about 40-220 ppmv (multiply
by mole weight ratio 18/44 = 0.41 to convert to mass p p m assuming ideal gas at low pressure). This is in the correct range
for use on LPG equilibrium vapor, so it can likely be adapted
to use for LPG. This would be very similar to the GPA and
CGSB field methods for mercaptan odorant (see odorization),
that use similar stain tubes calibrated in traditionetl natural
gas industry units, with appropriate conversion factors.
At present there is no standard test method for the use of
stain tubes, or electronic hygrometers or dew point meters
for LPG specifications. The ASTM natural gas standards
that use these m e t h o d s currently do not include LPG in

CHAPTER
the scope. This is another area of recommended research and
stEmdardization.
R e s i d u a l Matter (Oil Stain & R e s i d u e )
Non-volatile materials that are soluble in liquid propane tend
to a c c u m u l a t e at the point of p r o p a n e vaporization as a
residue or gum that can interfer with the proper operation of
some equipment. The oil stain test attempts to concentrate
non volatile residues that can be visually detected by putting
it dropwise on a clean filter paper. This test is quite subjective a n d can be influenced by the grade of filter paper, or
color of the residue. Historically, the main purpose of the test
was to detect traces of compressor oils, a c o m m o n occurence
in the early days of the industry, but less c o m m o n today.
Other sources of heavy naaterials can be heat transfer fluids
from distillation processes, caustic, amine and glycols used
in some processes, greases and "pipe dope," sample cylinders, hose plasticizers, or cross contamination with other hydrocarbon fuels and lubricants if any c o m m o n equipment is
used in distribution.
Contaminants that form "oily residues" or "waxy solids"
with auto-refrigeration of vaporizing propane, especially in
association with fine particulates, can interfere with proper
operation of safety lock-offs, overpressure vents and regulators. Non volatile additives are generally not recommended
for use in propane intended for vaporizing service, and specific warnings are included in D130 copper corrosion test
pertaining to corrosion inhibitors ("masking agents"). Some
higher boiling or polymeric materials may interfere with catalytic heaters or automotive catalysts if present in the liquid
propane. ASTM specifications currently do not include limites for higher t e m p e r a t u r e evaporation limits. This is a
potential area of future research a n d standardization.
Propane is a very poor solvent for parafin wax (n-parafins
or near parafins) or for asphaltenes, and has been used in
commercial de-waxing and de-ashpalting processes. Contamination of LPG with "black" oils that contain asphaltenes
(IFO, HFO, Bunker, Pitch, Crude) or distillate fuels that contain wax (diesel, furnace oil, marine gas oils, kerosene, Jet)
can result in the precipitation and collection of waxy or asphaltene solids. This can cause m u c h more severe operational
problems than an oily liquid because of more severe impacts
on equipment. Care must be taken to prevent cross contamination of these materials. Sources for such contamination can
include leaking heat exchangers, pipeline "dead legs" or idle
p u m p loops, meter provers or other distribution equipment
that may be inadequately cleaned from a previous service.
Nonvolatile additives may be beneficial for certain applications, such as detergent/dispersant additives for autopropane,
similar to gasoline. However, this can introduce the need for
a segregated fuel, since they can still be detrimental to vaporizing services. Maintaining a single universal grade would
require additive injection at the point of dispensing. This is a
potential area of future research and standardization.

2: LIQUEFIED

PETROLEUM

GAS

49

door use. The original "lamp" method is still listed in most


specifications, but rarely, if ever used. A variety of newer instrument methods are in common use, and are under consideration for inclusion in LPG specifications. Recently, the
requirement was changed to include the sulfur contribution
from added mercaptan odorant, which is effectively a tightening of the standard. The California ARB "HDIO" standard
has an 80 p p m maximum sulfur limit.
All LPG specifications have some provision for the control
of corrosive sulfur compounds to protect copper and copper
based alloys commonly used in fittings and connections in
storage, transportation, a n d appliances. ASTM D1838 is essentially a modified ASTM D130 copper coupon corrosion
test using pressure rated equipment for LPG. The same grade
of copper strip and preparation procedures are used, and the
strip is suspended on a hook fixed to the outage (ullage) tube
in a purpose built stainless steel test cylinder with an O-ring
removable top closure.
Sulfur based corrosion in LPG is a surprisingly complex
subject, due to the chemistry of the reactive sulfur species that
can be present, smd the nature of the test [76]. Mixtures of certain sulfur compounds are more corrosive than each alone,
even if the individual compounds were present at higher concentrations. This can lead to occasionally bizarre situations
where two on-spec propane batches go "off-spec" upon mixing. The classic case is w h e r e one batch contains a small
amount of dissolved elemental sulfur (S8), and the other a
trace of H2S (hydrogen sulfide) or COS (carbonyl sulfide).
Each batch can be on spec by a wide margin, but the mixture
can show a persistent fail, or even worse, an occasional fail.
There is nothing like a persistent occasional fail to go into "dispute mode," with no hope of short-term technical resolution.
Many hours of stimulating conversation are made possible
between shippers on a c o m m o n pipeline system or storage facility with such events. Each may sanctimoniously claim the
others to b e at fault, presenting credible data to prove their
innocence with consistent Cu corrosion passes. Try devising
a "round robin" to resolve that dispute.
In the vast majority of cases, corrosion problems in LPG
are associated with H2S, Sg (elemental sulfur, eight member
ring), COS (carbonyl sulfide), RSSxR (alkyl polysulfides),
HSSxH (polysulfanes), H2O (water) and O2 (in air). The most
important are usually H2S (improper treating), Sg (usually
from oxidation of H2S) and COS hydrolysis (reaction with
H2O to form CO2 and H2S). Mixtures of H2S and elemental
sulfur (Sg) form very reactive polysulfur intermediates that
are very corrosive, and react very quickly with most common
metals. Trace H2S and Sg U'e legendary for their difficulty to
sample and analyze. Fortunately, lead acetate paper is very
sensitive as a field test for H2S. Sampling and analysis for
trace Sg is always problematic.
Almost all copper corrosion problems are a direct result of
inadequate treating at the time of manufacture, and/or the
highly non-linear blending characteristics of different sulfur
types in propane from different sources.

Corrosion, H2S, a n d Sulfur

Contziminants

Historically, the total sulfur content of LPG (sometimes


called the volatile sulfur content) was always much lower
than for other fuels, and this was important, especially for in-

Magnetic

Residues

("Black Deposits")

and

Particulates

The occurance of iron oxide/sulphide magnetic residues was


studied by the Propane Gas Association of Canada (PGAC

50

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

[77]) as a result of widespread problems especially in automotive LPG fuel systems [78]. Iron particulates either from
heat treating "mill scale" or corrosion processes can adversely affect the operation of components that magnetically
attract and trap these materials in the working mechanisms
(e.g., magnetically coupled level gauges and electronic
solenoid valves). Collection of gross a m o u n t s of solid
residues (magnetic or otherwise) can adversely affect operation of filters, filter lock-offs, regulators, mixers, pressure release valves, etc., by mechancial blockage. Two to ten micron
(absolute. Beta 5000) filters have been found to be effective to
remove these materials with good filter life (granular well
behaved filter calie).
Ammonia
A m m o n i a is not used in the production process, a n d is
generally removed by gas stripping and distillation if it is
present. Anhydrous a m m o n i a is widely used in agriculture as
a fertilizer, and is transported in the same pressure rated
equipment as LPG. It is c o m m o n for rail and truck cargo vessels to transport "anhydrous" during the spring and s u m m e r
growing season. The s a m e rail or truck cargo tanks are
converted to LPG service for the fall and winter heating season. This is advantageous for optimal use of transportation
equipment, but offers increased chance of cross contamination without adequate cleaning in the change of service
procedure.
Anhydrous e q u i p m e n t a n d LPG p r o d u c t i o n e q u i p m e n t
generally use only carbon or stainless steel fittings. Brass
(copper alloy) veilves and fittings are commonly used in LPG
systems, particularly those at the dealer and consumer level.
Ammonia can cause stress crack corrosion in brass and copper fittings at concentrations above about 5-10 ppmv [79].
There is no firm specification or guideline on the maximum
allowable ammonia concentration of propane for either short
or long term exposures, Eind a level of < l p p m (detection by
field litmus paper test) is usually recommended.
Field tests based on color change of wet red litmus p H
paper are adequate to detect ammonia down to about 1 ppm,
and provide an effective go/no-go test after change of service
or at any time during distribution [80].
The time required for the color change due to the field test
can also be used to judge the severity of the contamination.
Very high (>20 ppm) concentrations cause a strong color
change in only a few seconds. Moderately high (5 ppm) will
cause a medium color change in about 10 s and low ( < l p p m )
will cause slight change in about 30 s.
The litmus test is very sensitive to any material with even a
slightly higher than 7.0 pH. This includes saliva (depending
on what was last eaten), high p H potable ("tap") water in
some regions, or soaps or detergents that may have been used
to wash the hands or equipment.
Controlled tests indicated that p r o p a n e with low concentrations of a m m o n i a would have n o effect on the
concentration of ethyl mercaptan odorant [81].
Halocarbons

(Refrigerants)

There have been rare occasions of contamination of LPG


with halocarbon refrigerants or fire retardant (Freon ^M or
Halon ''*'). These materials are miscible with propane, and
will form noxious gases upon combustion.

Naturally Occurring Radioactive Materials


(NORM)
Sludges and tank scale from propane storage tanks, trucks
and rail cars, and filters/screens may contain Naturally
Occurring Radioactive Material (NORM) in the form of lead
210 (Pb'^'"). Similarly, equipment used for the transfer of
propane such as product pipelines, pumps and compressors
may have detectable levels of radioactive lead 210 on inner
surfaces. Workers involved in cleaning, repair or other
maintenance of inner surfaces of such equipment should
avoid breathing dust generated from such activities. Suitable
codes of practice should be developed for these activities detailing appropriate occupational hygiene and disposal practices [82].

VOLUME CORRECTION FACTORS (VCF)


FOR LPGS AND NGLS [83]
LPG has the lowest density, largest thermal expansion and
compressibility and highest operating pressure of the comm o n fuels. It is the only fuel where compressibility is significant e n o u g h that it can be taken into account both for
calibration of composition test methods and custody transfer
metering. The original set of Volume Correction Factors
(VCF) were developed in an NGAA (GPA) sponsored research
p r o g r a m in 1942. It was first published as GPA standard
2142. These factors were later adopted as national and
international measurement standards as ASTM/IP 1250.
The Volume Correction Factors (VCFs) are used to correct
observed volumes to the volume that would be observed at
standard conditions (60F, 14.969 psia). These standard conditions serve as a way to equitably use volumetric measures
in general commerce. They are derived from actual density
measurements on a wide range of LPG/NGLs, and are essentially the average values of the coefficients of thermal and
pressure expansion. These factors are strongly correlated to
the density of the material (e.g., the lower density the mixture, the more compressible it is). As a result, the calculations
are iterative, and separate tables are published, each covering
a narrow range of densities. The differences are small, but
they do have large economic impacts because of the large
volume of material involved.
D 1250 is the ASTM standard for calculating the VCF of a
petroleum mixture. This standard essentially directs the use
of procedures published in the American Petroleum Institute
(API) Manual of Petroleum Measurement Standards (MPMS).
As of 1999, there are several procedures that may be used to
calculate the VCFs:
Chapter 11.1, Volume Correction Factors, gives procedures
to determine the VCFs due to temperature for crude oils,
refined products, and lubricating oils. However, since the
upper limit on API gravity is 100 it applies only to the
heaviest of LPG.
Chapter 11.2.1, Compressibility Factors for Hydrocarbons:
0-90 "API Gravity Range, and 11.2. IM, Compressibility Factors for Hydrocarbons: 638-107 kg/m^ Range, give procedures to determine the VCFs due to pressure. Like Chapter
11.1, since the upper limit on API gravity is 90 it applies
only to the heaviest of LPG.

CHAPTER
Chapter W.l.l, Compressibility Factors for Hydrocarbons:
0.350-0.637 Relative Density (60F / 60"F) and -50F to
140 F Metering Temperature, and 11.2.2M, Compressibility
Factors for Hydrocarbons: 350637 kg/m^ Density
(ISV)
and 46C to 60C Metering Temperature, also give procedures to determine the VCFs due to pressure. These
procedures cover the lower densities indicative of most
LPG and NGL.
Until 1998, the VCFs due to temperature for the LPG and
NGL not covered by Chapter 11.1 were calculated from a variety of sources. The major source was a set of Petroleum
Measurement
Tables published in 1953 by ASTM International and the Institute of Petroleum (IP). New implementation procedures for liquids with relative densities (60760)
of 0.3500 to 0.6880 (272.8 to 74.2API) were p u b h s h e d
in 1998 as Technical Publication TP-25 Temperature Correction For The Volume Of Light Hydrocarbons. This is a GPA
publication, but GPA, API, and ASTM have jointly adopted it
[84]. These procedures are based on an experimental program sponsored by all three above organizations. Based on
this expanded database the TP-25 factors are different by as
much as 0.2-0.8% from the 1953 Table factors.
The underlying procedure in TP-25 is quite different from
the fairly empirical equation forms used in the other standards. The TP-25 factors are determined from the interpolation of the properties of reference fluids via a corresponding
states formulation. Corresponding states theory has a rich
history for the use of correlating various t h e r m o d y n a m i c
properties. This particular formulation is unique in that it
uses the relative density at 60F as the interpolating variable.
The calculation of the density at a temperature is based on a
comparison of the properties of the reference fluids at the
same reduced conditions. All the reference materials and critical properties required to do the calculations are available in
the standard.
The organization of the VCF standards in the API Manual
of Petroleum Measurement Standards is being changed. The
revised Chapter 11.1, Temperature and Pressure Volume Correction Factors for Generalized Crude Oils, Refined Products,
and Lubricating Oils, will combine the previous Chapter 11.1
and 11.2.1 temperature and pressure correction procedures
into a single unified procedure. The nominal API gravity
range will be 10 to 100, so it will still only cover the heaviest of LPG. Two important changes will be that the single set
of procedures will be valid for the customary and metric standard temperatures (60F, 15C, and 20C) and for measurem e n t temperatures and pressures in customary or metric
units. Chapter 11. Iwas approved for D 1250-2002 and will be
published in 2003.
The revised Chapter 11.2, Temperature and Pressure Volume Correction Factors for Light Hydrocarbons, will use the
TP-25 procedure as the basis for the temperature portion of
its VCF procedures. It will cover the range of relative densities (60/60) of 0.3500-0.6880 (272.8-74.2API), just like TP25. Like the revised Chapter 11.1, this will contain a single set
of procedures valid for the customary and metric standard
temperatures (60F, 15C, and 20C) and for measurement
temperatures and pressures in the customary or metric units.
Technical work is being done to incorporate pressure correction procedures. It is expected that this revised Chapter 11.2
will also be published in 2003.

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The VCFs are always based on averages on a range of materials, or by interpolation between reference standards. Individual mixtures that have similar density but different
composition than either the average or reference may have
significantly different expansion coefficients. Use of the
standard VCFs will give a biased result on these mixtures.
Provisions are made in the standards for contracting parties
to determine and use VCFs based on density measurements
on the individual material or mixture. Alternatively, to minimize uncertainty, contracting parties may specify that the
density determination used for custody transfer be obtained
as close to the standard conditions as possible. This is easily
done for temperature, but is more complicated for pressure.
In the past, pressure correction was often omitted or ignored,
or based on measurements done at the time and temperature
a n d pressure of custody transfer. To accommodate existing
industry practices, the new standard TP-25 contains two sets
of tables, one for temperature correction alone, and the other
for combined temperature and pressure correction.

AUTO PROPANE
LPG has been used as a spark ignition motor fuel for over 40
years, especially in fleet and workplace applications. The primary advantages over gasoline in these markets are related to
availability, cost, and tailpipe emission levels. Fleet operations can operate from centrally located refueling sites,
avoiding the need for widespread availability at retail gasoline service stations. The lower operating cost for fuel may
offset the cost of conversion, with a net benefit for high
mileage applications such as taxi or delivery fleets. The
breakeven mileage generally varies between 5000 to 25 000
km/year, depending mostly upon the presence and level of
Government incentives for conversion cost, registration and
differential fuel taxation. The tailpipe and environmental
benefits depend mostly upon the technology and calibration
of the engine using the fuel and to a lesser extent on the properties of the fuel itself. However, with equivalent levels of
technology, LPG tends to have a significant advantage with
emissions and emissions toxicity.
Historically, both gasoline and propane employed similar
carburetor and intake manifold configurations. This allowed
widespread "aftermarket" conversion of engines from gasoline to LPG, using engine coolant driven vaporizer/regulators
and various gas injector devices. These could be plates that
could be "bolted on" above or below the existing liquid gasoline carburetors for dual fuel operation, or gas carburetors
for dedicated LPG use.
LPG carburetor engines generally have lower tailpipe hydrocarbon and carbon monoxide (HC,CO) emissions than the
equivalent technology gasoline engine, when no computer
feedback engine control strategies are used. This is primarily
due to reduction/elimination of fuel enrichment for idle, throttle transient and high power engine operation. This made
propane a preferred fuel for such indoor engine applications
as forklifts, where indoor CO emissions must be minimized.
The widespread introduction of tailpipe catalysts and electronic fuel injection systems to meet increasingly more stringent emission standards has made aftermarket conversions
increasingly challenging on recent model automobiles to

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LPG. Second generation conversion systems attempted to


use the onboard sensors to control a parallel LPG injection
system, often with very good results. However, the increased
cost and engineering sophistication tends to limit application
to a few high volume platforms. Each has to be re-engineered
with every change to the gasoline system, and then maintained in the field. Even so, several of these conversions have
been quite successful, but the overall rate of North American
conversions declined.
Recently, the highly integrated fuel injector/intEike manifold
designs and more complex onboard control and diagnostic
systems have become the norm [85], but these significantly increase the cost and complexity of conversion. Current Tierl,
Tier2 and more recently hybrid gasoline electric vehicles offer
exceptional emissions performance. On the horizon are mandated lower emission standards and gasoline reformulation
that will further reduce or possibly eliminate the tailpipe
emission advantage once enjoyed by LPG conversions. With
reduced environmental credits. Governments have tended to
reduce incentives for conversion, resulting in longer break
even time for operators [86]. As a result, the size of the North
American LPG conversion fleet is declining rapidly, OEM
built LPG dedicated or dual fuel vehicles is increasing. Major
North American OEMs offer current technology LPG powered
low emissions light duty cars, trucks, and vans. Recently,
there has been renewed interest in development of low emission LPG vehicles in the Pacific Rim and in Europe.
OEM vehicles are predominately factory conversions of
truck and van platforms aimed at fleet use [87,88]. The North
American carmaker's message to the p r o p a n e industry is
clear: The carmakers expect the s u p p o r t of the major
p r o p a n e industry players if they are to produce, sell and
maintain OEM vehicles [89].
This experience is different in other parts of the world, depending mostly upon fuel cost and tax structure. There is a
general agreement that the technical problems either can or
have been solved (depending upon who you tcJk to). This includes gaseous or liquid fuel injection systems that address
many of the problems of earlier systems, including tolerance
to trace contaminants, same as gasoline or diesel fuel.
Several manufacturers of advanced fuel LPG injector
systems have experienced problems with particulate/residues
in various areas of the country. Magnetic residues (predominately magnetite "mill scale" and tank cortosion products)
have been especially disruptive to some electronic solenoid/
injector designs. Widespread introduction of these systems is
likely to put additional emphasis on "cleanliness" of propane,
similar to that required for gasoline for fuel-injected cars.
Several OEMs have expressed concern for the m a x i m u m
sulfur contents of "HD5" propane, although typical sulfur
contents are significantly less than current specification levels. These are now higher than some reformulated gasoline
specifications (RFG) This is a potential area of future
research and standardization.
The use of a sulfur containing odourant (ethyl mercaptan)
adds u p to 30 p p m w sulfur to propane, which is significant
with respect to future RFG regulations. This is another area
of recommended research and standardization.
There is an opportunity for LPG fuels to compete favorably, and even preferentially in future "clean fuels" markets,
especially if factored into future engine/drivetrain design.

LPG could be an ideal fuel for emerging micro-turbine applications a n d high-temperature partial oxidation (POx) fuel
cells. LPG can be produced in high purity and low sulfur that
may be necessary for these applications.
LPGSAFETY AND HANDLING
LPG F l a m m a b i l i t y
Propane is flammable in the a t m o s p h e r e at ambient
conditions between about 2-9.5 vol%, the Lower and Upper
Explosive Limit (LEL a n d HEL), respectively. This corresponds to about 0.3 psia peirtial pressure for the LEL, and
about 1.4 psia partial pressure for the HEL. LPG is normally
handled at pressures m u c h higher than this. LPG must be refrigerated to less than 100C before the equilibrium vapor
pressure enters the explosive range. This is virtually unattainable in normal operations and would only be a concern in
some research or specialty applications. Thusly, physical
mixtures of gases, especicdly in air, is always more important
for LPG t h a n "flash point" considerations.
Flammability is not a fundamental or t h e r m o d y n a m i c
property of any material. It depends upon the circumstances
at the time, including gas mixture, temperature, pressure, ignition energy, turbulence, aerosol, catalyst and even the nature of the surface and shape of the containment vessel. The
lower explosive limit is less sensitive to these effects than the
higher explosive limits. For example, the LEL is almost totally insensitive to the a m o u n t of "diluent" gas added [90,91].
The HEL is the most impacted with dilution by inert gas, essentially decreasing almost linearly to near the LEL at about
40-50% dilution (10-13% oxygen vs. 2 1 % undiluted). The
flammable envelope terminates at the point that the HEL
meets the LEL.
The explosive envelope tends to enlarge at higher temperatures, but again more on the HEL side vs. the LEL side. The
change in LEL is in fact quite small, with only an 8% relative
change in LEL with a 100C increase in temperature from
ambient [92].
In general, it appears that any increase in temperature,
pressure, gas composition, ignition energy, or configuration
has a m u c h more profound effect on the HEL than the LEL.
Use of the LEL determined at ambient conditions can reasonably be expected to apply over a very wide range of conditions in typical LPG handling situations. This is not true for
the HEL, which varies widely with similar changes in gas
composition, temperature, and pressure.
LPG H a n d l i n g
Most jurisdictions require that persons involved with the
handling or transport of LPG or installing LPG equipment
be trained and licensed. This generally does not include final connection of portable cylinders to consumer appliances
using approved fittings, but usually does include filling
of the portable cylinders or automobiles at the point of retail sale.
LPG, like any fuel, is safe if properly handled. It has a relatively n a r t o w explosive range, so explosions are rare. However, spills and fires are similar to other volatile fuels and
solvents. Certain properties of propane should be understood

CHAPTER
to p r o m o t e safety in handling the fuel, and a p p r o p r i a t e
responses in the event of a spill or emergency response.
LPG vapor is about 50% heavier t h a n air (molecular weight
44 versus 29). Vapors will tend to settle in low points and cavities in the absence of a ventilating air flow. Propane/air mixtures have densities closer to air, and are more easily mixed
and dispersed from thermal or a m b i e n t air currents. For
example, a mixture of one volume of propane vapor (MW 44)
diluted 9:1 with air will only be 5% heavier than air (about
the same relative difference as sea water a n d fresh water). It
will still be above the explosive range, but will be prone to
dispersion from ambient air currents. The heavier than air
vapor density allows a potential and usually temporary pooling. Leaking gases tend to exit from high-pressure sources at
a sufficient velocity to stir the air mass and cause mixing.
They will only tend to accumulate in low spots only in very
quiescent conditions.
When propane or propane/air mixtures (above the HEL)
collect in low spots, there will cilways be an interface at the
top of the vapor pool that is in the flammable range. This will
b u m very similarly t o any other flammable liquid. A very
good safety demonstration is to fill a tall (high 1/d) nominal
500 m L beaker with pure LPG vapor, and leave it open in full
view for the duration of the training session. When asked after several hours, most attendees generally believe that the
"volatile gas" has escaped and is rapidly dispersing itself
through the cosmos. However, lowering a match slowly below the rim convinces everyone that not very much gas has
escaped, a n d for approximately the next 15 s, you can see the
flame level drop in the beaker, as the pool fire consumes the
propsme. This is a "worst case" demonstration, as ambient air
currents cannot penetrate and mix a tall vessel very far. However, it does serve to show that propane rich pockets of gas
can be stable for hours, days, and even weeks in the absence
of strong wind or air currents of a velocity sufficient to mix
the ambient atmosphere. It is important to vacate and properly ventilate an enclosed area that may have been subject of
a propane leak in the absence of ventilating airflow.
Small liquid leaks can turn large volumes of area into explosive mixtures under "ideal" circumstances. At room temperature, one liquid liter of propane expands to about 240
Liters of gas, which at 2% LEL is sufficient to create 12 000 L
of explosive atmosphere. It takes only a small liquid leak to
create a n explosive atmosphere in a confined area, if the
propane becomes well mixed. Since the entire system is under pressure, leaks can occur even when equipment is idle,
and collect over a long period of time.
Gas-Air mixtures may be brought below the flammable
limit by dilution with large volumes of non-flammable gasses
such as nitrogen, carbon dioxide, steam or air [93] (see
flammability above). Some precautions should be taken to
prevent ignition by static discharge with some CO2 fire extinguishers. A gas inerted area may still present an asphjrxiation
hazard. The rapid venting of gas and especially of gas/liquid
aerosols can create static chcirging situations. As a result, ignition of vented "vapors" can occur at any time, depending
u p o n circumstance.
Gas mixtures inside of the flammable region do not "bum"
like a pool fire. They forcefully explode, generating a shock
wave a n d a sharp "firecracker" type of sound. The largest energy release is when the mixture is at stoicheometric, and the

2: LIQUEFIED

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potential of the resulting explosion is at its most powerful


point. A one foot (25 cm) diameter round balloon filled with
a stoicheometric mixture will provide a bang loud enough to
startle m o s t people in a typical small training room. The
same bcJloon filled with p u r e propane vapor (no air) will produce a fireball that will rise 6-8 feet. A larger balloon will
leave a black scorch mark from the pool fire on the ceiling
(measure carefully, do your safety checks, and have a fire
extinguisher at hand).
The flammability of n e a r explosive mixtures has not been
extensively studied in the presence of a stable combustion
source. Witness descriptions and injuries indicate that very
large h e a t energy releases are possible in n e a r explosive
atmospheres.
Very few people have ever seen liquid propane. It is a clear
colorless liquid that can easily be mistaken for water under
certain circumstances, particularly in cold weather. When
propane liquid is sprayed into a collection container, only a
portion of the liquid initially vaporizes^just enough to provide the heat of vaporization and cool the remaining liquid
down to the 42C boiling points at ambient pressure. For
example, if liquid propane at 70F is sprayed into a collection
container, only about 40 wt% of the propane will vaporize,
and the majority will be collected as a liquid in the container.
The lower the starting temperature, the higher the yield of
liquid. Propane liquid must be over 200F (near the critical
point) before all of the propane will vaporize upon flashing to
ambient pressure.
Once collected, the liquid propane in the open container
will stay at its boiling point, and boil at a rate determined
by the heat transfer into the container. If the container is
made of a material that is a good insulator, such as a plastic cup or pail, it can take several hours for the liquid
propane to evaporate even at high ambient temperatures.
Under stagnant air conditions, the heavier than air cold vapor itself provides additioned insulation as it spills over the
top of the container. If the container is metal, then the boiling rate is generally very high initially, until a layer of accumulated ice or frost provides some insulation. If a spill occurs at low temperature onto frozen ground or snow, the
resulting liquid pool can be persistent for hours. If the spill
occurs at r o o m temperature onto a concrete floor, the evaporation rate is extremely fast. Liquid propane at room temperature on a horizontal surface tends to exhibit the
"Liedenfrost effect" where the liquid behaves like water
droplets bouncing on the top of a hot stove, essentially riding on its own rapidly forming vapor. A spill under such circumstances, for example a severed hose or inadvertently
opened valve, can barely leave time for occupants to vacate
the area. Some jurisdictions require "excess flow" valves on
consumer cylinders to limit the flow rate of a free flowing
propane discharge in the absence of a backpressure.
Any propane or BP mix liquid at atmospheric pressure has
a normeJ boiling point that is far below the freezing point of
water (and flesh and skin) and can cause "frost bite" or freezing "bums." Many a finger has been superficially frozen with
LPG liquid inadvertently sprayed inside of a difficult to
remove glove.
The rapid removal of vapor from a tank will cause the
remaining liquid in the tank to sub-cool. For example, in the
"worst case," if the valve is opened wide venting to the atmo-

54

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sphere at 70F, the hquid will cool down to the boiling point
(-42C) after about 40 wt% of the liquid has vaporized. High
appliance demand and rapid vapor withdrawal rates generally results in a large amount of condensation or frost accum u l a t i o n on the exterior of the c o n t a i n e r due to this
refrigeration effect.
LP-Gas vapor upstream of the regulator can condense to a
liquid if the lines external to the tank are at a lower temperature than the tank, and this requires special attention to detail, especially in cold climates. For example, during snap
cool situations, outside vapor lines cool down faster than the
bulk storage tank, due to the higher thermal mass of the tank.
The higher storage tank pressure causes condensation of liquid propane in the vapor lines. This can result in vapor lines
becoming filled with condensed liquid propane under snap
cool conditions.
Propane has a m u c h higher coefficient of thermal (and
pressure) expansion than other hydrocarbon fuels. Heating
an overfilled propane vessel can result in thermal expansion
of the liquid until the cylinder is fully liquid filled (the vapor condenses as the liquid expands). Very high pressures,
exceeding several thousand psi, can be generated with further heating and liquid expansion in a liquid filled ("hydraulically locked") cylinder. Pressure safety vents will generally prevent this, b u t the resulting leak of liquid can
become a fire hazard. All transportation codes require cylinders to be only partially filled for this reason, but it is not
commonly appreciated that this is relative to a reference
temperature (traditionally 80vol% fill at 60F). This protects
against hydraulic lock u p to over 140F for liquid fill at
60F. If the cylinder is filled at a temperature lower than
60F, it may be necessary to further reduce the fill density
for storage and transport. Consult the authority having jurisdiction for the applicable requirements.

LPG S a m p l e C y l i n d e r A p p r o v a l s
Consult the Authority having Jurisdiction for pressure vessel
certification r e q u i r e m e n t s for LPG sample cylinders (US
DOT in United States and Transport Canada in Canada). At
present there is no international approval process for pressure cylinders. Authorities in adjacent or other jurisdictions
m a y not approve cylinders approved in one jurisdiction.
Cylinders must be approved in all the jurisdictions in which
they are used for sample transport. Cylinders approved by the
Authority having Jurisdiction u n d e r "equivalent level of
safety" criteria are acceptable provided that they are used in
accordance with the applicable permits or exemptions. For
example, users may not subsequently alter valves or pressure
venting devices that are part of a permit or exemption. Periodic cylinder inspections may be required [94].
LPG E x p o s u r e
The health effects caused by exposure to LP Gases are much less
serious than its fire and explosion risk. LP gases at low concentrations are non-toxic, and liquids have limited ingestion routes
due to the physical properties of the materials. The Occupational Exposure Limits (GEL) are based mostly on the need to
avoid the explosive hazards by a wide margin. This is t5^ically
20% of the LEL or lower, which is a much lower level than
would be set for short or long term toxicity, or Eixphyxiants.

LP Gases at very high (explosive) concentrations are believed to be non-toxic, fast acting anaesthetic agents, as well
as being simple asphj^iants. The terminology "propane narcosis" is sometimes used, but this is not accurate. Narcotics
generally refer to drugs that act at opiate receptor sites,
which is not where general anaesthetic gases act. However,
the term "narcosis" is quite generic. The c o m m o n definition
is "to put to sleep, partially or totally" due to a general depression of the Central Nervous System (CNS), even though
sleep, anaesthesia and narcotics are distinctly different in
medical terms. There are some early references to LP gas
being tried or used as a medical anaesthetic, and one of the
LPG patent claims by F.P Peterson in 1914 was for use "in
surgery as an anesthetic" [95]. However, only cyclopropane,
nitrous oxide, ethers, and various halocarbons were used
clinically as anaesthetic gases, usually in combination with
other drugs.
Persons exposed to high levels of LPG gas and experiencing CNS depression effects are in a very dangerous
situation, since they are breathing explosive gas mixtures.
Any ignition source could produce a fire or explosion, resulting in injury or death. Individuals vary widely in their
susceptibility and tolerance to these effects. At high concentrations, the effects of narcosis and h3^oxia will be confounded, as they are outwardly similar in many respects,
and will occur simultaneously. There is a range of symptoms with increasing concentration from the onset of CNS
effects, hypoxia, and asphyxiation: disorientation, lightheadedness, dizziness, drowsiness, loss of physical coordination, impaired judgment, drunkenness, unconsciousness,
and death.
The CNS effect is believed to be dependent upon the concentration of the gas in the lipid bi-layer (cell wall m e m brane) of nerve cells. Different gases would be expected to
have a different potency, and require higher or lower exposures to obtain the same CNS effect. The relative solubility of
different gases in olive oil (surrogate for lipid), water (surrogate for blood), can be compared to a very wide range of
materials that have well known physiological responses. By
this method, the onset of einaesthetic effects is estimated to
be n e a r the lower explosive limit (2%) for butane, a n d
about twice the LEL (4%) for propane. Iso-butane causes
drowsiness in a short time in concentrations of 1%, with no
apparent injuries from i-C4 or n-C4 after 2-hour exposure at
concentrations u p to 5% [96].
The rapidity of both the onset and recovery of CNS effects
from gas exposure depends upon the speed at which the gas
is transported into and out of the body. This is dependent
upon the concentration of the gas in air, the breathing and
blood circulation rate, and the relative solubility of the material in lipid (oil) and blood (water). Gases with low water
(blood) solubility and high oil (lipid) solubility tend to be the
fastest acting. The large volume of blood/water in the body
tends to act as a "buffer" for water-soluble compounds, slowing accumulation and depletion from the nerve cells. The solubility properties of LPG lie close to cyclopropane, between
those of nitrogen and nitrous oxide/diethyl ether, where the
rates are well known. Cyclopropane anaesthetic, which is 4-5
times more soluble in water than propane, is not altered or
combined in the body; the major part is exhaled within 10
min, while full desaturation takes several hours [97]. LPG
exposure above the explosive limit would be expected to in-

CHAPTER
duce CNS effects quickly, certainly in less than 15 min, and
probably in less than 5 min.
Persons installing new equipment, flushing lines, repairing,
or re-lighting appliances, or investigating gas leaks are also
the most likely to be exposed to high LP-gas concentrations. A
Consumer Products Safety Commission (CPSC) study noted
that new LPG installations are more prone to accidents than
new natural gas installations and sponsored a n u m b e r of studies relating to LPG odorization [98]. While the lighter than air
density and higher LEL of methane are undoubtedly major
factors, the CNS effects may help explain the occasionally
bizarre circumstances of some LPG accidents.
The knowledge of possible impairment can be critical in
making decisions effective in reducing the accident rate. For
example, a person flushing a line might realize the need to
take a fresh air break instead of a "smoke" break, or ventilate
the area if it is u n d e r s t o o d t h a t the light-headed or tired
feeling may be due to explosive gas concentrations.
Anaesthetics also sensitize the myocardium to the effects
of epinephrine. Cardiac a r r h y t h m i a can occur when very
high concentrations of LP gases (above the HEL for propane)
are inhaled when the epinephrine level is elevated (e.g., anxiety, exertion) cind possibly during hypoxic conditions. Ccirdiac arrhythmia can have a sudden onset even with brief
exposures a n d may result in sudden death. This is an extreme
condition that is usually associated with substance abuse
(commonly called "huffing"). Similar problems have been reported in the nitrous oxide bottle gas industry. Additional
information is available on the web site of the Compressed
Gas Association [99].
LPG Odorization
LPG odorization requirements reside in different jurisdictions in different countries. The U.S. requirements are not in
the ASTM D1835 specifications, but in NFPA 58 and 19 CFR,
and State Regulations. Canadian requirements are in the
CGSB LPG product specifications that are referenced in various Provincial and Federal Regulations.
Historically, manufactured gas was odorized as a warning
aid due to the risk of carbon monoxide poisoning. Manufactured gas often contained high levels of CO, which was a
higher risk than flammability. Over time, a variety of matericils, including mercaptans, acetylene, and mixed refinery sulfides were used as odoureints. LPG production from sweet
natural gas wells had no olefins and a low sulfur content, so
had a n intrinsically low odor. Initially, there was no requirement to odorize gas distributed for fuel purposes, as it was
non-toxic relative to manufactured gases. However, a number of fires and explosions with non-odorized natured gas and
LPG highlighted the need to odorize as a warning aid to detect leaks. LPG odorization is now a regulated requirement in
all North American jurisdictions.
Natural Gas Euid LPG odorization has been the subject of
substantial product liability litigation, stretching over several
decades of work on the technical, political, and legcd issues
involved. These are summarized in a series of IGT sponsored
technical symposia [100], CPSC, GPA, NPGA, PGAC, and
BERC sponsored rescEirch, as well as transcripts of various
product liability cases. Current North American Odorization
practices are based on 1977 BERC smalysis [101] indicating
ethyl mercaptan (EtSH, or EM) to be a preferred odorant

2: LIQUEFIED

PETROLEUM

GAS

55

over tetrahydrothiophene (THT). N u m e r o u s other studies


continue to indicate the EtSH remains the odorant of choice,
particularly for cold climates, where the relatively high
volatility of EtSH is the closest to that of propane at low temperature [102]. The volatility of E t S H and other potential
odorants has been extensively studied and reported in IGT
and GPA research reports.
Odorants are not effective wEiming agents in all cases.
Propane vapor is heavier than air and initially tends to settle Eind accumulate in low points and cavities. Persons in
the vicinity of low points and cavities may not be exposed to
localized gas pockets, b u t m a y b e at risk from an ensuing
fire or explosion. S u b s e q u e n t diffusion or convection
can distribute LPG vapors t h r o u g h o u t a n area. Certain
odorants are polar and/or chemically reactive, and can be
depleted by reaction or adsorption. People differ in their
ability to smell, and the sensitivity to odors generally decreases with age or with impaired physical conditions such
as colds or respiratory allergies. Prolonged exposure to
odorants can cause olfactory desensitization. Other odors or
distractions can reduce the effectiveness of odorants as
warning agents [103].
Mercaptan odorants are susceptible to oxidation u n d e r
certain conditions, especially at high temperature and in the
presence of water, oxygen, or high oxidation state (red) rust
[3]. This is commonly referred to as "odorant fade"[103]. It is
now genercdly accepted that propane tanks in continuous service do not experience odorant fade since there is no source
of oxidant [104,105,106]. Much industry activity continues to
focus on identifying a n d eliminating situations that can
result in odorant fade. In general there is a m u c h higher
awareness in the industry for the detrimental effects of air,
rust, and water in pressure vessels [107-109].
Recent changes to rail car pressure vessel certification requirements provide another opportunity to further reduce
the use and occurrence of steam cleaning and hydrotesting of
large pressure vessels (truck/rail). Work is ongoing in this
area and several programs are being planned.
Odourants can be partially or fully removed by absorption,
for example in cases where the LPG has permeated through
clay-like soils that have high surface absorption capacity.
GPA, ASTM, and CGSB have developed field tests for
mercaptan odorants using stain tubes, and this allows reliable semi-quantitative monitoring of odorant levels during
distribution. ASTM D 6273-98 Standard Test Method for Natu r a l Gas Odor Intensity (odor m e t e r "sniff test") can be
applied to LPG as well natural gas. These are not necessary
for monitoring odourization equipment, as verification of
proper tj'pe and quantity of odourant can be done by a variety of means. These include measures of weight, volume,
injection pulses, on-line analysis, calibrated "day pots," etc.
and these features are generally included in commercially
available odorant injection systems. An NPGA/PGAC Joint
Task Force on LP-Gas Odorization developed a set of recommendations in 1991 to assist in their desire to improve LPG
safety. All producers and terminal operators w h o odorize LPGas should establish formal, rigid procedures and responsibilities for proper odorization [110]. These sire advisory in
n a t u r e a n d compliance is voluntary. I n d e p e n d e n t crosschecks have found to be effective to detect several "single
fault" injector system failure m o d e s that could otherwise
have gone unnoticed [111].

56

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

USES OF LPG
Industrial
fork lifts, indoor carburetor engines (floor sweepers, washers, etc.)
oxy/propane cutters, heating/annealing, high pressure
welding
"plumber" torches, portable soldering irons, small torches
hand torches (pallet shrink wrap, localized heating/burning)
worksite heating/ventilating (lineman's tents, below grade
sites)
refrigeration (compressor cycle), evaporation, or specialty
(vap pipes)
pavement heating for grinding/recycling, roofing tar
heating
ground thawing, ice/snow melting, concrete heating, etc.
propellant for aerosol sprays, cosmetics, shaving cream,
perfumes, etc.
propellant for paint sprayers, paint airbrush (including PB
mix)
solvent for cleaning, reaction, diluent/chilling, precipitation
remote "smart" gen sets with remote start/stop, telemetry
integrated standalone packages (power generation, ventillate, heat/cool)
portable soil/trash reclamation, sterilization
jackhammers (construction road work)

portable generator sets (fixed on larger RVs)


golf carts, maintenance equipment, turf and lawn mowers
pyrotechnic/flame special effects
Aviation
airport r a m p equipment (i.e., airstairs, luggage tugs, etc.)
12/24 Vdc piston engine pre-heat (indirect fire)
hot air balloon
Marine
LPG powered "jet" boats
"overslung" barbecue/cooking
Emergency
standby generators, compressors, heat/cool
stable long term emergency fuel supply
Mining
mineshaft ventilation air heating
mine site cookhouse stoves, quarters heating
water pumps to liberate coal seam methane
Medical

Power

cyclopropane anesthetic
microturbine and distributed power systems
stationary generators
standby fuel for gas interruptible supply

Transportation
autopropane (conversions) and OEM
cargo heaters, engine coolant pre-heaters, ice removal
heavy duty truck alternate fuel (fumigation and OEM)
hydrocarbon fuel for reforming fuel cell applications
retrofit of small engines to tighter emission standards
utility right of way maintenance
micro-turbine hybrid vehicles
Agriculture
grain drying, bam/brooder heaters, orchard heaters, weed
control
general shop heat/power/oxy welders, etc.
Colorado Potato Bug eradication, potato guns
farm animal m a n u r e dehydration/sterilization (esp. swine/
chicken)
weed control as alternative to herbicides to control runoff
"scare crow" devices
irrigation water pumps
Utility

Gas

bulk or refrigerated storage for peak shaving in NG systems


bulk vaporizer, distribution of LPG like NG

Acknowledgments
The author acknowledges review and significant technical input from Dr. H. ICing, ExxonMobil Research (hydrates), John
Jachura (VCF/density), Dr. D.Y. Peng (Peng-Robinson EOS),
Dr. H.J. Ng, DBRA Research Associates (Ng-Robinson EOS,
hydrates), Larry. R. Robertson, DaimlerChrysler (autopropane), Alex Spatura, Adept Group, (autopropane a n d
extensive review), Ian Drummond, lOL Industrial Hygiene
(exposure/CNS), Dr. Byrick, Uof Toronto (CNS), Dr. Roth,
University of Calgary (CNS), Nancy Bourque, lOL Research
Library (literature and patent searches), Tim Eaton, Superior
Propane Inc.(uses). Thanks to Mark Sutton and Ron Brunner
(GPA) for access to draft publication TP16 on history of LPG
specs (hopefully to continue to publication). Special thanks
to Ron Cannon (GPA, retired) for input, review, and liberal
reference to his excellent book "The Gas Processing IndustryOrigins and Evolution." This is highly recommended
reading for anyone in the industry, and a good book for both
libraries and reception areas.
The author acknowledges the support of Imperial Oil Ltd.
for the information/communications resources used in the
preparation of this chapter.

Residential
cooking, heating, clothes drying, hot water
catalytic/radiant/pipe radiant heaters, mantel lights
h o m e barbeques, refillable lighters, hair curlers, b b q
lighters
fixed installation mobile home heating/cooking
Recreation
mobile RVs/trailers cooking/heating, absorption cycle
refrigeration

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CHAPTER 2: LIQUEFIED PETROLEUM GAS 57


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CHAPTER 2: LIQUEFIED PETROLEUM GAS 59


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Institute, 1990.
Parclay, A. T., et al., "Rail Car Field Test Evaluation Ethyl Mercaptan Odorant in Propane," Symposia on Natural Gas and
LPG Odorization, Chicago, IL, Institute of Gas Technology/GAS Research Institute, 1992.
Poirer, M. A., Falkiner, R. J., and Pickard, A. L., "Odorant
Fade in Stenched Rail Car Cleaning," Symposia on Natural
Gas and LPG Odorization,
Chicago, IL, Institute of Gas
Technology/GAS Research Institute, 1998, Available:
www.npga.org.
www.adspec.net/safety/report/report.htm, April 8, 2003.
Bull, D. E. and Falkiner, R. J., "Risk Management: Verifying
LPG Odourization Rates," Symposia on Natural Gas and LPG
Odorization, Chicago, IL, Institute of Gas Technology/GAS
Research Institute, 2001.

MNL37-EB/Jun. 2003

Motor Gasoline
B. Hamilton^ and Robert J. Falkiner-^

nology levels, and have produced the "World Wide Fuel Charter" (WWFC) on this basis. The WWFC receives serious
consideration when nations and economic regions are revising fuel specifications, even though it is not an accredited
consensus standard, and is the subject of ongoing technical
debate. ASTM Standard Practices, Test Methods and Specifications continue to be key to domestic and International
Specifications and Regulations, and are used globally
through affiliated ISO Standard Writing Organizations.
Specifications for n e w generations of engines (electric/
hydraulic hybrids, gasoline direct injection, fuel cells, microturbines) and catalysts (lean b u r n , heated, selective reduction, HC absorption, particulate trap) have yet to be
developed. The trend continues to be more restrictive in composition and variation than in previous gasolines.

T H E SPARK IGNITION ENGINE HAS REMAINED THE POWER PLANT OF

CHOICE for personal transport for almost a century, and the


fuel specifically formulated for SI engines is called gasoline
(U.S.) or petrol (UK). Gasoline h a s evolved continuously
since it was first produced in quantity to meet the burgeoning demand from mass production of the automobile in the
early 1900s. It was first produced from light naphtha batch
distilled from crude oil and liquid condensate from natural
gas production, and in the early days, had no test methods or
specifications at all (see Chapter 2, Liquefied Petroleum Gas).
It became a carefully formulated mixture of hydrocarbons
and additives, seasonally blended to m a t c h local ambient
conditions, providing good performance and efficiency for
constantly changing vehicle fleet. More recently, gasoline has
been reformulated to reduce various emissions and minimize
the impact of automobiles on urban air quality.
For the first 60 years of gasoline production, formulation
and manufacture were focused on optimizing desirable performance properties, cost, and yield. Increased octane allowed increased engine power and fuel efficiency. Volatility
was controlled to minimize vapor lock, carburetor icing,
stalls, sag, hesitation, hard starting, and other measures of
"driveability" performance. Stability additives were developed to minimize auto-oxidation, and detergents to keep carb u r e t o r s clean. Increased yield from crude oil and other
sources made gasoline more available and affordable. Gasoline properties are increasingly influenced by regulatory requirements intended to reduce air and water pollution during
manufacture, distribution, and use. Gasoline is controlled at
many regulatory levels, including national, state/provincial,
and in some cases, city or municipal.

HISTORY OF GASOLINE
L e a d e d Gasoline ("Pre-control")
In the late 19th century, fuels, for the automobile were coal
tar distillates and the lighter fractions from the distillation of
crude oil. It's believed that a gasoline fraction was separated
by Joshua Merrill in Boston, and was used for lighting. It was
also used in Nicolaus Otto's first four-stroke cycle engine in
1876. By the late 1800s the early refiners were producing
volatile gasoline by batch distillation from crude oil. Natural
gas producers were making volatile naphtha from the hydrocarbon condensed from compressed natural gas (condensate,
casinghead, or "natural" gasoline). There were no standard
test methods or national specifications, or definition of quality. Some of the earliest standard test methods were not developed until the 1920s, allowing development of the first
widely accepted gasoline specifications. Some test methods
developed in the 1920s are still in use today, such as the Reid
Vapor Pressure (originally developed for casinghead gasoline) and Distillation (the oldest currently used ASTM gasoline test method, first published in 1930). The D86 was based
on tests developed for casinghead or "natural gasoline" by the
predecessor organization of the Gas Processors Association
(GPA). The data triggered a n intensive discussion of the relationship between gasoline distillation profile (volatility) and
engine performance, such as vapor lock, oil dilution, knock,
and "sooting."

The current generation of North American "Tier 0" and


"Tier 1" vehicles for current emissions standards have converged towards electronic fuel injected engines and "3-way
catalyst" emission control systems. Globally, automakers are
facing increasingly stringent "Tier 1" emissions limits for the
2004-2009 time period. While it has been recognized that
meeting the Tier 2 emission standards will be a challenge for
gasoline vehicles, the U.S. EPA does not expect t h a t any
major technological innovation will be required to achieve
compliance. However, low sulfur gasoline must be available
for these standsirds to be feasible. In turn, the automakers are
promoting global fuel specifications based on vehicle tech' Research Associate, Industrial Research Limited, P.O. Box 31310,
Lower Hutt, New Zealand.
^ Fuels Technical Associate, Quality Assurance and Development
Group, Imperial Oil Ltd., I l l St. Clair Ave. W., Toronto Ontario,
Canada.

Automotive engines were rapidly being improved and required a more consistent and suitable fuel. New test methods,
specifications, and refining processes were developed to better separate and increase the octane of components. Com61

Copyright'

2003 by A S I M International

www.astm.org

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pression absorption and continuous fractional distillation in


"pipestills" replaced batch distillation with a continuous process in the 1920s. The first "sweetening" processes were
developed to remove smelly and corrosive sulfur compounds.
Thermal cracking was introduced just prior to World Weir I,
followed by steam cracking, coking, fluid catalytic cracking,
reforming, catalytic hydrogenation (hydrotreating), a n d
many others. Gasoline specifications were developed to control the composition, properties and performance of the finished gasoline, with the three m a i n areas of octane, volatility,
and cleanliness.
Fixed bed cracking/reforming was introduced in the early
1930s, which significantly increased the octane of "cat-naphtha" relative to "straight-run" or thermally cracked naphtha,
with a good alkyl lead response. Higher octane of the gasoline
components allowed production of some of the first "premium" gasoline, called "high-test" at the time, a reference to
their higher octane n u m b e r test result. During World War II,
continuous fluid cat cracking and semi-continuous reforming processes were developed, along with cateJytic desulfurization, which further increased the alkyl lead response. Processes were developed to convert C3 and C4 olefins from cat
cracking into gasoline by polymerization (polygas) and alkylation (alkylate). Highly leaded cracked naphtha, reformate,
and alkylate blends were ideal for aviation gasoline for high
compression and turbo/supercharged aviation engines developed during WWII, using "performance number" octane ratings based on the increased percent power attained above the
baseline of 100% iso-octane fuel. With rare exception, all post
WWII North American automotive gasoline contained TEL.
In the early 1950s changes in engine designs and driving
patterns required the re-introduction of the Research Octane
Rating. Automakers utilized military technology to continue
to increase the engine compression ratio, requiring higher
octane n u m b e r fuels. The octane race occurred during the
1960s, as high performance engines required fuels with increased octane. The octane increase was non-linear with
alkyl lead concentration, with diminishing returns, so there
was an economic limit to the maximum amount used. The
m a x i m u m permitted concentration in gasoline was 1.14g
Pb/1, which was well above the optimum alkyl lead response
for most refinery streams. Highly leaded premium gasoline
was produced for use in high-compression ratio big-block
"muscle cars," with RON as high as about 105. For the interested reader, a more detailed discussion of the history of
gasoline is presented elsewhere [1-3].

H i s t o r y o f Alkyl L e a d i n G a s o l i n e
During the 1910s, laws prohibited the storage of gasoline on
residential properties, so Charles F. Kettering modified a
Spark Ignition (SI) engine to r u n on kerosene. However the
kerosene-fueled engine would "knock" and crack the cylinder
head and pistons. He assigned Thomas Midgley, Jr. to confirm that the cause was the kerosene droplets vaporizing on
combustion, as he presumed. Midgley demonstrated that the
knock was caused by a rapid rise in pressure after ignition,
not during pre-ignition as believed. The combination of TML
and TEL along with alkyl bromide and chloride alkyl lead
scavengers were widely used stEirting shortly after discovery
by teams led by Thomas Midgley Jr. in 1922 [4-6]. Several

e m i n e n t public health officials campaigned against the


widespread introduction of alkyl leads [7], but after a review,
the U.S. Surgeon General decided in favor of use in 1926. The
toxicity of TEL soon became apparent, as it was originally
handled and added in concentrated form at the point of sale.
This was changed to point of production to eliminate handling of alkyl lead concentrates outside of refineries, where it
could be better controlled.
Alkyl lead is unique among organometallic additives in that
alkyl halides were effective "alkyl lead scavengers" to prevent
buildup of alkyl lead oxides and related solids in the engine
and exhaust system. This allowed lead Eilkyls to be used at
m u c h higher concentrations than any other organometallic.
The alkyl lead chloride and bromide had a lower melting
point and higher vapor pressure than the oxide, resulting in
the alkyl lead being "scavenged" and expelled with the exhaust. About 1-1.5 times the molar amount ("theories") to
make the alkyl lead tetrahalide was used to provide good
scavenging. Aviation gasoline uses only one theory of alkyl
bromide to protect against chloride induced corrosion of the
hotter exhaust valves. Tricresyl phosphate (TCP) has also
been used as a alkyl lead scavenger (mostly in avgas), to form
alkyl lead phosphate that has a lesser tendency to form glowing deposits, foul spark plugs, or accumulate deposits in aviation exhaust side turbochargers.

History of Octane Ratings


In 1921, the Co-operative Fuel Research Committee (CFRC)
was formed to research fuels and engine performance [8].
The CFR engine was developed to evaluate knock performance of fuels under controlled conditions, measuring knock
intensity with a bouncing pin knockmeter. In 1927 Graham
Edgar developed a n octane rating scale based on high and
low reference fuels, and showed that fuels had Octane Ratings between 40-60. This became the C.F.R. Research Octane
N u m b e r in 1930. The RON test method was first published in
1932, became a tentative method in 1947, and was adopted as
an ASTM standard in 1951.
Graham Edgar used two pure hydrocarbon isomers that
could be produced in sufficient purity and quantity as reference fuels for rating the anti-knock ability of fuel. These were
"normal heptane," which was commercially available in sufficient purity from the distillation of Jeffrey pine oil, and "an
octane, named 2,4,4-trimethylpentane" that he first synthesized (commonly Ccdled isooctane today, although there are
17 different isomers possible, and about five prevalent C8 isomers from C4 alkylation). The heptane and iso-octane were
given the arbitrary octane n u m b e r s of 0 and 100, respectively. These have similar volatility properties (see Table 1),
specifically boiling point, thus the varying ratios 0:100 to
100:0 would have consistent vaporization behavior. The volu m e percentage of isooctane in the binary blend that gave the
same knock intensity as the fuel being tested was assigned as
the Octane Number of the sample.
The early work quickly identified that the "highest useful
compression ratio" (efficiency, power) was related to the CFR
Research octane number. The sulfur-containing gasoline was
initially restricted because sulfur in gasoline inhibited the octane-enhancing effect of the alkyl lead. In addition, different
fuels had different "susceptibility" or octane response to the

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63

TABLE 1Selected properties of normeil heptane and iso-octane.


Normal heptane
Iso octane

Melting Point, C
-90.7
-107.45

Boiling Point, "C


98.4
99.3

alkyl leads. Parafins have the best alkyl lead response, followed by napthenes, olefins, and aromatics, while the response of alcohols is negative. The RON of the gasoline could
be increased from 60 to 75, and the "highest useful compression ratio" increased from 5.3 to 6.8, increasing the constantspeed fuel economy by about 30%.
The Motor Octane N u m b e r (MON) was developed in 1932,
using conditions that better matched actual vehicle knock
performance climbing the long constant grade hill at Uniontown, Pennsylvania. This method is similar to the operating
conditions of the current Motor Octane procedure [9,10]. The
MON test was a tentative method from 1933 to 1939, when it
was adopted as a n ASTM standard. During the late 1940s
through the middle 1960s, the Research method became the
m o r e i m p o r t a n t rating because milder conditions m o r e
closely represented the octane requirements of the vehicle
current engines and driving conditions. Most retail fuels were
marketed according to their research octane rating.
1 9 6 3 C l e a n Air A c t , V e h i c l e E m i s s i o n S t a n d a r d s
a n d Alkyl l e a d P h a s e d o w n
During the late 1950s and 1960s, ambient air quality deteriorated, especially in densely populated urban areas. ReseEirch
quickly identified the "primary pollutants" in raw exhaust
(HC, CO, and NOx) and sunlight driven photochemical reaction to be a major source of SMOG (SMoke + fOG). Ground
level ozone and other "secondary poUutcints" are formed by
photochemical reactions driven by sunlight. The concentrations of pollutants followed a daily pattern determined by
driving cycles ("rush hours"), daytime sunlight intensity, and
local geography and wind patterns, with the most severe area
in the U.S. being southern California. The original Clean Air
Act was passed in 1963 "to protect and enhance the quality of
the Nation's air resources." The first vehicle emissions standards were imposed in California in 1966 a n d Federally in
1968. The early attempts to reduce HC and CO with carburetor calibrations and thermal reactor ("thermactor," air +
time delay) type exhaust systems were only about 60% effective for HC. However, this was still a larger drop (est. 10.6
g/mile to 4.1 g/mile HC) than all of the emission reductions
since, due to the high emission rates at the time. A n u m b e r of
attempts were made to develop "lead-tolerant catalysts" and
"alkyl lead traps" that would allow continued use of leaded
gasoline. However, several new potential problems with continued widespread use of leaded gasoline were found, and
R&D to develop viable exhaust oxidation catalysts went into
high gear.
Alkyl lead is a toxin by itself, and there was a drive to reduce exposure levels from m a n y sources, ranging from alkyl
lead solder in pipes, food cans, toothpaste tubes, alkyl lead
pigment in paints, and edkyl leads in gasoline. In addition, the
alkyl lead scavengers ethyene dibromide and ethylene dichloride could react with u n b u m e d hydrocarbons in the exhaust

Density, g/ml
0.684
0.6919

Heat of Vaporization, MJ/kg


0.365 at 25C
0.308 at 25X

to form traces of organo-halogen c o m p o u n d s , including


dioxins [11]. It is unlikely that high levels of TEL use would
have continued even if a lead-tolerant catalyst h a d been
found.
Separate regulations were put in place to minimize the
amount of alkyl lead (primeirily TEL) used in the remaining
leaded gasoline produced and sold, creating "low lead" in a
series of reductions in 1985/86. A smaller fill nozzle diameter
was adopted for nonleaded gasoline to prevent misfueling
catalyst cars with leaded gasoline. In the United States, alkyl
lead could not be knowingly added to nonleaded gasoline,
and the maximum allowable concentration of 0.05 g/usgal
(13 rng/L) was applied as a contamination limit for "incidental contact" with leaded fuels during distribution. Other jurisdictions have slightly different legal definitions and cont a m i n a t i o n limits for nonleaded gasoline, b u t the t e r m s
"nonleaded" and "unleaded" tend to be used interchangeably,
even if this is not technically or legally correct in all cases.
Octane ratings of leaded gasoline decreased from the "octane
race" levels, a b o u t 1.5-3 AKI lower for RUL a n d PUL,
respectively.
Some predominately smEJl engines were designed for 87
AKI nonleaded fuel, but were "alkyl lead tolerant," because
they could meet the emission standards of the time without a
catalytic converter, so could use either leaded or nonleaded
gasoline.
The last p r e m i u m leaded gasoline was sold in 1981, and the
last regular leaded in 1996 in the United States, and in 1990
in Canada.
Alkyl alkyl lead has been credited variously with allowing
rapid development of high power Eind efficiency SI engines,
and even being a deciding factor in aviation in World War II.
It is not widely appreciated that Thomas Midgley's other famous discovery, perfluorocarbon refrigerEint, had the same
dichotomous history [12] as alkyl lead. It provided enormous
social benefits, b u t was eventually b a n n e d d u e to stratospheric ozone depletion. It was replaced with less long-lived
halocarbons that are decomposed at lower altitudes.
Nonleaded Gasoline
Introduction of the first Conventional Oxidation Catalyst
(COC) systems required nonleaded a n d low phosphorous
gasoline to protect the exhaust catalyst over the useful lifetime of the car. Alkyl lead Euid phosphorus are potent catalyst
"poisons" that slowly decreased catalytic activity, eventually
resulting in near total deactivation of the converter. Phosphorous contents were reduced to sub-ppm levels by eliminating the use of phosphate ester based corrosion inhibitors.
Alternate corrosion inhibitor additives were readily available,
so phosphorus reduction did not pose a problem to fuel manufacturers. It did require the automzikers to significEintly reduce oil consumption, as the only remaining significant
source of phosphorous was from crankcase lubricant. Re-

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placing the octane boost from alkyl lead was a big problem
for the fuel manufacturers, as there was n o readily available
replacement. This required significant changes to both fuel
and engine design.
Gasoline manufacturers found that it was possible to produce, on average, a nonleaded regular gasoline with an 87
AKI and about 91 RON in the United States, and a premium
95 RON in Europe and elsewhere. United States automakers
built engines with EGR and reduced compression ratios initially around 8:1 for use on 87 AKI non-leaded gasoline to reduce engine-out NOx to regulated levels. Air injection reduced HC and CO by oxidation over a COC. Efficiency and
fuel economy were reduced because of the compression ratio
reduction. However, this was more t h a n offset by Corporate
Average Fuel Economy (CAFE) regulations in 1975 that required average LDV fuel economy determined in standard
tests to increase over a period of years u p to 27.5 mpg. This
was accomplished with a variety of technologies. Vehicle
size, weight, and rolling/wind resistance were dramatically
reduced ("downsizing"). The majority of the fleet converted
to front wheel drive, using more efficient transverse L4 and
V6 engines and transmissions, both using lower viscosity and
friction modified lubricants.

The United States EPA may grant waivers for nonleaded


gasoline formulations that are shown by testing to not cause
or contribute to emission device failures. A waiver request is
granted if the EPA does not decline the application after 180
days. In 1978, the EPA granted the first waiver for 10% by volu m e of ethanol. The EPA subsequently issued waivers for
gasoline containing a variety of alcohols, ethers, and mixtures, of which MTBE and ethanol (gasohol) are the most
commercially important today. A complete technical assessment (including extensive references) for the application of
alcohols and ethers as fuels and fuel components is available
from API [14].
In 1981 the EPA ruled that fuels with u p to 2 wt% oxygen
from aliphatic alcohols or ethers were "substantially similar"
and thus did not need a waiver. In 1991 the maximum oxygen
content was increased to 2.7 wt% oxygen. To ensure sufficient base gasoline was available for ethanol blending, the
EPA also ruled that gasoline containing u p to 2 vol% of
MTBE could subsequently be blended with 10 vol% of
ethanol.

Premium unleaded (PUL) gasoline was introduced in the


United States later, in response to the higher Octane Requirement Increase (ORI) relative to historical experience
with leaded fuels. This allowed production of "premium preferred" or "premium required" cars, predominately turbocharged and knock sensor equipped engines that could
take advantage of the increased octane. ASTM specifications
do not m a n d a t e octane number, and historically U.S. fuel
producers set octane numbers in response to market forces.
In North America the most c o m m o n octane grades are now
RUL87, MUL89, PUL91/92, and SUL93/94.

As the tailpipe emissions were reduced by improved exhaust


emission control systems, other h y d r o c a r b o n emission
sources became more important. This includes hydrocarbons
from evaporation or fugitive emissions of gasoline during
distribution and storage, vehicle refueling, vehicle at rest, or
vehicle during use. The United States CAA required summer
reductions in VP in two phases in 1989 and 1992, to reduce a
number of fugitive emission sources (running loss, diurnal,
refueling.. .). Summer vapor pressure controls have virtually
eliminated hot driveability problems. They tend to be design
related, appearing as "select model" problems when they
occur.
Stage 1 vapor control systems reduce truck loading vapor
emissions at terminals and at service stations during loading
and unloading of trucks. At the service station, the vapor
space of the truck is connected to the vapor space of the underground tank, whose vapor is displaced ("vapor balanced")
back into the truck during fuel delivery. The truck returns to
the terminal, where the hydrocarbon saturated air delivery
truck are collected and sent to a Vapor Recovery Unit (VRU)
or to a Vapor Destruction Unit (VDU, combustor, flare) as the
truck is loaded.
Stage 2 systems reduce point of sale vehicle refueling emissions. Vapors from the vehicle tank are vapor balanced with
the underground storage tank, or sent to an absorber or combustor. Newer systems incorporate vapor p u m p s to remove
the exact amount of air from the fill pipe as volume of gasoline dispenses, and do not require the rubber nozzle "snout"
to make a vapor tight seal. These systems are recognized by
air slots near the nozzle tip to remove air from the fill spout
via an annular tube in the delivery hose. Vehicles are also
equipped with enhanced activated carbon canisters (bigger
capacity than required for diurnal control) to treat the vehicle tank vapor while refueling. These are subsequently desorbed by a small airflow and burned in the engine during
normal use, once specified vehicle speeds and coolant temperatures are reached. Some activated carbons used in older
vehicles do not function efficiently with oxygenates, but mod-

1 9 7 0 U S E P A C l e a n Air A c t a n d 1 9 7 7 A m e n d m e n t
The 1970 U.S. Clean Air Act (CAA) established the Environmental Protection Agency and required a 90% reduction in
automotive emissions by 1975 (HC/CO) and 1976 (NO^). This
resulted in the widespread introduction of conventional oxidation catcilysts and nonleaded gasoline in 1975 in response
to the HC and CO standards. These regulations were "technology forcing" especially for NO^, and the U.S. Congress put
an interim NOx standard in place until 1978. The 1977 Clean
Air Act Amendments required reduction in HC in 1980 and
CO and NOx in 1981. This resulted in the widespread introduction of sophisticated "three-way catalysts" computer controlled closed loop air-fuel ratio control with exhaust oxygen
sensors in most 1981 model year cars. The 1977 CAA amendments contained the first provisions that controlled the properties of "future" gasoline. It had a general requirement that
gasoline be "substantially similar" to fuel or fuel additives
used to certify 1975 or subsequent years vehicles [13]. The
intent was that future gasoline would not render the new catalysts or emission controls ineffective over time. The EPA
subsequently promulgated the "substantially similar" ruling,
which had a more detailed definition of the meaning. It eilso
provided that additives containing only C, H, O, N, S (which
combust to the regulated emissions) did not require a waiver
at concentrations below 0.25 vol%.

Vapor Controls

CHAPTER
ern carbon canister systems can reduce evaporative emissions by more than 95% from uncontrolled levels. On-board
canister systems tend to make Stage 2 balancing redundant
as the on-road population equipped with enhanced canister
systems increases.
1 9 9 0 CAA A m e n d m e n t s ( R e f o r m u l a t e d a n d
Conventional Gasoline)
A more complete technical discussion on Reformulated Gasoline (RFG) is contained in ASTM Research Report D02:1347
[15], and in numerous other Government and Industry Publications [16]. Officially published sources of information should
always be used for regulatory compliance purposes. A summary
of the United States EPA gasoline, additive, and related regulations is available at http://www. epa.gov/otag/gasoline.htm.
A chronology of EPA emissions control regulations is available at http://www.epa.gov/ otag/12-miles.htm.
The 1990 Clean Air Act (CAA) amendments and California
Air Resources Board (CARB) Phase 2 (1996) specifications
required further reductions in tailpipe emissions, more stringent test procedures and vehicle on-board monitoring technology, and new "clean fuels" programs. These established
emission limits for reformulated gasoline, compared with
typical 1990 "baseline" gasoline. The first stage, the "Simple
Model" was an interim stage between 1 Jan. 1995 to 31 Dec.
1997. The second stage, the "Complex Model" h a d two
phases: Phase I (1995-1998) and Phase II (2000+).
Metropolitan regions with severe ozone air quality problems were required to use reformulated gasoline containing
at least 2.0 wt% oxygen to reduce 1990 volatile organic carbon compounds by 15% (1994), and reduce specified toxic
emissions by 15% (1995) and 2 5 % (2000). Because of a lack
of data, the EPA was unable to define the required parameters for the CAA, so an advisory committee containing representatives of regulatory, petroleum industry, environmental,
and consumer interests recommended a two-stage system for
implementation ("reg-neg"). The EPA also gave the refining
industry a choice of standard, based on either "per gallon,"
(Never To Exceed, NTE, or "cap" limit), or "averaged," based
on volumetric averages over an annual or seasonal production period (Yearly Pool Average, YPA, or summer/winter). In
some jurisdictions, regulations include requirements around
sampling, test methods, and validation/demonstration of test
proficiency, as well as certified third party testing, auditing,
and field "attest" monitoring.
Areas in attainment with air quality objectives continued to
use "conventional gasoline." The "anti-dumping" provisions
of the regulation ensured that the quality of conventional
gasoline was not degraded to facilitate production of RFG.
Conventional gasoline must be blended to provide equivalent
emissions of the national baseline gasoline (default for domestic or import), or individual refiner's baseline based on
prior production. The intent of these "anti-dumping" restrictions was to ensure emission improvements and non-attainment did not result in emission increases in areas currently
in attainment with the National Ambient Air Quality Standards (NAAQS). Emission improvements had to be made by
increased refinery processing for the manufacture of RFG.
The Auto-Oil Air Quality Improvement Research Program
(AQUIRP, "Auto-Oil") provided the basis for the "simple" and

3: MOTOR

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65

"complex" models used in EPA and most other North American gasoline regulations. Measured emissions were correlated to gasoline properties in a wide variety of vehicle emission system types. These spreadsheet type correlation models
predict emissions from all sources associated with using
gasoline in vehicles. They tcike into account the time of year
(winter/summer), gasoline composition as measured by eight
parameters (called the model parameters), and an assumed
on-road vehicle fleet with a mixture of various generations of
emission control tjrpes. A copy of the complex model spreadsheet ("Final.exe") can be downloaded from the EPA web
site. California Phase 2 RFG allows a "Predictive Model,"
similar to the EPA complex model, as an alternative to the
original Phase 2 composition based requirements.
For Phase I, for example, the CAA specifies no increase in
NOx emissions, reductions in VOC by 15% during the ozone
season, and specified toxins by 15% all year. These criteria
indirectly established vapor pressure and composition limits
that refiners had to meet. The percent reductions are calculated with the complex model, which predicts volatile organic
compounds (VOC), specified toxic air pollutants (TOx), and
nitrogen oxides (NOx) as a function of eight composition related model inputs. Sulfur, benzene, vapor pressure, %oxygen and aromatics have the largest impact on predicted emissions. D86 evaporation volumes E200 and E300, and olefin
content have lesser, but still significant impact. Federal regulations reduced vapor pressure and benzene directly, however, aromatics or other parameters could be limited to meet
emissions criteria [17]. For example, a fuel with the maxim u m permitted 1.0% benzene requires total aromatics to be
limited to about 27% to meet the emissions reduction
requirements.
Federal (EPA) RFG and California Phase 2 RFG composition limits require the use of oxygenate. The California Phase
2 RFG requires the hydrocarbon composition of the RFG to
be significantly more modified than the existing oxygenated
gasoline to reduce unsaturated hydrocarbons, volatility, benzene, sulfur, and the reactivity of emissions. California Phase
2 does not require the use of oxygenates in the summertime
if using the "Predictive Model" except for federal ozone noncompliance areas of the state where the EPA RFG limits apply as well.
Oxygenates were first added to gasoline as a high percentage level blend component (as opposed to a p p m level deicer) to extend gasoline supply supported by some State and
Provincial Governments with a reduced gasoline tax rate. In
1992, 2 wt% oxygen gasoline was mandated in cold, high altitude areas starting in 1994, as a means to "lean" the mixture, and reduce unburned HC and CO by over 10% in carb u r e t e d vehicles. However, some oxygenates such as
methanol, ethanol, and light ethers increase the vapor pressure of the gasoline, causing increased evaporative emissions
that reduced or reversed the benefit. Newer Tier 0 and later
technology cars have very fast adaptive feedback loops to
control the oxygen content in the exhaust to near stoichiometric using the oxygen sensor [18]. These vehicles are much
less sensitive to fuel effects, so the net benefit of oxygenates
decreases with time, as the older predominately carbureted
engines are retired from service. Other researchers have observed similar reductions when oxygenates are added to reformulated gasoline on older and newer vehicles, but have

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also shown that NOx levels may increase, as also may some
regulated toxics [19-21].
By 2000, MTBE was the preferred oxygenate in RFG, but
concerns about toxicity and water pollution were mounting.
MTBE has a m u c h higher (4.3 wt%) solubility in water t h a n
hydrocarbons, a relatively low bio-degradability, and very
low o d o r threshold. This makes MTBE objectionable in
potable water at trace concentrations, and a concern for water contamination from spills, leaks and marine engines using gasoline-containing MTBE. In 1999, California applied to
the Federal government for a waiver from the Federal RFG
requirement concerning oxygen content to eliminate MTBE.
However, that application was declined in J u n e 2001. In
March 2000, the EPA provided advance notice of its intent to
initiate rulemaking pursuant to section 6 of the Toxic Substances Control Act (TSCA) to eliminate or limit the use of
MTBE as a fuel blend component. Several U.S. FederEil and
individual state bills have proposed elimination of MTBE
since t h e n including two U.S. Federal Energy bills. At the
time of this writing, use of MTBE is likely to be either banned
or significantly restricted.
Canadian refiners m u s t meet either a 1.0 wt% benzene
NTE, or optionally a 0.95 wt% YPA and 1.5 wt% NTE, effective July 1, 2000. In addition, a 72/91 summer/winter Benzene Emission N u m b e r (BEN) requirement is based on the
complex model, not including olefins. The BEN is the s u m of
exhaust a n d n o n e x h a u s t benzene, excluding calculation
terms of the complex model using olefins. There eire several
measurement and reporting differences between the U.S. and
Canadian RFG regulations. One Canadian province (BC) has
VOx and NOx requirements based on the full complex model,
but using a BC baseline gasoline for the calculation. Severed
other Canadian Provinces have standalone s u m m e r Vapor
Pressure regulations. Canadian vehicle emission standards
have tended to follow closely u p o n U.S. 49 state requirements, with some differences in phase in schedules.

2 0 0 4 + Vehicle and Fuel Regulation (Future RFG)


In April 2000, new Federal Tier 2 criteria for vehicle emissions and fuels were announced phased in beginning in 2004
and extending to 2007+. OfficieJly published sources of information should always be used for regulatory compliance
purposes. Full details of the regulations cire available on the
United States EPA website at http://www.epa.gov/otaq/cert/veh-cert/bOOOOl.pdf (Document EPA420-B-00-001). Copy of
the final rulemaking is available at http://www.epa.gov/OMS/regs/ld-hwy/tier-2/frm/fr-t2pre.pdf.
These stcindards apply to both diesel and gasoline powered
light duty vehicles, and to fuels for these vehicles. The regulations allow early-adopters to obtain credits that cEin be used
later and traded, encouraging rapid introduction of low sulfur gasoline, starting in 2000, well ahead of the 2006 deadline. Temporary, less stringent standards will apply to a few
small refiners t h r o u g h 2007. I n addition, temporary, less
stringent steindards will also apply to a limited geographic
cirea in the western U.S. for the 2004-2006 period.
Most U.S. refiners and importers must meet a corporate
average gasoline sulfur standard of 120 p p m and a cap of 300
p p m beginning in 2004. In 2005 the cap remains at 300 ppm,
with the corporate average reducing to 90 p p m and refinery

average at 30 ppm. In 2006, the average will be 30 p p m and


cap 80 p p m , with some areas and refineries having until
2006-2009 to comply. The EPA also n o t e d that gasoline
should not be advertised as "low sulfur gasoline" unless it
contains 95 p p m sulfur or lower.
California has legislated faster implementation of a 30
YPA, 80 NTE sulfur standard, and others, such as North Carohna's SB 953. Part II of that law, NCOS 119-26.2, proposes
the same for after January 1, 2004.
The Tier 2 LDV stcindards are the same for cars and light
duty trucks, whether diesel or gasoline, so include both nonmethEuie organic gases (NMOG) and Particulate Matter requirements (PM essentially for diesels and NMOG essentially
for gasoline). Different phase in periods apply for different
size vehicles. Light duty car a n d truck phase-in starts in 2004
with 100% compliance by 2007. M e d i u m duty passenger
vehicles and heavy light duty trucks will be phased in beginning in 2008, with full compliance in 2009. A new class of
medium-duty passenger vehicles (MDPV), < 10,000 GVW, includes large Sport Utility Vehicles (SUV) and vans intended
to carry less thzin 12 passengers. These will be treated the
same as HLDT and have interim emission standards that expire in 2008.
The standard defines 11 "Bins" rEinging from Bin #1 "Zero
Emission" to Bin #11, which is compEirable to current LDV
standards. The average Bin #5 NOx = 0.07 g/mile which represents a reduction of about 70% from current levels. The
highest emissions Bin #9 to #11 expire after the phase in period, contributing to a lower long-term average. More stringent particulate matter emission standards are established in
2004 for most light trucks. The NMOG standards vary depending on which of various individual sets of emission standards manufacturers choose to use in complying with the average NOx standard.
The Tier 2 Vehicle emission program increases the useful
life of the vehicle to 120 000 miles and introduces new, more
severe evaporative emission test procedure. This is expected
to result in widespread adoption of "deadhead" gasoline fuel
systems, that place the fuel p u m p , filter, and pressure regulator inside of the gasoline tank, with n o liquid gasoline
return line from the engine compartment back to the teink.
This eliminates a n u m b e r of external mechanical connections that contribute to the fugitive emissions etnd life of vehicle compliance.
The Canadian Environmental Protection Act (CEPA) requires refiners and importers to meet either a 170 ppmw sulfur NTE over a 30 month interim period ending Dec 31, 2004,
or a 150 p p m average with an 300 NTE in the last half of the
interim period. Gasoline is required to be 30 p p m YPA, 80
p p m NTE starting Jan 1, 2005. One Province (Sask.) has impending oxygenate (ethanol) requirements for 2005.

GASOLINE PROPERTIES
Gasoline Composition
Hydrocarbons
Gasoline can contain over 500 different hydrocarbons with
between 4 and 14 carbon atoms per molecule. Detailed descriptions of structures can be found in any chemical or
petroleum text discussing gasoline [22]. The C3 and lighter

CHAPTER
hydrocarbons are too volatile to be used as a blending component of gasoline. Both methane and propane are widely
used as an SI engine fuel using pressurized fuel systems and
various designs of gaseous carburetors or fuel injectors. Hyd r o c a r b o n s larger t h a n about C14 are too heavy (nonvolatile), and tend to contribute inordinately to oil dilution
and incomplete combustion a n d "soot" related problems.
These functional limitations result in gasoline having a typical boiling range of about 25-225C at atmospheric pressure.
Vapor pressure, Driveability Index (DI) a n d model based
emission criteria all tend to narrow this boiling range by removing the highest and lowest volatility ranges.
The type and concentration of the various hydrocarbons in
any given gasoline blend can be determined by high resolution gas chromatography, typically using 50-100 meter capillary columns to obtain the high resolution required. The
n u m b e r of different hydrocarbons in any given blend depends upon the tj^e and severity of processing at any given
refinery. Composition surveys [23] on nonleaded gasoline
showed that gasoline blended with high percentages alkylate
or low severity reformate could contain less than 175 different hydrocarbon types. Gasoline blended with catalytically
cracked naphtha tended to contain more than 350 different
molecules.
U.S. regulations use a n ASTM external calibration GCMass Spec method for regulatory benzene and aromatic reporting. Current versions of the ASTM GC method peak
tables identify over 400 different hydrocarbons by formula,
and a n additional 50+ as "unknown." Most methods also
measure the c o m m o n oxygenates if present. Since the FID
detector is linear, the percentages of parafins, olefins,
napthenes, indanes, aromatics, and unknowns can be estimated by linear sum (commonly called a PONAU or PIANO
methods, which are acronyms of the first letter of the hydrocarbon t5rpes detected). With over 400 compounds identified,

3: MOTOR

GASOLINE

67

there is usually less than 2.5% "unknown" content in a typical RUL and less than 1% in a typical PUL. There are small
concentrations of additional isomers that are undoubtedly
present below the nominal 50 p p m w detection level of the
standard methods using Flame Ionization Detectors. These
tend to be highly branched CIO to C14 olefins, isoparafins,
and napthenes because of the large n u m b e r of isomers that
can be produced within each carbon n u m b e r in this range.
The magnitude of the "undetected" hydrocarbons can be inferred to be less than about 0.5% for a complex gasoline by
comparing results of high and low resolution methods.
The m u c h smaller number of isomers possible for aromatics makes the measurement of aromatics by FID detectors
more feasible since essentially all of the possible aromatics
up to about CI2 are identified. As a result, Canadian regulations use a Cap-GC/FID method for both benzene and total
aromatic reporting.
Saturated

Hydrocarbons

(Paraffins,

Alkanes)

Saturates are the most chemically stable species, and comprise 20-80% of gasoline, with 30-60% being typical. The octane ratings of these compounds depend on the branching
and n u m b e r of cEirbon atoms. The octane primary reference
fuels are both saturated hydrocarbons (0 = heptane, 100 =
224 trimethylpentane). Additional information is presented
in Table 1. The interested reader is directed to a standard organic chemistry text for further detail on these and the other
classes of hydrocarbons.
Unsaturated

Hydrocarbons

Unsaturated hydrocarbons are less stable as compared to


saturates. The upper limit of both olefins and aromatics can
be limited by emissions or other specifications. Table 2 contains information about the various classes of unsaturated
hydrocarbons.

TABLE 2Unsaturated hydrocarbons.


Alkenes

Dienes

Alkynes
Arenas
(Aromatics)

PNA (Polynuclear
Aromatics)
PAH (Polycyclic Aromatic
Hydrocarbon)

Olefins, contain single carbon-carbon double bonds


Usually stable, depends upon molecular type
Clean burning, reduces VOC but increases NMOG reactivity
More reactive than alkanes, higher octane ratings.
Present in gasoline 0-25% (10-15% typical)
Olefins containing more than one carbon-carbon double bond
Usually unstable especially if conjugated (n, n+2 double bonds)
More be significantly higher reactivity, toxicity and air reactivity
<<1 % generally required for stability
Acetylenes, contain carbon-carbon triple bonds
Considered very reactive, only present in trace amounts, and usually in some poorly-refined gasolines
<<0.1% generally required
Very stable, high octane. 10-50 vol% (25-35 vol% typical).
Tend to be limited by emission models
Benzene > > > toxicity than other aromatics, regulated separtately
Alkyl benzenes not considered smoke precursors, as they have vaporized and are not present at the
end of combustion, (see PNA)
Condensed ring aromatics (naphthalenes, alkyl napthalene, trace 3 ring)
Generally controlled to < < 1 vol% by boiling point or other specifications (220-225C vs. 260C
dimethyl napthalene)
Di-alkyl PNA are potent smoke precursors, and are very detrimental to spark ignition engine
operations.
Naphthalene and methylnaphthalene boil at 218C and 230C and are not considered to be potent
smoke pre-cursors. Di-methylnaphthalenes boiling above allows it to ring close on de-hydrogenation
to form a larger PNA. It turns it from a "chain ender" molecule to a "smoke precursor". The extra
methyl group on the aromatic allows this process to continue to completion of a multi-ring smoke
molecule.
Many other control measures can be used to control the same property.

68

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37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 3Properties of selected oxygenates.

Methanol
Ethanol
MTBE
ETBE
TAME
Gasoline

Oxygenates

Energy Content,
Net MJ/kg

Heat of Vaporization
MJ/kg

Oxygen Content
Wt%

19.95
26.68
35.18
36.29
36.28
42-44

1.154
0.913
0.322
0.310
0.323
0.297

49.9
34.7
18.2
15.7
15.7
0.0

(as Blend

Components)

See History of Gasoline (nonleaded and RFG). Table 3 provides properties of selected oygenates that are used as gasoline blend components.
Gasoline Additives
Additives are compounds added in trace a m o u n t s (<2500
p p m in the EPA "substantially similar" ruling), to enhance
some property of the fuel, or performance of the engine, vehicle, or emissions. Specifications and regulations allow for
additive use, and in some cases, require additive use, for example deposit control additives (DCA), which are beneficial
for in-use emissions.
Oxygenates

(De-icers,

Gas Line

Anti-Freeze)

Aliphatic alcohols and ethers added at 5-15 vol% are considered to be blending components and not "additives." However, at lower concentrations, low molecular weight alcohols,
especially methanol, ethanol, and iso-propanol, are effective
de-icing additives, commonly available as "gas line antifreeze." Alcohols are typically used in the 500-2500 ppmv
(0.05-0.25 vol%) range for this purpose, and function by preventing traces of water (typically from temperature drop and
condensation) from freezing in the vehicle fuel system. A
higher rate may be required for larger water contaminations,
or to prevent carburetor icing, which is accumulation of ice
in the carburetor throat and throttle plate. The cooling of
high humidity combustion air is caused by throttling (Joule
Thompson cooling) and fuel evaporation heat of vaporization
(auto-refrigeration). Gasoline with higher VP, Eind lower TIO
and T50 (high "front end" volatility) has a higher propensity
for producing carburetor icing
IPA is approved as aviation fuel system icing inhibitor
(FSII Type 2) at a treat rate of 1 vol% in aviation gasoline
(ASTM D 4171). Other alcohols and glycols have also been
used for carburetors or fuel line icing, including hexylene glycol, propylene glycol, dipropylene glycol, and various glycol
ethers. Methanol is the most commonly used for gasoline fuel
line freezing protection in fuel-injected vehicles in cold climates. De-icers are not commonly used in automotive fuels
in warm/cool climates, due to the low population of carbureted engines susceptible to carburetor icing. Some carbureted utility engines may require alcohols for operation in severe icing conditions ( > 8 5 % relative humidity, 0-10C).
Alkyl Lead

Compounds

Alkyl lead compounds are n o longer used in North American


automotive gasoline, because of the detrimental effects on
exhaust catalysts and concerns for health effects of alkyl lead

in the environment (see History of Gasoline). Nonleaded


specifications and regulations limit alkyl lead contamination
to 5 mg/L (Canada) and 0.05 g/gal (13 mg/L) (U.S.).
ASTM D 910 Aviation Gasoline lOOLL (low lead) has been
reformulated from the original 100/130 grade with the addition of aromatics (toluene) to reduce TEL to the lowest level
necessary to maintain the octane number and aircraft performance. Avgas is generally handled in segregated distribution systems, so is generally not a significant source of alkyl
lead contamination in automotive gasoline. With no other
source of alkyl lead contamination, typical trace alkyl lead
levels in North American gasoline are usually undetectable
by standard test methods.
Methylcyclopentadienyl

Manganese

Tricarbonyl

(MMT)

As the toxicity of the alkyl lead and the halogenated scavengers became of concern, alternatives were considered. The
most notable of these is methylcyclopentadienyl manganese
tricarbonyl (MMT), an organo-manganese compound with
similar antiknock properties as TEL, but at m u c h lower concentrations to obtain about 1-2 octane n u m b e r increase. It
was used in the United States in nonleaded gasoline in the
mid 1970s, b u t a n application for an EPA waiver was declined in October 1978, effectively banning it in nonleaded
gasoline in the United States. In December 1995, the EPA was
forced to grant the waiver in U.S. conventional gasoline (not
RFG), and MMT can be used in conventional gasoline up to
1/32 g Mn/usg (8.3 mg/L) in all states except California, where
it is regulated separately [24]. In a separate case, the court
held that EPA's new rules that require pre-meirket testing of
new gasoline additives did not apply to MMT. The EPA has
stated it intends to monitor MMT use, but MMT was used in
only 0.02% of gasoline in 1998.
MMT has a high toxicity in concentrated form, but the
combination of relatively low volatility and its miscibility
with aromatic hydrocarbon solvents allows it to be stored
and handled with tj^ical equipment. MMT is light unstable
with a half life of about 30 s in strong sunlight, forming a
characteristic red "rust" colored precipitate (Mn02). This oxide is softer t h a n iron oxides, and is not considered to be
abrasive even at much higher concentrations than typically
used in gasoline.
MMT has been in continuous use in Canada since the first
introduction of nonleaded gasoline in 1972 to a maximum of
18 mg/L Mn, without major incidents. Most problems attributed to MMT are associated with excessive exhaust or catalyst temperatures. These cause the manganese oxide to "ceram" and form a gas impermeable glass that can coat and
effectively deactivate the catalyst [25] This is also associated
with front face catalyst plugging, due to the "sticky" nature of
the glass. Field experience indicates that this is not a serious
problem in tj^jical driving cycles, including Tier 0 and 1 vehicles equipped with OBDII emission control monitoring systems. Two provincial inspection a n d m a i n t e n a n c e (I&M)
programs using IM240 (d3mo driving cycle) and ASM2525
(25 m p h steady state dyno) test cycles have not found or identified any emissions related problems due to MMT on model
years 1982 to present.
Proponents claim benefits in NOx reduction, protecting the
catalyst from long term deactivation by sequestering catalyst
poisons (Zn, P, Pb) or coke, fuel cost benefits, emissions re-

CHAPTER
duction from reduced refining severity, and lack of adverse
health effects. Opponents cite high exhaust temperature catalyst plugging, exhaust gas sensor "rich shift" for the NOx effect, spark plug tracking, and the potential for adverse health
effects.
Dozens of controlled and noncontrolled tests and surveys
over 35 years have failed to conclusively resolve the debate
[26,27,28], probably because the test result depends upon the
specific automobile year and model being tested and how the
test is done.
Several countries are considering MMT as an alkyl lead replacement additive to facilitate alkyl lead phasedown.
Iron based

Organo-metallics

Other compounds that enhance octane have been suggested,


b u t usually have significant problems such as toxicity, cost,
a n d increased engine wear, especially if used at high
concentrations.
Dicyclopentadienyl iron (ferrocene) a n d nickel carbonyl
have been promoted as alternatives to alkyl lead and MMT.
For example, the addition of 0.02-0.04 g/L ferrocene with
0.05-0.10 g/L tertiary butyl acetate is reported to increase the
AKI of susceptible gasoline hydrocarbon feedstocks by 4-6.
More recently, ferrocene has been promoted as an octane
enhancer at lower levels of 9 mg/L Fe to avoid any significant
deposition or wear problems. The benefit is reduced to about
1-1.5 octane n u m b e r at this level (similar to MMT). Unlike
m a n g a n e s e oxides, iron oxides do not ceram at high
temperature.
Iron pentacarbonyl (Fe(CO)5) was used in Germany at levels of 0.5% or less in gasoline during the 1930s. While the cost
was low, the carbonyl decomposed rapidly when the gasoline
was exposed to light to form iron oxides. It also has a relatively high vapor pressure, and is extremely toxic in concentrated form, so must be handled with care. Use of the additive
at high concentrations in gasoline caused excessive deposition of iron oxide (Fe304) on the spark plug insulator, causing short circuits. The precipitation of iron oxides in the lubricating oil also led to excessive wear rates [29].
Iron picrate (trinitro phenate) and related oil soluble iron
chelates are sometimes sold as aftermarket additives with
various performance claims, but are not used in commercial
production.
Performance

Additives

Most other additives are added to address specific safety or


p e r f o r m a n c e properties of gasoline. Typical examples
include:
1. Oil-soluble dye was originally added to leaded gasoline at
about 10 p p m to prevent misuse of leaded gasoline as an
industrial solvent, and is now also used to identify grades
or brand of product. Red dyes are currently used in the
U.S. and Canada to mark fuels that have different taxation
rates for different uses.
2. Antioxidants (oxidation inhibitors) typically phenylene diamines (PDA) or hindered alkyl phenols, are added to slow
down oxidation of hydrocarbons, especially unsaturated
hydrocarbons. These additives are "sacrificial," and once
consumed, the oxidation reactions rapidly become autocatalytic, increasing exponentially in rate to form soluble
and insoluble gum ("varnish").

3: MOTOR

GASOLINE

69

3. Metal Deactivators, typically about 10 p p m of chelating


agent such as N,N'-discJicylidene-l,2-propanediamine is
added to inhibit copper catalyzed air oxidation of gasoline
4. Ferrous Corrosion Inhibitors, about 5-20 p p m of oilsoluble surfactants, are added to prevent aqueous-based
corrosion caused either by water condensing from watersaturated gasoline, or from condensation from air onto the
walls of almost-empty gasoline tanks that drop below the
dew point. Many pipelines require addition of corrosion
inhibitor for protection of pipeline and storage tanks. The
NACE 0172 "rust" test is commonly used to establish
addition rate for corrosion protection. A variety of comp o u n d s are effective as corrosion inhibitors, including
dimer carboxylic acid esters, amides, alkanolamides, and
hydroxyesters. Phosphorus based corrosion inhibitors are
no longer used in nonleaded gasoline because phosphorus
is a potent catalyst poison, and is controlled by both ASTM
specification and regulation. ASTM specifications allow,
but do not require, corrosion inhibitor or corrosion
testing.
5. Lubricity additives are occasionally used in gasoline, and
are usually similar in chemistry to corrosion inhibitors,
but at higher treat rates.
6. Copper corrosion inhibitors are occasionally used to mitigate sulfur-based corrosion of copper or other easily corroded base metals if/when used in fuel systems.
7. Anti-wear additives are used to control wear in the upper
cylinder and piston ring area that the gasoline contacts,
and for valve sticking. They are usually very light hydrocarbon oils ("top" oils, "solvent" oils), although synthetics
are now preferred, due to potential problems with combustion chamber deposits. If permitted, phosphorus-based
additives can also be used in engines without exhaust catalyst systems.
8. Cleanliness or Deposit-modifying Additives are used to
mitigate (keep clean) or reduce (clean up) deposits. Some
specific types of deposits are discussed below.
Carburetor DepositsAdditives
were required w h e n
crankcase blow-by positive Crankcase Ventilation (PCV)
and exhaust gas recirculation (EGR) controls were introduced (in the 1950s on some engines). Some fuel
components reacted with these gas streams to form deposits on the throat, throttle plate and idle air bleeds of
carburetors and some throttle body injectors.
Fuel Injector DepositsDeposits can form in the annulus
or sealing surfaces in some pintle needle or poppet valve
injector designs during hot soak (>100C), suspected to
be mainly from the oxidation and polymerization of the
least volatile or unsaturated hydrocarbons. The additives that prevent and unclog these tips are usually polybutene succinimides, polyisobutylamines, or polyether
amines, and are often used in combination with "fluidizer" or "solvent" oil.
Intake Valve DepositsIVDs caused major problems in
the mid-1980s with widespread introduction of electronic fuel injectors a n d three way catalyst systems.
Some vehicles experienced severe driveability problems
even when fully warmed, even though the amount of deposit was considered acceptable by historical carbureted
engine standards. It was proposed those new fuels and
engine designs were producing a more porous deposit

70

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

on the valve tulip (fuel side) face. The close proximity of


the liquid fuel injector caused some liquid fuel to be absorbed in the deposit, causing lean/rich transients resulting in hesitation, misfire, and excess emissions. Deposit Control Additives (DCA) were mandated in 1992 in
California and Federally in 1995 and by CGSB specification in 1994 due to the emissions increase. Intake valves
operate about 300C, and if the valve is kept wet with
thermally stable oil in conjunction with a dispersant/detergent, deposits tend not to form. Solvent oil/dispersant/detergent additives that are effective with IVD also
tend to be effective for fuel injector deposits. Gasoline
factors implicated in these deposits include unsaturates
and alcohols, as well as oil leakage through the valve
guides.
Combustion Chamber DepositsCCD were targeted in
the 1990s, as they are responsible for significant increases in emissions. Severe deposit accumulation resulted in CCD interference (CCDI) where the deposit
contacted the cylinder head at TDC, resulting in noise,
and eventual engine damage. Additives have a limited
ability to remove pre-existing CCD, so DCA additives are
tested for their propensity to avoid formation of CCD relative to the base gasoline. Gasoline factors that contribute to heavier deposits are the presence of alcohols
or olefins. Gasoline manufacturers now routinely use
additives that prevent IVD and also maintain the cleanliness of injectors. These usually include surfactant and
light oil to maintain the wetting of important surfaces.
Intake valve deposits can also have significant adverse
effects on emissions, and deposit control additives are
now standard to reduce emissions and provide clean engine operation.
Trace Constituents

and

Contaminants

1. Free Water"haze" is considered to be a contaminant, associated with corrosion, filter plugging, and freezing problems. The large difference in density usually allows water
to settle out from traditional gasoline, and most additive
packages are checked for any propensity to stabilize a water haze and prevent water dropout. Gasoline components
are often dried at the refineries supplying gasoline into
very cold winter distribution systems, to prevent water to
phase separate due to condensation on cooling down.
Most specifications have a dryness, "clear and bright,"
(such as ASTM D 4176 for distillate fuels) or some similar
"suitable for use" criteria.
2. Sulfur, nitrogen, and oxygen are naturally occurring trace
constituents of crude oil, and are present in fuels at the
p p m level. These CEin be present as ashless, combustible,
additives. Nitrogen is typically not regulated in gasoline
formulation because the source of nitrogen in NOx emissions is from atmospheric N2, and not the fuel. The maxim u m sulfur specification prior to regulation was t3^ically
0.1-0.15 wt%. Current California a n d future U.S. a n d
Canadian regulations will reduce sulfur to a yearly pool average 30 p p m by 2005/6. Regulated changes to the baseline
gasoline used in any predictive model based regulation
equates to a change in the gasoline production required for
equivalence, including sulfur, which has a large impact on
the predicted emissions. This would restrict the use of any

sulfur containing additives in the future. (See Reformulated Gasoline for more detail.)
3. Gasoline may be contaminated by other partially soluble
or miscible liquids, such as kerosene, diesel, and oxygenates. Oxygenated fuel can have a higher solubility of
water-soluble contaminants, as well as allowing water-soluble c o m p o n e n t s to c o n t a m i n a t e any fresh water that
comes into contact with it.
4. "Adulterants" or "extenders" have occasionally been deliberately added to gasoline to increase the volume sold. Materials used have included new or used solvents, used lube
oil, formic/acetic acid, heJogenated solvents, refrigerants,
dry cleaning solvents, silicon oils/caulking/adhesives, and
even PCBs. Deliberate adulteration is usually involved
with a criminal activity for illegal waste disposal or fuel tax
fraud. Some jurisdictions now have "contaminated fuels
regulations" that prohibit these activities.
5. Particulate contaminants, such as dirt and corrosion products, can be readily removed by standard filtration procedures, and increasingly stringent cleanliness requirements
are resulting in a n increasing use of microfiltration at
truck loading and/or point of sale.

GASOLINE COMBUSTION
Spark Ignition

Engines

Spark ignition engines are ideally suited for light duty transportation uses. Their relatively lightweight (compared to
other internal combustion engines), wide REM range, broad
torque band, and high maximum RPM/power provide good
performance with a m i n i m u m number of transmission gears.
Vehicle spark ignition engines are air throttled to control
power, a n d have inherent limitations on peak cylinder temperatures and pressures due to engine "knock," so are thermally less efficient than compression ignition engines. As a
result, diesel engines d o m i n a t e the high torque, low r p m
heavy-duty truck, marine, locomotive, and stationary power
applications. Smaller high-speed diesel engines comprise
only a small percentage of the light duty vehicle market in
North America, but are more prevalent in Europe. This is
driven mainly by their significantly higher fuel efficiency,
which provides a significant market advantage, especially in
regions with high fuel prices.
Electronic fuel injection has replaced carburetors on essentially all Tier 0, Tier 1, and later model automobiles. This
facilitates "closed loop" computer control of air/fuel ratio, to
maintain exhaust composition within a n a r r o w range required for optimal operation of a "3-way" catalyst. The name
"3-way" is a reference to effectiveness for all three regulated
exhaust emissions: u n b u r n e d hydrocarbons (HC), carbon
monoxide (CO) by air oxidation, and oxides of nitrogen (NOx)
by chemical reduction with HC/CO. These systems require
the engine to operate in a narrow air-fuel ratio band on both
rich and lean side of stoichiometric, to maintain both the regulated emissions HC, CO, and NOx and O2 in the optimal
range where they react to extinction.
Hybrid gasoline-electric vehicles couple internal combustion engines with an electric motor for peak power and transient engine operations to obtain ultra-low "steady state"
emissions with no significant loss in performance. A smaller,

CHAPTER
generally m u c h higher voltage battery set stores enough
power for several minutes of high power electric motor operation for cold start or accelerations. This allows a n u m b e r of
very efficient and ultra low emission driving cycles, since the
majority of SI engine emissions are due to transient operations and cold start, before the catalyst heats up. The SI engine can shut down (zero emissions) during cold start or if
required for urban ZEV emissions. It can run at steady state
(for example on the highway) letting the electric motor handle variable power requirements (hills, wind load, comers,
etc.) that would otherwise cause increased emissions from
transient SI operation. It can be r u n at a higher steady state
power, using the electric motor as a generator to recharge the
batteries. Elimination of transients tends to provide highway
fuel efficiency in urban driving cycles, and ultra low emissions (lower t h a n the Super Ultra Low Emission Vehicle
(SULEV) level. The 2004 Tier 2 LDV Bin #2 NMOG standard
of 0.01 g/mile is about a 90-95% reduction from current levels (0.125-0.25 g/mile), over 99.8% reduction from the 1990
levels (4.1 g/mi), and 99.9% reduction from precontrol
(est. 10.6 g/mile).
Other hybrid vehicle types have been proposed, such as
diesel-electric or gasoline-hydraulic, or gasoline-flywheel,
but only gasoline-electric are being commercialized at this
time. It is anticipated that both current RFG and 30 p p m sulfur future RFG will be compatible with hybrids, but that the
lower sulfur will provide slightly lower in-use emissions.
Gasoline Direct Injection (GDI) engines (Spark Ignition Direct Injection, SIDI, etc.) have thermodynamic efficiencies
between SI and diesel engines, and may be commercialized
in the near future. Fuel requirements for GDI have not been
established. Exhaust particulate matter may be more critical
for GDI than for current engine/emissions systems.
Engine

Management

Systems

Engine management systems are now an important part of


the strategy to reduce automotive pollution. A typical m o d e m
engine system would monitor and control: mass airflow (or
MAP/RPM calculated air flow), exhaust oxygen sensor
(lambda sensor), knock (vibration/noise) sensor, EGR, throttle plate angle, manifold air temperature and pressure, crank
angle, and transmission gear. These systems can compensate
for altitude (MAP), ambient air temperature (MAT), fuel oct a n e (knock sensor), humidity, a n d gasoline composition
(oxygen sensor, adaptive map). The engine control module
(ECM, computer) then sets the ignition timing and fuel injector open time (fuel flow), and fuel injection timing with
crank angle that are appropriate for the current engine operating conditions.
Almost all TierO/1 engine control systems incorporate
"adaptive memory maps" or adaptive learning strategies. The
fuel m a p (or schedule) conceptually consists of three blocks
of data organized like three sheets in a spreadsheet, with the
rows and columns representing different RPM and manifold
vacuum, which together define the engine load. The three
sheets contain fuel injector open time for the factory "baseline" settings, the long-term block learn, and the short-term
block learn. Conceptually, the data is a c o m p u t e r binary
n u m b e r such as 0 to 255 for an 8-bit computer. This might
represent, for example, how many milliseconds the fuel injector should be held open, since open time is proportional to

3: MOTOR

GASOLINE

71

fuel volume delivered at constant pressure. The adaptive


maps would start out at mid-range (128), and the total number of milliseconds injector open time would be the sum of
the corresponding cells of the three tables for the engine
speed and load at that instant of time. The ECM would modify them according to the response of the oxygen sensor. If it
was consistently lean for several seconds (too much oxygen
in the exhaust) then the ECM will add one n u m b e r to the fast
learn block, making it 129, and adding one unit of time to the
injector open time, slightly enriching the mixture. This continues until the fast learn block hits its upper limit, when the
ECM t3?pically adds one to the long term block cell, and resets
the fast learn to its mid value. The long term and fast learn
blocks are similar to a "course and fine" control, where the
fast learn steps are smaller, but occur faster. The long term
map, as the n a m e implies, adjusts for long term trends, for
example a slow drop in fuel rail pressure due to a p u m p wearing out over the lifetime of the car, a partially plugged fuel filter, or slowly fouling fuel injectors. The fast learn block takes
care of smaller but faster changes, such as changing altitude,
humidity, or tank to tank gasoline composition differences,
such as switching between high and low aromatic or oxygenated gasoline. This is also the reason that composition
mandates are less effective for newer cars than older cars,
especially oxygenates for cold high altitude CO control, as the
ECM quickly adjusts the air-fuel ratio according to the oxygen sensor readings at the time.
One artifact of this system is that a dead or disconnected
battery can cause memory loss of the adaptive maps, so that
the vehicle drivability can be very poor while the ECM
reloads the m a p with data appropriate for the car, engine,
fuel, and ambient conditions at the time.
All U.S. a n d Cdn LDVs n o w have on-board diagnostics
version II (OBDII) that monitor the critical emission system
components for conditions that cause high tailpipe emissions
or are detrimental to continued operation. The ECM lights
the Malfunction Indicator Light (MIL) light on the dash,
commonly called the "check engine" light. OBDII warns of
malfunctions such as engine misfires, exhaust catalyst failure
(inferred from oxygen sensor time delays), and evaporative
emissions failure such as a leaking gas cap (fuel tank pressure). Chronic misfire, for example causes combustion of unb u m e d air/fuel on the catalyst, with the potential to generate
so much heat that the catalyst activity drops, or the catalyst
substrate melts.
The air-fuel ratio is controlled at part throttle by a closed
loop system using the oxygen sensor in the exhaust and the
knock sensor (if equipped). Typical engine calibrations
enrich the air-fuel ratio for smoother, stall free idle when in
closed loop control, and hold a faster idle after cold start
when in open loop, until the catalyst becomes heated and
"lights off." The a m o u n t of idle enrichment used is often
adjusted according to the air t e m p e r a t u r e at the time of
engine start (similar to the function of a choke on a carburetor acting against a bimetal temperature spring that held the
choke on longer when cold until the engine heated up).
Air - Fuel Ratio and

Stoichiometry

Ideally, hydrocarbons and oxygenates in gasoline combust


smoothly to form water, carbon dioxide, and heat energy,
with no other by-products. Non-ideal combustion affects

72 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


emissions, efficiency, engine durability, and vehicle operation. Severe engine knock is associated with loss of efficiency
a n d engine damage. If there is excess fuel ("rich" air/fuel
ratio), the combustion is not complete, and carbon monoxide
(CO) will be formed, Eilong with u n b u m e d or partially burned
hydrocarbons (HC). As CO can be burned to produce CO2, it
is " u n b u m e d " fuel, so t h e r e is a d r o p in efficiency a n d
increase in emissions. Nitrogen oxides are formed as a result
of conversion of nitrogen (N2) in air to various nitrogen
oxides (NOx). High peak combustion temperatures promote
NOx ("lean" air/fuel ratio, high intake air temperature, low
humidity, high barometric pressure, high load).
The required mass or volume of air to provide sufficient
oxygen to achieve this complete combustion is the "stoichiometric" mass or volume of air. Insufficient air creates "rich"
mixtures, and excess air creates "lean" mixtures. The stoichiometric mass of air for a gasoline is related to the carbon:
hydrogen ratio of the fuel. The procedures for calculating the
stoichiometric air-fuel ratios are fully documented in SAE J
1829 [30]. However, oxygen (20.9476 vol%). Nitrogen
(78.084%), and Argon (0.934%) comprise 99.966 vol% of the
atmosphere. The use of nominal masses (O2 = 16) versus natural abundance masses (O2 = 15.994) and ideal gas assumption (vol% = mole) will result in errors of less than 0.5%, because the errors tend to cancel (nominal MW of nitrogen
lower than natural abundance offset by higher MW of Argon
vs. nitrogen).
As a result, it is c o m m o n to assume that the non-oxygen
component of the air is nitrogen, which can be added to the
equations when the exhaust compositions are required. The
error is generally m u c h smaller than the analytical uncertainty of the actual carbon hydrogen ratio of a real gasoline,
by elemental analysis or cap GC. If needed, exact molecular
weights can be calculated from molecular formula and standard periodic tables weight, or from ASTM GC method peak
tables for individual hydroccirbons.
For n o r m a l h e p t a n e C7H16 with a molecular weight =
100.204:
C7H16 + 1 1 0 2 ^ 7CO2 + 8H2O
The chemical stoichiometric combustion of hydrocarbons
with oxygen can be written as:
CxHy + (x + (y/4))02 -^ XCO2 + (y/2)H20
t h u s 1.000 kg of CyHife requires (1/100.204) * 11 * 2 *
16 = 3.513 kg of O2 and using approximation,
(3.513 kg of O2 + (3.513/32)
* (28*79.0524/20.9476) = 15.113 kg of air.
(Air-fuel ratio = 15.113 vs 15.179)
Gasoline

Energy

Content

The energy content (heat of combustion) is the total amount


of energy obtained by combustion of gasoline under standard
conditions, usually at STP, as if the fuel and air started at STP,
and the combustion products are cooled down to STP. Energy
captured at other conditions will be different. For example,
emitting a hot exhaust from an engine will not capture the
heat energy from cooling the exhaust back to STP.
The heat of combustion is useful to compare fuels under
the same standard conditions. It is measured by combusting

all the fuel inside a b o m b calorimeter and measuring the heat


released as evidenced by a t e m p e r a t u r e increase u n d e r
controlled conditions. If the combustion is not complete,
carbon monoxide (CO) and/or unburned or partially combusted fuel will be formed, resulting in a lower than true
energy content. The reported heat of combustion depends on
what happens to the water produced from the combustion. If
the water remains as a gas, then it cannot release the heat of
vaporization, thus producing the net (or lower) heat of combustion. If the water were condensed back to the original fuel
temperature, then the gross (or higher) heat of combustion is
reported.
For internal combustion engines, the net heat of combustion is more appropriate, as the water is emitted as vapor.
The engine cannot utilize the additional energy available
when the steam is condensed back to water. This is sometimes confused for lower emd higher thermal efficiency of
diesel versus spark ignition engines or the lower/higher net
heating value of diesel fuel versus gasoline. However, the
net/gross or lower/higher heating value oiany fuel is simply a
reference to whether the water of combustion is condensed
and captured by the process, or exhausted as a vapor and lost
to the process.
Standard heats of combustion for hydrocarbon molecules
and for reactions involved in combustion are available from
a number of engineering and chemistry texts and references.
This includes ASTM Dataseries DS4B, Physical Constants of
Hydrocarbon and Non-Hydrocarbon Compounds, and others.
Because all the data are available, the calorific value of fuels can be estimated quite accurately from calculation detailed GC analysis or by correlation with hydrocarbon fuel
properties such as the density, sulfur content, and aniline
point (which indicates the aromatics content).
Oxygenates contain oxygen that has already reacted in the
production process, and cannot provide additional energy at
the point of use in the engine, so they have significantly lower
energy contents. For an engine that can be optimized for oxygenates, more volumetric fuel is required to obtain the same
power. However, the decrease in volumetric fuel efficiency
(mpg) tends to be less than the energy content decrease. See
Table 4 for properties of selected oxygenates.
For a water-cooled SI engine with 2 5 % useful work at the
crankshaft, the losses may consist of 35% coolant, 33% exhaust, and 12% surroundings. SI engines have inherently
lower thermal efficiencies than diesel engines, mainly due to
throttling of the engine at partial power, and higher diesel engine compression ratio. Even at wide open throttle, equivalent displacement CI engines have higher thermal efficiency
because of higher compression ratio, so this advantage extends over the entire operating range.
Octane rating is fundamentally not related to the energy
content, although the actual hydrocarbon a n d oxygenate
components used in the gasoline will determine both the energy release and the antiknock rating. However, it is possible
to make correlation between energy content and octane that
are mostly meaningless and often confusing. For example,
addition of ethanol to a blend can increase the octane, while
decreasing the energy content, while adding pure aromatic
increases both. Add to this the difference between energy per
fuel liquid volume versus energy per fuel weight, and one can
generate octane versus energy graphs that go up, down, or

CHAPTER

3: MOTOR

GASOLINE

73

TABLE 4ASTM research and motor octane number test conditions.


ASTM D 2700 MON
ASTM D 2699 RON
Cooperative Fuels Research
Cooperative Fuels Research
Engine
(CFR)
(CFR)
600 RPM
Engine Speed
900 RPM
Variable with Barometric P.
38C
Intake Air Temperature
88 kPa at 19.4X,
101.6 kPa at 52.2C (Temperature
Tuned with Toluene Standardization
Fuel 22C from lAT)
Intake Air Humidity
3.56-7.12 g HzO/kg dry air
3.56-7.12 g HaO/kg dry air
149C (Temperature Tuned with
Not Specified
Intake Mixture Temperature
Toluene Standardization Fuel
141-163''C)
lOOX
100C
Coolant Temperature
57C
Oil Temperature
57C
Ignition Advance
Variable with Comp. Ratio
13 degrees BTDC (fixed)
14-26 degrees BTDC
Carburetor Venturi
14.3 mm
Variable with Altitude
14.3 mm at 0-500 m
Test Method

sideways, dependent entirely on what materials and units are


chosen.
Gasoline Octane Performance Properties
Combustion

and Knock

in

Engines

The critical fuel property of gasoline for internal combustion


engines is resistance to engine "knock," expressed as the octane n u m b e r of the gasoline. During a normal (no knock)
combustion cycle, a flame front travels smoothly from the
point of ignition at the spark plug outweird toward the cylinder walls. While this is occurring, the "end gas," or u n b u m e d
fuel/air mixture ahead of the flame front is heated and compressed. If the end gases ignite before the flame front arrives,
the resulting sudden pressure wave reverberates across the
combustion chamber, causing an audible engine knock. This
adversely affects output power and dramatically increases
heat transfer to the piston and other combustion chamber
surfaces. While this can cause damage on its own if severe
enough, knock induced preignition can cause rapid catastrophic engine failure. This tends to be a runaway condition.
Once started, it gets progressively worse until eventual engine failure, unless the throttle/load is cut quickly, as failure
can occur in less than a few minutes. High heat transfer during heavy knock can cause deposits or sharp edges (for example combustion chamber deposit or exposed thread of a
spark plug) to overheat. This can act as a "glow plug" type ignition source, causing ignition of the charge before the spark
on the next combustion stroke "preignition." This leads to excessively high combustion chamber temperature and pressure from combustion closer to TDC, and rapidly increasing
knock intensity. Initial stages of knock damage look like pitting on the piston top, as if it had been attacked with an ice
pick or awl. The increased temperature and heat transfer to
the piston top eventually causes melting of the crown land
down to the rings. The final stage is either catastrophic engine failure from thrown connecting rods (metal softening
near the piston wrist pin, causing the piston to separate from
the connecting rod), or engine seizure (expansion of the piston, excessive friction heat, and loss of lubrication). Either

condition is sufficient to ruin one's day (in addition to the


engine).
The octane (and autoignition temperature) of various hydrocarbons is related to their ability to withstand preflame
conditions without decomposing into species t h a t could
auto-ignite before the flame-front arrives. Unburned "end
gases" ahead of the flame front encounter 700C temperatures due to compression and heat transfer, and commence a
series of complex preflame reactions. These reactions occur
at different t h e r m a l stages, with the first stage (around
400C) commencing with the addition of molecular oxygen to
alkyl radicals. The internal transfer of hydrogen atoms within
the new radical forms an unsaturated, oxygen-containing
species following this stage. These new species are susceptible to chain branching involving the HO2 radical during the
intermediate temperature stage (400-600C), mainly through
the production of OH radicals. Above 600C, the most important reaction that produces chain branching is the reaction of
one hydrogen atom radical with molecular oxygen to form O
and OH radicals.
' Common antiknock additives work by interfering at different points in the preflame reactions. The alkyl lead antiknock
compounds interfere with hydrocarbon chain branching in
the intermediate temperature range, where HO2 is the most
important radical species. Alkyl lead oxide, either as solid
particles, or in the gas phase, reacts with HO2 and removes
it from the available radical pool. This reduces the major
chain branching reaction sequence that results in undesirable, easily auto-ignitable hydrocarbons [31,32]. Oxygenates
retard the progress of the low t e m p e r a t u r e or cool-flame
reactions, consuming radical species, particularly OH radicals and producing u n s a t u r a t e d hydrocarbons like isobutene. The iso-butene would, in turn, consume additional
OH radicals and produce unreactive, resonantly-stabilized
radicals, such as allyl- and methyl allyl-, as well as stable
species such as allene, which resist further oxidation [33,34].
Anti-knock

Ratings

of Fuels

The Anti Knock Index (AKI) is the average of the Research


Octane Number (RON, D 2699) and Motor Octane Number

74

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

(MON, D 2700), sometimes expressed as (RON+MON)/2 or


(R+M)/2. The on-line Comparitor Engine method D2885 determines octane numbers that are equivalent to "lab" RON
and MON values, and can be used for blend certification and
release. The RON and MON methods use two primary reference fuels, n-heptane and 224 trimethyl pentcine, assigned octane numbers of 0 and 100, respectively. The knocking intensity of the test fuel is c o m p a r e d to that of reference fuel
blends. The volume percent of iso-octane in the blend that
gives the same knock intensity as the test fuel is taken as being the octane n u m b e r of the test fuel (See History of Octane
Rating).
The same standard engine is used for both tests, but r u n at
different test conditions. The conditions of the MON engine
tend to simulate hot, highway driving, whereas the RON test
is more like heavy acceleration from a traffic light. The difference between the RON a n d MON for a given gasoline
("sensitivity") depends upon the composition of the blend.
The RON and MON of parafins and isoparafins is almost the
same, so high isoparafins (low aromatic, low olefin) blends
tend to have low sensitivities, sometimes below four numbers. Aromatics have intermediate sensitivities and olefins
have the highest sensitivity, so gasolines that have high catalytically cracked content (high olefins) will have high sensitivity (RON-MON), as high as about 14.
ASTM D 4814 recommends a m i n i m u m MON of 82 for Regular grade gasoline heavy-duty engine applications, but uses
AKI for all other recommended uses. Two different 87 AKI
gasolines with extreme compositions could have a RON/MON
of 94/80 or 89/85. On average they would give similar perform a n c e over a range of engine operating conditions, but for
certain applications one may be preferred over the other. For
a n engine operating under more MON like conditions, the
87/85 blend will provide knock free operation at more severe
conditions than the 97/80 blend. In the late 1960s select European automakers experienced catastrophic engine failures
on high speed Autobahn runs, even though the Research Octane of the fuel was within specification. They discovered that
either the MON or the Sensitivity (the numerical difference
between the RON and MON) also had to be specified to ensure
adequate performance under severe high speed Autobahn
condition. Similarly, many marine and utility engines run at
high load and WOT, and are susceptible to knock damage
from too low a MON. In the late 1970s and early 1980s several
automotive and marine OEMs promoted development of an
even more severe octane method, due to concerns that the
high octane contribution from alcohol in the MON test did not
appear under their most severe wide open throttle engine operating conditions. However, this was not pursued, Eind some
OEMs recommended higher octane 89-91 AKI grades or no
oxygenates or methanol for severe marine, snowmobile, outboard, or utility engine applications.

and cylinder casting can be adjusted relative to the


crankshaft using a crank handle to obtain the desired compression ratio. The engines have a special four-bowl carburetor that permits individual bowl air-fuel-ratio adjustment
and provides rapid switching between reference fuels and
samples. A magnetorestrictive detonation sensor in the combustion chamber now measures the rapid changes in combustion chamber pressure caused by knock, and the amplified signal is measured on a "knockmeter" with a 0-100 scale.
Only one company currently manufactures these engines, the
Waukesha Engine Division of Dresser Industries, Waukesha,
Wisconsin, 53186.
Two related methods can be used to obtain the octane
n u m b e r of the test fuel, the bracketing procedure or the
"compression ratio" procedure. For the bracketing method,
the engine compression ratio is adjusted to produce a m i d
range knock intensity of about 50 on the knockmeter, with
the air-fuel ratio adjusted on the carburetor bowl to obtain
m a x i m u m knock. At least two blends of primary reference fuels are made, one that is one octane n u m b e r above the expected rating, and another that is one octane number below
the expected rating. The PRF blends are placed in different
bowls with their air-fuel ratios adjusted for maximum knock
during rating. The higher-octane reference fuel should produce a reading of around 30-40, and the lower reference fuel
should produce a reading of 60-70. The actual fuel rating is
interpolated from the knockmeter readings of the sample and
the two PRFs.
For the CR procedure, a calibration curve is prepared of
knock intensity versus compression ratio for a PRF blend
that has a n octane n u m b e r within prescribed limits from the
sample. The octane n u m b e r of the sample is the octane number of the single PRF used to calibrate the engine, corrected
for barometric pressure and difference in knock intensity using the calibration curve. The D2885 "comparator" method
uses the CR procedure, but using a Standard Reference Fuel
(SRF) instead of a PRF (see D 2885).
Motor Octane Rating ASTM D 2700
The conditions of the Motor method represent severe, sustained high engine speed, high load (but not wide-open throttle) driving. For most hydrocarbon-fuels, including those
with either alkyl lead or oxygenates, the Motor Octane Number (MON) will be lower than the Research Octeine Number
(RON).
Research

For Anti-Knock

Rating

Fuels

Automotive octane ratings are determined in a standardized


single-cylinder engine with a variable compression ratio (CR
4:1 to 18:1), operated under standard conditions (Table 4)
Cooperative Fuels Research (CFR) engine. The cylinder bore
is 82.5 m m ; the stroke is 114.3 m m , giving a displacement of
612 cm^. The piston has four compression rings, and one oilcontrol ring. The intake valve is shrouded. The single head

ASTM D 2699

The research m e t h o d settings represent typical high load


(throttle opening) and low to medium engine speeds resulting in low inlet mixture temperatures and moderate loads on
the engine. See Table 5 for test conditions
On-Line

Procedure

Octane Rating

Analyzer

Octane Rating ASTM

D 2885

On-line octane rating analyzers used in refineries are described in ASTM D 2885, taking a continuously flowing slip
stream of gasoline from current production, and measuring
the RON and MON continuously. The same engines and conditions are used, so consequently results Eire equivalent to the
laboratory MON or RON procedure.
Instead of "bracketing" the test fuel with primary reference
fuels, D 2885 uses "Standard Reference Fuels," commonly

CHAPTER
called "protos" or "gold protos" that are production gasoline
that have been rated by about 20 different laboratories, and
assigned the average value determined by the group. The SRF
is required to be close in octane to the test fuels, so that the
difference in octane n u m b e r can be derived from the difference in knock intensity between the SRF and the test fuel.
Standard Reference Fuels are developed through cooperative exchange programs, usuedly administered in association
with an accredited Standcirds Writing Organization. Examples in North America are National Exchange Group under
the auspices of ASTM, the Canadian Cooperative Exchange
under the auspices of the CGSB, and the Rocky Mountain Exchange, representing refiners in high altitude areas (now associated with the NEG).
Octane Distribution

Throughout

Fuel Boiling

Range

Severe knock can be experienced in some engines if octane


level is not distributed throughout the boiling range of a fuel,
for example a low octane front end with a high octEine back
end. This "octane distribution" is most critical during changes
in mixture flow in manifolds, such as sudden full throttle acceleration at low speed and high load. Under these conditions,
manifold pressure drops suddenly at low airflow. The fuel can
segregate by boiling range in the manifold, with the very
volatile fraction reaching the combustion chamber first and,
if that fraction is deficient in octane, then knock will occur until the less volatile, higher-octane liquid fractions eirrive.
Historically, small displacement engines tend to be the
most affected, as they experience the largest changes in manifold conditions during n o r m a l u r b a n driving. Large displacement engines equipped with "hot spot" manifolds, intake mEinifold runners, etc., tended to be the least affected.
Most urbcin driving was at relatively low throttle range and at
high manifold vacuum that tended to moderate these effects.
The delta RON ratings Eire not currently used in the U.S.
M o d e m engines with short inlet meinifolds and Port Fuel
Injection are usually less sensitive to fuel octane distribution.
However, the addition of nonhydrocarbon components into
reformulated gasoline of different volatility may affect sensitive engines.
Leaded fuel octane distribution was good, as the tetramethyl alkyl lead and tetraethyl alkyl lead octane volatility profiles were well characterized, and TML-TEL ratio could be
adjusted to provide distribution of octane throughout the
boiling range. Nonleaded gasoline must be properly blended
without using TML to obtain acceptable results.
The "Delta RON" test was developed to measure the difference in octane between the front ind back "half" of the gasoline. The fuel is distilled to a specified temperature, which is
usually 100C. Both the parent fuel and the distillate fraction
are t h e n rated using the Research Octane m e t h o d . The
difference between these is the delta RON (100C), usually
just called the delta RON.
During the 1990s, there have been some concerns in Europe about the high sensitivity of some commercially available nonleaded fuels.
Octane Number

Requirement

(ONR) of

Vehicles

The actual octane requirement of a vehicle is called the Octane N u m b e r Requirement (ONR). It is determined by monitoring for the onset of knock while accelerating the vehicle

3: MOTOR

GASOLINE

75

using a series of progressively lower octane fuels. Three sets


of fuels are used: the primary reference fuels (PRF), and two
full boiling range fuels with high and low sensitivity (RONMON). In Europe, delta RON (100C) fuels are also used. The
lowest octane fuel that provides knock free acceleration is the
ONR of the vehicle under the conditions of the test. Results
are then used to predict the performance of typical commercial gasolines.
The original "Uniontown" road octane rating procedure
used in development of the original MON test (see History
of Octane Ratings) has been replaced by a procedure developed by the Coordinating Research Council (CRC). In the
CRC E-15 procedure, the vehicle is tested under a proscribed
set of environmental conditions and loads. The procedure
"trained raters" to detect audible knock during a series of
part throttle accelerations using decreasing octane fuels until trace knock is detected. Three different series of gasolines
were used to establish the RON versus MON response of each
vehicle, a zero sensitivity primary reference fuel, and two full
boiling range fuels with low and high Severity (difference
between RON a n d MON). These three fuels represent the
extremes of RON and MON blending. By testing a large
n u m b e r of cars, it is possible to statistically predict what percentage of the on-road car population would be "satisfied"
(no knock) with different RON/MON fuel blends. It is comm o n to apply a correction factor or offset between technical
raters and typical drivers, who have a m u c h lower threshold
for detecting knock and perceiving it to be a problem.
Historically, operating conditions that require maximum
octcine are not consistent, but most often occur during fuUthrotde acceleration from low starting speeds using the highest gear available. These can be difficult to reproduce on a
chassis dynamometer, so a distinction was always made between an on-road and a dyno result. M o d e m dynomometers
with better simulation of inertial, road, and wind loads and
engine cooling, produce equivalent results. A benefit is that
the conditions can be more tightly controlled, so results do
not require corrections for temperature, pressure, and humidity differences from the standard conditions at the time
of the test.
Historical engine management systems used a system of
centrifugal "bob weights" in the distributor for speirk advance
and a "vacuum break" to delay spark advance/retard at low
speed, high load. With only two parameters to change in
addition to the basic spark timing of the engine, one or two
areas of high knock anywhere o n the speed/load range
resulted in conservative timing at other conditions. If the critical area was under MON like conditions, then the car would
be found to respond most to MON. M o d e m engine management systems can adjust the octane requirement by modifying engine conditions that will vary the octane n u m b e r
requirment, so adaptive learning systems are preconditioned
prior to testing.
The m a x i m u m ONR is of most interest, as that usually
defines the r e c o m m e n d e d fuel. However, it is recognized
that trained raters are more sensitive to engine knock than
typical drivers, and that the general populace will have a
higher threshold for both detecting knock and perceiving it
as being severe. As a result, it is common to apply a correction factor or offset from technical ratings to predict consumer satisfaction.

76

MANUAL

ONREngine

3 7 ; FUELS AND LUBRICANTS


Design

HANDBOOK

Parameters

The design of the engine and vehicle significantly affect the


fuel octane r e q u i r e m e n t for b o t h RON a n d MON. In the
1930s and 40s, most vehicles would have been sensitive to the
Research Octane of the fuel, almost regardless of the Motor
Octane. In North America, this tended to change after WWI
with widespread adoption of automatic transmissions, which
made engines operate under more MON like conditions more
of the time. For many years, the CRC did octane surveys of
each new model year of cars, and the results were widely used
to estimate the on-road octane requirement, and the best
RON/MON combinations to satisfy the most cars (on average) with the lowest octane blends. Different weightings were
p u t on RON a n d MON, for example (R+3M)/4 to better
match the measured octane n u m b e r to the average octane requirement of the on-road car population.
The advent of electronic adaptive engine controls and use
of knock sensors tends to have a more consistent spark and
fuel m a p over the entire engine speed and load range, including transients like transmission shift points. This tends
to m a k e adaptive feedback control cars equally likely to
knock under any condition and equally responsive to RON
and MON. This tends to make the AKI a good predictor of
field performance in recent model cars.
Retarding spark timing for the purpose of knock reduction
causes loss of power a n d efficiency that can be incorporated
into knock rating procedures, for example by measuring increase in acceleration times with progressively lower octane
rating fuels.
ONRManifold

Air Temperature

and

Pressure

Increasing the air-fuel charge temperature and pressure increases the peak cylinder temperature and pressure, and thus
the tendency to knock. M o d e m engines generally pre-heat intake air to a controlled temperature above ambient. Throttling the air to a lower manifold pressure results in a much
lower peak cylinder pressure/temperature, and a lesser tendency to knock. Fuel evaporation and PVT expansion across
the throttle plate cool the intake mixture, making it slightly
sensitive to the engine temperature, which adds heat in the
manifold and during the compression stroke. Increasing the
coolant temperature in a CFR engine by about 10C increases
the octane n u m b e r r e q u i r e m e n t by about 2 AKI, so the
coolant temperature must be tightly controlled for octane
rating. Increasing the intake air (RON) or intake mixture
(MON) temperature increases the octane requirement (increases the severity of the test). This is used to advantage in
the RON and MON tests to "temperature tune" engines in different laboratories using Toluene Standardization Fuels
(TSF). This ensures that the test severity of different engines
is a relative constant over a broad range of fuel compositions,
since PRF are low aromatic, and TSF are high aromatic.
ONRCompression

Ratio

An increase in Compression Ratio will require an increase in


fuel octane for the same engine design. Increasing compression ratio increases the theoretical thermodynamic efficiency
of an engine according to the standard equation
Efficiency = 1 ((l/compression ratio)^(gamma1)),
where G a m m a = ratio of specific heats at constant pressure

and constant volume of the working fluid (for most purposes air is the working fluid, and is treated as an ideal gas).
Thermal efficiency reaches a maximum at a compression
ratio of about 17:1 for gasoline fuels in a SI engine, and
fuel-injected engines with carefully designed mixture charge
concentrations and intake/combustion chamber design has
reached 12:1 on retail fuels with 98-100 RON. Continued
advances in engine technology have allowed gradual increase in compression ratio without increasing ONR from
87 AKI. This has been used to either increase fuel efficiency
in economy cars or to have higher power engines at the
same fuel efficiency in larger cars. These engines have substantially higher compression ratio t h a n the "historical"
curve established with the CRC engine (see History of Octane Rating].
ONRThe

Air-Fuel

Ratio

Stoichiometric combustion (air-fuel ratio = 14.7:1 for a typical non-oxygenated gasoline) is neither maximum power,
which occurs around air-fuel 12-13:1 (Rich), nor maximum
thermal efficiency, w h i c h occurs a r o u n d air-fuel 16-18:1
(Lean). Air-fuel ratio can also be used as a knock control
strategy, although at a severe emissions debit for a three-way
catalyst emission system. Enrichment is also used during full
throttle operation to reduce knocking while providing better
power and driveability. Recent changes in U.S. emissions
testing cycles will promote more control of wide-open throttle mixture settings. Enrichment has also been used as a n
"emergency" strategy in turbocharged cars, as an alternative
to suddenly dropping turbo boost (power) to prevent runaway knock during an emergency or passing maneuver. On
average, there is an increase or decrease in ONR of about 2
AKI for each unit's increase (leaning) or decrease (enriching)
of the air-fuel ratio, respectively. This response varies considerably between engines and at different RPMs. In the CFR
octane n u m b e r tests, the carburetor float bowl level is adjusted to change the air-fuel ratio. The air-fuel ratio that produces the maximum knock intensity for that fuel is then used
to determine the octane n u m b e r of that fuel.
ONREngine

Spark

Timing

Advancing the spark timing dramatically increases the


tendency to knock. The tendency to knock increases as spark
advance is increased. For an engine with recommended 6
BTDC (Before Top Dead Center) timing and 93 RON fuel,
retarding the spark 4 lowers the octane requirement to 91,
whereas advancing it 8 requires 96 octane fuel. This
response varies considerably between engines and is most
pronounced at high RPM for any given engine (mostly an
artifact of delay time being measured by crank angle rotation
rate).
In older engines, the basic timing was set by rotating the
distributor until the #1 cylinder spark was set at a prescribed
crank angle. Spark was advanced for RPM with a centrifugal
"bob weight" on the distributor shaft, and retarded for load
with a manifold vacuum diaphragm actuator acting against
the spring loaded distributor plate. The timing of the spark is
advanced sufficiently to ensure that the fuel-air mixture
b u m s in such a way that maximum pressure of the burning
charge is about 15-20 after TDC. Heavy knock will tend to
occur if peak temperature/pressure occurs earlier than this

CHAPTER 3: MOTOR GASOLINE


point early in the power stroke, involving a larger quantity of
end gases igniting at high pressures (gas densities). Light
knock usually occurs later in the power stroke, involving less
end gas and a lower cylinder temperature and pressure (gas
densities). A good analogy is that larger waves in higher density mercury inherently carry more energy and destructive
power than smaller waves in lower density water.
Knock sensors equipped engine management systems retard ignition timing if knock is detected. If very low octane fuels are used, several octane numbers below the vehicle's ONR
at the time, the ECM will have to retard spark timing so much
to eliminate the knock that both performance and fuel economy will significantly decrease. Maximum efficiency occurs
when the engine is at incipient knock for the fuel being used
at the time, so trace or incipient knock is sometimes referred
to as "the sound of economy."
Unlike fuel maps, knock sensor data is generally not used
to advance timing, only to retard it as an engine protection
strategy. The ECM will retard timing ("knock back spark")
quickly until knock sensor indicates that it has stopped. It
will then slowly advance the timing toward baseline, until
trace knock re-appears, and store that value in the memory
map. Strategies to actively advance timing are more risky,
since a failed knock sensor could cause the ECM to advance
timing into sustained heavy knock and engine damage. Some
systems are capable of "testing" the knock sensor by advancing timing on individual cylinder firings to create a single or
small number of knocking cycles, to see if the knock sensor is
still functioning. A "dead" knock sensor can be particularly
damaging on a turbocharged car, or a "premium required"
car, if run on too low an octane fuel.
ONREffect of Engine Deposits
Typical new engines using nonleaded gasoline have an ONR
of about 4-6 AKI lower than the same engine at 25 000 km,
although some may experience 6-9 ONI, and some engines
can experience ONI of over 12 octane, depending upon driving cycle, engine, and fuel/lube. This Octane Requirement Increase (ORI) is attributed to the formation of a mixture of organic and inorganic deposits resulting from both the fuel and
the lubricant. They build up and tend to reach an equilibrium
quantity in about 10-15 000 miles. However, differences in
driving cycles can result in different equilibrium levels, with
sustained hot engine operation tending toward the low end,
and cooler "stop and go" driving cycles tending toward the
high end.
Combustion chamber deposits produce the ORI by several
mechanisms:
Reducing the combustion chamber volume, effectively
increasing the compression ratio
Reducing wall thermal conductivity, increasing the
combustion chamber temperatures
Catalyzing undesirable pre-flame reactions that produce
end gases with low auto-ignition temperatures.

GASOLINE SPECIFICATIONS.
ASTM or CGSB gasoline specifications are not legal requirements unless they are required (referenced) in a regulation by
a government authority having jurisdiction.

77

In the United States and Canada, a mixture of Federal,


State, and Provincial Government legislation and attendant
regulations proscribes gasoline requirements. Some states
and associations of states may also specify regional gasoline
properties to achieve regional environmental objectives
that are within their jurisdiction. These regulations may
reference accredited ASTM consensus standards, with or
without modifications. In some cases, ASTM sampling
and test methods are reproduced in regulations. This can
cause update problems, such as use of the wrong procedures for regulatory purposes, when either party changes
procedures.
The U.S. gasoline specifications and test methods are listed
in several readily available publications, including the
Federal Register, and the current Annual Book of ASTM
Standards.
ASTM D 4814, Specification for Automotive
Spark-Ignition Engine Fuel
The scope of the standard states that "This specification
guides in establishing requirements of automotive fuels
for ground vehicles equipped with spark-ignition engines."
It was first published as ASTM D 439 in 1937, and significantly revised to include oxygenates including "gasohol"
(10% ethanol) and other alcohol blends that had EPA waivers
(see 1970 EPA Clean Air Act). Several test methods were
developed or modified for use with oxygenated fuels, such
as Dry Reid Vapor Pressure, Tv/1, and new methods added
such as water tolerance and phase separation temperature
requirements.
It is a complex specification with many details that are beyond the scope of this chapter. However, in all cases, the requirements and the test method for each requirement fall
into one of two categories, those that measure the properties
or quality at the time of sampling, and those that predict
some future condition or performance. For example, a "Clear
and Bright" procedure evaluates whether the fuel is "suitable
for use" at the time of custody transfer or sale to end consumer. An oxidation stability result, on the other hand, is a
"predictive" test, intended to predict if the fuel will be acceptable in the future, after some time in storage prior to sale
or use. Many tests are "rig" tests that rate relative performance of the gasoline to provide a reasonable estimate of
how the gasoline will perform in actual use. For example, D
130 (Test Method for Detection of Copper Corrosion from
Petroleum Products by the Copper Strip Tarnish Test) measures the relative degree of corrosivity under a proscribed set
of conditions. It uses a static coupon of a specified copper alloy, prepared in a specified way, exposed to the product for a
specified period of time at a specified temperature. In the
vast majority of cases, a "pass" on the D 130 test means that
the fuel will not cause significant corrosion to any copper
alloy parts exposed in the fuel system, and will be widely
acceptable to a broad range of vehicle fuel systems. However,
if the in-use conditions for any fuel system component
are more severe than the D 130 test conditions, then damage
could occur even with a fuel that passes D 130. This could
happen if the component is heated hotter than test conditions, or the part is in a "rubbing or rolling" tjfpe of service that continually removes the protective oxide/sulfide

78

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

layer, or the part metallurgy is more easily corroded than the


D 130 copper strip.
ASTM has two publications that are highly recommended
to those not familiar with details or intent of the test methods
or specification. ASTM Manual on Significance of Tests for
Petroleum Products [35] and Guide to ASTM Test Methods for
the Analysis of Petroleum Products and Lubricants [36] are
both instructive on reasons for the test and explanation of
what and how the test is intended to measure. IdecJly, performance or "rig" tests Eire representative of actual in-use vehicle requirements. Hopefully these two goals always coincide, but it is always possible to "pass the test and fail the
field" as any experienced fuels chemist will agree. Passing all
the tests does not guarantee that the fuel is "suitable for use"
in all cases, especially in cases such as unusual contamination, or new car technology for which the existing standard
tests don't consider, or when in-use conditions are more severe than in the standard test method. Specifications Emd test
methods are in a continual state of being updated as technology continually advances.
Some gasoline requirements pertain to all volatility classes
(see Table 5).
Anti-knock

Index

(AKI)

Anti-knock Index (AKI), also k n o w n as (RON+MON)/2,


"Pump Octane," ((R+M)/2), or "Road Octane" is the average
of the Research Octane Number and Motor Octane Number.
Dispensing p u m p "posting" requirements are based on AKI.
The only accurate m e t h o d of m e a s u r i n g knock is to use
standard knock rating engines in ASTM D 2699/D 2700 or D
2885, although several "field test m e t h o d s " are used for
screening purposes. The ASTM gasoline standard does not
mandate octane levels, but lists levels appropriate for different applications. While limits are not specified, changes in
engine requirements according to season and location are
discussed. Fuels with an AKI of 87, 89, 91 (nonleaded), and
88 (leaded) are listed as typical for the U.S. at sea level.
However, higher altitudes may specify lower octane numbers. Altitude derating of octane is m u c h less for nonleaded
versus leaded gasoline because Tier 0/1 cars use manifold
absolute pressure/temperature (MAP/MAT) sensors to calculate air density, or absolute mass air flow sensors to control
air fuel ratio.

TABLE 5Detailed requirements for all volatility classes.


Lead Content, max, g/L
(g/U.S. gal)
Non leaded
Leaded
Copper Strip Corrosion,
max
Solvent-Washed Gum
Content, mg/100 mL,
max
Sulfur, max, mass%
Non leaded
Leaded
Oxidation Stability,
minimum, minutes
Water Tolerance

0.013 (0.05)
1.1 (4.2)
No. 1

0.10
0.15
240
Water tolerance limits in terms of
maximum temperature for
phase separation are given in
Table 13 of the specification.

Volatility
Volatility is measured by the ASTM D 86 distillation, the
Vapor/Liquid ratio Temperature (Tv/1 = 20), and one of
several vapor pressure test methods, most commonly ASTM
D 5191, which is used for regulatory reporting. All of the
volatility measurements are somewhat related thermodynamically, being various combinations of vapor pressure
and cumulative boiling volumes. However the relationships
are not exact, because the standard tests are not ideal
thermodynamic processes. Some examples of various ASTM
D 86 distillation effects are given in Figs. 1-3. An illustration of approximate vapor pressure and volatility relationships is given in Fig. 4, comparing typical fuels with pure
hydrocarbons.
Distillation, Evaporation Temperatures, and Driveability IndexThe distillation volatility of a finished gasoline can be
expressed in several ways. One set uses the temperature at
fixed distillation points, such as the TIO, T50, and T90, related indices such as Volume Average Boiling Point (VABP)
or ASTM Driveability Index (DI)
Driveability Index = DI = 1.5 * TIO + 3 * T50 + 1.0 * T90
Maximum DI limits are specified in ASTM D 4814 for each
Volatility Class, ranging from 569-597C, or 1200-1250F.
Note that the conversion of DI from Centigrade to Farenheit
units is DI(F) = DI(C) * 9/5 + 176, where 176 is the sum of
the coefficients (1.5 + 3.0 -f- 1.0) * 32. Many companies use
volume percent evaporated (%Evap, or D-l-L) at fixed temperatures, which have an advantage over Txx controls, because they blend more linecirly, and are more easily adapted
to linear programming (LP) optimization controls. Both are
in c o m m o n use at the operational level, because ASTM requires Txx type controls while the complex model requires
E200 a n d E300. The complex model spreadsheet has a conversion from Txx to Exxx built into the model.
Vapor Pressure and Tvfl^ASTM vapor pressure specifications
are based on VP measured under standard conditions of 4:1
vapor liquid ratio at 100F and Tv/1 20 to control gasoline
front-end volatility. The Tv/120 is the temperature at which 20
volumes of vapor cire formed from one volume of the original
liquid, measured by ASTM D 2533 or D 5188. The intent is to
produce an isobaric flash prediction, something that is well
within the capabilities of m o d e m thermodynamic equation
of state (EOS) calculations.
A Tv/120 corresponds to about 10% of the gasoline vaporized under conditions of the test (a fully vaporized gasoline
would have a V/L of about 220-280 depending upon the
blend). As a result, there is a good correlation between measured Tv/1 and linear sums of the VP a n d TIO, T20 u p to
T50, so it is much more common to calculate Tv/1 than to
measure it. Some companies use an index based on VP emd
%Evap at lower temperatures, historically 70C (158F).
These are often called Vapor Lock Indices or "Hot Fuel
Handling," a reference to the origined purpose of these specifications. A v/1 of 20 was originally chosen because, on average, a carbureted engine diaphragm type fuel p u m p could
handle about 20 volumes of vapor along with the 0.9 volume
of the remaining liquid (Tv/1 = 20). Any higher temperature
(more vapor) would cause the p u m p to become "vaporlocked," and not be able to satisfy engine fuel dememd, cans-

CHAPTER 3: MOTOR GASOLINE


-Base

Max Summer Dl

Msx Dl High Mid-fill

79

-High Volatility

250

JMax Final Boiling Point (FBP) = 225 C

200
Max Summer T90 = 190 J

150u
p

I
100
Typical Summer RUL
Volatility Dl = 1150 .

IMin / Max Summer


T50 Range = 77-121

50

Higliest Summer
Volatility T50 = 70
Max Summer T10 = 70

10

20

30

40

li
50

60

70

80

90

100

Volume % Evaporated
FIG. 1ASTM D 86 distillation and driveability index.

ing stalls or rough engine operation. The temperature when


this occurs is called the Vapor Lock Temperature. The
ASTM specification has vapor-lock protection temperatures
based on a regional database of ambient temperature and
elevation (barometric pressure).
Fuel injected vehicles generally have submerged in-tank
fuel pumps, and operate at much higher liquid fuel line
(fuel rail) pressures, so eire much less prone to vapor lock
problems. However, certain forms of vapor lock can occur.

but are usually due to other mechanical factors and not


high ambient temperature. For example, a worn out fuel
pump may not put out enough pressure to prevent vapor
formation in the fuel rail during a hot shutdown. The vehicle could experience a hard hot starting or no-start condition, because much lower mass vapor flow through the injector would cause an over lean air-fuel ratio. Similarly, a
partially blocked primary filter ("pick-up sock") can cause
vapor lock on the suction side of the submerged pump at

80 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


-Ethanol

MTBE

Base

250

200

/
/
150

100

50
Significant decrease in T50 caused by
azeotrope effect of ethanol

10

20

30

40
50
60
Volume % Evaporated

70

80

90

100

FIG. 2ASTM D 86 distlllation-ethanol and MTBE.

high temperatures. Routing fuel lines in areas that have


high shutdown heat soak temperatures can also cause a hot
restart problem.
Gasoline and Gasohol Blending
The distillation volatility is controlled within specification
limits by varying the relative ratios of blend components to
make a finished gasoline. These range from butane (normal
boiling point 0C) to the highest boiling components with Final Boiling Points slightly higher than the 225C FBP specifi-

cation for the finished gasoline. The vapor pressure is controlled below specification maximums by limiting the
amount of butane in winter and northern summer grades,
and butane plus some pentanes in the lowest vapor pressure
summer grades (below about 8 psi VP.)
Ethanol at 10 vol% (gasohol) increases the measured VP at
100F by about 0.8 in a high aromatic gasoline to about 1.2
psi in a low aromatic gasoline. Ethanol is more soluble in
aromatics than saturates so the vapor pressure increase is
slightly influenced by aromatic content of the base fuel.

CHAPTER 3: MOTOR GASOLINE

81

- A S T M D 8 6 P R EOS
250 ^

TypiCcil inoroase in ASTM DBG final


di&hllalioM tuiiippidluic due to higher
tlian one theoretical plate and icflux
due to he.it lush at higci toinpci.ituics

JThcmiodynaniic Bubble Point


200 -

I Sciniplcs of this gasoline will not flash oi boil .it


toinpcratuicR bolow the bubble point, even if it is
at .1 tcnipciaturp iiighcr than thn ASTM D86 Initial
' Boiling Point

O 150
^ rhcoieticnl Single pl.itc distilkition cuivc

ffl 100

'Typical liiiti.il volume loss .iiid "hool" on start of ASTM D8b


distilljtiuii b.iuscd by cumbin.ition of.

50

- gipatiii than one theoictii..)! pl.itp distillation finin licitiiig of


glassw.irc .iiid reilux duiing starl of thn distilLition
- nun condensing ,iir HC v.ipor mixturi> at st.iit of test

AS1MD86lnili.ii
Boiling Point iJBP)

20

10

40

30

50

70

60

90

80

100

Volume % Evaporated

FIG. 3ASTM D 86 versus Peng-Robinson Equation of State.

100000
ASTM V.ipur Pri<s-.iiii- ri-iii^ji'i.iliiip

10000

1000

..-
Ntiiiii.il riu'lini) Piiiiil rii-.<.-iir>-

100

10

0.

CJ
A|iuiuxiiii.1li R.m.ii-! V.i|iiii l>ii-.-iiii'

'C5
CM'

il -W" i" Fl.i .'1 ''HI.; T.>ii,|.i 1...SII11

C6

Cq

CIO
- 0.1

-0.01

-100

-80

100

-50

200

Temperature ( C )
FIG. 4Vapor pressure relationships for fuels. Log P versus 1/T.

300

82

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

Several jurisdictions allow a nominal 1 psi waiver to accommodate "splash bending" of ethanol with a base gasoline.
EPA has issued a waiver that does not require conventional
gasoline with 9-10% ethanol to meet the required specifications between 1 May and 15 September (see Nonleaded
Gasoline).
ASTM

Volatility

Class

Specifications

ASTM D 4814 gasoline specification defines six volatility


classes of increasing vapor pressure, Tv/1 and Driveability
Index (DI). The TIO, T50 min/max and T90, FBP max limits
define the allowable range of individual parameters within
each volatility class. VP and DI are generally the key blending p a r a m e t e r s for b o t h regulatory and specification
compliance.
Insufficient volatility may result in difficult starting in cold
weather, poor cold start and warm-up driveability, engine
deposits and crankcase oil dilution, and increased tailpipe
emissions. Excessive front-end volatility can produce poor
fuel economy, poor hot driveability in fuel injected engines,
vapor lock a n d c a r b u r e t o r icing in older engines, and
increased r u n n i n g loss and evaporative emissions. The
higher boiling fractions of the gasoline have significant
effects on the emission levels of undesirable hydrocarbons
and aldehydes. A reduction of 40C in the final boiling point
will reduce the levels of benzene, butadiene, formaldehyde,
and acetaldehyde by 25%, and will reduce HC emissions by
20% [37]. Similar emission effects were found in the auto-oil
program, and as a result, there are three volatility model parameters in the complex model,VP, E200, E300 (Vapor pressure, percent evaporated at 200F and 300F, respectively)
that influence predicted evaporative, tailpipe, and toxics
emissions. The E200 and E300 model parameters have the
least influence of all the model inputs on the predictive model
emissions, and are often set at "worst case" values for the
purpose of blend planning (although actual values must be
used for reporting).
Maximum

Alkyl lead

Content

The alkyl lead limits remain to cover fuels for off-road vehicles. Leaded fuels can contain u p to 0.1 g Pb/usg (equivalent
0.029 g Pb/L low alkyl lead in Canada), but none are made
commercially. Nonleaded gasoline can contain u p to 0.013 g
Pb per liter in the U.S. (contamination limit with no deliberate addition) and 0.005 g Pb/L in Canada to protect catalytic
converters. (See sections on alkyl lead phasedown and nonleaded gasoline for more detail).
Copper

Corrosion

Copper, silver, brass, and other "soft metal" alloys are susceptible to corrosion from reactive sulfur molecules. The ASTM
D 130 "copper corrosion" test is intended to ensure that fuels
are not corrosive to these trace components under normal use
conditions. More severe conditions could require even lower
levels of corrosive sulfur. The total sulfur content is not correlated with D 130 test performance, and in fact, some additives that are effective at mitigating copper corrosion themselves contain sulfur (see additives). Only the most reactive
types of sulfur molecules cause or contribute to D 130 copper
corrosion. The copper strip test responds to reactive sulfur,
whereas the sulfur content reports the total sulfur content.

The D 130 test is a "static" coupon test, and may overpredict durability for more easily corroded alloys such as silver,
or for rubbing, rolling, or heated soft alloy fuel system components. Field problems have been experienced with some
copper fuel p u m p commutators, silver alloy fuel sender unit
resister arrays and silver plated crankcase bearing cages with
gasoline that passes D 130. In general, silver alloys should not
be used in gasoline fuel systems without provisions for protection from sulfiding. Copper alloy components that are exposed to heat or rolling/rubbing action that removes the protective oxide layer should be tested for long-term durability
with a gasoline containing traces of corrosive sulfur (H2S,
elemental sulfur).
Maximum

Sulfur

Content

Current ASTM and CGSB standards allow 0.10% mass maxim u m sulfur content for nonleaded gasoline, but lower levels
are required by various sulfur regulations (California or
Canadian Sulfur in Gasoline regulation). Sulfur is oxidized to
SO2 over the catalyst, so essentially competes for reactive
sites that could otherwise be effective for HC, CO or NOx conversion. This appears as a temporary decrease in catalyst activity at high fuel sulfur levels, and leads to the requirement
for ultra low sulfur fuels to attain ultra low emissions.
Sulfur can be indirectly limited by RFC composition
controls based on emission models (U.S. EPA complex
model, BC TOx/NOx a n d Canadian CEPA Benzene in
Gasoline regulation Benzene Emission N u m b e r (BEN) requirements. Both Canada and the United States have regulations in place that will reduce sulfur to 30 p p m YPA phased
in between 2002 and 2010, coincident with introduction of
low emission Tier 2 vehicles (See "Reformulated Gasoline"
for more details).
Maximum

Phosphorus

Content

The EPA limits phosphorus in all gasoline to 1.3 mg/L P, because phosphorus is a potent catalyst poison, and this limit
is reflected in the ASTM specification (see alkyl lead
phasedown section for additional details). Typical levels of
phosphorus in nonleaded gasoline are undetectable by the
standard test methods.
Oxidation

Stability

Like all organic material, hydrocarbons are susceptible to air


oxidation over long periods of time. The peroxides formed
from hydrocarbon oxidation are auto-catalytic, leading
to "runaway" reaction if not controlled. Reaction rates are
generally higher with u n s a t u r a t e d hydrocarbons, and are
catalyzed by parts per billion levels of soluble metals such as
copper. Motor gasoline may be stored up to six months, or
m o r e . They must not form soluble g u m that collects
at the point of vaporization, or precipitated insoluble g u m
("varnish"), or form soluble peroxides that will attack
rubber/elastomers in the fuel system.
Antioxidants are added to most gasolines to slow down the
rate of oxidation and prevent the oxidation from becoming
autocatalytic, by forming a stable radical oxidation product
that does not react further. The antioxidant is sacrificial, and
is gradually consumed during this process. Once depleted,
the reactions will become autocatalytic, and the gasoline will
eventually "break" and form peroxide gums as fast as oxygen

CHAPTER
can diffuse into the liquid (mass transfer controlled oxidation). Some gasolines also require metal deactivators to mitigate catalysis from 10-100 p p b traces of copper (most commonly from trace level corrosion of copper and brass alloys
in contact with the gasoline during manufacture, distribution, or use).
Oxidation stability tests generally expose a heated sample
of gasoline to oxygen for a prescribed period of time to accelerate the rate of oxidation and predict on a relative basis
how long the fuel will be stable under more tj^ical conditions. In the ASTM D 525 Oxidation Stability test, the fuel
sample is heated with oxygen inside a pressure vessel, and the
time until significant oxygen uptake (pressure drop, "break
point") occurs is a relative measure of stability. The criteria
are where the pressure drop exceeds 2 psi per 15 min. The autocatalytic reaction rate increases exponentially, becoming
mass transfer controlled, and consuming all of the remaining
oxygen in only 15-30 min. ASTM D 4814 requires a m i n i m u m
of 240 min (4 h) breakpoint, which is sufficient for most storage and distribution systems. This may require a higher level
at the point of manufacture, since the measured oxidation
stability will decrease over time as the sacrificial anti-oxidant
is consumed. Other procedures not used in D 4814 are to
weigh the oxidative g u m formed after a breakpoint test,
(commonly termed a "4 hour gum"), or longer term storage
time tests at milder conditions to better simulate field storage
conditions.
It is common practice to add sufficient antioxidant to meet
a 360-600 min oxidation stability at the point of production,
so that 240 min is obtained at the point of sale. Factory fill
gasoline generally requires a much-fortified gasoline for this
purpose, as storage times of automobiles prior to Scile can be
several months. This is especially true for some specialty fleet
applications, such as police fleets, that may be made in large
production runs, with the cars stored for six m o n t h s or
more before going into service. Hydrocarbons air oxidation
has been extensively studied, and is well documented in the
literature.
Soluble
Gum")

Gum

(Unwashed

and Solvent

Washed

"Existent

ASTM D 4814 limits unwashed gum to 5 mg/100 mL, and has


no washed (Existent Gum) requirement (used for aviation
gasoline). D 381 measures the amount of fuel soluble oxidative gums and nonvolatile additives remaining after evaporation in the air (i.e., total nonvolatile materials in solution).
Solvent washed "Existent Gum" measures the a m o u n t of
gums remaining in fuel evaporated u n d e r air and t h e n
washed with heptane to remove additives and heavier hydrocarbons. Heptane is a poor solvent for highly oxidized, high
molecular weight gums. The heptane soluble portion is relatively low molecular weight material that can accumulate at
any point of gasoline vaporization (intake system deposits)
and react further to form insoluble gums. The heptane insoluble portion is representative of the more fuel-insoluble gum
that can contribute to gum/varnish residue problems, for example filter plugging, sticking carburetor float bowl pintle
needles where there is no vaporization, as well as intake system deposits where there is vaporization.
Washed and unwashed gums measure the amount of gum
formed in the fuel u p to the time of the test, as no significant

3: MOTOR

GASOLINE

83

additional gum is formed under the relatively mild conditions of the test procedure. It is not predictive of future
quality. It can identify help identify stale "peroxidized" fuels
in the marketplace; Washed Existent gum is often reported
to verify that a high unwashed gum is due to the presence
of Deposit Control Additives that contribute to unwashed
gum. A fuel that has both high ( > 1 0 mg/lOOmls) washed
and u n w a s h e d g u m are generally considered suspect or
unacceptable.
Water

Tolerance

D 6422 Water Tolerance (phase separation) method measures the highest temperature at which phase separation of
gasoline - alcohol blends occur. It is not applicable to hydrocarbon or ether oxygenated fuels. Water tolerance is particularly critical for gasoline containing alcohol. The separated
lower phase alcohol-water-hydrocarbon phase settles to the
bottom of the tank where the p u m p suctions are, and tends
to get moved down the distribution system and into cars if
not found and removed. The remaining gasoline layer is often off-spec after phase separation due to loss of octane from
alcohol and aromatics extracted into the alcohol layer. If dispensed into a vehicle tank, it will not burn in engines, and so
it causes immediate stalls, and requires a complete fuel system draining and cleaning. Like water, aqueous alcohol separated phases contribute to corrosion and pickup of rust/dirt,
etc., and are also associated with accelerated filter plugging.
Methanol has a low solubility in gasoline and requires a
cosolvent if used in gasoline blending for that reason. Adding
methanol to an oxygenated fuel will increase the measured
separation temperature while adding ethanol, IPA, or other
low MW alcohols will decrease the measured separation temperature.
Water tolerance of gasoline with alcohols is very temperature dependent; consequently diverse limits are established
for the U.S. The limits vary according to location and month.
For Alaska, North of 62 latitude, it changes from 41C in
Dec-Jan to 9C in July, but remains 10C all year in Hawaii,
since it never gets that cold. This is the same control strategy
as for s u m m e r t i m e high temperature and Tv/1 or VP, but
using the daily low t e m p e r a t u r e s versus the daily high
temperatures.
Other Nonspecification Properties
Autoignition

Temperature

The autoignition temperature of a fuel or even a single


molecule is not a thermodynamic property. It is the temperature at which high temperature decomposition products
will spontaneously c o m b u s t without a n external ignition
source. It is heavily dependent on the conditions at the time
of the test, including such factors as what type and shape of
container is used, and how long to wait to see if autoignition
occurs. The conditions can be varied to simulate a specific
situation, and it is not intended to reflect engine conditions.
There is a general correlation between the octane n u m b e r
of a fuel and the auto ignition temperature, because both are
determined by molecular structure. Long straight chain hydrocarbons produce large amounts of easily auto-ignitable
pre-flame decomposition, and tend to have low auto ignition
temperatures and octane numbers. Branchy and aromatic

84

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

hydrocarbons are more resistant, and have higher auto ignition temperatures and octane numbers. However, correlation
is not precise enough to be useful, and several lab rig tests
based on auto ignition temperatures or related "cool flame"
or "pre-flame" properties to predict engine octane numbers
have failed to date. Autoignition temperature of gasoline and
other fuels can be measured by ASTM E 659, Standard Test
Method for Autoignition Temperature of Liquid Chemicals.
Heat of Combustion

and Adiabatic

Flame

Temperature

See section on Gasoline Energy Content for a discussion of the


gross and net heat of combustion (He). The He of gasoline
can be measured by ASTM D 4809, Heat of Combustion of
Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method), or estimated by a n u m b e r of ASTM and other correlations.
The adiabetic flame temperature is the highest temperature that combustion gases can attain under standard starting conditions u n d e r adiabatic (no heat loss) conditions,
where all of the energy of combustion goes toward heating
the combustion gases. There are only slight differences in
combustion temperatures of blended gasolines, and the actual temperature in the combustion chamber is determined
by other factors, such as load, spark timing, and engine design. The exhaust gas temperature is much below the adiabatic flame temperature because m u c h of the energy combustion has been extracted as PVT work.
The adiabatic flame temperature can be measured directly
as a peak flame t e m p e r a t u r e (no applicable ASTM test
m e t h o d ) , or estimated from the carbon/hydrogen ratio,
stoichiometric formula and heat of combustion, or calculated from composition with a suitable thermodynamics calculation, or estimated from density correlations (similar to
the He).
Flammability

(LEL and

HEL)

The Lower and Higher Explosive limits (LEL, HEL) are the
m i n i m u m and maximum hydrocarbon vapor concentrations
that will support combustion. The LEL is related the flash
point of distillate fuels. Below the LEL there is too little hydrocarbon fuel to support combustion, while above the HEL
there is too little air (oxygen) to support combustion. The stoichiometric mixture lies between the LEL and HEL, and represents the mixture of complete combustion, maximum adiabatic flame temperature, and maximum energy release from
combustion of explosion. Distillate fuels are handled below
their LEL (Flash Point). Gasoline and naptha fuels are normally handled above their HEL. Mixtures of gasoline and distillate fuels, or fuels with equilibrium vapor pressures that
place the vapor space in the explosive range are extremely
dangerous. Any ignition source can cause Ein explosion in the
vapor space or in fuel lines and vents. Once ignited, a flame
can propagate down any pipe or vent that contains a combustable mixture. Fuels with vapor spaces in the explosive
range require specialized equipment and procedures for safe
handling (flame arrestors, anti-static provisions, gas inerting,
etc.).
The higher and lower explosive limits for gasoline are only
rarely a concern. The vapor pressure of gasoline keeps it well
over the HEL most of the time. It is only in extremely cold
weather that a properly formulated winter gasoline can enter

the HEL explosive range. This can be estimated from PengRobinson Equation of State calculations, since the LEL will
occur when the vapor phase concentration of butane/pentane
hydrocarbons will be in the 1.5-2 vol% range, and the HEL in
the 7-8 vol% range. At 14.7 psia barometric pressure, this
corresponds to a range of 0.1-0.2 psia and 1.0-1.2 psia hydrocarbon vapor pressure for the LEL and HEL respectively.
Using these values, a typical 14.5 VP winter gasoline would
be expected to have an LEL ranging from about 75 to - 6 0 F
and HEL from about 25 to 15F, depending upon composition. A t5^ical 7.8 VP s u m m e r gasoline would be expected
to have an LEL ranging from about 50F to 35F and an
HEL from 5-15F. Canadian CGSB gasoline standards have a
m i n i m u m VP to provide a wide margin between the HEL and
the VP at extreme cold temperatures for various times of
year.
Diluent gases are much more effective at reducing the HEL
than increasing the LEL for all flammable hydrocarbon gas
mixtures. The flammable region disappears with the addition
of about 30% CO2 or 45% N2, and almost all of this change is
due to reduction in HEL and not increase in LEL hydrocarbon concentration [38,39]. From this it can be estimated that
N2 gas containing less than about 10 vol% oxygen is nonflammable with hydrocarbon vapors, a "rule of t h u m b " that
is often useful for developing procedures for safe handling of
gasoline in nonstandard conditions.
Heat Capacity, Thermal
and Heat of
Vaporization

Conductivity,

The thermodynamic bulk properties of gasoline are rarely a


concern for automotive gasoline, but are occasionally required for the sizing of specialized handling equipment.
Gasoline has a heat capacity of about 0.5 BTU/lb.F (0.5
cal/gm.C), which is about half that of water. Hydrocarbons
would be considered to be a good insulator in the absence of
convective flow heat transfer with a thermal conductivity of
about 0.08 BTU/hr.ft.F near room temperature, about 20%
that of water (.35 BTU/hr.ft.F). Because they are essentially
nonpolar, the heat of vaporizations of gasoline hydrocarbons
are only about 10-20% that of water on an enthalpy per mass
basis. Light aliphatics, such as butane, are in the low range,
while branched isoparafins, etc. are in the high range, with
single ring aromatics in mid range. As a result, a fully blended
gasoline has a heat of vaporization near a midrange of about
15% of water, or about 140 BTU/lb (80 kcal/kg). More detailed information is available in standard chemistry and engineering handbooks and manuals. There are no standard
ASTM tests for these properties, but they are well documented in the thermodynamics literature.
Viscosity

and

Lubricity

The viscosity of gasoline is rarely a concern for automotive


gasoline. It is considered to be a very low viscosity fluid at
typical a m b i e n t t e m p e r a t u r e s with a typical viscosity of
about 0.5 cSt at room temperature, which is only slightly
lower than water (0.9 cSt) at the same temperature. Viscosity
does not change very much with temperature, similar to density, thermal conductivity, etc. Unlike more viscous lubricants and heavier fuels, inherently low viscosity liquids such
as gasoline and LPG are not very sensitive to temperature.
For example, a 0.7 cSt liquid would only be expected to de-

CHAPTER
crease viscosity to about 0.1 cSt, with an increase of 100
centigrade [40]. Lubricity is determined by trace polar
molecule content, b u t is generally very p o o r for gasoline.
Clean absorbent treated gasoline range hydrocarbons (low
polar content) are often used as the "poor" standard in lubricity test calibrations. Pumps for gasoline service must be
chosen carefully due to the low lubricity and propensity for
accelerated p u m p wear. Centrifical, gerotor, internal gear,
and other low contact p u m p designs are preferred over ordinary gear pumps, which are seldom suitable for gasoline service. Similar wear problems can occur in some positive displacement meters. The high vapor pressure of gasoline can
result in localized cavitation in some p u m p designs, with the
damage easily misdiagnosed as corrosion and/or wear. Engine mounted fuel p u m p s are usually diaphragm pumps, and
low pressure in-tank fuel p u m p s are usually turbine (centrifical) p u m p s for these reasons. High pressure automotive in
tank fuel p u m p s are usually two stage turbine/positive displacement pumps, with the second stage tjrpically usually being a roller vane or gerotor type for use in a very "dry" (low
lubricity) fuel.
There are a n u m b e r of standard ASTM viscosity test methods suitable for gasoline, such as D 445, S t a n d a r d Test
Method for Kinematic Viscosity of Transparent and Opaque
Liquids (the Calculation of Djoiamic Viscosity). Adaptations
of several lubricity test m e t h o d s originally developed for distillate fuels can be applied to lighter hydrocarbons, although
not covered with the scope (naptha range solvents are used as
calibrants). These include D 6078 and D 6079, Scuffing Load
Ball on Cylinder and High Frequency Reciprocating Rig Tests.
Conductivity

and Static

Electricity

Conductivity is rarely a concern for automotive gasoline, but


is occasionally m e a s u r e d if there is a concern for static
buildup during p u m p i n g . Retail dispensing hoses/nozzles
and vehicle fill spouts Eire internally grounded, so there is
generally enough static dissipation to avoid problems. Some
static incidents have occurred with very low conductivity
gasoline in plastic fuel lines (replaced by more conductive
plastic). Recently, ignitions have occurred during cold
weather with containers filled while sitting in plastic bed liners (insulators) of pick-up trucks. Ignitions from static discharge from gloves/clothing during refueling are believed to
be due to static accumulation on clothing, and not to charge
accumulation from gasoline.
Conductivity dissipating additives are effective in gasoline,
but do not provide protection if the charging rate is excessively high, and hardware changes are required. The same
principles of electrostatics apply to gasoline as to other hydrocarbon fuels, except that the vapor space of gasoline tanks
are normally well above the HEL at the time and temperature
of use [41]. This is rarely a factor for automotive, as there is
little opportunity for vapor accumulation a n d ignition. In
generzJ, gasoline should only be transferred under conditions
where there is free flow of air and good ventilation.
Several standard ASTM test methods are available to measure conductivity of gasoline and other fuels. Static cheirging
tendency is highly dependent upon equipment configuration.
Consult ASTM D 4865, Guide for Generation and Dissipation
of Static Electricity in Petroleum Fuel Systems for more information.

Density,

Refractive

Index,

3: MOTOR
and Dielectric

GASOLINE

85

Constant

Density, Dielectric Constant, and Refractive Index are all


"bulk properties" of hydroccirbons that depend upon the n u m ber of atoms, charges, and electrons per unit volume. When
the composition is limited to only hydrogen and carbon in hydrocarbon fuels, there are strong scientifically based relationships between these properties, and a strong correlation between them for all fuels. Dielectric constant is rarely a concern
for gasoline, but is occasionally needed for some capacitance
gauging systems. For reasons of composition, the dielectric
constant of hydrocarbon fuels (not oxygenates) can be estimated as the square of the refractive index at the required
temperature. The dielectric constant is a "bulk property" of
the fluid, similar to refractive index and density. All can be estimated with reasonable accuracy for oxygenates blends by
volumetrically averaging the oxygenate and the hydrocarbon
component dielectric constants, refractive index, or density.
Both refractive index and dielectric constant can be used to
estimate the density of a blend, which in turn is strongly correlated to Eiromatics content for typiccil blends. Both dielectric
constant and refractive index have been used as control parameters for racing fuels for these reasons. Some commercially available field instruments use these principles to estimate oxygenate contents from optical measurements.
Gasoline vapor (predominately butane/pentane) is heavier
than air and can accumulate in low spots and cavities in the
absence of a ventilating flow of air (see Chapter 2, Liquified
Petroleum Gas).
Several s t a n d a r d ASTM test m e t h o d s are applicable to
liquid a n d gas density, refractive index, a n d dielectric
constant.

ASTM/IP METHODS
ASTM No.
D 4806

IP No.

D 4814
D86

123

D 130

154

D 323
D 3 81

131

D 525

40

D665

135

D 1266

107

Title
Specification for Denatured Fuel
Ethcinol for Blending with Gasolines
for Use as Automotive Spark-Ignition
Engine Fuel
Specification for Automotive SparkIgnition Engine Fuel
Test Method for Distillation of
Petroleum Products
Test Method for Detection of Copper
Corrosion from Petroleum Products
by the Copper Strip Tarnish Test
Test Method for Vapor Pressure of
Petroleum Products (Reid Method)
Test Method for Existent Gum in Fuels by Jet Evaporation
Test Method for Oxidation Stability of Gasoline (Induction Period
Method)
Test Method for Rust-Preventing
Characteristics of Inhibited Mineral
Oil in the
Presence of Water
Test Method for Sulfur in Petroleum
Products (Lamp Method)

86 MANUAL 37: FUELS AND LUBRICANTS


D 1298

160

D 1319

156

D2276

216

D2533
D2622
D2699

237

D2700

236

D2709

D2885

D3116
D3120

D3227

342

D3231
D3237
D3341
D3348

D3606

D3710

D3831

D4052

D4045

365

HANDBOOK

Test Method for Density, Relative


Density (Specific Gravity), or API
Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method
Test Method for Hydrocarbon Types
in Liquid Petroleum Products by
Fluorescent Indicator Adsorption
Test Method for Particulate Contaminant in Aviation Fuel
Test Method for Vapor-Liquid Ratio
of Spark-Ignition Engine Fuels
Test Method for Sulfur in Petroleum
Products by X-Ray Spectrometry
Test Method for Knock Characteristics of Motor Fuels by the Research
Method
Test Method for Knock Characteristics of Motor and Aviation Fuels by
the Motor Method
Test Method for Water and Sediment in Distillate Fuels by Centrifuge
Test Method for Research and Motor
Method Octane Ratings Using OnLine Analyzers
Test Method for Trace Amounts of
Lead in Gasoline
Test Method for Trace Quantities of
sulfur in Light Liquid Petroleum
Hydrocarbons by Oxidative Microcoulometry
Test Method for Mercaptan Sulfur in
Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels (Potentiometric Method)
Test Method for Phosphorus in
Gasoline
Test Method for Lead in Gasoline by
Atomic Absorption Spectroscopy
Test Method for Lead in GasolineIodine Monochloride Method
Test Method for Rapid Field Test for
Trace Lead in Unleaded Gasoline
(Colorimetric Method)
Test Method for Benzene and
Toluene in Finished Motor and
Aviation Gasoline by Gas Chromatography
Test Method for Boiling Range Distribution of Gasoline and Gasoline
Fractions by Gas Chromatography
Test Method for Manganese in Gasoline by Atomic Absorption Spectroscopy
Test Method for Density and Relative Density of Liquids by Digital
Density Meter
Test Method for Sulfur in Petroleum
Products by Hydrogenolysis and
Rateometric Colorimetry.

D 4053
D 4057
D 4294

336

D 4420
D 4815
D 4953
D 5059

228

D 5188
D 5190
D 5191
D 5453
D 5482
D 5580

D 5599

408

D5845

D 6422

Test Method for Benzene in Motor


and Aviation Gasoline by Infrared
Spectroscopy
Practice for Manual Sampling of
Petroleum and Petroleum Products
Test Method for Sulfur in Petroleum
Products by Energy Dispersive X-ray
Fluorescence Spectroscopy
Test Method for Aromatics in Finished Gasoline By Gas Chromatography
Test Method for Determination of C,
to C, Alcohols and MTBE in Gasoline
by Gas Chromatography
Test Method for Vapor Pressure of
Gasoline and Gasoline-Oxygenate
Blends (Dry Method)
Test Methods for Lead in Gasoline
by X-Ray Spectroscopy
Test Method for Vapor-Liquid Ratio
Temperature Determination of Fuels
(Evacuated Chamber Method)
Test Method for Vapor Pressure of
Petroleum Products (Automatic
Method)
Test Method for Vapor Pressure of
Petroleum Products (Mini Method)
Test Method for Total Sulfur in Light
Hydrocarbons, Motor Fuels, and
Oils by Ultraviolet Fluorescence
Test Method for Vapor Pressure of
Petroleum Products (Mini Method Atmospheric)
Test Method for Benzene, Toluene,
p,/m xylene, o-xylene, C9 and Heavier Aromatics in Finished Gasoline
by Gas Chromatography
Test Method for Oxygenates in Gasoline by Gas Chromatography and
Oxygen Selective Flame Ionization
Detection
Test Method for MTBE, ETBE,
TAME, DIPE, Methanol, Ethanol,
and tert - Butanol in Gasoline by Infrared Spectroscopy
Water Tolerance (Phase Separation)
of Gasoline - Alcohol Blends

BIBLIOGRAPHY
[1] Owen, K. and Coley, T., Automotive Fuels Reference Book, 2nd
ed.. Society of Automotive Engineers, Warrendale, PA, 1995.
[2] Gibbs, L. M., "Transportation FuelsAutomotive Gasoline,"
Encyclopedia of Energy Technology and the Environment, John
Wiley and Sons, NY, 1995, pp. 2675-2698.
[3] Poulton, M. L., Alternative Fuels for Road Vehicles, Computational Mechanics Publications, Wit Press, Southampton, UK,
1994.
[4] Goodger, E. M., Hydrocarbon Fuels, Macmillan, London, 1975.
[5] Goodger, E. M., Alternative Fuels, MacmillEin, London, 1980.
[6] "Alcohol Fuels," "Gasoline and Other Motor Fuels," "Hydrogen

CHAPTER 3: MOTOR GASOLINE


Energy," and "Fuel Cells," Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., M. Howe-Grant, Ed., Wiley, NY, 1993.
[7] The Automotive Handbook, any edition, Bosch, Society of Automotive Engineers, Warrendale, PA.
[8] Automotive Electrical/Electronic Systems, Society of Automotive
Engineers, Warrendale, PA.
[9] Heywood, J. B., Internal Combustion Engine Fundamentals, 1st
ed., McGraw-Hill, NY, 1988.
[11] Heisler, H., Advanced Engine Technology, Edward Arnold, London, 1995.
[12] Poulton, M. L., Alternative Engines for Road Vehicles, Computational Mechanics Publications, Wit Publishers, Southampton,
UK, 1994.
[13] SAE J312 and J1297, SAE Handbook, Vol. 1, Society of Automotive Engineers, Warrendale, PA, 1994.
[14] Proceedings of the International Symposium on Alcohol Fuels, Held
every two years and most of the ten conferences have good technical information, especially the earlier ones, various publishers.
[15] Alternative Transportation Fuels: An Environmental and Energy
Solution, D. Sperling, Ed., Quorum Books, Wetport, CT, 1989.
[16] Hunt, V. D., The Gasohol Handbook, Industrial Press, NY, 1981.
[17] Part 4, "Detonation and Combustion," The Science of Petroleum,
Oxford University Press, 1938.
[18] Hobson, G. D., Modem Petroleum Technology, any edition, Wiley, NY.
[19] DS 4B, Physical Constants of Hydrocarbon and Non-Hydrocarbon Compounds, ASTM International, West Conshohocken, PA,
1991.
[20] Technical Data Book for Petroleum Refiners, American
Petroleum Institute, Washington, D.C.
[21] Engineering Data Book, Gas Processors Suppliers Association,
Tulsa, OK.
[22] Handbook of Chemistry and Physics, CRC Press, Boca Raton, FL.
[23] Chemical Engineers Handbook, McGraw Hill, NY.
[24] Chemistry Webbook, National Institute of Standards and Technology (NIST), Gaithersburg, MD, www.webbook.nist.gov.
[25] An Index of Selected Thermodynamic Data Handbooks, Thermodex, http://thermodex.lib.utexas.edu.
[26] "Chemiccd and Physical Properties," LSU Libraries, Louisiana
State University, Baton Rouge, LA, http://www.lib.lsu.edu/sci/
chem/properties .html.
[27] TRC Thermodynamic TablesHydrocarbons, Thermodynamics
Research Center, Texas A&M University, College StationTexas,
NIST, Boulder, CO.

REFERENCES
[1] Owen, K. and Coley, T., Automotive Fuels Reference Book, First
ed.. Society of Automotive Engineers, Inc., Warrendale, PA,
1990.
[2] Gibbs, L. M., "How Gasoline Has Changed," SAE Report No.
932828, Society of Automotive Engineers, Warrendale, 1993.
[3] Purdy, G. A., Petroleum, Prehistoric to Petrochemicals,Copp
Clark Publishing Co., Toronto, 1958.
[4] Kaufman, K. B., "Midgley: Saint or Serpent?," Chemtech, December 1989, pp. 717-725.
[5] Midgley, T. and Boyd, T. A., Industrial and Engineering Chemistry Research, Vol. 14, 1922, pp. 589, 849, 894.
[6] Midgley, T., "Problem + Research -I- Capital = Progress," Industrial and Engineering Chemistry Research, Vol. 31, 1939, pp.
504-506.
[7] Dying for Work: Workers' Safety and Health in 20th Century America, D. Rosner and G. Markowitz, Eds., Indiana University Press,
Bloomington, IN, 1987.
[8] Goodger, E. M., Petroleum and Performance, Butterworths Scientific Publications, London, 1953, p. 166

87

[9] Campbell, J. M. and Boyd, T. A., "Methods of Knock Rating. 15.


Measurement of the Knocking Characteristics of Automotive
Fuels," The Science of Petroleum. Oxford University Press, Oxford, Vol. 4, 1938, pp. 3057-3065.
[10] Gibbs, L. M., "How Gasoline Has Changed," SAE Report
#932828, Society of Automotive Engineers, Warrendale, PA,
1993.
[11] Kaiser, E. W., Siegl, W. O., Cotton, D. F., and Anderson, R. W.,
"Effect of Fuel Structure on Emissions from a Spark-Ignited Engine. 2. Naphthene and Aromatic Fuels," Environmental Science
and Technology., Vol. 26, 1992, pp.1581-1586.
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2002.
[13] Gibbs, L. M, "Transportation FuelsAutomotive Gasoline," Encyclopedia of Energy Technology and the Environment, John Wiley and Sons, NY, 1995, pp. 2675-2698.
[14] Gibbs, L. M., et al, Alcohols and Ethers A Technical Assessment
of Their Application as Fuels and Fuel Components, API Publication #4261, American Petroleum Institute, Washington D.C.
[15] "Research Report on Reformulated Spark-Ignition Engine
Fuel," ASTM RR: D02-1347, ASTM International, West Conshohocken, PA (updated regularly).
[16] "Federal Reformulated Gasoline," Chevron Technical Bulletin
FTB 4, Chevron, San Ramon, CA, 1994.
[17] Gibbs, L. M, "Transportation Fuels^Automotive Gasoline," Encyclopedia of Energy Technology and the Environment, John Wiley and Sons, NY, 1995, pp. 2675-2698.
[18] "Motor Gasolines Technical Review (FTR-1)," Chevron Products Company, San Ramon, CA, 1996.
[19] "Initial Mass Exhaust Emissions from Reformulated Gasolines," Technical Bulletin No. 1, Auto/Oil Air Quality Improvement Research Program, Coordinating Research Council, Inc.,
Atlanta, GA, December 1990, pp. 5-7.
[20] "Mass Exhaust Emissions Results from Reformulated Gasolines," Technical Bulletin No. 4, Auto/Oil Air Quality Improvement Research Program, Coordinating Research Council, Atlanta, GA, May 1991
[21] "Exhaust Emissions of Toxic Air Pollutants Using RFGs," Technical Bulletin No. 5, Auto/Oil Air Quality Improvement Research Program, Coordinating Research Council, June 1991.
[22] Kettering, C. F., "The Effect of the Molecular Structure of Fuels
on the Power and Efficiency of Internal Combustion Engines,"
Industrial Engineering and Chemistry Research, Vol. 36, 1944,
pp. 1079-1085.
[23] Composition of Canadian Unleaded Gasoline, available from
Canadian Petroleum Products Institute, Ottawa Ontario,
Canada, 1994.
[24] Reisch, M., "EPA Told Not To Ban Ethyl's Fuel Additive," Chemical & Engineering NewsM, 24 April 1995, p. 8.
[25] "Gasoline and Other Motor Fuels," Kirk-Othmer Encyclopedia of
Chemical Technology, 4th ed.. Vol. 12, M. Howe-Grant, Ed., Wiley, NY, 1993.
[26] Kozole, K. H., "1996 In-Use Vehicle Emission Survey Program,"
CPPI Report No. E12-B005248-Final, Canadian Petroleum
Products Institute, Ottawa, 1996, Available: http://www.cppi.ca.
[27] "Response to the Sasol report of 23 May 01 and the Ethyl report
of July 2001," presented at the IPIECA, September 2001, Delta
Motor Corporation, Shannon, Ireland, Aug. 24, 2001.
[28] "MMT Global Update to IPIECA," presented at the IPIECA,
Shannon, Ireland, September 2001.
[29] Calingaert, G., "Section 11, Anti-knock Compounds," The Science of Petroleum, Vol. 4, Oxford University Press, Oxford, 1938,
pp. 3024-3029.
[30] SAE J 1829: Stoichiometric Air-Fuel Ratios o f Automotive FuelsRecommended Practice, SAE Handbook, Vol. 1, Society of
Automotive Engineers, 1994.

88 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[31] Westbrook, C. K. a n d Pitz, W. J., "The Chemical BUnetics of Engine Knock," Energy and Technology Review, Feb/Mar 1991,
pp. 1-13.
[32] Westbrook, C. K. and Pitz, W. J., "The Chemical Kinetics of Engine Knock," Energy and Technology Review, Feb/Mar 1991,
pp. 562-566.
[33] Westbrook, C. K. and Pitz, W, J., "The Chemical Kinetics of Engine
Knock," Energy and Technology Review, Feb/Mar 1991, pp. 1-13.
[34] Westbrook, C. K., "The Chemistry Behind Engine Knock,"
Chemistry & Industry (UK), 3 Aug 1992, pp. 562-566.
[35] Dyroff, G., Manual on Significance of Tests for Petroleum Products, 5th ed., MNL-1, ASTM International, West Conshohocken,
PA, 1993.
[36] Nadkami, K., Guide to ASTM Test Methods for the Analysis of
Petroleum Products and Lubricants, MNL-44, ASTM International, West Conshohocken, PA, 2000.
[37] Schuetzle, D., Siegl, W. O., Jensen, T. E., Dearth, M. A., Kaiser,
E. W., Gorse, R., et al., "The Relationship between Gasoline

[38]

[39]

[40]
[41]

Composition a n d Vehicle Hydrocarbon Emissions: A Review of


Current Studies and Future Research Needs," Environmental
Health Perspectives Supplements, Vol. 102, No. 4, 1994, pp. 3-12.
Coward, H. F. and Jones, G. W., "Limits of FlammabiHty of
Gases and Vapors," U.S. Bureau of Mines Bulletin 503, U.S.
Government Printing Office, Washington, D.C., 1952.
MoUer, W. O., Molname, M., and Sturm, R., "Limiting Oxygen
Concentration: Recent Results and their Presentation in Chemsafe," Presented at the 9th International Symposium on Loss Prevention and Safety Promotion in the Process Industries, May
1998, Barcelona, Available: http://www.ptb.de/de/org/3/33/331/
moeIler.htm.
Perry, R. H. and Chilton, C. H., Chemical Engineer's Handbook,
Fifth ed., pp. 3-346.
Bustin, W. M. and Dukek, W. G., "Electrostatic Hazards in the
Petroleum Industry," Electronic and Electrical Engineering Research Studies, Research Studies Press Ltd., UK, John Wiley and
Sons, NA, 1983.

MNL37-EB/Jun. 2003

Aviation Fuels
Kurt H. Strauss^

publication of a specification for a n 82 octane unleaded


grade, intended for the certification of new engines having
low octane requirements. Table 1 lists the pertinent aviation
gasoline properties in D 910, while Table 2 contains the requirements for D 6227, Grade 82 UL.

HISTORY
Aviation Gasoline
EARLY AIRCRAFT ENGINES WERE OPERATED o n ordinary straight-

r u n motor gasoline well into the 1920s [ 1 ]. Research then isolated uncontrolled combustion as a major source of engine
overheating and failures, prompting a search for ways to cure
the problem. The big step came in 1921 with the invention of
tetraethyl lead (TEL), a n unequaled knock resistance enhancer. The same period saw the development of the heptane-isooctane scale still in use today for rating antiknock
properties in terms of octane numbers. For aviation gasoline,
the concept of rating knock resistance in special single cylinder engines resulted in the Aviation Octane Test Method (D
614), which tested fuels under lean fuel mixture conditions
simulating cruise operation. (In 1970 this method was replaced in the specification by the Motor Octane Method, D
2700.) An aviation gasoline specification, issued by the U.S.
Air Corps in 1938, listed a 68 octane grade containing n o lead
and a 92 octane grade with a m a x i m u m of 6 mL TEL/gallon.
As engine power output was increased by supercharging the
fuel/air mixture, a second rating method, D 909, came into
use to evaluate performance u n d e r rich take-off conditions,
so that by World War II both rating methods were required.
Engine designers soon discovered the performance benefits
of high octane, which permitted a higher octane fuel t o develop more power in a given engine or allowed a reduction in
engine size with the same power output. Research on high
octane fuel thus received a high priority and resulted in a 100
octane fuel by the beginning of World War II. While t h e
heroic performance of the RAF is widely recognized, it would
have been impossible without the 100 octane fuel.

Jet Fuel
Because of different combustion requirements, jet fuel
started as a completely different portion of the petroleum
barrel [2]. Early British engines used domestic kerosine, a
fuel that has not changed drastically over the years. German
engines, also military, were operated on a mixture of kerosine and naphtha, probably to extend fuel availability. The
progression of U.S. military fuels is illustrated in Table 3.
Both JP-3 and JP-4, which are blends of kerosine and naphtha, reflected Air Force concern over fuel availability, while
JP-5 is tailored t o Navy r e q u i r e m e n t s for carrier combat
safety. JP-7 is a supersonic fuel in very limited use. Today, the
Air Force operates almost entirely on JP-8; in fact, this grade
has become the primary battlefield fuel to be used in gas turbine and diesel powered ground vehicles as well as combat
aircraft.
For civil use, ASTM issued specification D 1655 in 1959,
containing three grades. Jet A and A-1 were kerosine-type fuels differing only in freezing point, while Jet B was the civil
version of JP-4. Currently consideration is being given to removing Jet B from D 1655 and placing it into a separate specification. The key properties of Jet A and A-1 are illustrated in
Table 4. Corresponding specifications are issued by the UK
Ministry of Defence as defence standards (Def Stans), with
Def Stan 91 -91 [3] being the technical equivalent of ASTM Jet
A-1. Jet A meeting D 1655 is the civil aviation fuel in the U.S.;
Jet A-1 meeting the combined requirements of D 1655 and
Def StcUi 91-91 is the civil fuel elsewhere. There is no British
grade corresponding to Jet A. The latest effort at a true international jet fuel standard is a series of guidelines [4] issued in
1999 by the IntemationEd Air Transport Association (lATA),
which includes Jet, A, Jet A-1, the Russian TS-1, and a Jet B
grade.

The dramatic j u m p in aviation activity in the late '30s and


'40s witnessed a n increasing n u m b e r of aviation gasoline
grades, ultimately standardizing on five grades ranging from
80/87 to 115/145. ASTM recognized this situation by issuing
D 618 as a civil aviation gasoline specification in 1944 to be
replaced in 1947 by D 910. However, jet engine introduction
forced a steady decrease in gasoline volume and reduced the
n u m b e r of grades over time so that by the '70s only two
grades, a low lead content 80 and a high lead 100 grade, remained in commercial production. The 100 Low Lead grade
(lOOLL) was introduced late in that period, permitting a single fuel t o satisfy the requirements of both low and high octane engines. The latest change in this picture was the 1997

AIRCRAFT A N D ENGINE DESCRIPTIONS


Aviation Gasoline
Although a n u m b e r of military and some commercial aircraft
engines were liquid cooled, all engines produced after World
War II have been air cooled. These engines are generally of

' 69 Brookside Rd., Portland, ME 04103.


89
Copyright'

2003 by A S I M International

www.astm.org

90 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


TABLE 1Key specification requirements for aviation gasoline."
Knock Value, lean mixture
Motor method
Octane number, min
tCnock value, rich mixture
Superchange rating
Octane number, m i n
Performance number, min
Tetraethyl lead, mL TEL/L max
gPb/L max
Dye content
Blue dye, mg/L max
Yellow dye, mg/L max
Red dye, mg/L max

Grade 80

Grade lOOLL

Grade 100

80.0

99.5

99.5

ASTM Test MeAod


D2700
D909

87.0
0.13
0.14
0.2
none
2.3

130.0
0.53
0.56

130.0
1.06
1,12

2.7
none
none

2.7
2.8
none

D 3341 or D 5159

Requirements for All Grades


Density at 15C, kg/m^
Distillation
Initial boiling point, '
Fuel evaporated
10%vatC
40%v at C
50%v at C
90%v at C
Final boiling point, C
Sum of 10% + 50% evap. temperatures. "C
Recovery volume, %
Residue volume, %
Loss volume, %
Vapor pressure, 38C, kPa
Freezing point, C
Sulfur, %m
Net specific energy, MJ/kg
Corrosion, copper strip, 2 h @ 100C
Oxidation stability (5 h aging)
Potential gum, mg/100 mL
Lead precipitate, mg/lOOmL
Water reaction, vol change, mL
Electrical conductivity, pS/m

Report

D 1298 or D 4052
D86

Report
max
min
max
max
max
min
min
max
max
min
max
max
max
min
max

75
75
105
135
170
135
97
1.5
1.5
38.0
49.0
-58
0.05
43.5
No. 1

max
max
max
max

6
3

D 323 or D 5190
or D5191
D2396
D 1266 or D 2622
D 4529 or D 3338
D323
D873

D 1094
D2624

2
450

''For complete specification requirements, refer to D 910.

TABLE 2 --Key requirements for grade 82 UL aviation gasoline."


Property

Knock value, lean mixture


Motor method octane number
Color
Dye content
Blue dye, mg/L
Red dye, mg/L
Distillation temperature, C at % (svaporated
10%v
50%v
90%v
End point
Residue, %v
Recovery, %v
Loss, %v
Net speciflc energy, MJ/kg
Freezing point, C
Vapor pressure, kPa
Lead content, g/L
Cu strip corrosion, 3 h @ 50C
Sulfur, %m
Potential gum (5 h aging)
mg/L
Alcohols and ether content
Combined methanol and etheinol, %ni
Combined aliphatic ethers, methanol and
ethanol as %m oxygen
"Refer to D 6227 for complete specification requirements.

Requirement

ASTM Test Method

D2700
min

82.0
purple

max
max

7.5
1.9

max

70
66-121
190
225
2
95
3.0
40.8
-58
62
38
0.013
No. 1
0.07

D2392
D86
max
max
max
min
max
min
max
max
min
max
max
max

D 3338, D4529 or D 4809


D2386
D 4953, D 5190, D 5191,
or D 5482
D 3237 or D 5059
D130
D 1266, D 2622, D 3120
D 4294 or D 5453
D873
D4815, D 5999, or D 5845

0.3
2.7

CHAPTER 4: AVIATION FUELS 91


TABLE 3U.S. military jet fuel chronology.
Date of
Issue

Grade

Specification

1944

JP-1

1946
1947

JP-l"
JP-S"

1951

JP-4

1952

JP-5

1956

JP-6''

AN-F-32, changed
to MIL-F-5616
not issued
AN-F-58, changed
to MIL-F-5624
MIL-F-5624, now
MIL-PRF-5624
MIL-F-5624, now
MIL-PRF-5624
MIL-F-25656

1980

JP-7

1979

JP-8

MIL-T-38219, now
MIL-PRF-38219
MIL-T-83133, now
MIL-DTL-83133

NATO
Symbol

the intermittent combustion, four cycle variety with a wet


crankcase oil system. In radial engines the cylinders are arranged in a circle with 7 o r 9 cylinders in a row and a n engine
having one or m o r e rows. Alternately, in flat engines the
cylinders lie horizontally and oppose each other. Most of today's production engines are the flat or pancake type with 4
to 8 cylinders. Some engines contain a supercharger to compress the air and thereby increase the mass flow through the
engine. The engine drives a propeller directly from the
crankshaft or through a set of speed reduction gears. Fuel is
carried either in rubber bladders or removable metal tanks,
often in the wings, and flows to cEirbureted engines by gravity or is pumped to a fuel-injected engine by a tank-mounted
submerged boost p u m p . A low pressure engine p u m p then
supplies the fuel into the carburetor to be mixed with air or
injects it into the intake manifold under low pressure. In either case the fuel has to be evaporated by the time it reaches
the cylinder because only vapors will b u m . Each cylinder
contains two spark plugs for safe operation. Water or a water-alcohol mixture may be injected both to help cool the en-

Volatility
and Freeze Point

l l O ^ F m i n flash
60C max freeze
2 psi max RVP
5-7 psi RVP
F-40

2-3 psi RVP

F-44

140F min flash


- 4 6 C max freeze
High thermal stab.
- 5 4 C max freeze
140F min flash
- 4 3 C max freeze
100F min flash
- 4 7 C max freeze

F-34

"Canceled.

TABLE 4Key specification requirements for jet fuel grades Jet A, A-1, and B.'
Property

Composition
Acidity, total, mg KOH/g
Aromatics, %v
Sulfur, mercaptan, %m
Sulfur, total, %m
Volatilitv
Distillation temp., C
10% recovered, temp.
20% recovered, temp.
50% recovered, temp.
90% recovered, temp
Final boil, point, temp
Distill, residue, %v
Distill, loss, %v
Flash point, "C
Density at 15C, k g W
Vapor pressure, 38C, kPa
Fluiditv
Freezing point, C
Viscosity, -20C, mm^/s
Combustion
Net specific energy, MJ/kg
One of following shall be met:
(1) Smoke point, m m
(2) Smoke point, m m and
Naphthalenes, %v
Corrosion
Copper strip, 2 h @ 100C
Stability
Thermal, 2.5 h at 260C
Filter press, drop, m m Hg
Tube deposit less thsm
Contaminants
Existent gum, mg/100 mL
Water reaction
Interface rating
Additives
Electrical conductivity, pS/m
If Additive is used
If required by purchaser

max
max
max
max

Jet A or Jet A-1

JetB

0.1
25
0.003
0.3

25
0.003
0.3

ASTM Test Method

D3242
D1319
D3227
D 1266, D 1552, D 2622
D 4294 or D 5453
D86

max
max
max
max
max
max
max
min

205
report
report
300
1.5
1.5
38
775-840

meix
max
max

- 4 0 Jet A
- 4 7 Jet A-1
8.0

145
190
245
1.5
1.5
751-802
21
-50

D 56 or D 3828
D 1298 or D 4052
D 323 or D 5191
D 2386, D 4305,
D 5901 or D 5972
D445

min

42.8

42.8

D 4529, D 3338 or D 4809

min
min
max

25
18
3.0

25
18
3.0

D1322
D1322
D 1840

max

No. 1

No. 1

D 130

max

25
Code 3

25
Code 3

D3241

max
max

7
lb

D381
D 1094

lb
D2624

max
min

"For complete specification requirements refer to D 1655.

450
50

450
50

92 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

gine and to increase power output. In addition to these traditional engines, other designs, particularly for ultralight aircraft, are being introduced but are not described in detail in
this chapter. Exhaust gases are discharged through mufflers,
turbochargers or directly into the atmosphere. Compared to
today's automobile engines, all these aircraft engines are relatively simple and unsophisticated.
With rare exceptions, aircraft piston engines are operated
with separate throttle and manual fuel/air mixture controls,
whether carbureted or fuel injected. On high performance
aircraft the pilot also controls the engine speed by means of
separate manual propeller controls. During takeoff and climb
the fuel/air mixture is maintained "rich;" the purpose of the
excess fuel is to help cool the engine at high power conditions. The fuel/air mixture is "leaned out" during cruise for
optimum fuel consumption. "Rich" in this context refers to a
mixture in which the fuel/air ratio is well above the stoichimetric ratio, while lean operation is run as close as possible
to stoichimetric without overheating the cylinders.
Jet Fuel
Jet engines operate on a completely different principle. Air
flows through a compressor, is guided into a combustion section where fuel is injected and burned and the resulting exhaust gases are expanded in the turbine section, and then expelled into the atmosphere. The turbine section drives the
compressor, while the remaining energy in the exhaust
stream either reacts on the engine parts to push the engine by
"jet propulsion" or is used to drive a propeller in "turboprop"
fashion. For more efficient operation, a large single stage

compressor or "turbofan" may be mounted in front of the engine. This fan is driven by its own turbine section by a shaft
running through the core engine. Military engines may add
extra thrust by injecting fuel into the exhaust stream and
burning it in an afterburner at the expense of greatly increased fuel consumption. Unlike reciprocating internal
combustion engines, these engines operate with continuous
combustion where an igniter serves only to start combustion
and is then turned off. Gas turbine engines operate with lean
fuel/air ratios well below stoichimetric (with considerable excess air) to provide turbine inlet gas temperatures below the
normal combustion temperatures.
The fuel system of a modem transport aircraft is illustrated
in Fig. 1. The fuel is carried mostly in the wing structure
where metal junctions are sealed with an elastomer and the
entire inside surface is coated with epoxy paint to prevent
corrosion. Elastomeric bags are generally not used for fuel
storage, mostly to save weight. From the tankage, fuel is
pumped by boost pumps to the engine high pressure pump.
The engine pump normally builds fuel pressure in two stages
with the first stage a centrifugal pump and the second stage
a gear pump capable of delivering fuel at pressures as high as
10 MBCa (1400 psi.). The fuel control, the heart and brains of
the fuel system, then meters the proper amount of fuel to the
combustion system with the excess fuel being bypassed back
to the second stage pump inlet. Fuel enters the combustion
system through a fuel manifold, which distributes fuel
around the engine and into fuel nozzles in the combustion
chamber. Note that the fuel passes through a series of heat
exchangers, which reject heat from the hydraulic system,
from the engine oil system, and from the auxiliary power sys-

Fueltank
Fuel quantity
gage

Nozzles

uiuaiiuu
umiij
lanifold /
ssembly /

A/Cheat
exchanger
Fuel bypass

iLPress Stage\HPress Stage|

Engine oil heat


exchanger
tkiti

Fuel
Control

FilterX
Engine Pump
Assembly
FIG. 1Turbofan fuel system.

Integrated
gen. drive
oil heat exch.

CHAPTER 4: AVIATION FUELS

93

Horizontal
Stabilizer
I Tank (optional)
Surge Tank

Reserve Tank No. 3


Main Tank No. 3

Main Tank No. 4

Reserve Tank No.2

\y<

>y

DryBay

Center Wing Tank


Surge Tank\
Main Tank N o . 2 /

/
MainTankNo.l f

Tank

Fuel Tank Volumes


Liters

Main Tanks No. 2 and 3


Main Tanks No. 1 and 4
Center Wing Tank
Reserve Tanks No. 2 and 3
Horizontal Stabilizer Tank
Total Usable Volume

Gallons

47 675
17 030
65 220
5020
12 540

12 594
4499
17 229
1326
3313

217 211

57 381

FIG. 2Boeing 747-400 fuel tankage.

tern. (In some systems the heat from the hydraulic system is
rejected in the fuel tanks.) Additional heat is added to the fuel
by energy losses in the pump and by fuel recirculation
through the pump. More heat goes into the fuel from the
compressor discharge air, which the fuel passes through to
get into the combustion system. This heat path highlights another important function of the fuel, to serve as the heat sink
that carries away excess heat from other systems and allows
other systems to operate.
Figure 2 illustrates the tankage arrangement of a Boeing
747-400 aircraft. At takeoff, each engine is supplied fuel from
its own tank. After takeoff, fuel is taken selectively from the
center wing tank first to control wing stresses. For a typical
flight each engine is started by rotating the compressor spool
to start air flowing. When airflow is sufficient to start combustion, fuel is injected and the fuel/air mixture is ignited.
The engine then accelerates under its own power to idle operating speed and above. Maximum power at take-off is limited by either throttle demand or turbine inlet temperature
limits. Take-off power is reduced as the aircraft climbs and is
further reduced at cruise altitude to minimize fuel consumption. At the end of cruise, power is further decreased to near
idle for descent. Because heat rejection is almost constant
but fuel flow is near minimum, the descent portion of the

flight creates the highest fuel temperatures. In this entire


flight the pilot controls all engine power settings with a single throttle lever, while the engine fuel control adjusts, for all
the variables.

PERFORMANCE REQUIREMENTS AND


THEIR IMPLEMENTATION
A review of aviation gasoline and jet fuel specifications will
show that all are based on Vcirious performance tests rather
than closely defined product compositions. In turn, most of
the performance tests are empirical and do not define a property on an absolute basis; indeed many were developed to
solve specific operating problems. The following sections
outline vetrious challenges faced by aviation fuels and their
solutions.
Low TemperatureFuel Related
Jet Fuel
Aviation fuels have to operate in an extremely wide temperature environment. In particular, jet fuel is exposed to very low
temperatures due to operating conditions and fuel system de-

94

MANUAL

3 7: FUELS

AND LUBRICANTS

HANDBOOK

sign. This leads to two differing problems, one being normal


operation at cJtitude, the other involving steirting at very low
temperatures. In the wing tanks the fuel is in direct contact
with the lower wing skin which in turn is exposed to ambient
t e m p e r a t u r e s as extreme as 100C (148F). Although
aerodynamic heating at cnaise will wEirm the bottom wing
surface some 20-25C or 36-45F, the resultant fuel temperatures at the wing skin Ccin still be very low. At these low temperatures certain types of hydrocarbons in jet fuel come out
of solution. The most critical molecules are straight chain
paraffins [5] because they have the highest crystallization
temperatures of the hydrocarbons normally in jet fuel. When
these compounds come out of solution, they form a wax crystal matrix that can prevent the liquid fuel within the matrix
from flowing into a boost p u m p inlet [6]. Only 8-10% of normal paraffins in the fuel are required to form such a matrix.
For safe operation the fuel freezing point is defined as the
temperature at which the fuel is 100% liquid. This temperature is determined by D 2386 in which a sample is cooled in
an isopropyl-dry ice bath until a crystal haze appears. The
sample is then weirmed until the last crystal disappears. That
melting temperature is reported as the "freezing point". Using the melting point avoids possible super cooling of the
sample during the cooling cycle. At this writing, three other
tests are permitted as alternates. They include D 5901 (Freezing Point of Aviation Fuels^Automated Optical Method), D
5972 (Freezing Point of Aviation FuelsAutomatic Phase
Transition Method) and D 4305 (Filter Flow of Aviation Fuels at Low Temperatures). However the last method cannot
be used when fuel viscosity exceeds 5.5 cs at 20C (4F).
In case of dispute, D 2386 is the referee method.

-50

-30

-10

10

In-flight aircraft operation is not permitted below a fixed


fuel temperature differential above the specification maxim u m freezing point. This limit is called out in the flight manual of each aircraft. For Boeing aircraft the differential is 3C
or 5F, and for Airbus aircraft it is 4C or 7F. Operation at
lower fuel t e m p e r a t u r e s is avoided by aircraft routing
through w a r m e r air, by using a fuel of lower freezing point,
or in flight by increasing aircraft speed or decreasing altitude
when this condition appears imminent [7]. Limited U.S. Air
Force research also shows possible promise for additives that
lower fuel freezing points [8]. However, the practicality of
such additives in unproven.
Viscosity is the limiting property for jet engine starting because of its influence on fuel droplet size during atomization.
Viscosity is measured by D 445 and typical fuel viscosities are
plotted against temperature in Fig. 3 [9]. Engines are designed to start with fuel viscosities u p to a m a x i m u m of 12 cs
[10], a viscosity reached around - 4 0 C ( - 4 0 F ) for either Jet
A or A-1. However, specifications allow a m a x i m u m viscosity
of 8 cs at 20C (4F), which is taken as equivalent to 15 cs
at 40C. Starting problems are therefore occurring at far
N o r t h e r n latitudes, particularly in helicopters, and are
avoided by the use of Jet B or JP-4 fuel, which has lower viscosity and increased volatility.
Aviation

Gasoline

Aviation gasoline low temperature performance tends to center on engine starting. While fuel volatility is the key to fuel
evaporation a n d engine starting, the tight volatility limits
allow little flexibility and force solutions other than fuel selection. Starting difficulties at low temperatures are com-

30

50

70

Ten^rature, C
FIG. 3Typical viscosities vs. temperature.

90

110

CHAPTER 4: AVIATION FUELS


0.10

0.06

95

0.04

0.02

Jet A, Jet A-1. JP-8


Aviation Gasoline

:
o
"2

II

0.007
0.006

20

40

60

80

100

Ten^rature, C
FIG. 4Water solubility vs. temperature.

pounded by increased lubricating oil viscosities and decreased battery performance. High altitude operation does
not normally present a low temperature problem because
gasoline has a very low freezing point and most piston engine
aircraft do not fly at extremely high eJtitudes.
Low TemperatureWater Related
All hydrocarbons can dissolve a very limited amount of water. Saturation limits for jet fuel and for aviation gasoline are
shown in Fig. 4 [9]. When water-saturated fuel is cooled, water comes out of solution as free water. These low levels of
free water do not present cin operating problem. However, as
the fuel temperature goes below 0C or 32F, this free water
freezes into ice crystals that can plug filters and other fine
passages. The problem is avoided by placing filters into a
warmer part of the fuel system, by applying heat to critical filters when water freezing temperatures are noted, or by including an anti-icing additive in the fuel. Diethylene glycol
monomethyl ether (diEGME), as described by specification
D 4171, Type III, can be added to jet fuel or aviation gasoline
as an anti-icer in concentrations of 0.10-0.15% by volume.
Ethylene glycol monomethyl ether (EGME) is no longer
listed in D 4171, but is still in limited use. Isopropyl alcohol,
per D 4171 Type II, may only be added to aviation gasoline.
Here specification D 910 warns that the addition of isopropyl
alcohol to the 100 grade may lower its knock ratings. Both
additives only keep limited amounts of free water from freez-

ing and neither affects wax precipitation. Water concentrations significantly exceeding saturation levels Ccin overwhelm
these additives. Techniques for monitoring free water levels
etnd keeping excess water out of aircraft are discussed later
under Quality Control. The freezing of atmospheric moisture
on the throttle plate causes carburetor icing in piston engines; it is due to evaporative cooling by gasoline and trace
levels of water in fuel play no part.
High Temperature
Exposure to high temperatures represents one major difference between aviation gasoline and jet aircraft fuel systems,
in fact, high temperature exposure has not occurred in aviation gasoline-powered aircraft. Jet fuel presents a completely
different picture. The first incidents, in the early 1950s, took
place in military J57 engines that suffered plugging of nozzle
filter screens by fuel-caused carbon deposits [11]. Such plugging radically altered the exhaust gas temperature pattern at
the turbine inlet and resulted in turbine blade failures. In this
engine the fuel manifold that distributed fuel to the individual nozzles was located in the hot compressor discharge air
and some fuels formed carbon deposits in the manifold under reduced fuel flow conditions. These deposits broke off
and plugged fuel nozzles. The particulsir problem was solved
by manifold redesign, but it also alerted the industry to the
need for tailoring high temperature performance into the
fuel.

96 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

FIG. 5Jet Fuel Thermal Oxidation Tester (JFTOT).

Extensive research has pinpointed trace levels of certain


molecules and metals to be the criticeJ peirticipants in high
temperature oxidation reactions. Heteroatoms containing
sulfur and/or nitrogen have been investigated in a number of
model studies [12], which have found them to be as much as
20 times more reactive than the base fuel. Oxidation transforms these molecules into higher moleculctr weight materials, which become insoluble and can plug filters or screens or
deposit on hot surfaces. In turn, such deposits have broken
loose or have caused sliding parts to stick. Thus, these reactions involve only a tiny fraction of the total fuel going
through the engine, but their effect becomes significant because of the very large fuel volumes handled over a long period of time. Ultimately, the basic reason for fuel degradation
is the fuel's use as a heat sink as pointed out under Engine Descriptions. To curb the problem, the engine design approach
has been to limit liquid fuel temperature to a maximum of
190C (325F) [13]. However, fuel oxidation is a function of
both temperature and exposure time so that lengthy residence
times at temperatures below this maximum have resulted in
operating difficulties. Paradoxically, improving engine design
over the years has increased the severity of fuel exposure be-

cause more efficient engines have reduced fuel flows and


therefore cause higher heat inputs into the fuel [14].
Fuel constraints have also been instituted. Although specific heteroatoms have been found to oxidize rapidly in
model studies, the large variety of materials involved in high
temperature oxidation as well as their low concentration precludes their analytical identification on a routine basis.
Therefore, the jet fuel specification requires a performance
test, the Jet Fuel Thermal Oxidation Tester (JFTOT) by D
3241, to screen out product with unsatisfactory characteristics. The unit is illustrated in Fig. 5. In the apparatus, fuel is
pumped over a heated tube under pressure and then through
a metal screen with 17 micron openings, with both tube and
filter being maintained at a temperature of 260C (500F).
Filter pressure drop is monitored during the test, and at the
end of the test, tube deposit color is competred to a color
standard. Normally the test is run only at the specification
minimum requirement conditions and the quality margin
available above this limit is unknown. Like many other timedependent tests the thermal stability test has poor precision,
but the visual rating of deposit color plays a major part in the
poor precision [15]. Over the years, differing methods for rat-

CHAPTER 4: AVIATION FUELS


ing of tube deposits have been proposed and rejected. Most
recently, a method of measuring deposit volumes by an ellipsometric technique [16] has been developed as an alternate to
the visual rating but has not been adopted.
An interesting side issue has been the catalytic effect of certain metals on these high temperature reactions. This topic is
further discussed in the section on Corrosivity.
Combustion
More than any other performztnce requirement, combustion
requirements influence the differences between aviation
gasoline and jet fuel.
Aviation Gasoline
The requirements of spark-ignited reciprocating engines
have shaped aviation gasoline since its earliest uses. As the
mixture of air and fuel vapor enters the cylinder and is compressed, the mixture must be ignited at a critical time in the
engine cycle to provide maximum power through the expansion of exhaust gases. Mixture autoignition, either through
compression ("dieseling") or by glowing deposits, will cause
a loss of power and can result in detonation with severe mechaniccd damage. Aircraft engines Eire particularly vulnerable
because of the extensive use of aluminum alloys and other
low melting point meteJs. Compression ignition cjin be alleviated by spark timing retardation as well as maximum
power reduction. However, either approach causes a performance loss. Thus the importance of fuel knock resistance
through adequate octanes cannot be overemphasized.
Gasoline knock resistance is measured by the lean and rich
engine tests mentioned earlier. In the lean mixture method,
D 2700, the test variable is compression ratio, which is the ratio of the total volume displaced by the piston to the volume
above the piston at the top of the compression stroke. When
testing Ein unknown fuel in the single cylinder D 2700 engine,
this ratio is increased until knock is detected. The condition
is then rated by making blends of n-heptane and isooctane
and adjusting the ratio of the components until a match is
noted with the test fuel. The percent isooctane in the matching blend is the test fiiel's octane number. If fuel octane exceeds 100, the match is made with pure isooctane containing
differing levels of TEL. Because the specification requires

ratings by the old Aviation method, D 2700 contains conversion tables from the Motor method to the Aviation method. It
is noted in passing that the Motor Method is the only rating
method used for both aviation and motor gasolines.
The rich rating method, D 909, is more complex. Engine
output is measured and controlled by a dynamometer. Air
into the engine is compressed Eind cooled. Both fuel and air
flow to the engine are metered. Engine loading by the dynamometer is increased at constant fuel/air ratio until knock
occurs. The same process is repeated at increasing fuel/siir ratios to develop a curve of knock-limited engine output against
fuel/cdr ratio. This curve is bracketed by similar curves using
isooctane with varying concentrations of TEL as reference
fuels. The test fuel rating is established by interpolation between reference fuel curves cind is usually expressed in terms
of performzince numbers, which are directly proportional to
the engine power output. Thus, with a fuel having a performance number of 130 the engine developed 30% more power
than on straight isooctane.
There are currently several research programs [17] related
to knock testing and combustion requirements of aviation
piston engines. The first program is establishing the octane
requirements of a great variety of current production engines
to get an up-to-date definition of the relationship of the single cylinder laboratory engines to fl5'ing hardware. As part of
this effort, an Engine Octane Rating method has been issued
as D 6424. Preliminary results indicate that, while the old,
large radicd engines are sensitive to both lean and rich knock
characteristics, the flat or pancake engines seem to be critiCcJ in the cruise or lean operating mode only. The second program is pointed toward the development of a high octane, unleaded aviation gasoline. That search is driven by the fact that
100 octane aviation gasoline is the only lead-containing fuel
left in the U.S. petroleum inventory and there is environmental pressure to eliminate lead wherever it exists. Ultimately,
the two programs should indicate the practicality of developing an unleaded gasoline, which will satisfy the current inventory of engines requiring high octane fuel.
Jet Fuel
A typical jet fuel combustion system is illustrated in Fig. 6.
Air is discharged from the compressor at pressures up to 20

Outer combustor casing


Fuel nozzle

Inner liner

Turbine
inlet

Jet igniter

Primary comlnistion
zone

97

Secondary
zone

FIG. 6^Turbofan combustion system.

9 8 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

atmospheres (300 pounds per square inch) and temperatures


as high as 450C (840F) into the combustion system between
the outer and inner liners. The air then enters the inner Hner
through holes and slots carefully placed and sized to control
the air and gas flow patterns. Fuel is injected and atomized
through one or more nozzles into the primary combustion
zone, where, after ignition, it will bum at temperatures approaching 2000C (3500F). Such gas temperatures exceed
the operating limit of the turbine section and therefore more
air is added in the secondary zone to reduce exhaust gas temperatures to maximum levels of 800-1200C or 1500-2200F.
Thus, air provides oxygen for combustion, creates local turbulence to stabilize flame location, cools the inner liner surface, and finsJly reduces exhaust gas temperatures. Note that
the fuel line to the nozzle must go through the hot compressor dischcirge air and the engine designer must guctrd against
excess heat flow into this line.
In the early days much effort was spent to discover a jet
fuel property that would improve engine efficiency the way
that octane improves piston engine performance [18]. No
such performance parameter has been found for jet engines.
Fuel specification tests therefore serve primarily to limit undesirable components that could shorten engine life. In general, paraffinic molecules provide the cleanest combustion
while aromatics tend to create the opposite conditions.
Several tests are used to measure fuel combustion quality.
The simplest test is the Smoke Point, D 1322. A lamp with a
fuel reservoir contains a wick that can be lowered and raised
and furnishes fuel to a flame. When the wick is raised, the
flame increases in height, but at some height the flame begins
to smoke. This height varies with fuel composition. The maximum flame height at which no smoke occurs is defined as
the fuel smoke point. Although the smoke lamp represents a
very simple combustion process, a large amount of research
has validated the good relationship between this test and engine combustion, with fuels having higher smoke points
showing cleaner combustion with reduced engine smoke or
soot as well as decreased flame radiation in older engines.
Engine studies have highlighted the poor combustion quality
of double ring aromatics or naphthalenes and these are therefore measured by ultraviolet absorption at 245 nanometers
with a spectrophotometer (D 1840). Another much more
complex test, the Luminometer (D 1740), was designed to
rate fuels by measuring the radiation from a smoke lamp
flame, but the close correlation between this test and the
smoke lamp has caused the test to fall into disuse. Lastly, the
measurement of total aromatics by fluorescent indicator absorption (D1319) or by high performance liquid chromatography (D 6379) is also listed as a combustion test. However,
this measurement does not correlate as closely with engine
performance as does the Smoke Point and its prime significance is as an indication of elastomer compatibility. Hydrogen content by D 3701 has been proposed as a combustion
quality indicator and a substitute for aromatic content but
has not been accepted in civil specifications because its relationship to elastomer compatibility is not established. Specification combustion requirements are listed in Table 3.
Minor fuel composition changes have little or no effect on
combustion quality [19]. Therefore, low concentrations of organic materials as additives have little, if any, effect on combustion. Additives containing heavy metals have reduced en-

gine smoke or soot but are not permitted because of ash formation. [20].
The level of sulfur oxides in the exhaust is directly related
to the total sulfur content of the fuel and any required reduction of these oxides has to be achieved by reducing total sulfur content below currently allowed levels. Nitrogen oxides,
on the other hand, are purely an engine design function depending primarily on the maximum combustion temperatures, the amount of mixing in the primary combustion zone,
and the time at maximum temperature. Fuel characteristics
play no part [19]. The same can be said for carbon monoxide
emissions in which fuel does not play a significant role [19].
Because the ultimate purpose of fuel is to furnish heat energy, the minimum heat content or specific energy is controlled. Water vapor formed during combustion is not condensed in any aviation engine, therefore the net specific
energy is specified. As mentioned in D 910, the minimum
specification level for aviation gasoline is high enough to effectively limit the total amount of aromatics to about 25%.
Specific energy (formerly called heat content) can be measured in a calorimeter per D 4809, where a small amount of
fuel is burned in a pressure vessel, which in turn is immersed
in a water bath. The released energy is calculated from the
temperature increase of the water bath. Extremely precise
thermometry is required for the desired accuracy of the results. Specific energy can also be estimated by equations
based on pertinent fuel characteristics. One estimation
method, D 4809, uses fuel density and aniline point; another,
D 3338, includes density, boiling point and aromatic content
as variables. D 3338 is gaining in popularity because of aniline toxicity and because the required variables are already
being determined to assure overall specification compliance.
Volatility and Flammability
Volatility, a fuel's tendency to evaporate, plays a significant
part on the ground and in the air. Some performance requirements overlap between the two fuel t5rpes, others do not.
Aviation Gasoline
Aviation gasoline volatility is a major factor in engine operation because proper ignition requires fuel in vapor form. The
fuel, therefore, has to evaporate in the intake manifold before
reaching each cylinder. This is particuleirly important during
starting. Volatility also affects vapor formation in fuel lines,
which occurs when line pressure drops below the vapor pressure of the fuel, usually due to local overheating at low line
pressures. Vapor lock takes place when the combined volumes of vapor and liquid in the line exceed the volumetric capacity of the engine pump so that the engine no longer gets
the required amount of fuel. As a result, the engine will not
run until liquid fuel flow is restored. Lastly, volatility determines the flammability of the vapor space (ullage space)
above the fuel. This property is discussed later in this section.
Jet Fuel
Fuel volatility tends to have different effects on jet fuel operation. Too high a volatility CcUi cause excessive evaporation or
even boiling in aircraft tankage during rapid climb when fuel
vapor pressures equal the rapidly decreasing atmospheric
pressures at altitude. That problem caused the 1950s shift

CHAPTER 4: AVIATION FUELS


280

260
240
220
200
180
160

140
120
100
80
60
40
20
0

99

Jet A

JetA-l,JP-8

JetB,JP-4

\
\

'

1
20

1_
40

Avgas

60

80

100

Percent Evaporated

FIG. 7Fuel boiling ranges.

from JP-3 to JP-4 fuel by the U.S. Air Force [2]. Ullage
flammability in aircraft tankage is of concern and depends on
fuel type as well as in-tcink temperatures and pressures. Aside
from some effect on engine stcirting at very low temperatures,
fuel volatility is not a major factor in jet engine operation.
Fuel volatility is normally defined by the product's boiling
range and its vapor pressure. The boiling range is measured
in a simple distillation apparatus, D 86, in which fuel is
boiled off and then condensed at atmospheric pressure under
closely controlled conditions. The test result is a relationship
of boiling temperatures to fuel percent evaporated. Typical
results for Jet A [21 ], Jet A-l/JP-8 [23], Jet B/JP-4 [21 ] and aviation gasoline [22] are plotted in Fig. 7. The boiling range distribution can also be measured by gas chromatography, D
2887, where the molecular distribution of a sample is compared to a standard mixture of known boiling points.
Fuel vapor pressure is routinely measured at 38C (100F)
by D 323 or D 5191. The resuh of the test, called the Reid vapor pressure (RVP), is the sum of the partial pressures of the
fuel constituents plus the partial pressures of dissolved air
and water measured at a vapor to liquid ratio of 4:1. A true,
absolute vapor pressure where the vapor space approaches 0
can be obtained at any temperature with D 6378. A summary
of typical absolute vapor pressures against temperature is
shown in Fig. 8 [9], but absolute vapor pressure is not determined on a routine basis.
Reid vapor pressure is specified for aviation gasoline and
Jet B but not for Jet A or A-1 because for these fuels the RVP
results are too low to be reliable. Instead, volatility for the
kerosine-type fuels is measured by the flash point test. Fuel
in a closed cup is immersed in a water bath, which is warmed
at a specified rate. Starting 10C (18F) below the expected
flash point temperature, a small flame is repeatedly inserted
into the cup, which is closed between flame immersions. The
fuel temperature at which a flash of flame appears and disappears is reported as the flash point. The standard test in D
1655 is the Tag Closed Cup method, D 56, but other flash
point tests are also in use. Because of differing surface to volume ratios and different heating rates these tests often give
consistently different results and these differences have to be
considered when comparing test results [24].

Vapor pressure and flash point, while related, do not measure the same property. The former measures the pressure
exerted by a fuel at a specific temperature, while the latter indicates the lowest temperature at which a flammable fuel/air
mixture is created. Typical fuel flammability ranges at sea
level are summarized in Table 5 [9]. Below the lean limit
there is not enough fuel vapor in the air for combustion,
while above the rich limit there is not enough air. Only within
the flammability limits is the mixture ignitable with an energy source like a spark or flame. The drastic differences between aviation fuels are apparent. These flammability limits
are not absolute but are influenced by the test equipment and
test conditions and serve only as general guides with regard
to vapor space flammability. For example, the fuel/air ratio in
a large storage tank is maximum at the fuel surface and decreases with increasing distance above the fuel. Tank vapor
space or ullage flammability therefore can vary in a tank, particularly because temperature is also not usually uniform.
Flammability limits are also strongly influenced by the effect
of ambient pressure on evaporation rate. Thus the change in
flammability limits with increasing altitude (decreasing pressure) is shown in Fig. 9. The subject of aircraft tank flammability is being revisited as the result of the 1997 crash of TWA
Flight 800, which is attributed to the explosion of the "empty"
center tank in the fuselage [25].
Fuel Metering
The measurement of fuel quantity and fuel flow is important
both for ground and for flight operations. On the ground

TABLE 5TyplcEil fuelflammabilitylimits at sea level.


Flammability Concentration Limits, %v
Lower (lean) limit
Upper (rich) limit

Avgas

JetB

Jet A

JP-5

1.2
7.0

1.3
8.0

0.6
4.7

0.6
4.6

Flammability Temperature Limits, C


Lower (lean) limit
Upper (rich) limit

-44
-12

-23
18

53
77

64
102

100 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

>

20

40

60

80

100

120

HO

Temperature, "C
FIG. 8Typical vapor pressures vs. temperature.

product is bought, sold, or transferred on a volume basis.


Fuel volume changes with temperature, so the volume is usually corrected to a standcird temperature using the equations
or tables in D 1250. Use of the corrections results in consistent inventories and product transfers. In the U.S. the standard temperature is 60F, outside the U.S. it is 15 or 20C. Although different only in the fourth significant place, the
volume difference between 60F and 15C becomes significant for leirge fuel volumes. All aircraft fuel measurement is
on a mass basis: whether desiling with total aircraft take-off
and landing weight, maintaining mass balances and trim in
flight or when metering fuel flow into the engine and its combustion system.
Volume is measured in U.S. gallons or in liters. Mass units
include density in kg/m^ at 15C, relative density - the ratio of
fuel density to water density, usually at 15C, and API Gravity,

an arbitreiry scale, at 60F. All are measured by hydrometer, D


1298, or by digital density meter, D 4052. Fuel height in most
jet aircraft tcuiks is measured by gages based on fuel dielectric
constant. These fuel heights are converted into tank volumes
eind transformed electronically into mass units during aircraft
loading. Other aircraft gaging system use ultrasonic signals to
measure tank fuel height. To deliver the proper fuel flow to
the combustion system the engine fuel control is programmed
to meter volume and to correct for fuel density and fuel temperature as well as other parameters.
Aircraft Range
Aircraft range is controlled by the total heat content of the
fuel in the aircraft. Maximum range is limited either by the
maximum allowable aircreift take-off weight (weight-limited)

CHAPTER 4: AVIATION FUELS


or by the total volume of tankage on the aircraft (volume limited). Either one is determined by fuel density and, in special
cases, an optimum fuel density has been selected for a particular long distance flight. In normal operations such an approach is not feasible. Aircraft operations have to EJIOW for
the density range permitted by specifications and routes,
which require maximum range, are usually avoided, particularly because atmospheric conditions such as winds Eind payload variability play a major part in determining fuel quantity
requirements.
CoiTOsivity

Copper
One of the early compatibility problems has been fuel attack
of system metals, particulcirly copper or copper-containing
materials. In aircraft fuel systems this frequently involved
fuel attack on bronze pump bearings. The primary fuel constituents involved in copper corrosion are elemental sulfur
and hydrogen sulfide, although acidic components may also
play a part. The most common source of hydrogen sulfide has
been incomplete stripping of the gas after refinery hydrotreating. Elemental sulfur (S), which is sulfur uncombined with other elements, has tended to result from the
chemicEd reduction of water-soluble sulfates in tank bottoms
by sulfate reducing bacteria or by the oxidation of hydrogen
sulfide. Elementcil sulfur has also been a byproduct of older

101

mercaptan conversion processes such as Bender or Doctor


treating. Both elemental sulfur and hydrogen sulfide are corrosive to copper at levels of around 1 ppm [26], but exact levels at which unacceptable corrosion occurs seem to depend
on the presence of other trace materials such as mercaptans.
Rather them limit either elemental sulfur or hydrogen sulfide, copper corrosion is therefore minimized by the copper
corrosion test, D 130, where pure copper is exposed to fuel at
100C (212F) for 2 h. Copper appearance is compared to a
standard color chart and only minimal discoloration is permitted. In addition, contact with copper or copper-containing eilloys is avoided as much as possible in aviation fuel systems and good housekeeping will prevent the proliferation of
sulfate reducing bacteria.
For jet fuel systems there is zdso great concern over copper
content in the fuel as the result of copper corrosion. Copper
concentrations as low as 15-20 ppb have adversely affected
thermal stability and copper levels above 30-50 ppb have decreased this property below the specification minimum [27].
Copper sources have included refinery heat exchangers,
bronze heating coils in marine tankers as well as bronze fuel
systems in Navy aircraft carriers. The reactant in an old mercaptan conversion process, Linde sweetening, can also be a
copper source.
Unfortunately, the relationship between the corrosion of
copper or bronze parts and the pickup of copper in jet fuel is
not clesu-ly established. Compatibility with copper-containing parts in the fuel system is controlled by the copper corro-

80
Temperature, C
FIG. 9Flammability limits vs. altitude.

100

102 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

sion requirement in the specification, but fuel passing tfiis requirement can dissolve the very low levels of copper, which
in turn can wreck thermal stability. At present the most reliable way to avoid pickup is to avoid contact with the metal or
to add an approved metal deactivator to chelate and deactivate the trace levels of copper in fuel.
Cadmium
The corrosion of cadmium-plated parts has been attributed
to mercaptan sulfur compounds, particularly in the presence
of water [28]. Mercaptan sulfurs are measured by D 3227 or
are limited qualitatively by the Doctor test, D 4952.
Steel
A form of corrosion in which the fuel plays an indirect role is
the rusting of mild steel by free water in fuel. Such corrosion
shortens the life of steel components but also is the source of
solid contamination, which ultimately has to be removed
from aviation fuels. U.S. military jet fuels require the presence of fuel-soluble corrosion inhibitors, generally dibasic
acids, which form a protective molecular layer on the steel
surface. MIL-PRF-25017 defines the requirements for this
t3^e of additive and approved additives are listed in the Qualified Products List for the specification. The dual function of
these additives as lubricity agents as well as corrosion inhibitors is discussed later in this chapter. Because these materials are surface-active and can interfere with water removal in the filter-coalescing process, their use in civil fuels
is very limited. Multi-product pipelines are protected by placing the additive into the non-aviation products. Fuel systems
at airports are usually internally coated to prevent rusting.
Galvanizing or zinc coating is not an acceptable method for
rust prevention in aviation systems because of the sacrificial
nature of zinc, which can react with the TEL in aviation gasoline or dissolve into jet fuel to form an ash during combustion.
Storage Stability
Petroleum products in long term storage are subject to low
temperature oxidation, which may cause the formation of
high molecular weight products that become insoluble and
precipitate out. Olefins formed during cracking are particularly prone to such degradation and are avoided in aviation
fuels. Straight-run jet fuels have excellent storage stability
due to the presence of natural oxidation inhibitors. However,
processes such as hydrocracking or high pressure hydrotreating destroy these inhibitors, leaving the product vulnerable to oxygen attack. In jet fuels such peroxide formation
[29] has led to repeated localized incidents of nitrile rubber
deterioration in military service [28]. Such elastomer attack
has not been reported with civil fuel in the U.S., probably due
to the greater amount of fuel commingling. Similar degradation tends to occur in aviation gasoline, which contains no
natural oxidation inhibitors and is therefore routinely inhibited with oxidation inhibitor additives.
Peroxide formation is prevented by oxidation inhibitors,
normally hindered phenols, which scavenge free radicals that
are the first step in the complex oxidation process [12]. Acceptable inhibitors are listed by composition in the jet fuel
and aviation gasoline specifications. To be effective, these in-

hibitors must be injected into the fuel as early as possible,


preferably into the run-down line from the processing unit.
Aviation gasoline susceptibility to oxygen attack is evaluated
in the Oxidation Stability test, D 873, in which fuel is exposed
to pure oxygen under pressure at 100C (212F) for 5 or 16 h.
The fuel is then evaporated and the residue ("gum"), together
with any lead precipitate, is weighed. Based on storage tests
conducted during World War II, passing test results are considered equivalent to one year of desert storage.
Tests on straight-run jet fuels in the 1960s showed oxidation at high temperatures to occur before oxidation at storage
temperatures. In fact, storage stability has not been a problem for such fuels. The D 873 requirement was therefore removed from D 1655. However, heavily hydrotreated or hydrocracked jet fuels should contain oxidation inhibitor to
assure the absence of peroxide formation. A test to establish
peroxide-forming tendencies has been published by CRC
[30], but is not yet approved by ASTM and has not been included in specifications.
Lubricity
In jet engine fuel systems a number of sliding metal surfaces
are lubricated by fuel. Under low contact pressures (hydrodynamic lubrication conditions) fuel viscosity assures separation of these parts. Under increased contact pressures or
higher sliding velocities (boundary lubrication) fuel viscosity
alone will not prevent metal to metal contact and a thin layer
of adsorbed polar material is also required to prevent surface
damage. Such material is present in straight-run fuels in very
low but adequate concentrations, but it is destroyed by high
pressure hydrotreating or hydrocracking. Such fuels have
therefore allowed metal to metal contact resulting in destructive wear of gears in high pressure pumps and sticking
of close-fitting servo valves in flow controls [31].
"Harsh" or "hard" fuels can be identified in the Ball on
Cylinder Lubrication Evaluator (BOCLE test), D 5001. Under a specified load, a stationary steel ball rubs against a rotating cylinder for 30 min. The contact area is submerged in
the test fuel and the entire test atmosphere is maintained at
a temperature of 25C (77F) and a relative humidity of 10%.
Afterward the ball wear scar is measured under a microscope. There are currently no specification limits for this
test, but a wear scar above 0.85 mm represents a very "hard"
fuel. Today the test is used primarily by engine accessory
manufacturers who have to qualify their components on
very hard fuels to assure satisfactory field performance.
However, under pressure from the New Zealand airworthiness authorities, the latest issue of DefStan 91-91 is the first
international specification to include a lubricity requirement for certain fuels.
In service, very hard fuels can be rendered acceptable by
the addition of as little as 10% straight-run product [32]. This
effect illustrates why lubricity problems have not been more
wide spread, having generally been averted by the extensive
commingling in most jet fuel systems. Problems have occurred in locations where hard fuels from a single supply
point were not mixed with other fuels and were supplied directly to aircraft. Even then different components responded
differently and failures occurred only on certain parts, mostly
on older units not qualified on hard fuel.

CHAPTER 4: AVIATION FUELS


Aside from hardwEire improvements, problem solutions include blending of hcird fuels with strciight-run product or the
addition of lubricity agents. Experience has shown fuel soluble
corrosion inhibitors to perform as lubricity agents, although
minimum dosages may differ for each use. Acceptable additives are covered by two military specifications and their qualified products lists. U.S. specification, MIL-PRF-25017, and
British Standard Def Stan 68-251 define additives suitable as
both corrosion inhibitors and lubricity agents. Neither of these
additive types are currently listed in civil specifications.
Static Electricity
Hydrocarbons are extremely poor electriccJ conductors but
usually contain trace levels of ionizable materials, which
carry charges of static electricity. With the fuel at rest the
charges neutralize each other. When fuel is moved, ions of
opposite charge are separated and an electrical charge is generated [33]. Local turbulence generated by pumps or filters
increases the charge, which is carried along unless the flow
velocity is reduced sufficiently for the charges to recombine.
When the fuel comes to rest, the charge leaks to ground. The
time required for the charge to bleed off depends upon the
fuel's conductivity. If conductivity is low, the charge may not
leak off gradually but be dissipated instead in the form of a
spark, which can become an ignition source. This process
takes place independent of system bonding or grounding.
However, all components of the fuel system, including the
aircraft, are electrically interconnected or "bonded" to eliminate the possibility of spEirks due to stray currents or lightning.
Static electricity problems can be minimized by slowing
the flow in lines, particularly after a filter, by providing an inert atmosphere over the fuel or by adding a conductivity improver additive to the fuel. Stadis 450 is the only conductivity improver approved for jet fuel and for aviation gasoline.
Outside the U.S. the additive is required in all jet fuel. In the
U.S., conductivity improver use in jet fuel is limited because
commonly used clay treaters in terminals remove the additive so that the fuel would require additive reinhibition. Instead, the emphasis is on providing charge relaxation by system design and operation. Guide D 4865 provides an
excellent review of the subject.
Other Properties
Data on other jet fuel properties not covered by specifications
such as thermal conductivity, specific heat, enthalpy, heat of
vaporization, thermal expansion, dielectric properties, and
bulk modulus will be found in the CRC Handbook on Aviation Fuel Properties [9]. This handbook includes data on both
commercial and military fuels.
FUEL MANUFACTURING
Aviation Gasoline
Low octane aviation gasoline can be straight-run gasoline
(grade 80) or based on premium grade motor gasoline (grade
82UL). The high octane grades (100 LL or 100) are based on
alkylate made by the process described in the following equa-

103

tion:
Catalyst

C4 olefins + isobutcuie

Alkylate

The olefins are separated from catalytic cracker products


while the catalyst is hydrofluoric or sulfuric acid. Alkylate
consists of branched chain paraffins, mostly iso-octctne. This
composition makes it a very high octane material of high
veilue to the refinery which can use the material to increase
the octane of either aviation or motor gasoline. In view of this
competition, as well as the low demeind for high octane aviation gasoline compared to motor gasoline, there is concern in
the aviation community regarding the long term availability
of the high octane aviation gasoline. This concern is sharpened by the uncertain future of tetraethyl lead. Like other
petroleum products, the ultimate availability of this fuel is expected to be determined by market forces.
Some blending is usually cEirried out for the high octane
gasoline. Isopentane increases vapor pressure, while toluene
increases the "rich" rating. Tetraethyl lead, along with the required scavenger and dye, is normally needed to reach the
necessary minimum octane levels. Oxidation inhibitor is always added to obtain storage life. Overall, aviation gasoline
has become a specialty product and, in the U.S., it is the only
remaining fuel containing lead.
Jet Fuel
Jet fuel processing starts with its separation from crude oil by
distillation, with the jet fuel fraction in the 150-290C
(300-550F) boiling range. Depending on the crude, a few
such streams are directly suitable as jet fuel, but most require
further treating. Mercaptan sulfurs are converted to disulfides primarily by Merox treating; alternatively, they Eire converted by hydrotreating to hydrogen sulfide which is stripped
from the product. Other sulfur compounds may be removed
by more severe hydrotreating. An increasing number of refineries are hydrocracking heavier streams to make high
qucdity jet fuel with good low temperature characteristics. To
control thermal stability, streams from catalytic or thermal
cracking Eire excluded or are saturated by severe hydrotreating. Contacting by activated clay removes polar materials
that deteriorate fuel-water separation and which may also
adversely affect thermal stability. Salt driers may be used to
remove free water.
Unless a refinery makes jet fuel by hydrocracking, jet fuel
yield and quality are dependent on product boiling range and
on the crude slate. Table 6 shows the general effect of changing boiling range on jet fuel properties when the product is
made by distillation, followed by mercaptan treating [34].
Availability is maximized by making product with the widest
possible boiling range. In turn, the boiling range tends to be
limited on the low distillation end by flash point, while the
maximum distillation end point is controlled by the specification freezing point. The wide rEinge of yield and resultant
qucdity for some typical crudes are illustrated in Table 7 [35].
The table also reflects the difficulty of simultaneously improving critical properties when using a single crude oil.
As pointed out in the section on History, commercial kerosine was the original jet fuel. Today, mEiny refineries make a
single product saleable as either jet fuel, commerciEil kero-

104

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 6Effect of boiling range changes on product quality.


Lowering Initial Boiling Point
Increases
Decreases
Smoke point
Density
Hydrogen content
Flash point
MJ per kg
Aromatic content
Vapor pressure
Naphthalenes
Freezing point
Viscosity
MJ per m^

Increasing Final Boiling Point


Increases
Decreases
Density
Smoke point
Hydrogen content
Aromatic content
MJ per kg
Naphthalenes
Freezing point
Viscosity
MJ per m^

Leading to
Better combustion quality
Better low temperature properties
Higher gravimetric heat content
Poorer handling safety
Lower volumetric heat content

Leading to
Lower combustion quality
Poorer low temperature properties
Lower gravimetric heat content
Higher volumetric heat content
Unchanged handling safety

sine, or diesel blending stock by having this product meet the


specifications for the other products. Such a product is referred to as dual branded kerosine and is divided and suppHed to the differing uses at the distribution terminal. However, this approach has become more complex by differing
maximum sulfur limits for the two products in many parts of
the world. An additional complication in the U.S. is an EPA
requirement for red dye in high sulfur diesel fuel.
A current source of controversy and ongoing discussion is
the effect of non-petroleum crude starting materials and new
processing on jet fuel quality. Jet fuel specifications are performance based and reflect past experience. Therefore, they
cannot guarantee satisfactory performance when a major
change from past practice occurs. For example, using coal or
biomateriaJs as starting materials raises questions that can
only be answered by additional testing beyond current specifications.

compatibility with system materials. However, the procedures do not disclose whether an additive will affect performance that has to be evaluated by other testing. A similar
protocol does not exist for aviation gasoline, which has seen
very few additive changes over the years.
It should be noted that ASTM does not confer additive approval. Such approval must be initiated by the airframe and
engine manufacturers and approved by the airworthiness
agencies. Additive listing in ASTM aviation fuel specifications simply recognizes such approvals.
Specific Additives
Most additives are described in earlier sections of this chapter under specific properties, but Table 8 lists all jet fuel additives contained in D 1655 together with their permitted
dosages. Oxidation inhibitors, metal deactivator, and conductivity improver may be added at the discretion of the refiner. Other additives, such as fuel system icing inhibitors,
can only be added with the agreement of the purchaser. The
fuel manufacturer or fuel handler must declcire all additives
and their concentration. Several military specifications make
mandatory the addition of oxidation inhibitor, conductivity
improver, icing inhibitor, and corrosion inhibitors. Two new
additive categories are u n d e r active consideration by the
ASTM committee and could be in the specification by the
time this article is printed. These additives are leak detection
materials smd biocides.

ADDITIVES
General
Allowable additives in aviation fuels are tightly controlled for
safety and operational reasons. The procedures for evaluating the compatibility of additives with aviation turbine fuels
a n d with aircraft fuel system materials are spelled out in
ASTM Practice D 4054. The primary purpose of this practice
is to standardize additive testing requirements so that an additive manufacturer does not have to repeat the process for
each engine or airframe manufacturer. The testing procedures are very detailed and lengthy to assure satisfactory

A new jet fuel additive category in military use are thermal


stability improvers, termed JP-8 -1-100 because they are intended to add 100F (55C) to the u p p e r thermal stability
limit of the fuel [13]. The additive combination consists of ox-

TABLE 7Effect of crude oils on straight-run product quality.


Crude Oil Source
Property

Alaska

California

Boiling Range, C
Yield, %v
Density, kg/m^
Sulfur, %m
Smoke point, m m
Freezing point, C

Indonesia

Arabia

Libya

8.7
801
0.009
28
-32

12.3
817
0.214
24
-40

13.5

200-260
10.3
828
0.093
20
-44

5.7
0.43
17
-70

0.04
23
-40

CHAPTER
TABLE 8Jet fuel additives listed in D 1655-98b.
Antioxidants, 24 mg/L maximum
2,6-ditertiary-butyI phenol
2,6-ditertiary-butyl-4-methyl phenol
2,4-dimethyl-6-tertiary-butyl phenol
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
and tritertiary-butyl phenols
55% min. 2,4-dimethyl-6-tertiary-butyl phenol, plus 15% min, 2,6ditertiary-butyl-4-methyl phenol, remainder as monomethyl and
dimethyl tertiary-butyl phenols
72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. monomethyl and dimethyl tertisiry-butyl phenols
Metal deactivator, 2mg/L max at mainufacture of fuel, for retreatment
to total of 5.7 mg/L max N,N-disalicylidene-] ,2-propane diamine
Electrical conductivity additive, 3 mg/L max at manufacture of fuel,
for retreatment to total of 5 mg/L max
Stadis 450
Fuel system icing inhibitor, 0.10-0.15%v
Diethylene glycol monomethyl ether (diEGME)
Leak detection additive, 1 ppm max
Tracer A

idation inhibitor, metal deactivator and proprietary detergents and dispersants. Because the combination contains
powerful surfactants, currently only water-absorbing type filter media (commonly called filter-monitors) will operate in
the presence of water and the additive. However, a major effort to develop filter-separators capable of handling the additive holds considerable promise.
Table 9 shows the aviation gasoline additives and their permitted dosages as listed in D 910. They include tetraethyl lead
fluid, which must contain two atoms of ethylene dibromide
per atom of lead as well as one or more of three different
color dyes. Blending two or more of the approved dyes makes
additional colors. While dyes were originally required to
identify any fuel containing lead, today they serve both to
identify lead-containing fuel and to distinguish between the
several grades of aviation gasoline. Oxidation inhibitors, conductivity improver and fuel system icing inhibitors are also
permitted. Note that aviation gasoline can include isopropyl
alcohol as an icing inhibitor, but jet fuel Cctnnot.

TRANSPORTATION
Pipelines
In the U.S. most jet fuel is moved from the refinery by large
multi-product pipelines handling all fuels from gasoline to
diesel fuel. Lines with diameters as large as 40 in (100 cm) are
employed. These lines are normally operated on a fungible
basis where each product meets a single specification. All
suppliers meet that specification, the products then commingled and supplier identity is lost. Differing products are not
physically separated from each other, but operating the line
under turbulent flow conditions minimizes product mixing
at the interface between products. Each pipeline product cycle has its own product sequence to minimize interface material, which is an off-specification mixture of at least two
dissimilar fuels. Pipeline flow is maintained by controlling
pressure a n d flow volume while p r o d u c t s are constantly
added and removed. Products move at a speed of approximately 5 m p h (8 km/h) and, in one pipeline, take about two

4: AVIATION

FUELS

105

weeks to get from Texas to New Jersey, a distance of about


1500 miles (2500 km). Along each pipeline there are breakout
terminals, which are collections of tanks serving as distribution centers. Such tanks are also used to temporarily hold
product where pipeline diameters change. In a number of instances jet fuel is moved from a terminal to an airport by
pipeline as well. In most instances such pipelines are smaller
and are usually restricted to jet fuel.
Marine Transport
Outside the U.S., jet fuel tends to move from the refinery in
so-called "clean" tankersas distinguished from black oil
ships, which carry crude oil or residual fuel oil. Tankers vary
tremendously in size, although the largest ones carry only
crude oils. As in pipelines, product sequencing is carefully
controlled to minimize mixing. To reduce contamination by
other products, shippers try to maintain certain compartments or the entire vessel in jet fuel. Tanker compartments
today are usually epoxy coated to extend their life and also to
make t h e m easier to clean. E a c h c o m p a r t m e n t contains
cleaning equipment, which directs a high pressure spray of
hot or cold sea water against the inside of the compartment.
However, cleaning procedures must be CEirefuUy controlled
to avoid contaminating jet fuel with cleaning compounds. A
complicating factor in the handling of jet fuel is the inerting
of compartment ullage space with engine flue gases. Such
compartments are kept seeded under slight overpressure and
are normally not open for inspection or thorough cleaning.
Marine transport on inland waterways is usually by barges,
which may carry their own propulsion equipment or may be
moved by tugs. Their construction tends to be more basic
than that of tankers and usually does not include internal
cleaning equipment. As a result operators tiy to keep barges
in the same fuel grade as m u c h as possible.

TABLE 9Aviation gasoline additives listed in D 910-98.


Anti-knock agent, maximum dosage depends on grade
Tetraethyl lead plus sufficient ethylene dibromide to provide two
atoms of bromine per atom of lead
Dyes, maximum dosage depends on grade
Blue:
1,4-dialkylamino-anthraquinone
Yellow: p-diethylamino-azobenzene or 1,3-benzenediol 2,4bis[(alkylphenyl)azo-]
Red:
alkyl derivatives of azobenzene-4-azo-naphthol
Antioxidants, 12 mg/L max
2,6-ditertiary-butyl phenol
2,6-ditertiary-butyl-4-methyl phenol
2,4-dimethyl-6-tertiary-butyl phenol
75% min. 2,6-ditertiary-butyl phenol, plus 25% max. mixed tertiary
and tritertiary-butyl phenols
75% min. di- and tri-isopropyl phenyls plus 25% mstx. di- and tritertiary butyl phenols
72% min. 2,4-dimethyl-6-tertiary-butyl phenol, 28% max. monomethyl and dimethyl tertiary-butyl phenols
N,N'-di-isopropyl-para-phenylenediamine
N,N'-di-secondary-butyl-para-phenylenediamine
Fuel system icing inhibitors
Isopropyl alcohol (IPA, propein-2-ol), max dosage recommended
by aircraft manufacturer
Diethylene glycol monomethyl ether (diEGME), 0.10-0.15%v
ElectricjJ conductivity additive, 3 mg/L max, for retreatment 5 mg/L
max total dosage
Stadis 450

106 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Product is loaded into tankers by shore-based pumps or by


gravity if shore tanks have sufficient elevation above the
tanker. Off-loading, on the other hand, is by pumps located
in the lowest part of the tanker or barge. This mode of operation tends to leave a small amount of product at the bottom
of a compartment when the pump loses suction. The effect of
mixing this residue with the next product is covered in more
detail in the section on quality control.
Road Transport
Smaller volumes of product, particularly when moved relatively short distances, are handled by road transport. Such
tanker trucks have several compartments and do not have
pumps aboard. Product is unloaded by gravity into underground tanks or into a pump that lifts the product into aboveground tanks. Truck size and weight is limited by road restrictions. When possible aviation products are isolated to
specific trucks to minimize contamination. Most aviation
gasoline is moved by truck because the volumes are too small
for pipeline movements. Compared to large pipelines or water transport, truck transport is the most expensive mode of
product transportation.
Rail Transport
In some areas of the world aviation fuel is moved in rail Ccirs.
Rail transport does not have the flexibility of road transport;
in the U.S. it is limited to Alaska.
Airports
Airport fuel systems vary widely depending on the type of
product and the volumes handled by the airport. Low octane
aviation gasoline at small airports is handled through cabinet
dispensers similar to those in service stations. These units
contain a meter, a hose, and a simple filter. The aircraft is
parked at the dispenser and fuel is placed into the aircraft
"over wing" through the hose and a hand-held nozzle. At
larger airports, high octane gasoline or jet fuel is loaded into
tank trucks called fuellers, which drive to the aircraft. These
fuellers incorporate a fuel tank divided into several compartments, two or more hoses, a filter, a meter, a pump, and other
ancillary equipment. The hose may make a solid connection
with the aircraft through a pressure coupling or the fuel may
be placed into smaller aircraft over wing with a hand-held
nozzle. To avoid misfuelling, gasoline and jet fuel should not
be carried on the same vehicle. Also, where possible, different nozzle sizes with matching filler restrictors are used for
aviation gasoline and jet fuel. The advantage of fueller vehicles is their flexibility of positioning; the disadvantage is
ramp congestion, particularly when as many as four or five
truckloads are required for a jumbo jet. Airport congestion is
minimized by the use of hydrant systems. Two or more storage tanks are linked to the passenger terminal by a large diameter pipeline, which runs underground alongside the aircraft loading gates. Each gate has at least one hydrant pit
containing an underground pressure connection. Trucks,
termed hydrant vehicles, have one large hose, which is coupled to the underground connection. Fuel moves through
that hose, a meter, a filter and other plumbing and ultimately

gets into the aircraft through one or more hoses coupled directly to the aircraft fuel system. The entire hydrant system,
from the storage onward, is pressurized by a series of pumps
that maintain operating pressure right up to the aircraft. Underground pressures of 700-1000 kPa (100-150 psi) are common but must be reduced to 315 kPa (45 psi) maximum at the
aircraft inlet [36]. Unlike a fueller there is no pump abocird
the hydrant vehicle. A hydrant system avoids ramp congestion but permzinently fixes the location of fueling stations. All
major airports and many smaller ones incorporate hydrant
systems. VirtUcdly all airport fuel systems are commingled
systems where each fuel grade meets the same specification
and there is no segregation by individual suppliers.
B o n d e d Fuel
A separate fuel designation, applicable only to international
transportation, is "bonded fuel." Legally such fuel enters a
country under bond and must leave the country in international transportation use. Bonded fuel is not subject to domestic taxes such as excise or sales taxes. Depending on customs regulations, bonded fuel must be handled as a
completely segregated product in its own handling systems
while the fuel is in the country or it can be handled in regular distribution systems as long as its entire volume is accounted for. While originally developed for marine transport,
the concept is equcdly applicable to aviation and is used in
some airports for intemationsJ flights. Its use is limited by
economics as well as local customs regulations.

QUALITY C O N T R O L
General Philosophy
Quality control is intended to protect the fuel properties
needed for safe aircraft operation. Toweurd that purpose aircraft certification requires the fuel to fully meet the specification to which the aircraft was certified. This process starts
at the refinery where aviation fuel must fully meet the pertinent specification. In addition, fuel quality also has to meet
other requirements not in the specification. In their simplest
form those requirements are expressed as "clean and dry."
However, on its way from the refinery to the airport fuel is exposed repeatedly to water, solid contaminants and to other
fuels in multiproduct systems. Quality control therefore becomes an exercise in avoiding that type of contamination,
which cannot be corrected in the field, and removing other
contaminants at reasonable expense by placing appropriate
removal equipment at critical points in the system.
Contaminants
Any material not originally part of the fuel is considered a
contaminant. That definition includes free water, solids such
as rust or sand, microbial material, other fuels, unapproved
additives as well as more unusual materials such as solvents,
fertilizers, plastics, or paints soluble in aviation fuels.
Because aviation gasoline and jet fuel have different critical properties, quality control procedures as well as contamination removal equipment differ for each fuel type and are
described separately in the following sections.

CHAPTER 4: AVIATION FUELS


Aviation Gasoline
While all properties must meet pertinent specifications at the
aircraft, the most sensitive properties of high octane aviation
gasoline are the octane ratings and the volatility. Octane ratings are readily degraded by contamination with other distillate products. The lower the octane of the distillate, the
greater the adverse effect. Experience has shown the "rich"
rating to be the more sensitive, particularly because the
"rich" rating of most aviation gasolines tends to have less
margin above the specification minimum. This problem can
only be avoided by eliminating possible contact with other
fuels such as might occur in switching between different
products in transports. Volatility degradation occurs through
evaporation in storage and results in vapor pressure decreases and changes in distillation cheiracteristics. Depending on which component is lost through evaporation, there
may also be a decrease in octane rating. Unfortunately, none
of these effects are readily predictable. Instead it is necessary
to reestablish the specification compliance status at specified
locations or time intervals.
Solids and free water removal is carried out primarily by
settling in tankage at a rate of 15 min per ft (45 min per m) of
depth [37] and by further removal of solids with micronic filters. Because of the lower density and viscosity of gasoline
compcired to jet fuel, contaminant removed from aviation
gasoline is simpler and less complex as will be seen in the jet
fuel section.
There are no industry-wide quality control procedures for
aviation gasoline. Instead, each company foUows its own procedures, which tend to be similar throughout the industry.
Gasoline is fully tested against specification requirements at
the refinery and is then subjected to limited retesting upon
arrival at the distribution terminal. The tests normally run at
that location are listed in Table 10, but they can differ between suppliers. Sample handling must be done in accordance with D 5842 to avoid the loss of volatile components,
which can result in a low vapor pressure. Gasoline is again inspected on airport arrival for appeeirance, color, and density.
Only a single product grade should be carried in the transport
to the airport and in the fueling vehicle on the airport. In addition, product that has been in storage with no product
movement in or out should be checked for specification complicince at six-month intervals.
Jet Fuel
Jet fuel contamination can be divided into two broad categories: that which can be removed in the field and that which
cannot. The first category includes various solid contaminants and water, while the second category includes other fu-

TABLE 10Terminal receipt tests for aviation gasoline.


Knock rating by ASTM D 909 (If not available, knock rating by ASTM
D 2700)
Distillation by ASTM D 86
Reid vapor pressure by ASTM D 323, D 5191, or D 5190
Tetraethyl lead content by ASTM D 3341 or D 5059
Color by ASTM D 2392
Existent gum by ASTM D 381
Electrical conductivity (if required) by ASTM D 2624

107

els or other materials soluble in jet fuel. Unlike aviation gasoline, a major concern is over contamination with more
volatile materials that will lower the flash point. Solid and
water removal are more difficult with jet fuel because both
the density and viscosity of jet fuel are higher than those of
aviation gasoline. The equipment to remove contaminants as
well the quality control procedures are therefore more elaborate. In addition, a number of specialized field contamination detection procedures are in use.
Contamination Removal Equipment
Filter-Separators
The heart of contamination removal equipment is the filtersepcirator, shown diagrammatically in Fig. 10. Two sets of
cylindrical filter elements are mounted on a deck plate or a
meinifold in the case. First stage elements are termed coalescers, the second stage are separators. Both types usually
have a 6 in (15 cm) diameter; the total element length is proportioned to the maximum rated flow. Fuel flow in the first
stage elements is from inside to outside and outside to inside
in the second stage. In the first stage, at least one filtration
layer consists of tightly packed, hydrophobic glass fibers,
which force smeJl free water droplets to coalesce into leirger
droplets as fuel pushes the water droplets through the layer
[38]. Other layers remove and hold solid particulates. Most of
the coeJesced droplets slide down the outside of the first stage
elements. Those water droplets too small to settle between
stages Eire prevented from exiting with the fuel by the second
stage, which is also hydrophobic. This second stage is made
of Teflon-coated wire mesh or a special synthetic fabric supported by a perforated meted cylinder. The coalesced free water collects in a sump at the bottom of the case and is removed by manually opening a drain valve. A high water
indicator, usually a float or an electronic water level probe in
the sump, shuts off the entire fuel flow if the water level rises
too high and threatens to be carried out with the clean fuel.
A direct reading differential pressure gauge measures the total pressure drop across both sets of elements.
Filter-separators are designed to keep operating when subjected to contaminated fuel. Their minimum performance is
governed by an industry specification issued by the American
Petroleum Institute as API Specification 1581. This specification delineates the solid and free water concentrations
added during qualification testing and dictates the maximum
levels of both contamineint types permitted in the effluent.
The latest version of the specification, Issue 4, was published
in early 2000 and to take effect in January 2002. It contains
three test fuel types. Category C is Jet A plus a conductivity
improver, a corrosion inhibitor aind a sulfonate. Category M
is JP-8 or JP-5 containing military additives. Category MlOO
is Category M plus the JP-8 + 100 additive. Category C is intended for civil use, while the other two categories are for the
U.S. military. Two performance levels are called out. Type S
is to be used where significant solids and water are expected.
Type S-LD, with a lower dirt holding capacity, is intended
where significcint water but low solids are expected. The standard solid contaminant is 90%m A-1 ultrafine dust and 10%
m Copper as red iron oxide. These are major changes from Issue 3 which specified Fischer red iron oxide of about 0,1 micron particle size as the solid contamineint and did not in-

108 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

iST STAGE
COALSECER ELEMENTS
(INSIDE TO OUT fLOW)

2ND STAGE
SEPARATOR ELEMENTS
(OUTSIDE TO IN FLOW)

INLET MANIFOLD
UTLET MANIFOLD

INLET

OUTLET

FIG. 10Cutaway of filter-separator.

elude military fuels. Nominal coalescer pore size is expected


to be between 0.3 to 0.5 microns. Second stage pore size is
much coarser and is not designed for dirt removal. Approvals
cover only specific elements in specific housings and are not
transferable to other housings.
While the U.S. military has issued its own specifications in
the past, the current trend is toward the use of equipment
meeting the industry specification, API 1581.
Water-Absorbing Cartridges or Monitors
Sometimes called fuses, these units are designed as a last
chance safeguard, which shuts down a system in the presence
of water in the fuel. Their primary component is a cellulose
layer that normally expands when wetted. By tightly constraining this layer, it compresses when wetted and shuts off
fuel flow. Monitor elements are 2, 4, or 6 in. in diameter, depending on the application. The total length of elements is directly proportional to the rated flow of the filter. Because of
their operating mode, monitors are located only at the last filtration point just ahead of the aircraft, where they may be the
only final filter or be placed after a filter-separator. Alternatively, some operators use them as a second stage in place of
the separator elements. Monitors can also be the final filters
in aviation gasoline system. They are not normally placed

further upstream because the elements have to be replaced in


case of a shutdown by free water.
Two specifications govern monitor performance. MIL-M81380 is issued by the U.S. Navy. A specification issued by the
Institute of Petroleum (IP) is similar but requires a higher
solids holding capacity. This specification is being replaced
by a joint API/IP specification, API 1583. Both specifications
severely limit the amount of free water that Ccin pass through
the monitor before it closes off. These units generally have a
nominal 1 micron pore size rating. Latest specification revisions eJso guard against media migration under greatly reduced flow rates.
Clay Treatment Vessels
While similar in external appearance to filter-separators, the
elements in clay treatment vessels are filled with activated
clay to adsorb polar materials such as surfactants. This clay
is the same as mentioned earlier in the Manufacturing section, the big difference being in the depth of clay as well as
the rate at which fuel passes through the clay. This difference
results in a 50 times reduction in contact time and a similar
reduction in the vessel's capacity to remove surfactants. Field
clay treatment vessels are therefore considered "polishing"
units with rather limited adsorption capacity. They are nor-

CHAPTER 4: AVIATION FUELS


mally intended to remove traces of polar additives picked up
by jet fuel in multiproduct transportation systems. However,
this adsorptive capacity has mitigated against the general use
of conductivity additive because the wide presence of clay
field units in the U.S. would remove the additive and require
constant additive reinhibition. Conversely, outside the U.S.
the additive is in general use and clay treaters are not. There
are no government or industry performance specifications
covering clay treatment vessels.
Micronic Filters (also Microfilters or Prefilters)
Another weapon in the cleanup arsenal consists of filter elements, usually made of pleated paper and mounted in a pressure vessel. These units remove only solid particles, but they
do so at a much lower cost than filter-coalescers and are
therefore placed ahead of filter-separators when significcmt
solid contamination occurs. Nominal pore sizes rajiging generally from 0.3-2 microns are in widest use in jet fuel and
from 0.5-5 microns for aviation gasoline, with the optimum
pore size selected on the basis of operating experience. Here
again, there are no government specifications for these units.
A specification for microfilters dated April 2002 has been issued as API/IP 1590.

109

fuel usually being a water white color. Color rating methods


include Saybolt color by D 156, or the more recent tri-stimulus method, D 6045. Either method is seriously handicapped
by the fact that on-specification jet fuel can have a range of
colors and color, as such, is not a jet fuel performance parameter. Only a change from the original fuel color is therefore useful as a possible indicator of contamination, which
has to be ruled out by specification tests.
A requirement peculiar to the U.S. involves the use of red
dye to identify high sulfur diesel fuels and heating oils as well
as untaxed diesel fuel and heating oil. While the dye is not required in jet fuel, a number of cases of jet fuel contaminated
with red dye have occurred by the mixing of jet fuel with dyed
product. Because of possible adverse effects on thermal stability, the use of dye-contaminated fuel in aircraft is not permitted. A Boeing service letter [40] specifies the use of white
bucket appearance as the measure of fuel acceptability. A
portable spectrometer capable of measuring dye levels quantitatively is under development in ASTM but is not currently
approved. An extensive program is also underway at the
Southwest Research Institute to establish acceptable dye
concentrations in high temperature engine components [41].
Solid Particles

Filter Locations
Although there are no industry standards for terminal installations, fuel receipts tend to go through a micronic filter into
tankage. When going out of terminaJ tankage to an airport
the fuel passes through em optional micronic filter, followed
by a clay treatment vessel and last through a filter-separator.
At the airport the minimum filtration is through a filter-separator into storage, a filter-separator out of storage into fueling trucks, or into a hydrant system and through a final filterseparator on the fueling vehicle into the aircraft. Filtration
into storage may be supplemented by a micronic or a clay
unit, while the final filtration unit may be a monitor in place
of or in addition to the final filter-separator.
Contamination Detection Equipment
Much of the following equipment, while in extensive worldwide use, has not been standardized by ASTM, but is described in detail in ASTM Manual 5 [39].
Visual Appearance
The appearance of jet fuel is routinely checked in either a
one-liter jar made of clear glass or a white porcelain or stainless steel bucket. The glass is more likely to disclose the presence of fine, suspended material, while the bucket allows the
examination of a larger sample easily taken from a large
drain line. In addition, the white bucket has proven most sensitive to product color, which can indicate contamination
with other darker or dyed fuels. However, such appearance
checks are only a gross measure of possible contamination
and do not disclose levels of solids or free water that are not
visible to the neiked eye. More sensitive tests for contamination are described in the following sections.
Product Color
Quantitative color measurement can be used for the detection of other petroleum products having darker colors, jet

Solid particles are collected on special membrane filters


made of mixed cellulose acetate esters with an absolute pore
size of 0.8 microns. Filter membrane requirements are detailed in ASTM Research Report RR-D02-1012. For particle
collection the membranes are mounted in plastic monitors
that are encased in a brass housing. A fixed volume of fuel is
bled through the membrane off a flowing line under pressure. The solids content of the sample can be established
quantitatively by weighing the dried membrane or the dirt
level can be described by comparing the membrane color to
a standard chart. Both approaches are described in D 2276.
Because of the normal variability in particle size, color, and
density, there is no direct relationship between the two types
of assessments. The mass measurement must be done under
laboratory conditions, while the color rating is carried out in
the field.
Free Water
A number of water detection methods, ranging from coarse
to precise, are in general use. Water finding paste, which
changes color on contact with a water layer, is smeared on
gaging sticks or tapes to disclose the depth of the water layer
in a storage tank or ship's compartment. This process is often
called a "water cut." Suspended, free water is detected by several methods. Three methods used at plane-side include the
Shell Detector, the Velcon Hydrokit, and the Metrocator test
[39]. Each test is calibrated to show a visible color change at
the presence of either 15 or 30 ppm of free water, these levels
being called out in quality control procedures. These tests not
only eliminate the operator judgement involved in visual examinations, but are also more sensitive than the eye of a
trained operator who normally can detect a water haze down
to the 50 ppm level. The most sensitive test for undissolved
water is the Aqua-Glo test, D 3240, which can detect undissolved water down to 2-3 ppm. This test is based on the reaction of free water with a fluoresceine dye, which impregnates a fiberglass disk. After passing 500 mL of fuel through

110 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

the disk, einy increased level of fluorescence due to water is


measured under ultraviolet light and is translated into ppm
of free water.
Water content can also be established in the laboratory by
the Karl Fischer titration procedure, D 6304. However, this
procedure measures total water content or the sum of dissolved and free water. Because aviation fuel filters do not remove dissolved water, measuring only free water by the preceding tests is a more effective way of checking the operation
of filter-separators or monitors.
Surfactants
Surfactants, or more properly surface active agents, are
molecules in which one portion is polar and is water soluble
(hydrophilic). The other portion is non-polar and is oil soluble (hydrophobic). As a result surfactants affect the surface
characteristics of fuel-water systems. Their concentration is
highest at the interface between water and hydrocarbon and
results in a decrease of the interfacial tension. Mixing the
fuel-water-surfactant system will form emulsions, which can
prevent small water droplets from settling out. In addition,
surfactants can affect the surfaces of fibers in filter-coalescers and prevent them from coalescing small water
droplets. Such cocdescers Eire considered disarmed. On the
other hand, surfactants do not appear to affect monitor performance.
Surfactants are widely used in the petroleum industry as
corrosion inhibitors, lubricity agents, conductivity improvers, gasoline detergents, and cutting oil emulsifiers.
While coalescers are designed to operate with certain specific
jet fuel additives, which are surfactants, other surfactants
will disarm the elements and have to be detected and removed. Of two available tests the less sensitive test, D 1094,
measures the ability of water and fuel to separate cleanly after mild shaking. Because of its dependence on ultra-clean
glassware this test should be performed in the laboratory. A
much more sensitive test, D 3948, evaluates the ability of a
miniature coalescer to remove very fine fuel droplets from a
fuel-water emulsion. By being self-contained and utilizing
disposable components this procedure can be conducted in
the field and avoids possible contamination by sample containers. As already mentioned, surfactants are removed from
jet fuel by clay treaters, which adsorb polcir materials.
Microorganisms
Many microorgstnisms can metabolize hydrocarbons, others
can utilize sulfur. Some require oxygen, others need its absence. Mciny exist naturally in soil or ground water. All have
one common characteristicthey must have undissolved,
free water to grow and reproduce. As a result, most microbial
growth is at the fuel-water interface. Metabolic products,
usually acidic, tend to be corrosive to metals, particularly aluminum. These products may also act as surfactants. Microorganisms commonly form slimes or mats that can plug
screens or filters. Unfortunately for jet fuel, the problem microbes prefer to metabolize normEil paraffins in the C12 and
higher range [42], molecules that are a common constituent
in jet fuels.
The most reliable defense against microbicil growth is the
elimination of free water in jet fuel systems. Frequent draining of all sumps and system low spots is sai important part of

such precautions. An alternative is the use of approved biocides mentioned earlier, but the possible adaptation of specific microbes to a biocide has to be kept in mind. The simplest form of detection is a visual and olfactory examination
of water samples from jet fuel systems. Dark or black water,
together with a foul or rotten odor, are usually indicative of
microbial activity. Laboratory testing can indicate the viability and type of microorganisms, but system inspection is usually the best indicator of whether cleaning is required. Much
more detailed information on the subject of microorganisms
in hydrocarbon systems will be found in a new standard
guide, D6469.
Quality Control Procedures
U.S. Procedures
Similcir to aviation gasoline, jet fuel is fully certified against
pertinent specifications at the time of manufacture. In the
U.S. this is normally D 1655, Grade Jet A. Quality is often
rechecked after arrivEil in the terminal with the tests listed in
Table 11. However, this test lineup is experience-based and
Ccin differ significantly from one company to einother; thus,
some shippers require complete specification recertification
of product introduced into their system. Product is settled in
storage for one hour per foot of fuel depth [37]. The pressure
drop across each filter is checked daily. Sumps are drained at
least weekly and after receipt of product. Periodically, usually
once a month, the proper operation of the filter-separator is
checked by rurming a membrane test emd a free water check.
Once approved and settled, the product is shipped to the
airport by transport or pipeline. However, none of these operations are governed by industry standcirds and it is the responsibility of the operating company to furnish on-specification, "clear and bright" fuel to the airport.
Airport quality control is more systematic. The Air Transport Association of America (ATA) has issued a specification,
ATA 103, which is recommended for its member airlines or
virtually EJI U.S. eind Canadian airlines. Additionally, member airlines can require the specification to be followed by independent airport biel dealers who supply these airlines. All
jet fuel delivered to U.S. airports must meet ASTM D 1655 in
order to meet the certification requirements of the various
aircraft. As indicated in Table 12, when ATA 103 is to be followed, certain tests must be furnished by the shipper on the
specific shipment. Other tests are conducted at the airport
during and after product receipt. Additional periodic testing
to be carried out at the airport is listed in Table 13. Failure to
meet any of these requirements is cause for immediate investigation.

TABLE 11Terminal receipt tests for jet fuel.


Density by ASTM D 1298 or D 4052
Distillation by ASTM D 86
Flash point by ASTM D 56 or D 3828
Freezing point by ASTM D 2386, D 4305," D 5901, or D 5972
Existent gum by ASTM D 381
Water reaction by ASTM D 1094
Electrical conductivity (if required) by ASTM D 2426
"If D 4305 is used it must be accompanied by measuring viscosity
at -20"'C by ASTM D 445.

CHAPTER
It should be noted that ATA 103 includes other aspects of
airport quality control as well, but these do not directly involve fuel quality.
International

Procedures

Somewhat similar procedures are followed outside the U.S,


the primary difference being the issuing authority. Here the
procedures are being issued as guidelines by the Interna-

TABLE 12Airport quality control per ATA 103.


Airport Receipt Requirements
Specification: ASTM D 1655, Jet A or A-1
Pipeline or Marine Delivery
Truck or Rail Delivery
Tests from Shipper

Visual-white bucket
API Gravity @ 60F (15C)
Distillation
Flash point
Freeze point
Water reaction
Copper corrosion
Existent gum

Visual-white bucket
API gravity eO^FClS^C)

FUELS

111

tional Air Transport Association (lATA) to be used by individual airline members as part of contractual requirements
with suppliers. Ultimately, it is hoped to merge ATA 103 with
the LATA Guidelines to create a single set of worldwide airport quality control procedures, but the success of this endeavor cannot be predicted at this time.
Aircraft

Procedures

Small amounts of water can become a problem if the water is


not removed from tank sumps. Older aircraft require a routine sumping procedure to remove the settled free water
while newer aircraft have a water scavenging system that performs this function automatically. If small quantities of water are allowed to accumulate, boost p u m p inlet screens can
ice over, biological growths can develop and, if large quantities are allowed to accumulate, exposure to engine flame-out
is possible.

OVERVIEW AND CONCLUSIONS

Testing During Receipt at Airport

When: Beginning (after line


displacement)
Every 2 h
Near end
What: Visual-white bucket
API gravity (within 1)
Membrane color
2 dry max/1 gsillon
3 wet max/1 gallon
A msix particles
Free water 15 ppm msix
Flash point (multiproduct
line only)

4: AVIATION

From compartment
before unloading
Visual-white bucket
API gravity (within 1)

After Receipt on Tank Contents

Visual-white bucket
API Gravity @ eCF (15C), within 1
Distillation, within 8C
Flash point, within SX"
Freezing point, within 3C
''Variability allowed from supplier's certificate.

For safety reasons, specifications and handling procedures


for aviation fuels are more tightly controlled than for other
products. Minor changes in fuel properties, cleanliness, or
contamination levels can have unanticipated effects on jet
engine performance because of the complexity of m o d e m jet
engines and the massive amounts of fuels that flow through
the engines. The current aviation fuel supply and delivery system is based on accumulated experience, which has evolved
over a long period of time. There is a reluctance to make
changes because the impact of such changes cannot always
be predicted without a thorough investigation. The challenge
for the future will be for the aviation technical community to
anticipate, identify, and eliminate possible fuel-related problems. These problems could arise from the incorporation of
new non-traditional supplies, changes in refinery processing,
the reformulation of transportation fuels resulting from
tough, new environmental regulations, changes in the transportation of fuel to the aircraft, and new engine emd aircraft
requirements. An additional challenge could come from measures required to improve aircraft safety. Resolution of prob-

TABLE 13Airport fuel quality requirements per ATA 103, other required checks.
Daily Required Checks
Filter pressure drop
Change elements at 15 psi
Monitor pressure drop
Change elements at 25 psi
Drain filter sumps
Inspect with white bucketone gallon sEimple minimum
Drain storage tank sumps
Inspect with white bucketone gallon sample minimum
Drain fueling truck
Inspect with white bucketone gallon sample minimum
Monthly Required Checks

Downstream each airport filter

Free water
Membrane color
Particulate assessment

15 ppm max
2 dry/gal or 3 wet/gal
A max

Drain hydrant system low points


Other Requirements

Filter element specification


Monitor element specification
Replace coalescer elements
Replace monitor elements
Inspect storage tanks
Suggested settling time

API 1581, Group B (Group C for final vehicle)


IP specification for monitors
Yearly, with one year extension
Every two years
Yearly
1 h per ft (3 h per m) of vertical depth

112 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

lems can have an impact on legal issues such as the assignment of liability and can have large financial consequences.
The complexities of the interactions between the technical,
legal, and financial aspects associated with aviation fuels can
therefore make it difficult at times to resolve problems, but
such problems must be addressed to maintain and, if possible, improve the reliability of the entire system.

ASTM STANDARDS
Unless otherwise indicated all of the following standards are
current.
No.

Title

D 56
D 86
D 130

Test Method for Flash Point by TAG Closed Tester


Test Method for Distillation of Petroleum Products
Test Method for Detection of Copper Corrosion
From Petroleum Products by Cu Strip Tarnish Test
Test Method for Saybolt Color of Petroleum Products
Test Method for Vapor Pressure of Petroleum Products (Reid Method)
Test Method for Kinematic Viscosity of Transparent cind Opaque Liquids
Test Method for Knock Characteristics of Aviation
fuels by the Aviation Method (discontinued 1970)
Specification for Aviation gasoline (discontinued
1946)
Test Method for Oxidation Stability of Aviation Fuels (Potential Residue Method)
Test Method for Knock Characteristics of Aviation
gasoline by the Supercharge Method
Specification for Aviation Gasoline
Guide for Petroleum Measurement Tables
Practice for Density, Relative density (Specific
Gravity) or API Gravity of Crude and Liquid
Petroleum Products by Hydrometer Method
Test Method for Hydrocarbon Types in Liquid
Petroleum Products by Fluorescent Indicator Adsorption
Test Method for Smoke point of Aviation Turbine
Fuels
Specification for Aviation Turbine Fuels
Test Method for Luminometer Numbers of Aviation
Turbine Fuels
Test Method for Naphthalene Hydrocarbons in Aviation Turbine Fuels by Ultraviolet- Spectrophotometry
Test Method for Freezing Point of Aviation Fuels
Test Method for Color of Dyed Aviation Gasolines
Test Method for Knock Characteristics of Motor
and Aviation Fuels by the Motor Method
Test Method for Mercaptan Sulfur in Gasoline,
Kerosine, Aviation Turbine and Distillate Fuels (Potentiometric Method)
Test Method for Undissolved Water in Aviation Turbine Fuels
Test Method for Thermal Oxidation Stability of Aviation Turbine Fuels (JFTOT Method)
Test Method for Estimation of Net Heat of Combustion of Aviation Fuels

D 156
D 323
D 445
D 614
D 618
D 873
D 909
D 910
D 1250
D 1298
D 1319
D 1322
D 1655
D 1740
D 1840
D 2386
D 2392
D 2700
D 3227
D 3240
D 3241
D 3338

D 3701 Test Method for Hydrogen Content of Aviation Turbine Fuels by Low Resolution Nuclear Magnetic
Resonance
D 3948 Test Method for Determining Water Separation
Characteristics of Aviation Turbine Fuels by
Portable Separometer
D 4052 Test Method for Density and Relative Density of
Liquids by Digital Density Meter
D 4171 Specification for Fuel System Icing Inhibitor
D 4305 Test Method for Filter Flow of Aviation Fuels at
Low Temperatures
D 4809 Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method)
D 4865 Guide for Generation and Dissipation of Static
Electricity in Petroleum Fuel Systems
D 4952 Test Method for Qualitative Analysis of Active Sulfur Species in Fuels and Solvents (Doctor Test)
D 5001 Test Method for Measurement of Lubricity of Aviation Turbine Fuels by the Ball-On-Cylinder Lubricity Evaluator (BOCLE Test)
D 5191 Test Method for Vapor Pressure of Petroleum Products (Mini Method)
D 5842 Practice for Sampling and Handling of Fuels for
Volatility Measurement
D 5901 Test Method for Freezing of Aviation Fuels (Automatic Optical Method)
D 5972 Test Method for Freezing of Aviation Fuels (Automatic Phase Transition Method)
D 6045 Test Method for Color of Petroleum Products by the
Automatic Tristimulus Method
D 6227 Specification for Grade 82 Unleaded Aviation Gasoline
D 6304 Test Method for Determination of Water in
Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fisher Method
D 6378 Test Method for Determination of Vapor Pressure
(VPx) of Petroleum Products, Hydrocarbons and
Hydrocarbon-Oxygenate Mixtures (Triple Expansion Method)
D 6424 Test Method for Octane Rating Naturally Aspirated
Spark Ignition Aircraft Engines
D 6469 Standard Guide for Microbial Contamination of Fuels and Fuel Systems
OTHER STANDARDS
U.S. Military Aviation Turbine Fuel and Additive
Specifications^
No.

Title

MIL-PRF-5624

Turbine Fuel, Aviation Grades JP-4, JP-5,


and JP-5/JP-8 DT
MIL-PRF-25017 Inhibitor, Corrosion/Lubricity Improver,
Fuel Soluble
MIL-DTL-27686 Inhibitor, Icing, Fuel System
MIL-PRF-38219 Turbine Fuel, Low Volatility (Grade JP-7)
^ These standards are available from Defense Printing Service Detachment Office, 700 Robbins Ave., Piiiladelphia, PA 19111-5094.

CHAPTER 4: AVIATION FUELS 113


MIL-M-81380
MIL-DTL-83133

Monitor, Contamination, Aviation Fuel


Dispensing System
Turbine Fuel, Aviation, Kerosine Type
(Grade JP-8)

U. K. M i l i t a r y A v i a t i o n T u r b i n e F u e l a n d A d d i t i v e
Specifications
These standards are available from Ministry of Defence, Directorate of Standardization, 65 Brown Street, Glasgow G2
SEX.
No.
Title
ATF High Flash AVCAT/FSII
ATF Wide Cut AVTAG/FSII
AVGAS Gasoline Aviation 80 and
lOOLL (low lead)
Turbine Fuel, Aviation Kerosine
Defence Standard 91-91
Type, Jet A-1
Defence Standard 91-251 Fuel System Icing Inhibitor
(FSII)
Defence Standsird 68-251 Fuel Soluble Pipeline Corrosion
Lubricity Improving Additive
Defence Standard 91-86
Defence Standard 91-87
Defence Standard 91-90

Industry Specifications
API/IP 1581 Specifications and Qualification Procedures for
Aviation Jet Fuel Filter/Separators
API/IP Specification for Similarity for API/IP 1581 Aviation
Jet Fuel Filter/Separators
API/IP 1583 Specifications and Qualification Procedures for
Aviation Fuel Filter Monitors with Absorbent T5rpe Elements
API/IP Specifications and Qualification Procedures for Aviation Fuel Microfilters
ATA 103, Standards for Jet Fuel Quality Control at Airports
LATA Guidance Material for Aviation Turbine Fuels Quality
Control and Operating Procedures, Incorporating Joint Inspection Group Guidelines for Joint Airport Depots and
Joint into Plane
lATA Guidance Material for Aviation Turbine Fuels

REFERENCES
[1] Ogsten, A. R, "A Short History of Aviation Gasoline Development, 1903-1980," Preprint No. 810848, SAE, West Coast International Meeting, Seattle, WA, 3-6 August 1981, Society of Automotive Engineers, Warrendale, PA.
[2] Dukek, W. G., "Aviation Fuel: Its Energy has Knit the World,"
Standardization News, ASTM International, West Conshohocken, PA, April 1998.
[3] Defence Standard 91-91: Turbine Fuel, Aviation Kerosine, Type
Jet A-1, Issue 3, Ministry of Defence, Directory of Standardization, Glasgow, FG2 SEX, United Kingdom, November 1999.
[4] Guidance Material for Aviation Turbine Fuel, fourth edition. International Air Transport Association, Montreal, Canada, March
1999.
[5] Winkle, T. L., Affens, W. A., Beal, E. A., Hazlett, R. N., and
DeGuizeman, R., "The Distribution of Higher n-Alkanes in Partially Frozen Middle Distillate Fuels," NRL Report 8869, Naval
Research Laboratory, Washington, DC, 10 April 1985.
[6] Smith, M., Aviation Fuels, G. T. Foulis & Co Ltd, Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 272-278.

[7] Honsberger, B. A., "Jet A Exposure to Freezing on Very Cold


Temperatures," Boeing Company CommercicJ Airplane Group,
presented to CRC Group on Low Temperature Performance of
Aviation Turbine Fuel, June 1991.
[8] Unpublished minutes of the CRC Low Temperature Performance of Aviation Turbine Fuels, Coordinating Research Council, Atlanta, GA, May 1999.
[9] Aviation Fuel Properties, CRC Report No. 530, Coordinating Research Council, Atlanta, GA, 1983.
[10] Final Report, Fuel Tank Harmonization Working Group of Aviation Rulemaking Advisory Committee, Federal Aviation Administration, Washington, DC, July 1998.
[11] Rogers, J. D., "Turbine Fuel Thermal Stability," SAE Preprint
103T, Society of Automotive Engineers, National Aeronautic
Meeting, Los Angeles, CA, 5-9 Oct. 1959.
[12] Thermal Oxidation Stability of Aviation Turbine Fuels, Monograph /, R. N. Hazlett, Ed., ASTM International, West Conshohocken, PA, 1991, pp. 72-91.
[13] Heneghan, S. P., Zabamik, S., Ballal, D. R., and Harrison, W. E.,
Ill, "JP-8 + 100: TheDevelopmentof High-Thermal-Stability Jet
Fuel," Transactions oftheASME, Vol. 118, September 1996.
[14] Strauss, K. H., "Survey of Current Engine Conditions," CRC Report 573, Coordinating Research Council, Atlanta, GA, 1983.
[15] Strauss, K. H., "Thermal Stability Testing of Jet Fuel - A Critical
Review," Technical Paper 881532, Society of Automotive Engineers, Aerospace Technology Conference, Anaheim, CA, 3-6
Oct. 1988.
[16] Baker, C, David, P., Taylor, S. E., and Woodward, A. J., "Thickness Measurement of JFTOT Tube Deposits by EUipsometry,"
Proceedings of 5th International Conference on the Stability and
Handling of Liquid Fuels, Rotterdam, 1994, pp. 433^47.
[17] Unpublished minutes of the Groups on Aviation Engine Octane
Rating and Unleaded Avgas Development, Coordinating Research Council, Atlanta, GA, 1995.
[18] Sherwood, W. D., "SST FuelsA Major Airline Concern,"
Preprint 911C, Society of Automotive Engineers, National Aeronautic and Space Meeting, Los Angeles, CA, 5-9 Oct. 1964.
[19] Gleason, C. C, Oiler, T. L., Shayeson, M. W., and Bahr, D. W.,
"Evaluation of Fuel Character Effects on FlOl Combustion System," AFAPL-TR-79-2018, General Electric Company, Cincinnati, OH, June 1979.
[20] Lefebre, A. H., "Influence of Fuel Properties on Gas Turbine
Combustion Performance," AFWAL-TR-84-2104, Purdue University, Lafayette, IN, January 1985.
[21] Dickson, C. L., "Aviation Turbine Fuels, 1998," National Institute for Petroleum and Energy Research, NIPER-175 PPS,
March 1998.
[22] Blade, O. C, "Aviation Fuels, 1964," U.S. Dept. of Interior, Bureau of Mines, Petroleum Products Survey No. 39, 1964.
[23] Rickard, G. K. and Fulker, R., "The Quality of Aviation Fuel
Available in the United Kingdom Annual Survey 1997," Technical Report DERA/MSS1/TR980069/1.0, Version 1.0, Department
of Defence, United Kingdom, May 1998.
[24] Gibbons, T. R., "Flash Point Methods Applicable to Jet Fuel,"
Factors in Using Kerosine Jet Fuel of Reduced Flash Point, STP
688, ASTM International, West Conshohocken, PA, 1979.
[25] Final Report, Fuel Taiik Harmonization Working Group of Aviation Rulemaking Advisory Committee, Federal Aviation Administration, Washington, DC, July 1998.
[26] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 369-371.
[27] Hazlett, R. N., Thermal Oxidation Stability of Aviation Turbine
Fuels, Monograph 1, ASTM International, West Conshohocken,
PA, 1991, pp. 111-113.
[28] Smith, M., Aviation Fuels, G. T. Fouhs & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 117-118.
[29] "Determination of the Hydroperoxide Potential of Jet Fuels," CRC
Report 559, Coordinating Research Council, Atlanta, GA, 1988.

114 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


[30] Pande, S. G, Black, B. H., and Hardy, D. R., "Development of a
Test Method for t h e Determination of the Hydroperoxide Potential and Antioxidant Effectiveness in Jet Fuel During Long
Term Storage," CRC Report 614, Coordinating Research Council, Atlanta, GA, 1998.
[31] "Aviation Fuel Lubricity Evaluation," CRC Report 560, Coordinating Research Council, Atlanta, GA, 1983.
[32] Defence Standard 91-91: Turbine Fuel, Aviation Kerosine, Type
Jet A-1, Annex B, Ministry of Defence, Directory of Standardization, Glasgow, FG2 8EX, United Kingdom.
[33] Bustin, W. M. and Dukek, W. G., Electrostatic Hazards in the
Petroleum Industry, Research Studies Press Ltd, Letchworth,
England, 1983.
[34] Strauss, K. H., "Future U.S. Jet FuelA Refiner's Viewpoint,"
AIAA-81-0770, AIAA/SAE ASCE 1981 International Air Transportation Conference, Atlantic City, 26-28 May 1981.
[35] "Crude Assays," Oil and Gas Journal, April through August 1983

[36] Smith, M., Aviation Fuels, G. T. Foulis & Co. Ltd., Henley-onThames, Oxfordshire, United Kingdom, 1970, pp. 192-196.
[37] Robertson, A. G., "Jet Fuel Settling," Shell Aviation News, Vol.
351, 1967, pp. 17-28.
[38] Hughes, V. B., "Aviation Fuel Handling: New Mechanistic Insight into the Effect of Surfactants on Water Coalescer Performance," Proceedings of 6th International Conference on Stability a n d Handling of Liquid Fuels, Vancouver, 12-17 Oct. 1997.
[39] Manual of Aviation Fuel Quality Control Procedures, Second
Edition, ASTM Manual 57, R. Waite, Ed., ASTM International,
West Conshohocken, PA, 1995.
[40] "Aircraft Use of Dyed Fuel," Boeing Service Letter for 707, 727,
737, 747, 757, 767, and 777 Series, 22 Nov. 1996.
[41] Unpublished minutes of the CRC Group o n Dye In Aviation Turbine Fuels, Coordinating research Council, Atlsinta, GA, 1996 to
date.
[42] Churchill, A. V., "Microbial Fuel Tank Corrosion: Mechanisms
andContributoryFactors,"MaferJaisProtecft'ora, Vol. 2,1963, p. 18.

MNL37-EB/Jun. 2003

Automotive Diesel and


Non-Aviation Gas Turbine Fuels
Steven R. Westbrook^ and Richard LeCren^

The diesel engine is now fully established in a variety of applications on land and in marine use. On land, it serves to
power trains, buses, trucks, and automobiles; to run construction, petroleum drilling, and other off-road equipment;
and to be the prime mover in a wide range of power generation and pumping applications. At sea, it serves both to provide main propulsion power and run auxiliaries.
Gas turbine engines also serve in a wide range of applications. Over half the larger industrial gas turbines are in electric-generation use. Other uses include gas pipeline transmission, co-generation systems, and transportation. In the
military, gas turbines power a number of combatant ships
both as main propulsion units and as the power source for
auxiliary uses. Gas turbines are also used to power some military ground vehicles such as main battle tanks.
The quality criteria and methods for testing fuels for land
and marine diesel engines and for non-aviation gas turbines
are sufficiently similar to address in a common chapter. Obviously, certain criteria and tests will apply to one or the
other rather than both. For example, the cetane number,
which is a critical property for diesel fuels, is of limited significance for gas turbine fuels. Conversely, sodium and vanadium content are important in assessing gas turbine fuels,
but not those used in diesel engines. This chapter presents information regarding fuels for both automotive diesel engines
and gas turbines.
The petroleum industry started in the 1850s. Two factors
were especially important as impetus. Machines were being
developed and they needed oil for lubrication. Also, oil lamps
were being used to light homes and offices and the whale oil
traditionally burned in these lamps was growing increasingly
expensive. James Young, a Scotsman, had recently patented
a process for converting coal to coal oil. Coal oil was less expensive than whale oil but smoked and produced a foul smell
when burned. Then, in 1857, lamp maker A.C. Ferris produced clean-burning kerosine that did not have a bad smell
[1]. The oil used for making the kerosine was being skimmed
from natural crude oil seeps until Colonel Edwin Drake
drilled into one of the seeps, near Titusville, Pennsylvania, using a rig of the type used for drilling brine wells. An oil boom
was bom.
During the 1860s, oil exploration and drilling expanded to
Ohio, Termessee, New York, Kentucky, Colorado, and Califor-

nia. From this time until about 1900, kerosine for oil lamps
was the most valuable fraction of the petroleum barrel. The
fraction now known as gasoline was considered surplus and
burned. The heavier residual fraction was typically dumped
into pits or other convenient dumping grounds. The middle
distillate fraction, which would eventually be used in diesel engines, was used in the town gas industry. It was used "either as
a source of domestic gas, or for enriching or carburetting water gas, or as an absorbing agent or 'wash oil' for removing condensable constituents from coal gas" [2]. This is the reason
that this fraction is still often referred to as gas oil. Throughout this time, the middle distillate fraction of the petroleum
barrel was primarily a leftover product with no leirge market.
The invention of the diesel engine changed that for the better.
Compression Ignition Engines

' Manager, Petroleum Products Technology, Southwest Research Institute, P.O. Drawer 28510, San Antonio, TX 78228.
^ Consultant Engineer, Gas Turbine Combustion & Fuels, Retired,
3760 Sioux Avenue, San Diego, CA 92117.

Since it's beginning in the 1890s, the diesel engine quickly became the engine of choice for many industrial and marine applications, applications where the larger, heavier, slower
speed engine excelled in cost and performance when compared to alternative power plants of the time. However, the
diesel engine saw only limited use in automotive and aviation
applications. After World War I, shortages of gasoline in Germany helped stimulate work on the diesel engine, especially
as an automotive engine. Diesel engines were used for
propulsion on the Hindenburg.
Suppljdng fuel to the engine was the major obstacle to a
higher-speed, lower-weight engine suitable for automotive
use. Compressed air injection was complicated and the required air pump could not be substantially reduced in either
size or weight. In 1922, Robert Bosch set out to develop a
fuel-injection system for diesel engines [3]. By early 1923,
about a dozen different designs had been developed and initial trials were underway by mid-1923. A final design was approved in 1925 and the first series production fuel-injection
pump was on the market.
The fuel-injection system opened the door for wide spread
use of the diesel engine in previously untried applications. By
the mid-1930s there were large numbers of diesel-powered
trucks and buses in service; but only small numbers of dieselpowered automobiles. By the beginning of World War II in
1939, the diesel engine was in widespread use as an automobile engine. The German military also used diesel engines for
many of their vehicles, including some aircraft [4]. Gasoline
engines, because of the logistics problems faced with a twofuel supply system, powered the Allied Forces almost exclusively. Following World War II; the greater fuel economy of

115
Copyright'

2003 by A S I M International

www.astm.org

116 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

>.
(0
Q

a.

m
CD

0 J

1950

1960

1970

1980

1990

2000

Year
Source: U.S. Energy Information Administration
FIG. 1Diesel fuel supplied to the transportation sector.

the diesel engine caused a rapid increase in the use of the engine for automotive applications throughout Europe. The
abundance of inexpensive gasoHne in the United States lowered incentives for adopting the diesel engine in trucks and
automobiles. Even still, throughout this period, the diesel engine climbed in popularity for use in railroad, marine, and
heavy-construction equipment applications. The use of the
diesel engine increased until virtually 100% of current marine, trucking, railroad, construction, and much of the stationary power generation applications operate on diesel engines. The fuels used in these engines have, over time, varied
from natural gas to crude oil but the middle distillate, number 2 grade liquid fuel, is the fuel of choice for many of these
applications. Figure 1 shows the increase in diesel fuel usage
for transportation since 1949 [5].

DIESEL FUEL SPECIFICATIONS


From the turn of the twentieth century until the mid-1930s
there existed no widely used consensus specification for fuel
for diesel engines. Those needing diesel fuel likely bought
whatever was available on the market that seemed like a usable fuel. In 1934, ASTM Committee D2 published D 396,
Standard Specification for Burner Fuels. This specification
covers fuels for fuel-oil burning equipment (such as home
heating oils). However, fuels of grades 1 and 2 in this specification would have probably been acceptable for most diesel
engines of the time. D 396 was used in many purchase contracts as the controlling specification, thereby allowing both
buyer and seller to agree on the minimum quality of the fuel.
Starting in the eeirly to mid-1930s, the demand for diesel fuel
began to rise at a steady rate in most of the industriEilized nations of the world. (During World War II, this demand slowed
some owing to the essentially 100% use of gasoline by the Allied Forces.) Diesel engines were becoming increasingly sensitive to the quality of the fuel in order to maintain optimum
engine performance.

Following World War II, it was recognized that D 396 did


not sufficiently specify the quality of the fuel needed for
newer diesel engines. D 396 contains no specification for the
ignition quality of the fuel, as an example. So, in 1948, Committee D2 published D 975-48 T, Tentative Specifications for
Diesel Fuel Oils.
Fuel Grades
When first published, D 975 contained specifications for
"three grades of Diesel fuel oils suitable for various t5rpes of
Diesel engines." The grades were No. 1-D, No. 2-D, and No. 4D. Table 1 provides a description, of each grade, from the
1948 standard and the 1996 standard. It is interesting to note
that the description of Grade 2-D in the 1948 version did not
include automotive applications, reflecting the fact that
diesel engines were for heavy-duty use and large trucks. Fuel
grades Low Sulfur No. 1-D and Low Sulfur No. 2-D were
added in 1993. These latter grades were added to comply with
40 CFR Part 80Regulation of Fuels and Fuel Additives: Fuel
Quality Regulations for Highway Diesel Fuel Sold in 1993
and Later Calendar Years.
The limiting properties included in the 1948 specification
were flash point, pour point, water and sediment, carbon
residue, ash, distillation, viscosity, sulfur, copper strip corrosion, and cetane number. Since then, pour point has been removed from the specification table. Other changes to the
specification table have also occurred over the years. Table 2
is a summary of many of the major changes.

DIESEL FUEL PROPERTIES


Table 3 contains the specific requirements for the fuels
covered by D 975. The properties listed in that table, along
with other selected properties of importance, are discussed
below.

CHAPTER 5: GAS TURBINE FUELS


TABLE 1Descriptions of the fuels covered by
Specification D 975.
Grade

D 975-48 T

D 975-98b

No. 1-D

A volatile distillate
fuel oil for engines
in service requiring
frequent speed and
load changes.

A special-purpose, light
distillate fuel for
automotive diesel engines
in applications requiring
higher volatility than that
provided by Grade No.
2-D fuels.

Low Sulfur
No. 1-D

Not Applicable

A special-purpose, light
distillate fuel for
automotive diesel engines
requiring low sulfur fuels
and requiring higher
volatility than that
provided by Grade Low
Sulfur No. 2-D.

No. 2-D

A distillate fuel oil of


low volatility for
engines in industrial
and heavy mobile

A general-purpose, middle
distillate fuel for
automotive diesel engines,
which is also suitable for
use in non-automotive
applications, especially in
conditions of frequently
varying speed and load.

Low Sulfur
No. 2-D

Not Applicable

A general-purpose, middle
distillate fuel for automotive diesel engines
requiring low sulfur fuel.
It is also suitable for use
in non-automotive
applications, especially in
conditions of varying
speed and load.

No. 4-D

A fuel oil for low and


medium speed
engines.

A heavy distillate fuel, or a


blend of distillate and
residual oil, for low- and
medium-speed diesel
engines in nonautomotive applications
involving predominantly
constant speed and load.

Density
Density is the mass per unit volume of the fuel. This property
is not specified in D 975. However density is a fundamental
physical property that can be used in conjunction with other
properties to characterize both the light and heavy fractions
of petroleum cind petroleum products. Accurate determination of the density of petroleum products is also necessary for
the conversion of measured volumes to volumes at the standard temperature of 15C (60F). While density is a factor
governing the quality of crude petroleum, it is an uncertain
indication of petroleum product quality unless correlated
with other properties.
The two methods most commonly used to measure density
are:
ASTM D 1298, Standard Test Method for Density, Relative
Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrometer
MethodThe sample is brought to the prescribed temperature a n d transferred to a cylinder at approximately the
same temperature. The appropriate hydrometer is lowered

117

into the sample and zJlowed to settle. After temperature


equilibrium h a s been reached, the hydrometer scale is
read, and the temperature of the sample is noted. If necessary, the cylinder and its contents may be placed in a constant t e m p e r a t u r e b a t h to avoid excessive t e m p e r a t u r e
variation during the test.
ASTM D 4052, Standard Test Method for Density and Relative Density of Liquids by Digital Density Meter^A small volu m e (approximately 0.7 mL) of liquid sample is introduced
into an oscillating sample tube and the change in oscillating frequency caused by the change in the mass of the tube
is used in conjunction with calibration data to determine
the density of the sample.
API gravity (D 1298) is another measure of the density of fuel
that has been used for years. A fuel with a high API gravity is
a low-density fuel and a low API gravity fuel is a high-density
fuel. It is calculated with the following formula:
API gravity, deg = (141.5/S)-131.5
Where 5 = density, kg/nr' at 15C

TABLE 2Summary of the major changes" to Specification


D 975 since it was first published.
Year
Changes
1948
First published as a tentative standard.
1950
Changes to pour point and viscosity limits.
1953
Further clzirification of pour point and copper strip
corrosion limits.
1959
Table 1 was revised to add a 90% distilled minimum
temperature for Grade 2-D, and add a revised minimum viscosity at 100F for Grade 2-D.
1960
The nomograph for the calculated cetane index
method (then an appendix to the specification)
was revised.
1964
Section 2 was added to specify that the properties of
the fuel apply at the time and place of delivery.
Section 4 was amended to permit use of Method D
56 as Ein alternate for Method D 93 to determine
flash points of Grade 1-D fuels.
1965
The viscosity and 90% distillation requirements for
Grade 2-D were revised.
1966
The sulfur limit for Grade 2-D was lowered from 1.0
wt% to 0.7 wt%. The cetane index method was removed from the appendix and became D 976.
1967
The standard was adopted without revision and was
no longer a tentative method.
1968
The sulfur limit for Grade 2-D was lowered from 0.7
wt% to 0.5 wt%.
1973
The allowable amount of water and sediment in
Grade 1-D was raised from trace to 0.05 volume
percent.
1974
The cloud point requirement and the U.S. 10th percentile temperatures were added as an appendix.
These are used to help set cloud point limits.
1978
The viscosity limits were lowered for all grades.
1988-1990
Several changes in format. Standard D 4737 replaced D 976 for the calculation of cetane index.
1992
Grades 1-D low sulfur and 2-D low sulfur were
added to the table. A footnote on the use of blue
dye in high sulfur fuel was also added to Table 1.
1994
An appendix on the lubricity of diesel fuel was
added.
1996
The footnote regarding the use of blue dye was
changed to reflect changes in the federal regulations, which now require red dye.
"Not all changes are included. Editorial revisions and most of the changes
to appendices were left oft this list.

118 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 3Detailed requirements for diesel fuel oils."

Property
Flash Point, C, min.
Water and Sediment, % vol, max
Distillation Temperature, C 90 % % vol
Recovered
min
max
Kinematic Viscosity, mm^/S at 40C
min
max
Ash % mass, max
Sulfur, % mass, max^
Copper strip corrosion rating mjix 3 h
at SOX
Cetane number, min''
One of the following properties must
be met:
(1) Cetane index, min.
(2) Aromaticity, % vol, msix
Cloud point, C, max
Ramsbottom carbon residue on 10%
distillation residue, % mass, max

ASTM Test
Method^

Grade Low
Sulfur
No. 1-D^

Grade Low
Sulfur
No. l-D"''

Grade
No. 1-D'

Grade
No. 2-0*'

38
0.05

52
0.05

38
0.05

52
0.05

D93
D2709
D 1796
D86

Grade
No. 4-D'
55
0.50

282'^
338

288

288

282^*
338

D445
D482
D 2622
D129
D130

1.3
2.4
0.01
0.05

1.9
4.1
0.01
0.05

No. 3

D613
916f
1319'"
2500
524

1.3
2.4
0.01

1.9
4.1
0.01

5.5
24.0
0.10

0.50
No. 3

0.50
No. 3

2.00

No. 3

40"

40"

40'

40'

40
35

40
35

0.15

0.

0.15

30'

0.35

"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''The test methods Indicated are the approved referee methods. Other acceptable methods are Indicated in 3.1.
"Under United States regulations. If Grades Low Sulfur No. 1-D or Low Sulfur No. 2-D are sold for tax exempt purposes then, at or beyond terminal storage
tanks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid
dye standard Solvent Red 26, or the tax must be collected.
''when a cloud point less than 12C is specified, the minimum flash point shall be 38C, the minimum viscosity at 40C shall be 1.7 mm^/s, and the minimum
90% recovered temperature shall be waived.
'Under United States regulations. Grades No. 1-D, No. 2-D, and No. 4-D are required by 40 CFR Part 80 to contain a sufficient amount of the dye Solvent Red
164 so Its presence Is visually apparent. At or beyond terminal storage tanks, they are required by 28 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'^Other sulfur limits can apply In selected areas in the United States and In other countries.
^These test methods are specified in 40 CFR Part 80.
''Where cetane number by Test Method D 613 Is not available, Test Method D 4737 can be used as an approximation.
'Low ambient temperatures as well as engine operation at high altitudes may require the use of fuels with higher cetane ratings.
'It is unrealistic to specify low temperature properties that will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appearance point) may be used as an estimate of operating temperature limits for Grades Low Sulfur No. 1; Low Sulfur No.2; and No.l and No. 2 diesel fuel oils.
However, satisfactory operation below the cloud point (or wax appearance point) may be achieved depending on equipment design, operating conditions, and the
use of flow-improver additives as described in X4.1.2. Tenth percentile minimum air temperatures for U.S. locations are provided in Appendix X4 as a means of
estimating expected regional temperatures. This guidance Is general. Some equipment designs or operation may allow higher or require lower cloud point fuels.
Appropriate low temperature operability properties should be agreed upon between the fuel supplier and purchaser for the Intended use and expected ambient
temperatures.

Even though, as use of the International System of Units (SI)


becomes more common, use of API gravity decreases, API
Gravity is arguably the most widely used cheiracteristic for
"mass" of petroleum.
Ignition and Combustion Characteristics
(Cetane Number)
The first diesel engines were large and slow-speed and were
not particularly sensitive to the quality of the fuel they
burned. As steady improvements were made to the engine,
there was a need to improve fuel quality as well. Gradually,
the heavier, more viscous, diesel fuels disappeared with
lighter and higher speed engines. The higher speed engines
are more sensitive to the ignition quality of the fuel; therefore, cetane numbers became the property of greatest concern to both producers and users. Diesel engine performance
is a function of compression ratio, injection timing, the manner in which fuel and air are mixed, and the resulting ignition
delay or time from the start of injection to the beginning of

combustion. The nature of the fuel is an important factor in


reducing ignition delay. Physical characteristics such as viscosity, gravity, and mid-boiling point are influential. Hydrocarbon composition is also important as it affects both the
physical and combustion characteristics of the fuel. Straightchain paraffins ignite readily under compression, but
branched-chain peiraffins and aromatics react more slowly.
The first widely used measure of ignition quality was the
diesel index, calculated as:
Diesel Index = [(API Gravity)(Aniline Point)] /100
The aniline point is the lowest temperature at which equal
amounts of fuel and aniline are completely miscible. Aromatic compounds tend to exhibit higher density than paraffinic compounds and they are better solvents. Therefore, a
fuel that is high in aromatics will generally have a lower aniline point than a fuel that is high in paraffins. So, a high
paraffin fuel will tend to have a higher API Gravity and a
higher aniline point. This combination results in a higher
diesel index, which indicates better starting characteristics.

CHAPTER 5: GAS TURBINE FUELS


The diesel index equation may be misleading, especially with
blended fuels and fuels treated with ignition-improver additives.
By the mid-1930s, it was determined that a better measurement of ignition quality was needed. The result was an
engine test:
ASTM D 613 Standard Test Method for Ignition Quality of
Diesel Fuels by the Cetane MethodThe cetane number of a
diesel fuel is determined by comparing its ignition quality
with those for blends of reference fuels of known cetane
numbers under standard operating conditions. Varying the
compression ratio for the sample and each reference fuel to
obtain a fixed "delay period," that is, the time interval between the start of injection and ignition does this. When
the compression ratio for the sample is bracketed between
those for two reference fuel blends differing by not more
than five ceteine numbers, the rating of the sample is calculated by interpolation.
This test involves operating a standard, single cylinder,
variable compression ratio engine using a specified fuel flow
rate and time of injection (injection advance) for the fuel
sample and each of two bracketing reference fuels of known
cetane number. The engine compression ratio is adjusted for
each fuel to produce a specified ignition delay, and the cetane
number is calculated to the nearest tenth by interpolation of
the compression ratio values.
The cetane number scale uses two primary reference fuels.
One, n-hexadecane (normal cetane), has excellent ignition
qualities and, consequently, a very short ignition delay. This
fuel was arbitrarily assigned a cetane number of 100. The second fuel, a-methylnaphthalene, has poor ignition qualities
and was assigned a cetane number of zero. The a-methylnaphthalene was later replaced with heptamethylnonane,
which was calibrated against the original fuels and assigned
a cetane number of 15. The cetane number scale is now defined by the following equation for volumetric blends of the
two primary reference materictls:
Cetane Number = % n-cetane
-F 0.15 (percent heptamethylnonane)
In practice, the primary reference fuels are only utilized to
calibrate two secondary reference fuels. These are selected
diesel fuels of mixed hydrocarbon composition, which are
designated as "T" and "U". "T" fuel typically has a cetane
number of approximately 75 while "U" fuel is usucilly in the
low 20 cetane number range. Each set of "T" and "U" fuels are
paired and test engine calibrations define the cetane numbers for volumetric blends of these two secondaries [6]. In
general, the contribution of various fuel components to bulk
fuel cetane number can be described as follows [7]:
Normal Paraffins > Branched Paraffins > Normal Olefins
> Branched Olefins > Naphthenes > Aromatics
=> Decreasing Cetane Number =>
Higher cetane number fuels tend to reduce combustion
noise, increase engine efficiency, increase power output,
start easier (especially at low temperatures), reduce exhaust
smoke, and reduce exhaust odor. To assure acceptable cold
weather performance, most modern diesel engines require a

119

minimum cetane number of 40 [8] and this is the requirement in D 975. Many engine manufacturers are now pushing
to raise the specification minimum limit to 50 cetane in order to meet new engine emission requirements (see the discussion of the Worldwide Fuels Charter below).
Cetane Index
Two ASTM test methods for calculating approximate cetetne
numbers were also developed for situations when performing
the engine test was not feasible. Two ASTM methods, and the
equations for each, are:
ASTM D 976, Standard Test Method for Calculated Cetane
Index of Distillate Fuels
Calculated Cetane Index = 454.74 - 1641.416 D
+ 774.74 0^-0.554 5 + 97.803 (log 5)^
Where:
D = density at 15C, g/mL, determined by Test
Method D 1298, and
B = mid-boiling temperature, C, determined by
Test Method D 86 and corrected to standard
barometric pressure.
ASTM D 4737, Standard Test Method for Calculated Cetane
Index by Four Variable Equation
CCI = 45.2 + (0.0892)(rioN) + [0.131 + (0.901)B][r50N]
+ [0.0523 - (0.420)B][r90N]
+ [0.00049][(rioN)^ - (T'OTN)^] + 1075 -H 605^
Where:
CCI - Calculated Cetane Index by Four Variable Equation,
D = Density at 15C, determined by Test Method D
1298,
DN =D- 0.85,
B

= [e(-3-5XDN)] _ 1^

Tio = 10% recovery temperature, C, determined by Test


Method D 86 and corrected to standard barometric
pressure,
TioN Tio 215,
Tso = 50% recovery temperature, C, determined by Test
Method D 86 and corrected to standard barometric
pressure,
T50N = Tso ~ 260,
Tgo = 90% recovery temperature, C, determined by Test
Method D 86 and corrected to standard barometric
pressure,
TgoN = T90 310
Both methods utilize fuel density and distillation values in
their calculations. Standard D 4737 is the more widely used
method since it is the most recent and it better represents
current diesel fuels. Some limitations of calculated cetane index include:
1. It is not applicable to fuels containing additives for raising
cetane number.
2. It is not applicable to pure hydrocarbons, synthetic fuels,
alkylates, or coal tar products.
3. Correlation is fair for a given type of fuel but breaks down
if fuels of widely different composition are compared.
4. Appreciable inaccuracy in correlation may occur when
used for crude oils, residuals (or blends containing residuals), or products having end points below 260C.

120

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

Numerous other cetane index equations/models have been


developed, used, and compzired to the ASTM equations but
they have never been formaHzed as a n ASTM standard. Additional information concerning some of these non-ASTM
methods can be found elsewhere [9-11].

Volatility / Distillation
The distillation characteristics of a diesel fuel exert a great influence on performance. Two methods are commolily used to
measure distillation characteristics:
ASTM D 86, Standard Test Method for Distillation
of
Petroleum Products^A 100 mL sample is distilled u n d e r
prescribed conditions that are appropriate to its nature.
Systematic observations of thermometer readings and volumes of condensate are made, and from these data, the results of the test are calculated and reported.
ASTM D 2887, Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
The boiling range distribution determination by distillation is simulated by the use of gas c h r o m a t o g r a p h y . A
non-polar packed or open t u b u l a r (capillary) gas chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing boiling point.
The column temperature is raised at a reproducible lineeir
rate and the area u n d e r the c h r o m a t o g r a m is recorded
throughout the analysis. Boiling points are assigned to the
time axis from a calibration curve obtained under the same
chromatographic conditions by analyzing a known mixture of hydrocarbons covering the boiling range expected
in the sample. From these data, the boiling range distribution can be obtained.
Method D 86 is the specified method in D 975 for measuring distillation characteristics. Figure 2 is a plot of distillation
data for a single, typical diesel fuel using both methods. It is
obvious from this plot that the two methods can give quite
different results. For most fuels, results like these are typical;

with more deviation at the beginning and end of the distillation Eind less deviation at the center. For this reason, D 2887
is not Ein accepted eJtemative to D 86 for specification purposes. That will remain the case until a suitable correlation
(correction factor) between the two is determined.
Figure 3 is the D 2887 gas c h r o m a t o g r a m for the fuel
shown in Fig. 2. The chromatogram illustrates the usefulness
of the D 2887 method. The time axis can be correlated to carbon n u m b e r by using a known standard. Therefore, it is possible to obtain a "picture" of the carbon n u m b e r distribution
in a given fuel. This method is also useful for identifying contaminants such as gasoline a n d engine oil.
The average volatility requirements of diesel fuels vary
with engine speed, size, cind design. However, fuels having
too low volatility tend to reduce power output Eind fuel economy through poor atomization, while those having too high
volatility m a y reduce p o w e r o u t p u t a n d fuel economy
through vapor lock in the fuel system or inadequate droplet
penetration from the nozzle. I n general, the distillation range
should be as low as possible without adversely affecting the
flash point, burning quality, heat content, or viscosity of the
fuel. If the 10% point is too high, poor starting may result. An
excessive boiling range from 10-50% evaporated may increase warm-up time. A low 50% point is desirable to minimize smoke and odor. Low 90% cind end points tend to ensure low carbon residuals and minimum crankcase dilution.
The temperature for 50% evaporated, known as the midboiling point, usucdly is taken as a n overall indication of the
fuel distillation chziracteristics when a single numerical value
is used alone. For example, in high-speed engines a 50%
point above 302C might cause smoke formation, produce
objectionable odor, cause lubricating oil contamination, and
promote engine deposits. At the other extreme, a fuel with excessively low 50% point would exhibit too low a viscosity eind
heat content per unit volume. Therefore, a 50% point in the
range of 232-280C is desirable for the majority of higher
speed diesel engines. This t e m p e r a t u r e range usually is
broadened for Icirger, slower speed engines [12].

100

D86
D2887

80

I
40

on

20 -

0-"
100

150

200

250

300

350

400

450

Distillation Temperature, C
FIG. 2Distillation curves for a typical no. 2 diesel fuel (methods D 86
vs. D 2887).

CHAPTER 5: GAS TURBINE FUELS

Time
FIG. 3D 2887 gas chromatogram of a typical diesel fuel.

For the above reasons, some points on the distillation curve


are considered more important and are included in fuel specifications more often. Specification D 975 contains only a
limit on the 90% point. Other specifications include requirements for initial boiling point (more so for gasoline), 10%,
50%, and to a lesser degree, 95% and final boiling point.
Viscosity
The method for measuring viscosity of diesel fuel is:
ASTM D 445, Standard Test Method for Kinematic Viscosity
of Transparent and Opaque Liquids (and the Calculation of
Dynamic Viscosity)The time is measured for a fixed volume of liquid to flow under gravity through the capillary of
a calibrated viscometer under a reproducible driving head
and at a closely controlled and known temperature. The
kinematic viscosity is the product of the measured flow
time and the calibration constant of the viscometer.
The unit of measurement for this method is square millimeters per second (mm^/s), also known as centistokes (cSt).
This is currently the most widely used unit of fuel viscosity
measurement in the United States. Other units used in the
past, and occasionally still used in the present, include Saybolt Universal Seconds (SUS) and centipoise.
For some engines it is advantageous to specify a minimum
viscosity because of power loss due to injection pump cuid injector leakage. Maximum viscosity, on the other hand, is limited by considerations involved in engine design and size, and
the characteristics of the injection system. Fuel viscosity exerts a strong influence on the shape of fuel spray. High viscosities can cause poor atomization, large droplets, and highspray jet penetration. With high viscosities, the jet tends to be
a solid stream instead of a spray of small droplets. As a result,
the fuel is not distributed in, or mixed with, the air required
for burning. This results in poor combustion, accompanied
by loss of power and economy. In small engines, the fuel
spray may impinge upon the cylinder walls, washing away
the lubricating oil film and causing dilution of the crankcase
oil. Such a condition contributes to excessive wear [13].
Low fuel viscosity results in a spray that is too soft and does
not penetrate far enough in the combustion chamber for

121

good mixing. Combustion is impaired and power output and


economy are decreased. Low viscosity can lead to excessive
leakage past the injection pump plunger. Fuel metering becomes inaccurate and engine efficiency is reduced. Wear of
the fuel system components may increase because lubricating properties of fuels tend to decrease with viscosity.
Fuel viscosities for high-speed engines range from 1.8-5.8
centistokes (cSt) at 38C. Usually the lower viscosity limit is
established to prevent leakage in worn fuel injection equipment as well as to supply lubrication for injection system
components in certain types of engines. During operation at
low-atmospheric temperatures, the viscosity limit sometimes
is reduced to 1.4 cSt at 38C to obtain increased volatility etnd
sufficiently low pour point. Fuels having viscosities greater
than 5.8 cSt usually are limited in application to the slowerspeed engines. The very viscous fuels commonly used in large
stationary and mcirine engines normally require preheating
for proper pumping, injection, and atomization.
Cloud Point
All diesel fuels contain dissolved paraffin wax. As the temperature of the fuel decreases, so does the solubility of the
wax in the fuel. At some point wax crystals will begin to precipitate. If enough wax precipitates the crystals can block fuel
flow through screens, filters, and other restricted passages in
the fuel system. The temperature at which the wax precipitation occurs depends upon the origin, type, refining, and boiling range of the fuel. This temperature is known as the cloud
point of the fuel. As the cloud point goes up, the suitability of
the fuel for low-temperature operation decreases. The cloud
point of the fuel can be measured by the following methods:
ASTM D 2500, Standard Test Method for Cloud Point of
Petroleum ProductsThe specimen is cooled at a specified
rate and examined periodically. The temperature at which
a cloud is first observed at the bottom of the test jar is
recorded as the cloud point.
The following methods are variations of D 2500, including,
both automatic and automated methods:
ASTM D 3117, Standard Test Method for Wax Appearance
Point of Distillate Fuels
ASTM D 5771, Standard Test Method for Cloud Point of
Petroleum Products (Optical Detection Stepped Cooling
Method)
ASTM D 5772, Standard Test Method for Cloud Point of
Petroleum Products (Linear Cooling Rate Method)
ASTM D 5773, Standard Test Method for Cloud Point of
Petroleum Products (Constant Cooling Rate Method)
For all grades of fuel listed in D 975, any of these test methods may be used to measure cloud point. Method D 2500 is the
specified method and the others are considered alternates. In
case of dispute. Test Method D 2500 is the referee method.
Cloud point is the only control for low temperature operability listed in the diesel fuel specification, D 975. Footnote
J to Table 1 in D 975 reads as follows:
It is unrealistic to specify low temperature properties that
will ensure satisfactory operation at all ambient conditions. In general, cloud point (or wax appearance point)
may be used as an estimate of operating temperature limits for Grades Low Sulfur No. 1: Low Sulfur No. 2; and No.

122 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

October10th Percentile Minimum Temperatures


FIG. 4Example 10th percentile minimum ambient temperature map from D 975.

1 and No. 2 diesel fuel oils. However, satisfactory operation below the cloud point (or wax appearance point) may
be achieved depending on equipment design, operating
condition, and the use of flow-improver additives... Tenth
percentile minimum air temperatures for U.S. locations
are provided.. .as a means of estimating expected regional
temperatures. This guidance is general. Some equipment
designs or operation may allow higher or require lower
cloud point fuels. Appropriate low temperature operability
properties should be agreed upon between the fuel supplier
and purchaser for the intended use and expected ambient
temperatures.
The tenth percentile temperatures Eire presented for each
U.S. state, except Hawaii, for each month from October to
March. They are presented in both tabular format and in
maps. Figure 4 is an example of one of the maps.
Realistic options to reduce the cloud point include:
1. Dilute the fuel with a low wax fuel such as grade No. 1 or
kerosine.
2. Treat the fuel with special additives.
3. Refine the fuel from crude(s) with lower wax content or refine the fuel to a lower end point.
4. It is also possible to add insulation and heaters to the vehicle fuel system. This will not change the cloud point of
the fuel but will improve the low temperature operation.

Pour Point
Before a fuel can be burned in an engine it must first be
pumped from the fuel tank. The lowest temperature at which
a fuel can be pumped is known as the pour point of the fuel.
Test methods for measuring pour point include:
ASTM D 97, Standard Test Method for Pour Point of
Petroleum ProductsAfter preliminEiry heating, the sample
is cooled at a specified rate and examined at intervals of
3C for flow characteristics. The lowest temperature at
which movement of the specimen is observed is recorded
as the pour point.
The following methods are variations of D 97, including,
both automatic and automated methods.
ASTM D 5949, Standard Test Method for Pour Point of
Petroleum Products (Automatic Pressure Pulsing Method)
ASTM D 5950, Standard Test Method for Pour Point of
Petroleum Products (Automatic Tilt Method)
ASTM D 5985 Standard Test Method for Pour Point of
Petroleum Products (Rotational Method)
The pour point should be considered only a guide to the
lowest temperature at which a fuel can be used. In general,
pour points are from 3-6C below the cloud point for a given
fuel; however, it is not uncommon for the difference to be as
much as 11 C.

CHAPTER 5: GAS TURBINE FUELS


For any given fuel, there will be no wax precipitation problems at temperatures above the cloud point. At temperatures
below the pour point, it is highly unlikely that the fuel will
give satisfactory performance. It is not unusueJ to obtain satisfactory engine performance with a fuel at ambient temperatures between the cloud point and pour point. The degree of
performance and the temperature depend on the engine, the
vehicle design, and the fuel system configuration. Vehicles
and fuel systems with small diameter lines, constrictions,
small porosity strainers and filters, and fuel lines exposed to
ambient temperatures or wind will tend toward poorer performance. Systems with insulation, supplemental heaters, or
large sections of the fuel system in close proximity to engine
heat can probably expect better performance at lower temperatures [14].
Low-Temperature Flow Test
As discussed above, the mere presence of wax crystals in a
fuel does not guarantee the fuel will plug filters or other fuel
system components. The tendency of a fuel to plug screens
and filters at low temperatures is a dynamic property dependent on the size and shape of the wax crystals. (Vehicle fuel
system design is also a factor as discussed earlier.) For this
reason, numerous dynamic tests for low temperature operability have been developed. ASTM standardized one such
test in 1985:
ASTM D 4539, Standard Test Method for Filterability of
Diesel Fuels by Low-Temperature Flow Test (LTFT)The
temperature of a series of test specimens of fuel is lowered
at a prescribed cooling rate. Commencing at a desired test
temperature and at each 1C interval thereafter, a separate
specimen from the series is filtered through a 1 l-fjun screen
until a minimum LTFT pass temperature is obtained. The
minimum LTFT pass temperature is the lowest tempera-

ture, expressed as a multiple of 1C, at which a test specimen can be filtered in 60 s or less. Alternatively, a single
specimen may be cooled and tested at a specified temperature to determine whether it passes or fails at that temperature.
Figure 5 is a diagram of the LTFT test apparatus. The LTFT
was designed to yield results indicative of the low temperature
flow performance of the test fuel in some diesel vehicles. The
test method is especially useful for the eveiluation of fuels containing flow improver additives. Please refer to Report No.
528 from the Coordinating Research Council for a more detailed discussion [15]. The LTFT was developed in the United
States to simulate the low temperature behavior of diesel fuel
in the fuel tank of a diesel truck left overnight, in a cold environment, with its engine off. J. E. Chandler, zmd others, have
demonstrated that this test has shown excellent correlation
with field studies [16-18]. In spite of the demonstrated correlation to field performance, the LTFT is not as widely used as
some other tests. The primary reason for this is the slow cooling rate (1C per hour), which means that the time required
completing an analysis can range from 12-24 h. Such test
times are generally impractical for routine fuel testing.
Cold FUter Plugging Point
The Cold Filter Plugging Point, CFPP, was developed for use
in Europe. The Institute of Petroleum publishes the method
under the designation IP 309. It is similar to the LTFT with
the following exceptions:
The fuel is cooled by immersion in a constant temperature
bath, making the cooling rate non-linear but comparatively
much more rapid (about 40C per hour).
The CFPP is the temperature of the sample when 20 mL of
the fuel first fails to pass through a wire mesh in less than
60s.

Glass Tubing
6 10 Min Throughout
Vacuum Gage
Point A

Heavy Rulit>er Ttibing


4 10 15 OD
2 Vacuum System
Rubber Stopper

Storage Lid

200 ML Sample
Glass Stem
Quality Flex lObing

Sample Container
300 ML Tall-Form
Beaker

123

Sample Receiver
400 ML Tall-Form
Beaker

All Diminensions in Millimeters

t-TFT Sample Filtration Assembly


FIG. 5LTFT sample filtration assembly (D 4539).

124 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

While the CFPP is the preferred method in Europe and is


used in several European specifications, it appears to overestimate the benefit of using some additives, most especially for
vehicles manufactured in North America [19,20].
Cleanliness
Diesel fuel cleanliness can mean many things to many people. It is safe to say that most users would consider any fuel
that is visually free of undissolved water, sediment, and suspended matter a clean fuel. Indeed, this is the cleanliness
(workmanship) requirement stated in D 975. However, it is
known that microscopic particulates in the fuel can lead to
problems just as serious as the visible contaminants. The
three most common methods of measuring cleanliness of
diesel fuel are:
ASTM D 2709, Standard Test Method for Water and Sediment in Middle Distillate Fuels by CentrifugeA 100-mL
sample of the undiluted fuel is centrifuged at a relative centrifugal force of 800 for 10 min. at 21-32C (70-90F) in a
centrifuge tube readable to 0.005 mL and measurable to
0.01 mL. After centrifugation, the volume of water and sediment that has settled into the tip of the centrifuge tube is
read to the nearest 0.005 mL and reported as the volumetric % water and sediment by centrifuge.
D 2709 is the method currently specified in D 975. It is used
to measure the amount of visible water, sediment, and suspended matter. This method gives no effective measurement
of the presence or amount of microscopic particulates. Many
would consider the level of contamination sufficient to produce readable results in this test to be gross contamination.
However, this is an extremely sensitive test for contamination. The human eye is capable of seeing very small macroscopic particles and the presence of 1 or 2 such particles
could be considered a failure. In practice, the person conducting the test must exercise judgment based on experience
and the requirements of the end use for the fuel.
ASTM D 4860, Standard Test Method for Free Water and Particulate Contamination in Mid-Distillate Fuels (Clear and
Bright Numerical Rating)Visual inspection of the fuel
sample for free water and particulate matter is performed
immediately when the sample is taken. A glass container is
used to view for water haze, and the fuel sample is swirled
to create a vortex to detect the presence of particulate matter. A numerical rating for free water is obtained by filtering a portion of the fuel sample at a programmed rate (50
mL/45 s) through a standard fiberglass coalescer/filter. A
portion of the effluent is used to establish a reference (100)
level by a light transmittance measurement. Another portion of the unprocessed (unfiltered) fuel sample is then
compared to the 100 reference-level. The results are reported on a 50-100 scale to the nearest whole number. A
test can be performed in 5-10 min.
D 4860 was developed to give a means to quantify the level
of cleanliness of a fuel. As with D 2709, D 4860 only provides
a valid measurement of visible contamination. The benefit of
this method is that the measurement is now an objective
measure of cleanliness. While this test does provide a quantitative result, it is far less sensitive than D 2709.
Three other methods used to determine cleanliness of
diesel fuels are D 6217, D 2068, and D 6426. D 6217 could be

considered a combination of the best features of the two previous methods. It is sensitive to small amounts of particles
and is even capable of detecting microscopic particulates. It
is also a quantitative measure of the cleanliness of the fuel.
The quantitative measure is milligrams of particulate (contamination) per liter of fuel. Currently there is no consensus
standard with a specification limit for D 6217. Many user
specifications, including some federal and military diesel fuel
specifications, include a limit of 10 mg per liter for the results
of this analysis. Most users have found fuel that meets this
limit to give satisfactory performance in the vehicle.
ASTM D 6217, Standard Test Method for Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration^A measured volume of about 1 L of fuel is vacuum filtered through one or more sets of 0.8 /u,m membranes.
Each membrane set consists of a tared nylon test membrane and a tared nylon control membrane. When the level
of particulate contamination is low, a single set will usually
suffice; when the contamination is high or of a nature that
induces slow filtration rates, two or more sets may be required to complete filtration in a reasonable time. After the
filtration has been completed, the membranes are washed
with solvent, dried, and weighed. The particulate contamination level is determined from the increase in the mass of
the test membranes relative to the control membranes, and
is reported in units of glw? or its equivalent mg/L.
ASTM D 2068, Standard Test Method for Filter Plugging Tendency of Distillate Fuel OilsA sample of the fuel to be
tested is passed at a constant rate of flow (20 mL/min)
through a glass fiber filter medium. The pressure drop
across the filter is monitored during the passage of a fixed
volume of test fuel. If a prescribed maximum pressure drop
is reached before the total volume of fuel is filtered, the actual volume of fuel filtered at the time of maximum pressure drop is recorded.
The primary weakness of visual and gravimetric method is
that there is no generally accepted correlation between the
results of the test and the performance of the fuel in a vehicle
fuel system. That is, how long could the vehicle operate on
that fuel before the fuel filter plugs or the water separator
fails? The British Navy first developed D 2068 as a dynamic
test of the cleanliness of fuel for shipboard gas turbine engines [21]. The test was designed around the specific requirements of gas turbine powered ships in the British Navy. The
most important requirement was that the shipboard fuel filters had a nominal porosity of 1 /am. As such, a 1 /u,m pore
size glass fiber laboratory filter is used in the test. Over the
years the test apparatus was upgraded, making it more automated.
ASTM D 6426, Standard Test Method for Determining Filterability of Distillate Fuel Oils^A sample is passed at a constant rate (20 mL/min) through a standard porosity filter
medium. The pressure drop across the filter and the volume of filtrate are monitored. The test is concluded either
when the pressure drop across the filter exceeds 170 kPa
(25 psi) or when 300 mL have passed through the filter. Results are reported as either the volume that has passed
through the filter when a pressure of 170 kPa (25 psi) has
been reached or the pressure drop when 300 mL have
passed through the filter. In the latter case, the volume, if
and when 105 kPa (15 psi) was exceeded, is also recorded.

CHAPTER 5: GAS TURBINE FUELS


D 6426 is a modification of Method D 2068. The first difference between the two methods is the pump used in each:
D 2068 uses a piston pump whereas D 6426 uses a peristaltic
pump. The second difference that D 2068 uses a 13-mm diameter, 1 fim pore size fiher and D 6426 uses a specially constructed test specimen, which is called an F-cell Filter Unit. It
is a disposable, precalibrated assembly consisting of a shell
and plug containing a 2 5-mm diameter nylon membrane filter of nominal 5.0/am pore size, nominal 60% porosity, with
a 17.7-mm^ effective filtering area. Figure 6 is a schematic diagram of the complete test apparatus.
Despite the differences in equipment, both D 2068 and D
6426 have the same pass/fail criteria. A fuel fails the test if the
pressure drop across the filter reaches 105 kPa (15 psi) before
300 mL of test fuel passes through the filter.

(D)

FLOW ADJUSTMENT KNOB

DISPLAYS
PRESSURE VOLUME VOLUME
(psi) ((Si 0-25 psi) ((a! 0-15 psi)

PRESSURE
TRANSDUCER
PERISTALTIC PUMP
\
PULSE
\
DAMPENrNG
/lECIIANISM

ay

PLA,STIC TIP
TYGON
TUBING
RUBBER STOPPER (VENTED)
FILTER CELL

METAL TUBE (STAINLESS STEEL)


TUEL RESERVOIR

"FUEL SAMPLE

FUEL FLOW
COLLECTION
CONTAINER

PROCESSED FUEL

FIG. 6Schematic diagram of filterability apparatus (D 6426).

At this writing, neither D 2068 nor D 6426 enjoys


widespread use in the U.S. However, of the two methods, D
6426 is gaining the greatest acceptance in the U.S. This is due
to two primary reasons: 1) the equipment to conduct D 6426
is more readily available than the equipment for D 2068; and,
2) the F-cell test specimen is regarded as more representative
of automotive fuel filters than is the filter in D 2068. Despite
the general recognition that the F-cell is more representative
of automotive fuel filters, numerous attempts to correlate the
results from D 6426 with fuel filter plugging/filter life have
failed [22].

Stability
For the purposes of this discussion, fuel stability is defined as
the resistance of the fuel to physical and chemical changes
brought about by the interaction of the fuel with its environment.
The chemistry of diesel fuel stability (instability) is complex. In general, it involves the chemical reaction of precursor species to form molecules of higher molecular weight.
The higher molecular weight species then become insoluble
deposits in the form of either gums or particulates. The precursor species are usually sulfur and/or nitrogen containing
compounds, olefins, and organic acids. The reactions are often initiated by the oxidation of the precursors. Some dissolved metals, especially copper but also zinc and even iron,
are known to catalyze the oxidation reactions. In the case of
copper, as little as 10-30 parts per billion of dissolved copper
is sufficient to catalyze deleterious reactions, depending on
the fuel. The mechanism proposed by Pedley [23] (shown in
Fig. 7) is perhaps the most cited example of these types of reactions. Although this mechanism explains many of the earlier findings on diesel stability, it does not account for the for-

oxldatlon

Phenalenes

125

1
Phenalenones

Indoles

Acid

Indolylphenalenes

Acid/Oxidation

Fuel Insolubles

FIG. 7Proposed mechanism of diesel fuel insolubles formation.

126

MANUAL

37: FUELS

AND LUBRICANTS

HANDBOOK

m a t i o n of all diesel fuel sediments. Other_useful reaction


schemes have been proposed [24-27]. The solvent strength of
the fuel is also a factor in that a high-solvency fuel can keep
some of the high molecular weight species in solution.
Because the reactions and interactions Eire so numerous
and complex, it is quite possible to blend two very stable fuels and obtain a very unstable fuel. In this case, each fuel possesses one or more of the required precursor compounds.
When the fuels are mixed, the reactions proceed, and sediment is formed. Yet, had these two fuels never been blended,
neither single fuel would have significantly degraded in storage. There are three tjrpes of stability usually of concern for
diesel fuel. They are thermal, oxidation, and storage. Each of
these will be discussed separately.

20

""" /

/ /
/ -^ '

18
16
M

tX

s,

s'

10

//

/ ""^
\

T h e r m a l stability is the resistance of the fuel to change


caused by thermal stress (elevated temperature). The recognized ASTM test method is:
D6468, Standard Test Method for High Temperature Stability of Distillate FuelsTwo 50-mL volumes of filtered middle distillate fuel are aged for 90 or 180 min at 150C in
open tubes with air exposure. After aging and cooling, the
fuel samples are filtered. The amount of filterable insolubles is estimated by measuring the light reflectance of the
filter pads. An unused filter pad and a commercial black
standard define the 100 and 0% extremes of the reflectance
rating range, respectively.
This method is based on a test that has been known by several names, such as: the Nalco 300F Test, the EMD-Diesel
Fuel Stability Test, the Union Pacific Diesel Blotter Test, the
du Pont F 21 Test, and the Octel F 21 test [28]. This test differs from most other accelerated stability tests in that the test
temperature is much higher and the amount of insolubles
formed is estimated rather than measured gravimetrically. In
the earlier versions of the test, the a m o u n t of insoluble
residue formed during aging was estimated by comparing the
test filter to a set of visual stEuidards called reference blotters.
Filter pads from the test were rated on a scale from 1 to 20
with a rating of 1 assigned to a filter pad that is essentially
free of sediment. A rating of 7 or less was typically considered
a pass. The reference pads were produced in both gray and
brown-tone prints. The reference pads were also produced to
represent samples that were filtered through a Biichner funnel or through a standard m e m b r a n e filter holder. The reference blotters were generally considered satisfactory to rate
test filters that had sediment similar in appearance (color
and shape) to that depicted on the reference blotter. However, the visual ratings were subjective and different raters
had been found to rate the same pad as everything from a 4
to an 11. Also, raters within the same laboratory tended to
train each other, thus compounding the possibility for error.
Henry [29] described a rating technique (originally proposed
by Chevron Oil Company) t h a t used a reflectance m e t e r
rather than a visual comparison. Figure 8 shows the relationship of visual and reflectance pad ratings. As expected, the reflectance meter method yielded greatly improved precision
compared to the reference blotters. The reflectance meter
was the technique selected when the method was standardized [30].

/
Thermal Stability

V^

/
//

/
^

ujl2

,y

\&

MULTILABORATORY
VISUAL RATINGS

y
/^

100

>

VISUAL RATINGS IN
ONE LABORATORY

'

80

60

"JO

20

PERCENT REFLECTION
(PHOTOVOLT MODEL 670 REFLECTION HETER WITH SEARCH UNIT W)

FIG. 8Relationship of visual and reflection pad ratings.

Arguably, this test is the most often used method to monitor/predict fuel stability. The primary reason for its popularity is the short test time and simple equipment requirements.
This has made the 150C test, in one form or another, especially popular with many pipeline companies and others with
the need to monitor the quality of fuel but do it rapidly. Stavinoha and Westbrook demonstrated that this test has poor
correlation to the generally accepted test for storage stability
of diesel fuel (see D 4625 below) [31]. Bacha [32] and Henry
[33] reported that the 150C test provides an indication of
thermal stability of distillate fuels exposed to high temperatures. The test method can be useful for investigation of operational problems related to fuel thermal stability. When D
6468 is used to m o n i t o r fuel in production or storage, a
change in filter rating can indicate a relative change in inherent stability of the fuel. No quantitative relationship exists
between pad ratings and the gravimetric mass of filterable insolubles formed during the test. Additional information on
the interpretation of results is found in Appendix XI of the
test method.

Oxidation Stability
Oxidation stability is the resistance of the fuel to change under severely oxidizing conditions. In addition to exposing the
fuel to excess amounts of oxygen, oxidation stability tests
usueJly incorporate elevated test temperatures to accelerate
reaction rates. The method commonly used to measure oxidation stability of diesel fuel is:
ASTM D 2274, Standard Test Method for Oxidation Stability
of Distillate Fuel Oil (Accelerated Method)^A 350-mL volu m e of filtered middle distillate fuels is aged at 95C
(203F) for 16 h while oxygen is bubbled through the sample at a rate of 3 L/h. After aging, the sample is cooled to ap-

CHAPTER
proximately room temperature before filtering to obtain
the filterable insolubles quantity. Adherent insolubles are
then removed from the oxidation cell and associated glassware with trisolvent. The trisolvent is evaporated to obtain
the quantity of adherent insolubles. The sum of the filterable and adherent insolubles, expressed as milligrams per
100 mL, is reported as total insolubles.
Because for m a n y years this was the only standardized
method to measure stability of middle distillate fuels, it became a part of n u m e r o u s fuel specifications (mostly government/military) and was widely used as a predictor of fuel
storage stability. Despite the wide acceptance as a storage
stability test, most researchers agreed that, in fact, the results
of D 2274 had very poor correlation to actual, ambient storage of the fuel. In addition, the precision of the test was extremely poor. Many researchers have worked to improve the
test. Chief a m o n g these is E. W. White of the U.S. Navy
[34,35]. Some of the factors he identified as having an effect
on the results of the test are: the purity of the oxygen, stray
light impinging the sample during aging (especially ultra-violet light), contact with metal surfaces (especially copper),
filter drying time, and heating bath configuration. Based on
the work of White and others, many needed improvements
were made to the method. The precision of the test is better
now than when it was first published by ASTM. However, despite the improvements, the results continue to have poor
correlation to ambient storage. Because this poor correlation
is now more widely known, the use of the method to assess
the stability of diesel fuels is very low.

5: GAS TURBINE

FUELS

127

TABLE 4Factors that influence the quality of


diesel fuel in storage.
Can lead to tank corrosion,
Presence of Water
microbiological growth, and
entrained water.
Can accelerate or slow chemical
Storage temperature
reactions in the fuel.
(ambient temperature)
Fixed roof tanks allow greater tank
Vented, fixed roof tank
vs. floating roof tank
breathing, which promotes water
condensation, oxygen replenishment
in the ullage, and increases airborne
contaminants in the fuel.
Lined vs. unlined
storage tanks

Lined tanks (those with an interior


coating) reduce or prevent exposure
of the fuel to metal surfaces. This
reduces corrosion of the tank. Metal
surfaces can also catsdyze some fuel
degradation reactions.

Microbiological
contamination

Leads to degradation of the fuel by


metabolic by-products, corrosion of
metallic storage tanks, and
emulsification of water and fuel.

Agitation of the fuel


through tank filling
and/or circulation of
the fuel
Crude oil source and
refining techniques

Promotes increased concentrations of


air/oxygen and water in the fuel.
These factors influence the chemical
composition of the fuel.

Commingling of fuels

The mixing of two stable fuels can, on


rare occasions, result in antagonistic
chemical reactions.

Storage Stability
Storage stability is generally defined as the fuel's resistance to
change during storage at ambient temperature and conditions. Ambient storage is storage of the fuel in drums, storage
tanks, vehicle fuel tanks, or similar containers in the out-ofdoors. There are many factors that can influence the storage
stability of a given fuel. The most c o m m o n factors are listed
in Table 4. The two tests for storage stability are:
ASTM D 4625, Standard Test Method for Distillate Fuel Storage Stability at 43C (nOF)Four-hundred
mL volumes
of filtered fuel are aged by storage in borosilicate glass containers at 43C (110F) for periods of 0, 4, 8, 12, 18, and 24
weeks. After aging for a selected time period, a sample is removed from storage, cooled to room temperature, and analyzed for filterable insolubles and for adherent insolubles.
ASTM D 5304, Standard Test Method for Assessing Distillate
Fuel Storage Stability by Oxygen OverpressureA 100-mL
aliquot of filtered fuel is placed in a borosilicate glass container. The container is placed in a pressure vessel that has
been preheated to 90C. The pressure vessel is pressurized
with oxygen to 800 kPa (absolute) (100 psig) for the duration of the test. The pressure vessel is placed in a forced air
oven at 90C for 16 h. After aging and cooling, the total
amount of fuel insoluble products is determined gravimetrically and corrected according to blank determinations.
All petroleum fuels u n d e r g o chemical reactions during
storage. The results of these reactions are usually g u m s ,
acids, and/or particulates. The n u m b e r and rate of these deleterious reactions depends on the concentrations of reaction
precursors, the concentration of oxygen available for oxida-

tion reactions, the presence of catalytic species such as metals, the a m o u n t of light, and the storage temperature. As
mentioned above, the resistance of the fuel to these reactions
is defined as its storage stability. Most researchers cJso go a
step further and define inherent storage stability as the resistance to change in the absence of environmental factors such
as metals and contaminants (i.e., in the absence of catalytic
effects).
The inherent stability is important because it is a measure
of the useful storage life of the fuel. For most diesel fuels under normal storage conditions,it may take several months or
even years for the deleterious reactions to generate enough
by-products to cause fuel-related p r o b l e m s . A user w h o
would like to store fuel would like to know what that length
of time is prior to putting the fuel in storage. To predict the
storage stability, therefore, we must simulate the storage and
measure the quantities of insolubles formed. To accelerate
the process, the test must be performed at an elevated temperature. The question is how high above ambient to conduct
the test so as to accelerate the reactions and still keep the results representative of storage at ambient temperature. The
Arrhenius [36] equation described in Fig. 9 can be used to estimate the reaction rates for fuels stored at ambient to
slightly above ambient temperatures. Under this relationship, the reaction rate is accelerated approximately 1.7-3
times for every 10C rise in temperature. The problem is that,
as the temperature rises, reactions that would not normeJly
occur during ambient storage (or would occur with very low
probability) now begin to occur. The high-temperature reactions result in other types of compounds, which can skew the

128

MANUAL

37: FUELS AND LUBRICANTS

k = Ae'^''

or

HANDBOOK

k=A,J^

where:
Ea = activation energy
R = gas constant
T = absolute temperature
A = frequency factor (collision frequency)
Taking the natural logarithm of both sides and rearranging gives:
lnfe=(-Ea/RXl/T) + lnA
Therefore, a plot of In A: versus 1/T gives a straight line whose slope is
equal to -Ea/R and whose intercept is In A
FIG. 9Arrhenius equation.

results of the aging test. Two early studies [37,38] demonstrated the correlation between storage at 43C and ambient
storage. They determined that 13 weeks at 43C is equivalent
to one year at ambient. Over the years, this relationship has
been redefined as 1 week at 43 C is equal to 1 month at ambient. These studies also established storage at 43C as the
standard accelerated storage test, against which all other accelerated storage stability tests are compared. This test works
so well because the test temperature is such a small increase
over ambient that the relative importance of the various reactions that create insolubles are not appreciably changed.
This makes the 43C storage test an ideal research tool for
studying storage stability of diesel fuels.
Ironically, that which makes the 43 C test such a useful research tool also makes it useless for quality assurance and
quzility control applications because of the long test times.
For this reason, m u c h effort has been expended over the past
25-30 years to develop a rapid test for fuel storage stability.
In this context, rapid is generally defined as test times of 16
hours or less. Very little success came of these efforts, with
one exception. The U.S. Navy developed a test method that
was eventucdly standardized as ASTM D 5304 \39'\. The applicability of the test method was demonstrated in a project
conducted during 1992-1993 [40].
Flash Point
Flash point is specified in D 975 primEuily for safety during
transport, storage, and handling. A low flash point fuel can be
a fire hazard, subject to flashing, with possible continued ignition and explosion. Low flash point can also indicate contamination with low-flash fuels such as gasoline. The flash
point of a fuel has no significant relation to the performance
of the fuel in the engine. Auto-ignition temperature is not influenced by variations in flash point.
There are five ASTM test m e t h o d s for measuring flash
point of diesel fuels:
ASTM D 56, Standard Test Method for Flash Point by Tag
Closed TesterThe specimen is placed in the cup of the
tester and, with the lid closed, heated at a slow constant
rate. An ignition source is directed into the cup at regular
interveJs. The flash point is taken as the lowest temperature at which application of the ignition source causes the
vapor above the specimen to ignite.

ASTM D 93, Standard Test Methods for Flash Point by Pensky-Martens Closed Cup Tester^A brass test cup of specified dimensions, filled to the inside msirk with test specimen and fitted with a cover of specified dimensions, is
heated and the specimen stirred at specified rates by either of two defined procedures (A or B). An ignition
source is directed into the test cup at regular intervals
with simultaneous interruption of the stirring until a flash
is detected.
ASrM D 3828, Standard Test Methods for Flash Point by
Small Scale Closed Tester Method AFlash/No Flash Test
A specimen of a sample is introduced by a syringe into the
cup of the selected apparatus that is set and maintained at
the specified temperature. After a specific time a test flame
is applied and an observation made as to whether or not a
flash occurred.
Method BFinite (or Actual) Flash Point^A specimen of a
sample is introduced into the cup of the selected apparatus
that is maintained at the expected flash point. After a specified time a test flame is applied and the observation made
whether or not a flash occurred. The specimen is removed
from the cup, the cup cleaned, and the cup temperature adjusted 5C (9F) lower or higher depending on whether or
not a flash occurred previously. A fresh specimen is introduced and tested. This procedure is repeated until the flash
point is established within 5C (9F). The procedure is then
repeated at 1C (2F) intervals until the flash point is determined to the nearest 1C (2F). If improved accuracy is
desired the procedure is repeated at 0.5C (1F) intervals
until the flash point is determined to the nearest 0.5C
(1F).
ASTM D 6450, Standard Test Method for Flash Point by Continuously Closed Cup (CCCFP) TesterThe lid of the test
chamber is regulated to a temperature at least 18C below
the expected flash point. A 1 mL test specimen of a sample
is introduced into the sample cup, ensuring that both specimen and cup are at a temperature at least 18C below the
expected flash point, cooling if necessary. The cup is then
raised and pressed onto the lid of specified dimensions to
form the continuously closed but unsealed test chamber
with an overall volume of 4.0 0.2 mL. After closing the
test chamber, the temperatures of the test specimen and
the regulated lid are edlowed to equilibrate to within 1C.
Then the lid is heated at a prescribed, constant rate. For the
flash tests, an arc of defined energy is discharged inside the
test chamber at regular intervals. After each ignition, 1.5
0.5 m L of air is introduced into the test chamber to provide
the necessary oxygen for the next flash test. The pressure
inside the continuously closed but unsealed test chamber
remains at ambient barometric pressure. The exceptions
are for the short time during the air introduction and at a
flash point. After each arc, the instantaneous pressure increase above the ambient barometric pressure inside the
test chamber is monitored. When the pressure increase exceeds a defined threshold, the temperature at that point is
recorded as the uncorrected flash point.
Each of these three test methods contains an introduction
that is similar to the following:
This flash point test method is a dynamic test method and
depends on definite rates of temperature increase to control
the precision of the test method. The rate of heating may

CHAPTER
not in all cases give the precision quoted in the test method
because of the low thermal conductivity of certain materials. To improve the prediction of flammability,
Test
Method D 3941, an equilibrium method was developed in
which the heating rate is slower. This allows the vapor
above the test specimen and the test specimen to be at
about the same temperature.
ASTM D 3941, Standard Test Method for Flash Point by the
Equilibrium Method with a Closed-Cup
ApparatusThis
method covers the determination of the flash point of hquids in which the specimen a n d the air/vapor mixture
above it are approximately in temperature equilibrium.
The test method is limited to a temperature range from
32-230F(0-110C).
Method D 3941 should b e used to measure Eind describe the
properties of material, products, or assemblies in response to
heat and flame u n d e r controlled laboratory conditions. It
should not be used to describe or appraise the fire hazard or
fire risk of materials, products or assemblies under actUcJ fire
conditions. However, results of this test may be used as elements of a fire risk assessment that takes into account all of
the factors that are pertinent to a n assessment of the fire hazard of a particular end use.
It is important to note that while D 3941 may be an acceptable alternative m e t h o d for some applications, the
method(s) listed in a given specification, such as D 975,
should not be replaced without prior knowledge and consent
of all interested parties. This is because the measured flash
point of a fuel is dependent not only on the composition of
the fuel but also on the apparatus used to make the measurement. ASTM Manual 9 describes many flash point test methods, both U.S. and international [41]. It also lists pertinent
specifications/standards worldwide.
Lubricity
Diesel fuel functions as a lubricant in certain items of fuel injection equipment such as rotary/distributor fuel p u m p s and
injectors. In limited cases, fuel with very specific properties
can have insufficient lubricating properties that can lead to a
reduction in the normal service life of fuel p u m p s or injectors. Two fuel chciracteristics that affect equipment wear are
low viscosity and lack of sufficient quantities of trace components, which have a n affinity for metal surfaces. If fuel viscosity meets the requirements of a particular engine, a fuel
film is maintained between the moving surfaces of the fuel
system components. This prevents excessive metal-to-metal
contact and avoids premature failure due to wear. Simileirly,
certain surface-active molecules in the fuel (such as acids and
heteroatomics) adhere to, or combine with, metallic surfaces
to produce a protective film that also can protect surfaces
against excessive wear. The concern about fuel lubricity is
limited to the use of fuels with viscosities lower than those
specified for a particulcir engine. Also of concern is the use of
fuels that have been processed in a manner that results in the
elimination of the trace levels of the surface-active species
that act as lubricating agents. Presently, the only fuels of the
latter type shown to have lubricity problems resulted from
sufficiently severe processing to reduce aromatics substantieJly below current levels. Research is in progress to identify
the chciracteristics of such fuels and where the use of a lu-

5: GAS TURBINE

FUELS

129

bricity improver additive is required, to ensure satisfactory


operation in the sensitive areas of the vehicle fuel system
[42].
Work in the area of diesel fuel lubricity is ongoing by several organizations, such as the International Organization for
Standardization (ISO) and the ASTM Diesel Fuel Lubricity
Task Force u n d e r Subcommittee E of Committee D2 [43].
These groups include representatives from the fuel injection
equipment manufacturers, fuel producers, and additive suppliers. The charge of the ASTM task force has been the recommendation of test methods and a fuel specification for
Specification D 975. At this writing, two test methods are approved:
ASTM D 6078, Standard Test Method for Evaluating Lubricity of Diesel Fuels by the Scuffing Load Ball-on-Cylinder Lubricity Evaluator (SLBOCLE)^A 50-mL test specimen of
fuel is placed in the test reservoir of an SLBOCLE and adjusted to the test temperature of 25C. When the fuel temperature has stabilized, 50% relative humidity air is used to
aerate the fuel at 0.5 L/min while 3.3 L/min flows over the
fuel for 15 min. During the remainder of the test sequence,
the 50% relative humidity air flows over the fuel at a rate of
3.8 L/min. A load a r m holding a non-rotating steel ball and
loaded with a 500 g mass is lowered until it contacts a partially fuel immersed polished steel test ring rotating at 525
rpm. The ball is caused to rub against the test ring for a 30s break in period before beginning an incremental-load or
a single-load test. Wear tests are conducted by maintaining
the beJl in contact with the particJly immersed 525- rpm
test ring for 60 s. For incremental load tests, the test ring is
moved at least 0.75 m m for each new load prior to bringing a new ball into contact with the test ring. The tangential friction force is recorded while the ball is in contact
with the test ring. The friction coefficient is calculated
from the tangential friction force. In the incremental-load
test, the m i n i m u m applied load required to produce a friction coefficient greater than 0.175 is an evaluation of the
lubricating properties of the diesel fuel. In the single-load
test, a friction coefficient less than or equal to 0.175 indicated the diesel fuel passes the lubricity evaluation, while a
friction coefficient greater than 0.175 indicated the diesel
fuel fails the lubricity evaluation.
ASTM D 6079 Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig
(HFFR)^A 2-mL test specimen of fuel is placed in the test
reservoir of an HFRR and adjusted to either of the staxidard
temperatures (25 or 60C). The preferred test temperature
is 60C, except where there may be concerns about loss of
fuel because of its volatility or degradation of the fuel because of the temperature. When the fuel temperature has
stabilized, a vibrator arm holding a non-rotating steel ball
and loaded with a 200-g mass is lowered until it contacts a
test disk completely submerged in the fuel. The ball is
caused to r u b against the disk with a 1-mm stroke at a frequency of 50 Hz for 75 min. The ball is removed from the
vibrator a r m and cleaned. The dimensions of the major
and minor axes of the wear scar are measured under lOOX
magnification and recorded.
A diagram of the test apparatus a n d a list of the test conditions for D 6078 and D 6079 are given in Figs. 10 and 11, respectively.

130 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


OUTFUTTO
rmcTioM necxMUMNO
DEVICE

LOAD
. " ^ Q

P'O.

3 ^ ^ COtfTACT U>Ap

MEAW-OUTT
FNCUMATIC
PWTOM
S c h e m a t i c D i a g r a m of t h e Scuffing L o a d Ball-on-Cylinder
Lubricity Evaiuator (not including Instrumentation)

MANDREL ASSEMBLY

SCREWS W REQ'a
BUTTON HEAD
8-32

DRIVESHAFT ASSEMBLY

Ring and Mandrel Assembly (Cylinder)


Parameter

Test Conditions Value

Fluid volume
50 1.0 mL
Fluid temperature
25 1C
Conditioned air^
50 1 % relative tiumidity at 25 1C
Fluid pretreatment: 0.50 U min air flowing through and 3.3 L/min air flowing
over the fluid for 15 min
Fluid test conditions: 3.8 L/min air flowing over the fluid
Cylinder rotational speed
525 1 rpm
Applied Load
Break-in period
500 g
Incremental-load test
500 to 5 000 g
Single-load test
user defined'
Test Duration
Break-in period
30 s
Wear tests
60s
*Fifty percent humidity should be achieved using equal volumes of dry and
saturated air. The SLBOCLE has a water column through which air passes and it
is assumed to be saturated when it exits this column.
"The applied load for the single test Is set at the pass/fail requirement for the fuel
being evaluated.
FIG. 1 0 T e s t e q u i p m e n t a n d t e s t c o n d i t i o n s f o r s c u f f i n g l o a d b a l l - o n cylinder lubricity e v a i u a t o r ( D 6 0 7 8 ) .

CHAPTER 5: GAS TURBINE FUELS

131

Lubricity Task Force is also working on possible revisions to


the standard HFRR test to make it more sensitive to low levels of lubricity additive.

Test Plata
Loading

Aromatics

Schematic Diagram of HFRR (not including


instrumentation)
Test Conditions
Fluid volume
Stroke length
Frequency
Fluid temperature

Relative humidity
Applied load
Test duration
Bath surface area

2 0.20 mL
1 0.02 mm
50 1 Hz
25 2C
or
60 2C
>30%
200 1 g
75 0.1 min
6 1 cm^

FIG. 11Test equipment and test conditions for high frequency reciprocating rig (D 6079).

The inclusion of a single fuel specification in the main


table of specification D 975 for Grade No. 2 requires further
research because:
1. the correlation of the data among the two test methods and
the fuel injection equipment needs further clarification,
2. both methods in their current form do not apply to all fueladditive combinations,
3. the reproducibility values for both test methods are large.
In the meantime, the following information may be of use
and serve as a general guideline to fuel suppliers and users.
Westbrook and coworkers recommended that users monitor their fuel injection pumps for possible trends of abnormal
wear rates if the fuel has a scuffing load value between 2000
and 2800 g in Test Method D 6078 [44]. According to this paper, fuels with values below 2000 g will, in all probability,
cause accelerated wear in fuel lubricated rotary-t5Tpe fuel injection pumps. It should be noted that a properly-additized
fuel might provide protection for fuel-wetted components
and yet not produce significant D 6078 test results as compared to the non-additized fuel.
Work at ISO indicates that a fuel with a 450-micron wear
scar diameter or lower value at 60C in Test Method D 6079
(380 micron at 25C) should protect all fuel injection equipment [45]. Other SAE publications present data to show that
some fuels and fuel/additive combinations can have values
above this level and still provide sufficient lubricity protection to the equipment.
Pump stand testing of fuels, although more expensive and
time consuming, is a more accurate means of evaluating the
lubricity of diesel fuel. At the time of this writing, the ASTM
Diesel Fuel Lubricity Task Force is working on the development and standardization of a pump stand test method. The

Diesel fuel contains many types or classes of compounds including paraffins, naphthenes, olefins, and Eiromatics. Compounds that contain heteroatoms such as sulfur, nitrogen,
and oxygen are also present. Aromatics warrant discussion
because 1) they have an effect on the combustion quality of
the fuel, 2) typically, they are the only hydrocarbon type
listed in diesel fuel specifications (including D 975), and 3)
increased amounts of aromatics can have a negative impact
on vehicle emissions.
It is well known that an increase in the total aromatics content of a diesel fuel can (and usually does) have an adverse effect on the ignition quality, i.e., cetane number of the fuel.
Several methods are available for the measurement of aromatic content. They eire described below:
ASTM D1319, Standard Test Method for Hydrocarbon Types
in Liquid Petroleum Products by Fluorescent Indicator AdsorptionApproximately 0.75 mL of sample is introduced
into a special glass adsorption column packed with activated silica gel. A small layer of the silica gel contains a
mixture of fluorescent dyes. When the entire sample has
been adsorbed on the gel, alcohol is added to desorb the
sample down the column. The hydrocarbons are separated
in accordance with their adsorption affinities into aromatics, olefins, and saturates. The fluorescent dyes are also
separated selectively, with the hydrocarbon types, and
make the boundaries of the aromatic, olefin, and saturate
zones visible under ultraviolet light. The volume percentage of each hydrocarbon type is calculated from the length
of each zone in the column.
This test method was originally developed for the analysis
of gasoline (spark ignition engine fuel). It is for determining
hydrocarbon types over the concentration ranges from 5-99
volume % aromatics, 0.3-55 volume % olefins, and 1-95 volume % saturates in petroleum fractions that distill below
315C. The test method may apply to concentrations outside
these ranges, but the precision has not been determined.
Samples containing dark-colored components that interfere
in reading the chromatographic bands cannot be analyzed.
D 1319 was applied to and specified for diesel fuel usually
because no other suitable method was available. As suitable
methods became standardized they grew in use but have not
replaced D 1319 in D 975. This is because the requirement for
aromaticity currently included in D 975 comes from the requirement in 40 CFR Fart 80. Since federal law requires D
1319, it is the method listed in D 975. Method D 5186, described below, is more appropriate for diesel fuel and is often
used in place of D 1319. However, in case of dispute, D 1319,
by virtue of it's status as the legislated method, is considered
the referee method.
ASTM D 5186, Standard Test Method for Determination of
Aromatic Content and Polynuclear Aromatic Content of
Diesel Fuels and Aviation Turbine Fuels by Supercritical
Fluid ChromatographyA small aliquot of the fuel sample
is injected onto a packed silica adsorption column and

132

MANUAL

3 7: FUELS AND LUBRICANTS

HANDBOOK

eluted using supercritical carbon dioxide mobile phase.


Mono-aromatics and polynucleEir aromatics in the sample
are separated from non-aromatics and detected using a
flame ionization detector. The detector response to hydrocarbons is recorded t h r o u g h o u t the analysis time. The
chromatographic areas corresponding to the mono-aromatic, polynuclear aromatic, and non-aromatic components are determined and the mass % content of each of
these groups in the fuel is calculated by area normalization.
This test method covers the determination of the total
amounts of mono-ciromatic and polynuclear aromatic hydrocarbon compounds in motor diesel fuels, aviation turbine fuels, and blend stocks by supercritical fluid chromatography (SFC). The range of aromatics concentration to
which this test method is applicable is from 1-75 mass %.
The range of polynuclear aromatic hydrocarbon concentrations to which this test method is applicable is from 0.5-50
mass %.
ASTM D 6591, Standard Test Method for Determination of
Aromatic Hydrocarbon Types in Middle Distillates, High Performance Liquid Chromatography Method with Refractive
Index DetectionA known mass of sample is diluted in the
mobile phase, a n d a fixed volume of this solution is injected into a high performance liquid chromatograph, fitted with a polar column. This column has little affinity for
the non-aromatic hydrocarbons while exhibiting a pronounced selectivity for aromatic hydroccirbons. As a result
of this selectivity, the aromatic hydrocarbons are separated
from the non-aromatic hydrocarbons into distinct bands in
accordcince with their ring structure. At a predetermined
time, after the elution of the di-aromatic hydrocarbons, the
column is back flushed to elute the polycyclic aromatic hydroccirbons as a single sharp band.
Method D 2425 offers a more detailed analysis but requires
considerable investment in i n s t r u m e n t a t i o n a n d sample
preparation time. For these reasons, it is not typically used
for routine ctnalysis of diesel fuel.
ASTM D 2425, Standard Test Method for Hydrocarbon Types
in Middle Distillates by Mass SpectrometryThis
test
method covers an analytical scheme using the mass spectrometer to determine the hydrocarbon types present in
virgin middle distillates 204-343C (400-650F) boiling
range, 5-95 volume % as determined by Method D86.
Samples with average carbon n u m b e r value of paraffins
between C 12 and C 16 and containing petraffins from C I O
and C 18 can be analyzed. Eleven hydrocarbon types are
determined. These include: paraffins, non-condensed cycloparaffins, condensed di-cycloparaffins, condensed tricycloparaffins, alkylbenzenes, indans or tetraJins, or both,
CH n.io (indenes, etc.), naphthalenes, CnH n.14 (acenaphthenes, etc.), CnH .i6 (acenaphthylenes, etc.), and tri-cyclic
aromatics.
Method D 5292 also offers more information than D 1319
or D 5186. However, the results are reported in mole% rather
than mass or volume percent, which are normally required in
specifications.
ASTM D 5292, Standard Test Method for Aromatic Carbon
Contents of Hydrocarbon Oik by High Resolution Nuclear
Magnetic Resonance SpectroscopyThis test method cov-

ers the determination of the aromatic hydrogen content


(Procedures A and B) 8ind aromatic carbon content (Procedure C) of hydrocarbon oils using high-resolution nuclear
magnetic r e s o n a n c e (NMR) spectrometers. Applicable
samples include kerosines, gas oils, mineral oils, lubricating oils, coal liquids, and other distillates that are completely soluble in chloroform and Ccirbon tetrachloride at
ambient temperature. For pulse Fourier-transform (FT)
spectrometers, the detection limit is t5^ically 0.1 mol %
aromatic hydrogen atoms a n d 0.5 mol % aromatic carbon
atoms. For continuous wave (CW) spectrometers, which
are suitable for measuring aromatic hydrogen contents
only, the detection limit is considerably higher and typically 0.5 m o l % aromatic-hydrogen atoms. The reported
units are mole percent, aromatic- hydrogen atoms and
mole% aromatic-Ccirbon atoms. This test method is not applicable to samples containing more than 1 mass % olefinic
or phenolic compounds. This test method does not cover
the determination of the percentage mass of aromatic compounds in oils since NMR signals from both saturated hydrocarbons a n d aliphatic substituents o n aromatic ring
compounds appear in the same chemical shift region. For
the determination of mass or volume% aromatics in hydrocarbon oils, chromatographic or m a s s spectrometry
methods can be used.
It should be noted that there are several standard methods
for the analysis of aromatics. Each method yields a slightly
different result and each is considered appropriate in different situations. One reason for this apparent inconsistency is
that since a single molecule can contain several chemical
moieties, it is possible to include it in several hydrocarbon
classes. For example, a molecule could contain an aromatic
ring, a pciraffinic side chain, and a naphthenic ring. How
should this molecule be classified? A hierarchy was established to address this situation. Under this hierarchy, aromatics are on top, then olefins, followed by naphthenes, and
finally paraffin. Using this hierarchy, the example compound
would be considered an aromatic compound.
The level of aromatics in the fuel is also important as it
relates to the potential for elastomer and seed swell problems. This is especially true for older vehicles/fuel systems.
Depending on the type of elastomer, prolonged exposure to
relatively high levels of aromatics, followed by a sudden decrease in the amount of aromatics, can cause elastomeric
seals to shrink and thus leak. If the elastomers are too old
and have taken a set, they Cctn also crack or break. This phenomenon was widely seen in late 1993 and early 1994 when
mcindated reductions in fuel sulfur and aromatics content
went into effect. In most instances, the problems were
solved by installing new seals made of less sensitive elastomer.
Heat Content
The heat content or heat of combustion of a fuel is the
amount of heat produced when the fuel is burned completely.
Gross and net heats of combustion are the two values measured for the heat of combustion.
The gross heat of combustion is the quantity of energy released when a unit mass of fuel is burned in a constJint volu m e enclosure, with the products being gaseous, other than

CHAPTER 5: GAS TURBINE FUELS 133


water that is condensed to the hquid state. The fuel can be either hquid or soUd, and contain only the elements carbon, hydrogen, nitrogen, and sulfur. The products of combustion, in
oxygen, are gaseous carbon dioxide, nitrogen oxides, sulfur
dioxide, and liquid water.
The net heat of combustion is the quantity of energy released when a unit mass of fuel is burned at constant pressure, with all of the products, including water, being gaseous.
The fuel can be either liquid or solid, and contain only the elements carbon, hydrogen, oxygen, nitrogen, and sulfur. The
products of combustion, in oxygen, are carbon dioxide, nitrogen oxides, sulfur dioxide, and water, all in the gaseous
state. For c o m p o u n d s with the same n u m b e r of c a r b o n
atoms, heat content increases as you go from aromatics to
naphthenes to paraffins, on a weight basis. The reverse order
is correct if you measure on a volume basis. The same is true
for fuels. Denser fuels, such as diesel, have higher heat content on a volume basis. Less dense fuels, such as gasoline,
have higher heat content on a weight basis. Chevron has reported typical heat content values that demonstrate this relationship (see Table 5).
Heat of combustion is usually reported in units of megajoules per kilogram (MJ/kg). Conversion factors to other
units are given in Table 6. Heat of combustion can be estimated by calculation from selected properties or measured
using b o m b calorimetry. The m e t h o d s typically used for
diesel fuel are discussed below.
ASTM D 4868, Standard Test Method for Estimation of Net
and Gross Heat of Combustion of Burner and Diesel Fuels
This test method covers the estimation of the gross and net
heat of combustion of petroleum fuel. The calculations use
the fuel density, sulfur, water, and ash content. The equations for estimating net a n d gross heat of combustion used
in this method were originally published in the National
Institute of Standards and Technology (NIST) Publication
No. 97. The equations are:
Calculate the gross heat of combustion of the fuel corrected
for the sulfur, water, and ash content in accordance" with the
following equation:
Q^ (gross) = (51.916

8.792^2 X 10- ')


[1 (x+y

+s)] + 9.420s

where:
Q

d
X
y
5

= gross heat of combustion at constant volume,


MJ/kg,
= density at 15C, kg/m^,
= mass fraction of water (% divided by 100),
= mass fraction of ash (% divided by 100), eind
= mass fraction of sulfur (% divided by 100).

TABLE 5Typical density and heat content value of


different fuels.
Fuel

Density,
g/cm^

Regular gasoline
Premium gasoline
Jet fuel
Diesel fuel

0.735
0.755
0.795
0.850

Net Heat of
Combustion,
Btu/lb

18
18
18
18

630
440
420
330

Net Heat of
Combustion,
Btu/gal

114
116
122
130

200
200
200
000

TABLE 6Conversion factors for heat


of combustion values.
1 cal (International Table calorie) = 4.1868 J
1 Btu (British thermal unit) = 1055.06 J
1 cal (I.T.)/g = 0.0041868 MJ/kg
1 Btu/lb = 0.002326 MJ/kg

Calculate the net heat of combustion of the fuel corrected


for the sulfur, water and ash content in accordance with the
following equation:
Qp (net) = (46.423 - 8.792^^ x 10"* + 3.70d X 10"^)
X[l

- (x+y

+ s)] + 9.4205 + 2.449;c

where:
Qp = net heat of combustion at constant pressure,
MJ/kg,
d = density at 15C, kg/m^,
X = mass fraction of water,
y = mass fraction of ash, and
s = mass fraction of sulfur.
This test method is useful for estimating, using a minimum
n u m b e r of tests, the heat of combustion of burner and diesel
fuels for which it is not usually critical to obtain very precise
heat determinations. This test method is purely empirical. It
is applicable only to liquid hydrocarbon fuels derived by normal refining processes from conventional crude oil. This test
method is valid for those fuels in the density range from 750
to 1000 kg/m^ and those that do not contain an unusually
high aromatic content. High aromatic content fuels will not
normally meet fuel specification criteria for this method.
This test method is not applicable to pure hydrocarbons. It is
not intended as a substitute for experimental measurements
of heat of combustion.
According to the m e t h o d the estimation of the heat of
combustion of a hydrocarbon fuel from its density, sulfur,
water, and ash content is justifiable only when the fuel belongs to well-defined classes for which a relationship between these quantities have been derived from accurate experimental measurements on representative samples of these
classes. Even in these classes, the possibility that the estimate
may be in error by large amounts for individual fuels should
be recognized. This test method has been tested for a limited
number of fuels from oil sand bitumen and shale oil origin
and has been found to be valid. The classes of fuels used to
establish the correlation presented in this test method are
represented by the following specifications:
1. D 396 Fuel Oils Grades 1, 2, 4 (light), 4, 5 (hght), 5 (heavy),
and 6
2. D 975 Diesel Grades 1-D, 2-D, and 4-D
3. D 1655 Aviation Turbine Jet A, Jet A-1, and Jet B
4. D 2880 Gas Turbine Grades 0-GT, 1-GT, 2-GT, 3-GT and 4GT
5. D 3699 Kerosine Grades 1-K and 2-K
ASTM D 4809, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method)This test method covers the determination of the heat of combustion of hydroccirbon fuels. It was

134 MANUAL 3 7: FUELS AND LUBRICANTS

HANDBOOK

designed specifically for use with aviation turbine fuels


when the permissible difference between duplicate determinations is of the order of 0.2%. It can be used for a wide
range of volatile and nonvolatile materials where slightly
greater differences in precision can be tolerated. Under
normal conditions, the method is directly applicable to
such fuels as gasoline, kerosine, Nos. 1 and 2 fuel oil, Nos.
1-D and 2-D diesel fuel and Nos. 0-GT, 1-GT, and 2-GT gas
turbine fuels.
The increased precision is obtained through the improvement of the CcJorimeter controls and temperature measurements.
ASTM D 240, Standard Test Method for Heat of Combustion
of Liquid Hydrocarbon Fuels by Bomb CalorimeterThis
test method covers the determination of the heat of combustion of liquid hydrocarbon fuels ranging in volatility
from that of light distillates to that of residual fuels. Under
normal conditions, this test method is directly applicable
to such fuels as gasoline, kerosine, Nos. 1 and 2 fuel oil,
Nos. 1-D and 2-D diesel fuel, and Nos. 0-GT, 1-GT, and 2GT gas turbine fuels. This test method is not as repeatable
and not as reproducible as Test Method D 4809.
In this method the net heat of combustion is represented
by the symbol Q n and is related to the gross heat of combustion by the following equation:
Q {net, 25C) = Qg {gross, 25C) - 0.2122 X H
where:
Q (net, 25C) = net heat of combustion at constant
pressure, MJ/kg
Q (gross, 25C) = gross heat of combustion at constant
volume, MJ/kg
H = mass % hydrogen in the sample

Total Sulfur
The test methods for measuring total sulfur in diesel fuel, as
prescribed in D 975 are:
ASTM D 2622, Standard Test Method for Sulfur in Petroleum
Products by Wavelength Dispersive X-ray Fluorescence SpectrometryD 2622 is prescribed for the measurement of total sulfur in Grades Low Sulfur No. 1-D and No. 2-D. This
test method covers the determination of total sulfur in liquid petroleum products and in solid petroleum products
that can be liquefied with moderate heating or dissolved in
a suitable organic solvent. The applicable concentration
range will vary to some extent with the instrumentation
used and the nature of the sample. Optimum conditions
will allow the direct determination of sulfur in essentially
paraffinic samples at concentrations exceeding 0.0010
mass%.
ASTM D 129, Standard Test Method for Sulfur in Petroleum
Products (General Bomb Method)The sample is oxidized
by combustion in a bomb containing oxygen under pressure. The sulfur, as sulfate in the bomb washings, is determined gravimetrically as barium sulfate.
D 129 is the prescribed method for the determination of total sulfur in Grades No. 1-D, No. 2-D, and No. 4-D. This test

method covers the determination of sulfur in petroleum


products, including lubricating oils containing additives, additive concentrates, and lubricating greases that cannot be
burned completely in a wick lamp. The test method is applicable to any petroleum product sufficiently low in volatility
that it can be weighed accurately in an open sample boat and
containing at least 0.1% sulfur.
ASTM D 4294, Standard Test Method for Sulfur in Petroleum
Products by Energy-Dispersive X-Ray Fluorescence SpectroscopyThis test method covers the measurement of sulfur in hydroccirbons such as naphthas, distillates, fuel oils,
residues, lubricating base oils, and nonleaded gasoline.
The concentration range is from 0.05-5mass%.
ASTM D 5453, Standard Test Method for Determination of
Total Sulfur in Light Hydrocarbons, Motor Fuels and Oils by
Ultraviolet FluorescenceThis test method covers the determination of total sulfur in liquid hydrocarbons, boiling
in the range from approximately 25400C, with viscosities
between approximately 0.2 and 10 cSt (mm/s^) at room
temperature. This test method is applicable to naphthas,
distillates, motor fuels and oils containing 1.0 to 8000
mg/kg total sulfur.
ASTM D 1266, Standard Test Method for Sulfur in Petroleum
Products (Lamp Method)This test method covers the determination of total sulfur in liquid petroleum products in
concentrations from 0.01-0.4 mass %. A special sulfate
analysis procedure is described in the method that permits
the determination of sulfur in concentrations as low as 5
mg/kg.
ASTM D1552, Standard Test Method for Sulfur in Petroleum
Products (High-Temperature Method)This test method
covers three procedures for the determination of total sulfur in petroleum products including lubricating oils containing additives, and in additive concentrates. This test
method is applicable to samples boiling above 177C
(350F) and containing not less than 0.06 mass% sulfur.
Two of the three procedures use iodate detection. One employs an induction furnace for pyrolysis, the other a resistance furnace. The third procedure uses IR detection following p5Tolysis in a resistance furnace.
The sulfur content of diesel fuel is known to affect particulate matter (PM) exhaust emissions because some of the sulfur is converted to sulfate particles in the exhaust. The
amount that is converted varies by engine; but reducing total
sulfur produces a linear decrease in PM in nearly all engines.
Fuel sulfur can also adversely affect cylinder wear (through
the formation of acids) and deposit formation (many sulfur
compounds are known deposit precursors).
Copper Strip Corrosion
The test method for copper strip corrosion is D 130.
ASTM D 130, Standard Test Method for Detection of Copper
Corrosion from Petroleum Products by the Copper Strip Tarnish Test^A polished copper strip is immersed in a given
quantity of sample and heated at a temperature and for a
time characteristic of the material being tested. At the end
of this period the copper strip is removed, washed, and
compared with the ASTM Copper Strip Corrosion Standards (this is an adjunct available from ASTM Headquarters).

CHAPTER 5: GAS TURBINE FUELS 135


The copper strip corrosion test covers the detection of the
corrosiveness to copper of aviation gasohne, aviation turbine
fuel, automotive gasohne, natural gasoline, or other hydrocarbons having a Reid vapor pressure no greater than 124
kPa(18psi).
Crude petroleum contains sulfur compounds, most of
which are removed during refining. However, of the sulfur
compounds remaining in the petroleum product, some can
have a corroding action on various metals and this corrosivity is not necessarily related directly to the total sulfur content. The effect can vary according to the chemical types of
sulfur compounds present. The copper strip corrosion test is
designed to assess the relative degree of corrosivity of a
petroleum product. It is very rare to find a commercially
available diesel fuel that fails the D 130 test.

such as amyl nitrate, hexyl nitrate, or octyl nitrate, causes a


higher carbon residue value than observed in untreated fuel,
which can lead to erroneous conclusions as to the coke-forming propensity of the fuel. Test Method D 4046 can detect the
presence of alkyl nitrate in the fuel.
The carbon residue value of burner fuel serves as a rough
approximation of the tendency of the fuel to form deposits in
vaporizing pot-type and sleeve-type burners. Similarly, provided alkyl nitrates are absent (or if present, provided the test
is performed on the base fuel without additive) the carbon
residue of diesel fuel correlates approximately with combustion chamber deposits. The carbon residue value of gas oil is
useful as a guide in the manufacture of gas from gas oil. In a
gas turbine it can be an indication of the tendency to form
carbon deposits in the combustor.

Carbon Residue

Ash

Carbon residue is the residue formed by evaporation and


thermal degradation of a carbon containing material. The
residue is not composed entirely of carbon but is a coke that
can be further changed by carbon pyrolysis. The term carbon
residue is retained in deference to its wide common
usage.The test method for carbon residue, as listed in the
diesel fuel specification is D 524.
D 524, Standard Test Method for Ramsbottom Carbon
Residue of Petroleum ProductsThe sample, after being
weighed into a special glass bulb having a capillary opening, is placed in a metal furnace maintained at approximately 550C. The sample is thus quickly heated to the
point at which all volatile matter is evaporated out of the
bulb with or without decomposition while the heavier
residue remaining in the bulb undergoes cracking and coking reactions. In the latter portion of the heating period,
the coke or carbon residue is subject to further slow decomposition or slight oxidation due to the possibility of
breathing air into the bulb. After a specified heating period, the bulb is removed from the bath, cooled in a desiccator, and again weighed. The residue remaining is calculated as a percentage of the original sample, and reported
as Ramsbottom carbon residue. Provision is made for determining the proper operating characteristics of the furnace with a control bulb containing a thermocouple, which
must give a specified time-temperature relationship.
This test method covers the determination of the amount
of carbon residue left after evaporation and pyrolysis of an
oil, and is intended to provide some indication of relative
coke-forming propensity. This test method is generally applicable to relatively nonvolatile petroleum products that partially decompose on distillation at atmospheric pressure.
Petroleum products containing ash-forming constituents as
determined by Test Method D 482 will have an erroneously
high carbon residue, depending upon the amount of ash
formed. Values obtained by this test method are not numerically the same as those obtained by Test Method D 189, or
Test Method D 4530. Approximate correlations have been derived (Fig. 12) but need not apply to all materials that can be
tested because the carbon residue test is applicable to a wide
variety of petroleum products. The Ramsbottom Carbon
Residue test method is limited to those samples that are mobile below 90C. In diesel fuel, the presence of alkyl nitrates

Ash is the non-combustible material in a fuel oil. It can be


present as either solid material or oil or water-soluble metallic compounds. These solid particles are the same as those often designated as sediments. The concern for fuel systems is
that these solid particles can result in wear and erosion ultimately resulting in substandard or failing performance. The
test method for ash is D 482.
ASTM D 482, Standard Test Method for Ash from Petroleum
ProductsThe sample, contained in a suitable vessel, is ignited and allowed to bum until only ash and carbon remain. The carbonaceous residue is reduced to an ash by
heating in a muffle furnace at 775C, cooled and weighed.
This test method covers the determination of ash in the
range 0.001-0.180 mass %, from distillate and residual fuels,
gas turbine fuels, crude oils, lubricating oils, waxes, and
other petroleum products, in which any ash-forming materials present eire normally considered to be undesirable impurities or contaminants. The test method is limited to
petroleum products that are free from added ash-forming additives.
Knowledge of the amount of ash-forming material present
in a product can provide information as to whether or not the
product is suitable for use in a given application. Ash can result from oil or water-soluble metallic compounds or from
extraneous solids such as dirt and rust.
Low-Sulfur Diesel Fuel and Dyed Diesel Fuel
The Clean Air Act Amendments of 1990 established standards
for highway diesel fuel. The standards, in part, made it illegal
as of October 1, 1993, to manufacture, sell, supply, or offer
for sale diesel fuel for highway use that has a sulfur content
greater than 0.05% by weight (this amount is also commonly
expressed as 500 ppm). Similarly, it is illegal for any person
to use fuel that has sulfur content greater than 0.05% by
weight in any highway vehicle. EPA also requires diesel fuel
not intended for use in highway vehicles be dyed in order to
segregate it from highway fuel. Internal Revenue Service
(IRS) regulations require that tax-exempt diesel fuel be dyed
regardless of the sulfur level of the fuel.
The original EPA regulation mandated the addition of a
blue dye to fuel with greater than 500-ppm total sulfur.
However, the Federal Aviation Administration soon ex-

136

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

100
80
60
40
30
20

i
s
s
t

CJ

Q_
i.r

^^.
*^

4
3
2

is
^5

li *o

eo
Q=

1.0
0.8
0.6

0.4
0.3

^
S

0.2

0.02 0.03

0.06

0.10
0.08
0.06
0.04
0.03
0.02

0.01
0.01

0.10

0.2 0.3 0.4 0.60.81.0

3 4

6 8 10

20

30 40 60 80 100

CONRAOSON CARBON RESIDUE, PER CENT BY WEIGHT


(ASTM D 189)

NOTE 1^All dimensions are in millimetres.


FIG. 12Correlation of conradson carbon residue (D 189) with ramsbottom carbon
residue (D 524).

pressed their concern that blue-dyed fuel might be confused


with the most c o m m o n grade of aviation gasoline, which is
also dyed blue. Based on this, the EPA changed the requirements to the use of red dye. The EPA now requires "visible
evidence of the presence of red dye" to identify high sulfur
fuels intended for off-road use. This typically requires that
oil companies add a level of red dye equivalent to 0.75
pounds per 1000 barrels of a solid Solvent Red 26 dye standcird. Solvent Red 26 was selected as the dye standard because it is a unique chemical and available in pure form.
Diesel fuels are actually dyed with liquid concentrates of
Solvent Red 164 because this dye is more fuel soluble and
less costly than the standard. Solvent Red 164 is a mixture
of isomers that are very similar to Solvent Red 26, except
the former incorporates alkyl chains to increase the solubility in petroleum [46].
Under the EPA regulations, any red dye seen in the fuel of
a vehicle operating on-road triggers a n analysis of the fuel's
total sulfur content. Penalties are assessed based on the measured sulfur content of the fuel, rather than the mere presence of red dye.
The IRS tcikes a slightly different path with its regulations.
They require that tax-exempt diesel fuels, both low sulfur and

high sulfur, have a m i n i m u m level of Solvent Red 164 that is


"spectrally equivalent to 3.9 pounds per 1000 barrels" of Solvent Red 26. This is over five times the a m o u n t required under the EPA regulations. The IRS holds that the excessive dye
amount is required to allow detection of attempted tax evasion even after a five-fold dilution of the dyed fuel with
undyed fuel. In practice, diesel fuel is taxed as soon as it
leaves a terminal unless it has been dyed.
The change, in 1993, to low sulfur diesel fuel for on-road
use brought numerous problems. Some of these include:
A marked increase in the number of fuel lubricity related
failures of fuel-wetted engine components. This is primarily attributed to the fact that the hydrotreating required to
remove the sulfur also removes naturally occurring fuel
components that would have improved the lubricity of the
fuel.
The requirements to dye the fuel at the early stages of the
distribution process m e a n that dyed fuel is often transported through pipelines. While not a c o m m o n occurrence,
red dyed diesel fuel has been known to contaminate other
fuels in the system. This occurs either through actual mixing of the diesel with the other product or contamination
of the other product with red dye residue on the wzJls of the

CHAPTER
pipeline following a shipnient of dyed fuel. In the cases
where the contaminated fuel has been aviation fuel, the result is usually the requirement to dispose of the contaminated fuel since most jet engines are not certified to operate on fuel with red dye.
Under the EPA regulations, kerosine used for home heating and other off-road applications must contain the red
dye. Since this fuel is not tcixed, the IRS does not require
the presence of the dye. Unfortunately, the evidence regarding the possible health effects of using red-dyed fuel in
un-vented kerosine heaters is minimal. Therefore, m a n y
users of these heaters are reluctcuit to use red-dyed kerosine. However, if the user wants un-dyed kerosine, they
must pay the tax so that it will not have to be dyed u n d e r
the IRS regulations. Understandably, m a n y kerosine
heater users are upset about having to pay the tcix. The laws
do allow a refund of the tax, however, and many users (and
in some cases, suppliers) are taking the necessary steps to
reclaim those monies. There is also work underway to develop information on the potential health effects of burning the dyed fuel in un-vented heaters. Users are encouraged to check with their fuel suppliers for additional
information.
Seal swell and elastomer compatibility problems brought
about by the reductions in ciromatic content in low sulfur
fuels. This is discussed in the section on aromatics.
It should be noted that the reductions in allowable sulfur
have also had some positive effects. Aside from the obvious
improvements in engine emissions, the hydrotreating required to remove the sulfur often means that the fuel has
significantly better stability characteristics (through the removal of precursors). The concomitant removal of aromatics can also bring some improvement to the ignition quality of the fuel.
The requirement to reduce sulfur levels in diesel fuel is now
a "fact-of-life" throughout the world. At the time of this writing, the EPA is proposing legislation to reduce the maximum
allowable sulfur level to I S p p m b y J u n e 1, 2006 [47]. The primary impetus for this continued reduction in sulfur is the
need to protect exhaust-treatment devices installed on diesel
engines, many of which are poisoned by sulfur.
World Wide Fuel Charter
The World-Wide Fuel Charter was jointly developed by the
E u r o p e a n Automobile Manufacturers Association (ACEA),
the Allieuice of Automobile Manufacturers, the Engine Mcinufacturers Association (EMA), the Japan Automobile Manufacturers Association (JAMA), and numerous associate mem-

5: GAS TURBINE

FUELS

137

bers and supporting organizations [48]. In a letter dated April


2000, the members stated that the "Charter was first established in 1998 to promote greater understanding of the fuel
quality needs of motor vehicle technologies and to harmonize
fuel quality world-wide in accordance with vehicle needs."
The Charter contains four categories of gasoline and diesel
fuel as follows (see Table 7 for a listing of selected diesel fuel
properties):
Category 1: Markets with n o or minimal requirements for
emission control, based primarily on fundamental vehicle/engine performance concerns.
Category 2: Markets with stringent requirements for emission control or other market demands. For example, meirkets requiring US Tier 0 or Tier 1, EURO 1 and 2, or equivalent emission standards.
Category 3: Markets with advanced requirements for emission control or other market demands. For example, markets requiring US California LEV, ULEV, and EURO 3 and
4, or equivalent emission standards.
Category 4: Markets with further advanced requirements
for emission control, to enable sophisticated NOx and particulate matter after-treatment technologies. For example,
markets requiring US California LEV-II, US EPA Tier 2,
and EURO 4.
Premium Diesel Fuel
As discussed above, environmental regulations promulgated
under the Clean Air Act Amendments have resulted in significant changes to the automotive diesel fuel manufactured
and sold in the United States. These changes, coupled with
rapidly changing engine technology, created the need to address several fuel properties to ensure proper performance,
while cJso minimizing engine maintenance problems. There
is also a segment of the automotive diesel fuel market that believes that they can benefit from a fuel supply with properties
different from or in addition to, the m i n i m u m ASTM D 975
specifications. Many fuel suppliers sell such fuels at a higher
price. As a marketing tool, this fuel is often called "premium
diesel fuel." Other terms or descriptions have also been used.
At the time of this writing, two major groups have proposed
definitions for premium diesel. Those two groups are the Nationeil Conference on Weights and Measures (NCWM) and
the Engine Manufacturers Association (EMA). In both cases,
the proposed premium diesel is based on varying one or more
fuel properties.
To ensure that the fuel consumer gets a "premium" product for the higher price, the National Conference on Weights
and Measures (NCWM) took steps to develop a standardized

TABLE 7Selected property specifications from world-wide fuel charter.


Property

Category 1

Category 2

Category 3

Category 4

Cetane Number, min


Cetane Index, min
Sulfur, max, mass %
Lubricity, HFRR scar dia @60C, (xm
Particulates, mg/L
Total Aromatics, mass %

48
45
0.50
400
No Requirement
No Requirement

53
50
0.030
400
24
25

55
52
0.003
400
24
15

55
52
Sulfur-free
400
24
15

138 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 8Diesel fuel properties referenced in NCWM definition


of premium diesel fuel.
Heating Value, Gross,
Btu/gallon, min

D240

Cetane number, min


Low temperature
operability

D613
D 2500 or
D4539

Thermal stability, 180 min.


150C, reflectance, min
Fuel injector cleanliness
Flow loss, % max
CRC rating, % max

D6468

138 700

47.0
2C maximum
above the D 975
tenth percentile
minimum
ambient air
temperature
80%

L-10 Injector
6.0
10.0

definition of premium diesel. An NCWM task force composed of representatives from the oil industry, additive manufacturers, independent labs, and government agencies, with
the assistance of ASTM, prepared a set of requirements to define premium diesel. In late 1997, the NCWM task force recommended that a fuel must meet any two of the five criteria
listed in Table 8 before it can be labeled "premium diesel."
The NCWM adopted the plan at its 84th conference in 1999
[49]. The definition became a model law and was automatically adopted by some states; elsewhere, it will only become
effective if a state specifically adopts it.
The EMA issued a Recommended Guideline (FQP-IA) for
a premium diesel fuel. The proposed values are listed in
Table 9. From the EMA consensus position:
This diesel fuel is considered to be "premium" insofar as it
may assist in improving the performance and durability of
engines currently in use and those to be produced prior to
2004. It is not intended to enable diesel engines to meet any
emissions standard or, in general, to improve engine exhaust emissions... It is intended as a "living document" in
that, as other needs or test procedures are identified, the
recommendation will be upgraded [50].
The most significant aspects of this Consensus Position are
its requirements for a minimum fuel lubricity, increased
cetane number, improved cold weather performance, detergency, thermal stability, minimum energy content, and specifications regarding overall fuel "cleanliness."
Alternative Fuels
As in the early 1980s, research with alternative fuels is again
on the increase. Whereas the earlier work centered on the
suitability of alternative fuels to power diesel engines; most
of the current work is evaluating the potential these fuels offer to reduce engine emissions [51]. Fischer-Tropsch Liquids
and Biodiesel are the fuels that seem to show up the most in
the current literature and reports.
Fischer-Tropsch Synthesis is the process whereby natural
gas or coal is converted into hydrocarbons. The product hydrocarbons are usually upgraded to middle distillate products such as kerosine and diesel fuel. Typically Fischer-Tropsch diesel fuels have high cetane numbers, often greater than
70 cetane, no aromatic compounds, no sulfur, and a density
of around 0.78 kg/L [52]. The Fischer-Tropsch liquids have

been evaluated as a diesel fuel and as a blend component


with conventional petroleum diesel fuel.
Schaberg, et al. [53] tested two variations of the Sasol distillate fuels, a 2-D diesel fuel, a CARB (California Air Resources Board) diesel, and three blends of the Sasol fuel with
the 2-D fuel. The Sasol fuels produced significantly lower engine emissions than the 2-D and CARB fuels. The fuel blends
reduced emissions in proportion to the amount of the Sasol
fuel in the blend. Other resesirchers have shown similar improvements in regulated emissions, with the use of FischerTropsch fuels, as well [54-56]. The most significant potential
problem associated with the use of these fuels is lubricity.
Fischer-Tropsch fuels have very poor lubricity properties.
There may also be some elastomer/seal swell problems, especially in older fuel systems, since these fuels have no aromatic compounds.
Biodiesel is also a potential alternative to conventional,
petroleum-derived diesel. Biodiesel is a renewable source of
energy. In the United States, Biodiesel is a fuel comprised of
mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated BIOO. Biodiesel is registered with the U.S. EPA as a fuel and a fuel additive under
Section 211(b) of the Clean Air Act. There is, however, other
usage of the term biodiesel in the market place. Biodiesel is
typically produced by a reaction of a vegetable oil or animal
fat with an alcohol such as methanol or ethanol in the presence of a catalyst to yield mono-alkyl esters and glycerin. The
finished biodiesel derives approximately 10% of its mass
from the reacted alcohol. The alcohol used in the reaction
may or may not come from renewable resources. Biodiesel
blend is a mixture of biodiesel fuel with petroleum-based
diesel fuel designated BXX, where XX is the volume % of
biodiesel.

TABLE 9EMA recommended guideline (FQP-IA).


Property

Flash point, C, min


Water Eind sediment, % vol, meix
Water, ppm max
Sediment, ppm max
Distillation, C, % vol recovery
90% max
95% max
Viscosity, 40C, cSt
Ash, % mass, max
Sulfur, % mass, max
Copper corrosion, max
Cetane number, min
Cetane index, min
Ramsbottom carbon on
10% residue, % mass, max
API gravity, max
Lubricity, g, min
Accelerated stability, mg/L, max
Detergency
CRC rating, max
Depositing test, % flow loss, max
Low temperature flow, C

Test Method

D93
D2709
D 1744
D 2276 or
D5452
D86
D445
D482
D2622
D 130
D613
D4737
D524
D287
D 6078(1)
D2274
L-10 Injector
D 2500 or
D4539

Requirements

52
0.05
200
10
332
355
1.9^.1
0.01
0.05
3b
50
45
0.15
39
3100
15
slO.O
s6.0
(2)

NOTE: Alternatively, lubricity can be measured by D 6079 with a maximum


wear scar diameter of 0.45 Jim at 60C.
Diesel fuels must pass the Cloud Point (D 2500) or Low Temperature
Flow Test (D 4539) at the use temperature.

CHAPTER 5: GAS TURBINE FUELS 139

OH
O

JL
\ ^ ^

J.
+

"^^lalyst

HO

3(GH30H)

3(RCOOCH3) +
OH

O.^ ^ O

Triglyceride

3 iVIetlianol

"^^*^'^'

3 methyi-estiiers +

Glycerol

R is usually 1 6 - 1 8 carbons with 1 - 3 0 = 0 bonds.

FIG. 13Reactions of vegetable oil to form methyl-esthers.

TABLE 10Detailed requirements for biodiesel (BlOO)."


Property

Flash point
(closed cup)
Water and
sediment
Kinematic
viscosity, 40C
Sulfated ash
Sulfur^
Copper strip
corrosion
Cetane number
Cloud point
Carbon residue"
Acid number
Free glycerin'^
Total glycerin^

Test
Method''

Limits

Units

D93

100.0

minC

D2709

0.050

max % volume

D445

1.9-6.0"

mm 2/s

D874
D2622
D 130

0.020
0.05
No. 3

max % mass
max % mass
max

D613
D2500

40
Report to
customer
0.050
0.80
0.020
0.240

min
C

D4530
D664

max % mass
max mg KOH/g
% mass
%mass

"To meet special operating conditions, modifications of individual limiting


requirements may be agreed upon between purchaser, seller, and manufacturer.
''The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 5.3.
"SeeXl.3.1.
'^Other sulfur limits can apply in selected areas in the United States and in
other countries.
"Carbon residue shall be r u n on the 100% sample (see 5.2.10).
'See Annex 1 for test method. A gas chromatographic technique is being
converted to a standard test method.
*The test m e t h o d is u n d e r ASTM consideration by Subcommittee
D02.04.OL.

Soybean oil is the largest source of biodiesel in the United


States, however, oil from other plants is sometimes used.
Biodiesel is a mixture of fatty acid methyl esters. The oils are
combined with methanol in a process known as transesterification (Fig. 13).
The resulting mixture of fatty acid methyl esters has chemical and physiccJ properties similar to those of conventional
diesel fuel. Provisional Specification 121 is the ASTM specification for Biodiesel Fuel (BlOO) Blend Stock for Distillate
Fuels. (At this writing, ASTM is working to approve PS 121 as
a standard specification.) Table 10 contains the detailed re-

quirements for BlOO as found in PS 121. Diesel engines can


run on B1 GO; however, most of the testing in this country has
been done on blends of biodiesel a n d low sulfur diesel. A
blend of 20% biodiesel with 80% low sulfur diesel (B20) has
been tested in numerous applications across the country. The
limited testing thus far completed has shown that this fuel
produces lower emissions of particulate matter, hydrocarbons, a n d carbon monoxide t h a n conventional diesel fuel.
NOx emissions can be slightly higher thcin with conventional
diesel, unless the fuel system injection timing is optimized
for B20.
BlOO has good lubricity properties and contains essentially
no sulfur or aromatics. However, it has a relatively high pour
point, which could limit its use in cold weather. Biodiesel is
biodegradable, but this property may lead to increased biological growth during storage. Biodiesel is also more susceptible to oxidative degradation than petroleum diesel.
Other eJtemative fuels that have been investigated for use
in diesel engines include ethers, alcohols, naphtha, and various gaseous fuels. Each of these has some advantage (such as
reduced engine emissions) associated with its use. However,
much work remains to be done with these fuels, including
building a distribution infrastructure, before they will be
widely used in diesel engines.

GAS TURBINE FUELS


This section discusses the fuels used in non-aviation (industrial) gas turbine applications. The specification for industrial gas turbine fuels is D 2880, Standard Specification for
Gas Turbine Fuel Oils. Table 11 contains the specific requirements for the fuels covered by D 2880. Comparison of
the specifications for diesel fuels and gas turbine fuels shows
that gas turbine fuels actually have fewer requirements.
Many of the individual property requirements of both specifications are equivalent for corresponding grades. This is
demonstrated in Tablel2. The main differences are due to
operational difference of diesel versus gas turbine. As an example, diesel fuel has a cetane number requirement whereas

140 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 11Detailed requirements for gas turbine fuel oils at time and place of custody transfer to user.'
ASTM
Test Method"

Property

Graded''
No. 0-GT
f
0.05

No. l-GT'^

No. 2-Gr

No. 3-GT

No. 4-GT

38 (100)
38 (100)
55(130)
Flash point C (F) min
D93
66 (150)
0.05
0.05
Water and sediment
D2709
1.0
% vol max
D1796
1.0
Distillation Temperature C (F)
D86
90 % volume recovered
282
min
max
288
338
Kinematic viscosity 2 mm/s^
D445
At40C(104F)
f
1.3
1.9
5.5
min
5.5
max
2.4
4.1
50.0
At 100C (212F) max
50.0
Ramsbottom
0.15
0.35
Carbon residue on 10% distillation
D524
0.15
Residue % mass, max
0.01
0.01
D482
0.01
0.03
Ash % mass, max
Density at 15C k g W
D 1298
max
850
876
-18
D97
-6
Pour pointC (F) max
"To meet special operating conditions, modifications of individual limiting requirements may be agreed upon between purchaser, seller, and manufacturer.
''Gas turbines with waste heat recovery equipment may require fuel sulfur limits to prevent cold end corrosion. Environmental limits may also apply to fuel sulfur in selected areas in the United States and in other countries.
"The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 6.1.
''No. 0-GT includes naphtha, Jet B fuel and other volatile hydrocarbon liquids. No. 1-GT corresponds in general to specification D 396 Grade No. 1 fuel and D
975 Grade 1-D diesel fuel in physical properties. No. 2-GT corresponds in general to Specification D 396 No. 2 fuel and D 975 Grade 2-D diesel fuel in physical
properties. No. 3-GT and No. 4-GT viscosity range brackets specification D 396 Grades No. 4, No. 5 (light). No. 5 (heavy), and No. 6, and D 975 Grade No. 4-D diesel
fuel in physical properties.
"Under United States regulations. Grades No. 1-GT and No. 2-GT are required by 40 CFR Part 80 to contain a sufficient amount of dye Solvent Red 164 so its
presence is visually apparent. At or beyond terminal storage taniks, they are required by 26 CFR Part 48 to contain the dye Solvent Red 164 at a concentration spectrally equivalent to 3.9 lbs per thousand barrels of the solid dye standard Solvent Red 26.
'when the flash point is below 38C (100F) or when kinematic viscosity is below 1.3 mm^/s at 40''C (104F) or when both conditions exist, the turbine manufacturer should be consulted with respect to safe handling and fuel system design.
*For cold weather operation, the pour point should be specified 6C below the ambient temperature at which the turbine is to be operated except where fuel
heating facilities are provided. When a pour point less than 18C is specified for Grade No. 2-GT, the minimum viscosity shall be 1.7 mm^/s and the minimum
90% recovered temperature shall be waived.

TABLE 12Comparison of specification requirements


for selected distillate fuels.
Parameter

D396

D975

D 2069

D 2880

D 3699

Flash point
Water & sediment
Distillation
Viscosity
Carbon residue
Ash
Copper strip corrosion
Density
Pour point
Sulfur
Cetane #
Cloud pt.
Freezing point
Burning quality
Saybolt color
NOTE: An asterisk indicates the property is included in the specification.

gas turbine fuel does not. Because the specifications are so


similar, most fuels sold under one specification would also
meet the requirements of the other. For this same reason, the
properties and test methods for diesel fuel, as discussed
above, are equally applicable to gas turbine fuels.
Gas Turbine Fuel Requirements
Industrial gas turbines are basically the same as aviation gas
turbines in operation. A simple gas turbine has three major

components: compressor, combustor, and turbine. The purpose of the compressor is to raise the pressure of the operating fluid usually a ratio of 10 to 20 to 1. It is desirable to accomplish this pressure increase as efficiently as possible to
maximize the available thrust or horsepower, because the efficiency determines how much horsepower is required for
the compression. The purpose of the combustor is to raise the
temperature of the operating fluid. The combustor inlet temperature depends on the pressure ratio and efficiency of the
compressor. In more complicated cycles some of the heat in
the exhaust is recovered and used to increase the combustor
inlet temperature, which reduces the required temperature
rise across the combustor and thus the amount of fuel required. Current combustor outlet temperatures are in the
1093-1482C (2000-2700F) ranges. The combustor must accomplish this temperature rise efficiently. Current combustion efficiencies are in the 99%-f range at most operating
conditions. Additionally the outlet temperature profiles have
specific requirements.
A gas turbine combustor operates at fuel-air ratios less
than stoichiometric and below the lower flammability level.
Figure 14 is a simplified diagram of how the air is introduced
in a conventional combustor i.e., not a low emission combustor. The figure shows the distribution of air for a combustor with an overall air to fuel ratio of 70 to 1. About four
parts of air per part of fuel are introduced in the swirler to
help stabilize the flame zone. Then, in the primary zone, 12
parts of air per part of fuel are introduced to provide enough

CHAPTER 5: GAS TURBINE FUELS

141

COMBUSTOR AIR DISTRIBUTION


FULL LOAD

46

Parts
Air

OVERALL
AIR-FUEL
RATIO = 70

P = PRIMARY
S = SECONDARY
D = DILUTION OR TERTIARY
SW = SWIRLER
F = FUEL

FIG. 14Simplified diagram of gas turbine.

air to provide approximately the stoichiometric amount of


air required, making a total of 16 parts of air per part of fuel.
In the secondary zone an additional 6 parts of air per of part
of fuel are introduced making a total of 22 parts of air per
part of fuel, which completes the reaction. The rest of the air
(48 parts of air per part of fuel) is used to cool the combustor
walls and to dilute the air-stream temperature down to the
design turbine inlet temperature.
The major difference between an aviation gas turbine and
an industrial gas turbine is that the aviation generates thrust
to propel the airplane by exhausting hot gases at high temperatures and velocities. The aviation turbine section only
has to generate enough horsepower to drive the compressor.
In an industrial gas turbine the gases that would be exhausted in an aviation gas turbine are expanded across additional turbine stages to generate shaft horsepower that can be
used to drive generators, pumps, gas compressor, etc.
Many industrial gas turbines use gaseous fuels but others
use a variety of liquid fuels ranging from naphtha to residual
oils. Aviation gas turbine fuel requirements are quite narrow
because of the varying operating conditions (altitude, temperature, etc.), which impose limitations on volatility, viscosity, distillation range, etc. Industrial gas turbines are usually
stationary. This means atmospheric conditions do not
change as drastically as with aviation gas turbines.
The operating conditions for the combustors for the two
applications vary. Many industrial gas turbines operate at or
necir design point for extended periods where an aviation gas
turbine operates at take-off (full power) for a short time eind
then the power level is reduced to cruise for the duration of
the flight. In the following paragraphs, selected requirements
specific to gas turbine operation will be discussed.
The first consideration is light-off (initiating the combustion process and accelerating the engine to idle). Factors such
as the tjrpe of fuel injection system, fuel viscosity, and fuel
volatility are important. In earlier gas turbines, the fuel injectors or nozzles were of the pressure atomizing type simileir

to those used in some heaters. Lower flow nozzles of this type


are particularly sensitive to viscosity, which is why many engine company specifications have a meiximum viscosity limit
regardless of temperature. More modern fuel injection systems, which utilize air to assist the atomization of the fuel,
are less sensitive to viscosity but some limit is still required.
Another factor to be considered for light-off is the volatility
of the fuel. The initial boiling point of the fuel must be considered because, even if the fuel is well atomized, if it is too
heavy, light-off might not consistently occur.
Smaller gas turbines (<10kW) tend to use distillates, while
larger engines also use a mix of distillates and residuals or
pure residuals. Additional problems resulting from residual
fuels include carbon deposits, increased combustor skin temperatures, and exhaust smoke.
Trace Metal Limits
The effects of trace metals such as sodium, potassium, vanadium and lead on gas turbines are discussed in Appendix X2
of D2880. The sulfur content also is important because of its
interaction with sodium and potassium as well as the effects
on exhaust emissions. These trace metals rarely occur in distillate fuels at the refinery. Since they can be introduced at
some point after the refinery, D2880 specifies that the limits
apply at the entrance of the combustor.
Trace metals refer both to those metals present as metallic
compounds in solution and to metals present in particulates
like rust. They are dissolved or suspended either in the fuel
hydrocarbons or in free water present in the fuel. Although
lower levels of trace metals in a fuel will promote longer turbine service from a corrosion standpoint, the specification of
excessively low levels may limit the availability of the fuel or
materially increase its cost. Table 13 suggests levels of trace
metals that would probably yield satisfactory service.
Sodium and potassium can combine with vanadium to
form eutectics, which melt at temperatures as low as 566C

142

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

TABLE 13Trace metal limits of fuel entering turbine


combustor(s).''
Trace Metal Limits, mg/kg
Designation
No. 0-GT
No. 1-GT
No. 2-GT
No. 3-GT
No. 4-GT

Vanadium
0.5
0.5
0.5
0.5

Sodium plus
Potassium

Calcium
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
(Consult turbine manufacturers)

Lead
0.5
0.5
0.5
0.5

"Test Method D 3605 may be used for determination of vanadium, sodium,


calcium, and lead.

and can combine with sulfur in the fuel to yield sulfates with
melting points in the operating range of the gas turbine.
These compounds produce severe corrosion, and for turbines
operating at gas inlet temperatures above 650C, additives
that control such corrosion are not yet in general use. Accordingly, the sodium-plus-potassium level must be limited,
but each element is measured separately. Some gas turbine
installations incorporate systems for washing oil with water
to reduce the sodium-plus-potassium level. In installations
where the fuel is moved by sea transport, the sodium-pluspotassium level should be checked prior to use to ensure that
the oil has not become contaminated with sea salt. For gas
turbines operating at turbine inlet gas temperatures below
650C (1200F), the corrosion due to sodium compounds is
of minor importance and can be further reduced by siliconbase additives. A high sodium content is even beneficial in
these turbines because it increases the water-solubility of the
deposits and thereby increases the ease with which gas turbines can be water-washed to obtain recovery of the operating performance.
Calcium is not harmful from a corrosion standpoint; in
fact, it serves to inhibit the corrosive action of vanadium.
However, calcium can lead to hard-bonded deposits that are
not self-spalling when the gas turbine is shut down, and that
are not readily removed by water washing of the turbine. The
fuel washing systems used at some gas turbine installations
to reduce the sodium and potassium level will also significantly lower the calcium content of fuel oil.
Vanadium can form low melting compounds such as veinadium pentoxide that melts at 691C, and causes severe corrosive attack on all of the high temperature alloys used for gas
turbine blades. If there is sufficient magnesium in the fuel, it
will combine with the vanadium to form compounds with
higher melting points and thus reduce the corrosion rate to
an acceptable level. The resulting ash will form deposits in
the turbine and will require appropriate cleaning procedures.
When vanadium is present in more than trace amounts either
in excess of 0.5 mg/kg or a level recommended by the turbine
manufacturer, it is necessary to maintain a weight ratio of
magnesium to vanadium in the fuel of not less than 3.0 in order to control corrosion. An upper limit of 3.5 is suggested
since larger ratios will lead to unnecessarily high rates of ash
deposition. In most cases, the required magnesium-to-vanadium ratio will be obtained by additions of magnesium-containing compounds to the fuel oil. The special requirements
covering the addition of and type of magnesium-containing
additive, or equivalent, shall be specified by mutual agreement between the various interested parties. The additive will

vary depending on the application, but it is always essential


that there is a fine and uniform dispersion of the additive in
the fuel at the point of combustion.
For gas turbines operating at turbine inlet gas temperatures below 650C, the corrosion of the high-temperature EJloys is of minor importance, and the use of a silicon-base additive will further reduce the corrosion rate by absorption
and dilution of the vEinadium compounds.
Lead Ccin cause corrosion and, in addition, it can spoil the
beneficial inhibiting effect of magnesium additives on vanadium corrosion. Since lead is only rarely found in significant
quantities in crude oils, its appearance in the fuel oil is primarily the result of c o n t a m i n a t i o n during processing or
transportation.

ASTM STANDARDS
No.
D 56
D 86
D 93
D 97
D 129
D 189
D 240
D 445

D 482
D 524
D 613
D 976
D 1266
D 1298

D 1319

D 1552
D 2068
D 2274
D 2425
D 2500
D 2622

D 2709

Title
Test Method for Flash Point by Tag Closed Tester
Test Method for Distillation of Petroleum Products
Test Methods for Flash Point by Pensky-Martens
Closed Cup Tester
Test Method for Pour Point of Petroleum Products
Test Method for Sulfur in Petroleum Products
(General Bomb Method)
Test Method for Conradson Carbon Residue of
Petroleum Products
Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by B o m b Calorimeter
Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity)
Test Method for Ash from Petroleum Products
Test Method for Ramsbottom Ceirbon Residue of
Petroleum Products
Test Method for Ignition Quality of Diesel Fuels by
the Cetane Method
Test Method for Calculated Cetane Index of Distillate Fuels
Test Method for Sulfur in Petroleum Products
(Lamp Method)
Test Method for Density, Relative Density (Specific
Gravity), or API Gravity of Crude Petroleum and
Liquid Petroleum Products by Hydrometer Method
Test Method for H y d r o c a r b o n Tjrpes in Liquid
Petroleum Products by Fluorescent Indicator Adsorption
Test Method for Sulfur in Petroleum Products
(High-Temperature Method)
Test Method for Filter Plugging Tendency of Distillate Fuel Oils
Test Method for Oxidation Stability of Distillate
Fuel Oil (Accelerated Method)
Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry
Test Method for Cloud Point of Petroleum Products
Test Method for Sulfur in Petroleum Products by
Wavelength Dispersive X-ray Fluorescence Spectrometry
Test Method for Water and Sediment in Middle Distillate Fuels by Centrifuge

CHAPTER
D2887

Test Method for Boiling Range Distribution of


Petroleum Fractions by Gas Chromatography
D 3117 Test Method for Wax Appearance Point of Distillate
Fuels
D 3828 Test Methods for Flash Point by Small Scale Closed
Tester
D 3941 Test Method for Flash Point by the Equilibrium
Method with a Closed-Cup Apparatus
D 4052 Test Method for Density a n d Relative Density of
Liquids by Digital Density Meter
D 4294 Test Method for Sulfur in Petroleum Products by
Energy-Dispersive X-Ray Fluorescence Spectroscopy
D 4530 Test Method for Determination of Ccirbon Residue
(Micro Method)
D 4539 Test Method for Filterability of Diesel Fuels by
Low-Temperature Flow Test (LTFT)
D 4625 Test Method for Distillate Fuel Storage StabiUty at
43C(110F)
D 4737 Test Method for Calculated Cetane Index by Four
Variable Equation
D 4809 Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision
Method)
D 4860 Test Method for Free Water and Particulate Cont a m i n a t i o n in Mid-Distillate Fuels (Clear a n d
Bright Numerical Rating)
D 4868 Test Method for Estimation of Net and Gross Heat
of Combustion of Burner and Diesel Fuels
D 5186 Test Method for Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel
Fuels and Aviation Turbine Fuels by Supercriticcd
Fluid Chromatography
D 5292 Test Method for Aromatic Carbon Contents of Hydrocarbon Oils by High Resolution Nuclear Magnetic Resonance Spectroscopy
D 5304 Test Method for Assessing Distillate Fuel Storage
Stability by Oxygen Overpressure
D 5453 Test Method for Determination of Total Sulfur in
Light Hydrocarbons, Motor Fuels and Oils by Ultraviolet Fluorescence
D 5771 Standard Test Method for Cloud Point of Petroleum
Products (Optical Detection Stepped Cooling
Method)
D 5772 Test Method for Cloud Point of Petroleum Products
(Linear Cooling Rate Method)
D 5773 Test Method for Cloud Point of Petroleum Products
(Constant Cooling Rate Method)
D 5949 Test Method for Pour Point of Petroleum Products
(Automatic Pressure Pulsing Method)
D 5950 Test Method for Pour Point of Petroleum Products
(Automatic Tilt Method)
D 5985 Test Method for Pour Point of Petroleum Products
(Rotational Method)
D 6078 Test Method for Evaluating Lubricity of Diesel Fuels by the Scuffing Load Ball-on-Cylinder Lubricity
Evaluator (SLBOCLE)
D 6079 Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig
(HFFR)
D 6217 Test Method for Particulate Contamination in Middle Distillate Fuels by Laboratory Filtration

D 6426
D 6450
D 6591

5: GAS TURBINE

FUELS

143

Test Method for Determining Filterability of Distillate Fuel Oils


Test Method for Flash Point by Continuously
Closed Cup (CCCFP) Tester
Test Method for Determination of Aromatic Hydrocarbon Types in Middle DistillatesHigh Perform a n c e Liquid Chromatography Method with Refractive Index Detection

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[3] Diesel Fuel Injection, 1st edition, U. Adler, Ed., Robert Bosch,
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[9] "Diesel Fuels: Performance and Characteristics," SAE SP-675,
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[10] Pande, S. G. and Hardy, D. R., " Ap Practical Evaluation of Published Cetane Indices," Fuel, Vol. 69, No. 4, April 1990, pp.
437-442.
[11] Gulder, O. M., et. al,, "Ignition Quality Rating Methods for
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[13] Manual on Significance of Tests for Petroleum Products, 6th ed.,
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[14] Westbrook, S. R., et. al., "Fuel System Design Considerations for
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[15] "Diesel Fuel Low-Temperature Operability Field Test," Coordinating Research Council Report No. 528, Coordinating Research Council, Inc., Atlanta, GA.
[16] Chandler, J. E., "Comparison of All-Weather Chassis Dynamometer Low-Temperature Operability Limits for Heavyand Light-Duty Trucks with Standard Laboratory Methods,"
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[17] Chandler, J. E., "Evaluation of Faster LTFT and SFPP for Protection of Low Temperature Operability in North American
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[18] Chandler, J. E. and Zechman, I. A., "Low-Temperature Operability Limits of Late Model Heavy-Duty Diesel Trucks and the
Effect Operability Additives and Changes to the Fuels Delivery

144 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


System Have on Low-Temperature Performance," SAE Report
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[19] "The Cold Filter Plugging Point of Distillate Fuels," A European
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[20] Coley, T., et. al., "New Laboratory Test for Predicting Low-Temperature Operability of Diesel Fuels," Journal of the Institute of
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Liquid Fuels, San Antonio, TX, July 29-August 1, 1986.
[22] Beal, E. J., Hughes, J. M., and Hardy, D. R., "An Improved Fuel
Filterability Test," Proceedings of the Sixth International Conference on Stability and Handling of Liquid Fuels, Vancouver, B.C.,
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[23] Pedley, J., et. al., "Storage Stability of Petroleum-Derived Diesel
Fuel," Fuel, Vol. 68, 1989, pp. 27-31.
[24] Taylor, W. F. and Frankenfeld, J. W., "Chemistry and Mechanism of Distillate Fuel Stability," Proceedings of the Second International Conference on Long Term Storage Stabilities of Liquid
Fuels, San Antonio, TX, July 1986.
[25] Beaver, B., "Long Term Storage Stability of Middle Distillate
Fuels from a Chemical Mechanistic Point of View. Part 1," Fuel
Science and Technology International, Vol. 9, No. 10, 1991, pp.
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[26] Beaver, B., "Long Term Storage Stability of Middle Distillate Fuels from a Chemical Mechanistic Point of View. Part 2," Fuel Science and Technology International, Vol. 10, No. 1, 1992, 1-37.
[27] Wechter, M. A. and Hardy, D. R., "The Use of Macromolecular
Oxidatively Reactive Species (SMORS) to Predict Storage Stability of Mid-Distillate Diesel Fuels," Proceedings of the 4th International Conference on Stability and Handling of Liquid Fuels,
Orlando, FL, November, 1991.
[28] Henry, C. P., "The du Pont F21 149C (300F) Accelerated StabiUty Test," Distillate Fuel Stability and Cleanliness, ASTM STP
751, L. L. Stavinoha and C. P. Henry, Eds., ASTM International,
West Conshohocken, PA, 1981, pp. 22-33.
[29] ibid.
[30] Research Report RR:D02-1463, ASTM International, West Conshohocken, PA.
[31] Stavinoha, L. L. and Westbrook, S. R., "Accelerated Stability
Test Techniques for Middle Distillate Fuels," Distillate Fuel Stability and Cleanliness, ASTM STP 751, L. L. Stavinoha and C. P.
Henry, Eds., ASTM International, West Conshohocken, PA,
1981, pp. 3-21.
[32] Bacha, J. D. and Lesnini, D. G., "Diesel Fuel Thermal Stability at
300F," Proceedings of the 6th International Conference on Stability and Handling of Liquid Fuels, Vancouver, B.C. Canada, October 13-17, 1997, pp. 671-684.
[33] Henry, C. P., "The du Pont F21 149C (300F) Accelerated StabiUty Test," Distillate Fuel Stability and Cleanliness, ASTM STP
751, L. L. Stavinoha and C. P. Henry, Eds., ASTM International,
West Conshohocken, PA, 1981, pp. 22-33.
[34] White, E. W., " A Study of Test Variables Affecting Results Obtained in the ASTM D 2274 Accelerated StabiUty Test," Proceedings of the Second International Conference on Long-Term Storage Stabilities of Liquid Fuels, San Antonio, TX, October 1986.
[35] White, E. W. and Bowen, R. J., "A Study of Variables Affecting
Resuhs Obtained in the ASTM D 2274 Accelerated Stability
Test; Parts 2 & 3-Effects of Selected Chemical and Physical Factors," Proceedings of the Third International Conference on Stability and Handling Liquid Fuels, London, U. K., September
13-16, 1988.
[36] Chang, R., Chemistry-5th ed., McGraw-Hill, New York, 1994.
[37] Anon., "Storage Stability of Distillate Fuels and Blends," Bureau
of Mines Summary Report 1, Petroleum Experiment Station,

[38]

[39]

[40]

[41]
[42]

[43]

[44]

[45]

[46]

[47]

[48]

[49]

[50]
[51]

[52]

[53]

[54]

[55]

[56]

Bartlesville, OK; WPRA-BuMines Cooperative Distillate Fuel


Storage Stability Program, published by Western Petroleum Refiners Association, Tulsa, OK, 1956.
Garner, M. Q. and White, E. W., "Correlation of Long-Term
Storage and Accelerated Stability Tests," Distillate Fuel Stability
and Cleanliness, ASTM STP 751, L. L. Stavinoha and C. P. Henry,
Eds., ASTM International, West Conshohocken, PA, 1981, pp.
34-46.
Hardy, D. R., Hazlett, R. N., Beal, E. J., and Burnett, J, C , "Assessing Distillate Fuel Storage Stability by Oxygen Overpressure," Energy and Fuels, Vol. 3, No. 1, 1989, pp. 20-23.
Turner, L. M., et. al., "Use of ASTM D 5304 in Assessing Unstable Diesel Fuel," Proceedings of the Fifth International Conference
on Stability and Handling of Liquid Fuels, Rotterdam, the
Netherlands, October 3-7, 1994.
Wray, H. A., "Memual on Flash Point Standards and Their Use,"
Manual #9, ASTM International, West Conshohocken, PA, 1992.
ASTM D 975-98b, Appendix X3, Annual Book of ASTM Standards, Vol 05.01, ASTM International, West Conshohocken, PA,
1998.
Nikanjam, M., Crosby, T., Henderson, P., Gray, C , Meyer, K.,
and Davenport, N., "ISO Diesel Fuel Lubricity Round Robin
Program," SAE Paper No. 952372, SAE Fuels and Lubricants
Meeting, October 16-19, 1995, Toronto, Canada.
Westbrook, S. R, et. al., "Survey of Low Sulfur Diesel Fuels and
Aviation Kerosines from U.S. Military Installations," SAE Technical Paper 952369, Society for Automotive Engineers, Warrendale, PA 1995.
Nikanjam, M., Crosby, T., Henderson, P., Gray, C , Meyer, K.,
and Davenport, N., "ISO Diesel Fuel Lubricity Round Robin
Program," SAE Paper No. 952372, SAE Fuels and Lubricants
Meeting, October 16-19, 1995, Toronto, Canada.
Bacha, J., Blondis, L., Freel, J., Hemighaus, G., Hoekman, K.,
Hogue, N., et al., Diesel Fuels Technical Review (FTR-2), Chevron
Products Company, Sein Francisco, CA, 1998.
"Proposed Heavy-Duty Engine and Vehicle Standards and Highway Diesel Fuel Sulfur Control Requirements," United States
Environmental Protection Agency, EPA420-F-00-022, May
2000.
The interested reader can find additional information at the following internet sites: www.acea.be; www.autoalliance.org;
www.engine-manufacturers.org.
Handbook 130, "Uniform Laws and Regulations in the Areas of
Legal Metrology and Engine Fuel Quality" (2000 Edition), as
adopted by the 84th National Conference on Weights and Measures, 1999.
EMA Consensus Position, Joint EMA/TMC P u m p Grade Specification for Premium Diesel Fuel.
Jett, B. T. and Kirkpatrick, A. T., "Alternative Fuels for DI Engines," SAE No. SP-1412, Society of Automotive Engineers,
Warrendale, PA, 1999.
Grimes, G., "Economics and Experience of Blending FischerTropsch Diesel at Paramount Petroleum," presented at Gas-toLiquids Processing 99, May 17-19, 1999, San Antonio, TX.
Schaberg, P. W., et al, "Diesel Exhaust Emissions Using Sasol
Slurry Phase Distillate Process Fuels," SAE No. 972898, Society
of Automotive Engineers, Warrendale, PA, 1997.
Clark, N. N., et. al., "Transient Emissions Comparisons of Alternative Compression-Ignition Fuels," SAE No. 1999-01-1117, Society of Automotive Engineers, Warrendale, PA, 1999.
Clark, N. N., et. al., "On-Road Use of Fischer-Tropsch Diesel Fuels," SAE No. 1999-01-2251, Society of Automotive Engineers,
Warrendale, PA, 1999.
Mintz, M. M., Wang, M. Q., and Vyas, A. D., "Fuel-Cycle Energy
and Emissions Impacts of Propulsion System/Fuel Alternatives
for Tripled Fuel-Economy Vehicle," SAE Report No. 1999-011118, Society of Automotive Engineers, Warrendale, PA, 1999.

MNL37-EB/Jun. 2003

Introduction to Marine
Petroieum Fuels
Matthew F. Winkler^

T H E MODERN PETROLEUM INDUSTRY began during the late 19th

century, although small quantities of petroleum were obtained as early as the 14th century. In Pennsylvania, Edwin
Drzike drilled the first oil well in 1859, striking oil at a depth
of 21 m. Drake's oil well was generally accepted as the start of
the petroleum industry. Kerosine or lamp oil was the object
of the early refining industry. The simple distillation process
was conducted to obtain as m u c h lamp oil as possible from
the Pennsylvania crude oil.
In 1870, the S.S. Constantine was the first of many sea vessels converted from coal to fuel oil. While trading in t h e
Caspian Sea, the vessel burned the residue from refined Russian crude oil. Early oil burners were primitive a n d ineiBcient, b u t the crude oil was plentiful a n d n o attempt was
m a d e to b u m the fuel oil economiccJly.
In the early years of oil firing, t h e marine industry a n d
Lloyd's Register considered oil-fired instcJlations as experimental, with the vast majority of vessels still powered by coal
at t h e end of the 19th century.
Early 20th century fuel oils were used to a greater extent
in steam boilers and the marine industry experimented with
oil-fired diesel engines in the M/T Vulcanus in 1910 and the
MA'^ Seletndia in 1911. Then, during the period u p to the
outbreak of the first World War, fuel oil was used increasingly in Marine Merchant vessels, predominantly in steam
boilers.
In the early 1920s, zJmost all motor ships r a n on a distillate
fuel CcJled "diesel oil" while the oil-fired steam ships burned
a residual fuel called "boiler fuel." The quality difference between the diesel oil and the boiler fuel was considerable.
In t h e mid-1920s, some m o t o r ships h a d experimented
with burning boiler fuel in the m a i n a n d auxiliary engines.
However, there was no commercial benefit in burning boiler
fuel, since the smedl price differential between diesel fuel cind
boiler fuel was offset by the increased mainteneince costs (resulting from burning boiler fuel).
By the beginning of World W a r II, about half of the world
marine fleet was oil fired. Of those ships, half were steam a n d
half were diesel powered.
As society increased the usage of distillate fuels for automotive, truck, railroad, and aircrzift, the increasing demand
for distillate fuels increased the cost differential between distillate fuels and residuals. This economic incentive prompted
the Mcirine Industry to improve t h e technical feasibility of
burning residual fuels (boiler fuels) in marine diesel engines.
' Vice President, Seaworthy Systems, Inc., P.O. Box 965, Essex, CT
06426.

In the late 1940s and throughout the 1950s, motor ship fuel
systems a n d marine diesel engines struggled to operate on
residual fuels a n d to control reliability a n d m a i n t e n a n c e
costs. The successful combination of modified diesel engines,
improved fuel handling, a n d purification systems, together
with, new, reformulated cylinder lube oils led to the economic use of residual fuels in motor ships.
By the mid-1960s, about half of the world merchant fleet
tonnage was powered by diesel engines. Then, the distillate
and residual fuel costs were jolted sharply upward in 1973
and again in 1979 by t h e Middle Eastern oil suppliers restricting oil supplies and raising crude oil prices. This caused
the metrine fuel expenditure to become a significemt factor in
the ship owner's operating costs, and caused overeJl propulsive efficiency to take on renewed significance. The result
was the rapidly declining popularity of steam-powered vessels. The m u c h m o r e thermally efficient a n d economical
diesel engine led to the dominant position in merchant vessels that it still enjoys today.
The goal of m o d e m m a r i n e diesel engines is to operate
with fuel efficiency a n d reability on cracked a n d heavier
residual fuels. Marine residual fuels provide the main source
of energy that is used to transport the world's sea trade. More
ton-miles are moved by ship than by all other transportation
means combined. Therefore, marine fuels have become even
more importcint today to world trade.

PETROLEUM CRUDE OIL REFINING


Crude oil must be carefully refined to produce the main usable products, such as gases, gasoline, kerosine, jet fuels,
diesel fuels, lubricating oil base stocks, petrochemical feed
stocks, waxes, bitumens, residucJ fuels, and even petroleum
coke. The method and degree of the refining of crude oil a n d
its inherent properties determine the quality and quantity of
any petroleum product produced.
Refining, design, a n d production of main petroleum products are dictated by the local, national, or international requirements for light and middle distillate products as well as
for petrochemiceJ feed stocks, which are the higher profit
products produced from crude oil. Recently, govemmentcJ
regulations to reduce air pollution have controlled sulfur,
carbon/aromatic a n d oxygen content, etc., of distillate and
residual fuels.
The basic refining processes are distillation, cracking,
blending, and storage.

145
Copyright'

2003 by A S I M International

www.astm.org

146 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

Distillation
Fractional or atmospheric distillation is the oldest and most
basic refining process. The heated crude is charged to the
tower under pressure and a portion flashes to vapor while the
rest stays in the tower as a liquid residue. It consists of boiling
the crude oil in a pipe-still at atmospheric pressure up to
371F. Then the hydrocarbon vapors are directed to a fractionating tower, as shown in Fig. 1. As the various lighter hydrocarbons of the crude oil vaporize at different rates, the
lighter, more volatile vapors rise high in the tower before condensing and being drawn off. The heavier, less volatile vapors
condense and are collected lower in the tower. The residual
fraction is drawn off at the bottom. The fractions drawn from
the tower are called straight-run or virgin products.
In the 1950s, '60s, and early '70s, straight-run fuels produced from atmospheric distillation were the main residual
fuels used in marine diesel engines. Straight-run fuels provided good ignition quality, clean combustion, ease of fuel
handling, ease of water separation, storage stability, and
solid compatibility. Since the density was usually below 985
Kg/m^, the shipboard settling tanks and old style centrifugal
purifiers provided adequate treatment to remove water and
sediment from the fuel.
At complex refineries, the next refining process is vacuum
distillation of the heavy bottoms from the atmospheric distillation unit. This process is a modified atmospheric process
where the pressure in the fractionating tower is reduced below atmospheric to a partial vacuum, as in Fig. 2. The atmospheric tower residual is the feed stock for the vacuum distillation process to yield additional heavy distillates, and will
further concentrate the metals and carbon content into the
vacuum bottoms. The vacuum bottom residuals are generally
used as feed stocks for other refinery processes. They are generally not available as marine fuels due to the very high viscosity. The vacuum bottoms can be further refined by using

another (secondary) process called "viscosity breaking" or


"visbreaking." In this process, the vacuum bottoms are
heated to a higher temperature and higher pressure for
cracking, although not as high as in the thermal cracking process. The high viscosity feed stock is converted to a residual
fuel that is much lower in viscosity. While this visbroken fuel
could be used as marine residual fuel with little or no blending with a lower viscosity distillate, it has higher density,
higher carbon content, higher asphaltenes, and poorer ignition quality characteristics. Visbroken fuels are usually less
stable and less compatible with other residuals than the original vacuum feed stock. These characteristics can present
problems for the fuel handling, fuel purification, and diesel
combustion process, which could lead to vessel delays and increased maintenance for the diesel engine.
Cracking
When heat is applied to hydrocarbons, their molecular energy increases and these molecules move faster. Additionally,
if pressure is applied to the liquid hydrocarbon and temperatures are increased further, the energy within the molecules
can rupture the Ccirbon-carbon and carbon-hydrogen bonds,
and the molecules "crack" into more, smaller molecules that
have different chemical structures. Cracked products are hydrogen deficient compared to straight-run products of the
same boiling range and some of the new, smaller molecules
are unsaturated. Further, these unsaturated molecules tend
to be more volatile and can be more unstable.
Two basic cracking processes can be used. The older of the
two cracking processes is thermal cracking, which typically
occurs at about 13 bar and 520-560C. The long-chain residual oil molecules are cracked or broken, producing some
short chain molecules and additional long-chain molecules.
These cracked hydrocarbons are then vaporized in a flash
chamber and flow to the fractionating tower where they are

GASEOUS

FRACTIONING
TOWER

GASOLINE
NAPHTHA
KEROSENE
CRUDE
HEATER

NO. 2
DISTILLATE

REDUCED CRUDE
NO. 5 - 6 RESIDUE

FIG. 1Atmospheric distillation of crude oil.

_.CRUDE

OIL

CHAPTER 6: INTRODUCTION

TO MARINE PETROLEUM FUELS

147

VACUUM
DISTILLATION
CHARGE
HEATER

HEAVY
^
DISTILLATE

REDUCED
- CRUDE
OIL

VACUUM BOTTOMS

GASOLINE

"A,^

VISBREAKER
BLENDED WITH
CUTTING STOCKSNO. 6 EUEL OIL

DISTILLATE-

"^y"
RESIDUUM
FIG. 2Vacuum distillation.

condensed to produce additional light and heavy distillates.


Therefore, thermal cracking increases the yield of distillate
fuels from crude oil and reduces the yield of residual fuels.
Thermal cracking concentrates metallic content, carbon content, and asphaltene content into the residual fuel, which reduces combustion quality, increases carbon deposits, increases sulfur emissions, and decreases stability and
compatibility of the thermally cracked residual.
The more modem cracking process uses a catalyst to reduce the temperatures and pressures at which hydrocarbon
cracking occurs and, therefore, has been named (fluidic) catalytic cracking, or FCC, as shown in Fig. 3. Catalytic cracking
used a powdered (Quidized) catalyst, typically an alumina-silica based material, which is in direct contact with the liquid
hydrocarbon feed stock. By definition, a catalyst is a substance that aids and accelerates a chemical reaction, but
which itself undergoes no permanent compositional change.
When kept in constant agitation and circulation by air, steam
or hydrocarbon vapor, the fine powdered catalyst flows like a
fluid. In the beginning of the FCC process, hot, preheated hydrocarbon feed stock enters the reactor and is mixed with
hot, regenerated, powdered catalyst. Within the FCC reactor,
the hot feed stock vaporizes and fluidizes the catalyst at the
same time. Cracking then takes place within the reactor and
the hot, cracked hydrocarbon vapors pass into the fractionating tower. These lighter, cracked vapors are then separated
into gases, gasoline components, light gas oil, heat oil, and a
heavier product known as cycle oil.
The catalyst works in a continuous cycle. During the cracking reaction, the powdered catalyst particles become Ccirbon

coated and fall to the bottom of the reactor. The carbon coating is removed in the regenerator, since the catalyst is expensive. Once cleaned, the regenerated catalyst returns to the incoming hydrocarbon feed stock to start the cycle over.
During the FCC process, a small amount of slurry oil is produced that contains small particles of catalyst known as cat
fines. The slurry oil is normally decanted to reduce the concentration of "cat fines" and then the slurry oil is blended into
the residual fuel stream. A number of cases have been documented where catalyst fines have been delivered to ship owners in large quantities. These catalyst particles Eire very heird
and abrasive and have caused rapid and severe wear to fuel
injection pumps, fuel injectors, cylinder liners, piston rings,
piston grooves, and stuffing box seals. This is most evident
where conventional centrifugation and filtration have been
ineffective. Effective five to seven micron filtration of the
residual fuels has proven to control damages from cat fines.
Hydrocracking is a process that uses high pressures and
the addition of hydrogen to crack refinery residues and to upgrade the resulting products through the addition of hydrogen. Lighter hydrocarbon products exhibit lower viscosities
and lower sulfur levels because of hydrocracking. Since hydrogen is added during the process, this process is more expensive than thermal or catalytic cracking.
Refinery Blending and Storage
Marine fuel oils are blends of products from several different
processes. Combustion characteristics, handling properties,
stability characteristics, and storage stability are all affected

148 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

FRACTIONING
TOWER
GASOLINE
REACTOR

NO 2
DISTILLATE
- -e-ATALYST-

HEAVY
GAS OIL

FIG. 3Fluidic catalytic cracking.

by the composition of the blend. The blending processes begin at the refinery. Heavy products produced at the refinery
cire expected to be in the residual fuel blend to varying degrees. The blending process allows lower quality residuEils to
be converted into more suitable fuel oils by the addition of
small qucintities of lighter cutter stock, such as light or heavy
distillates, or by adding cycle oils. When distillate/residual
blends eire made, the solubility of the different components in
each other is important. When components Eire completely
soluble, the blend is considered compatible. Whenever a
blend is contemplated, the compatibility of the resulting
blend must be eveduated beforehand to prevent incompatibility problems that can cause excessive sludge accumulation
in storage, centrifugation, and filtration, and stratification in
the storage tanks.
As the refinery processes improve, and as crude oil distillate yields improve, a continuing decrease in the overall quality of cracked residuals used to produce blends for marine fuels can be expected.
In many refineries in the United States, all residual products are directed to the petroleum cokers, which convert the
residual products into light distillates and solid hydrocarbon
coke. At these refineries, n o residual fuels are sold or made
for the marine fuel industry. In the future, marine fuels could
compete with "cokers" for their feed stock requirements. Ano t h e r use for residual fuel for U.S. a n d E u r o p e a n power
plants is decreasing due to environmental restrictions,
thereby decreasing overall availability of residual fuel.
A large percentage of fuel contamination can be traced to
the hydrocarbon storage and transportation process. Water
and debris (solids and fibers) are frequently introduced into
the marine fuel originating from barge and tanker transport,
pipe line transport, and shore side tank storage. A more de-

tailed description of contamination can be found in the next


section.

PETROLEUM FUEL OIL CHARACTERISTICS


Fuel PropertiesPhysical
Viscosity

(D-445)

The viscosity of a fuel is a measure of the fuel's resistance to


flow. As a fuel is heated, the viscosity decreases, and as fuel
is cooled, the viscosity increases. Marine residual fuels Eire
still selected and purchased on the basis of a limiting viscosity due to restrictions on fuel storage, handling, or engine fuel
injection equipment. However, viscosity aJone is not the sole
quality indicator, despite the fact that many purchasers of
m a r i n e fuels believe this to be t r u e . When purchasing
straight-run (distilled, but not cracked) residuals, this practice of associating low viscosity with high quality became established. This false sense of quality assurance was then cEirried over into bu5ring m o d e m blended and cracked marine
residuals. As more intensive cracking and processing procedures are used to produce future marine fuels, the relationship between fuel viscosity and fuel qucJity becomes more
and more misleading. For example, some heavily cracked 180
cSt residuals have poorer overedl quality than the less-processed 380 cSt residuals.
Meirine residual fuels are preheated to lower the viscosity
for more efficient fuel bunkering, trsinsfer, settling, centrifugation, fuel injection, and atomization. With preheating, the
viscosity of residual fuels drops and it is easier to separate
solids and water from the fuel. However, a limitation of 99C
should not be exceeded because the water may flash to steeim

CHAPTER

6: INTRODUCTION

and, therefore, the centrifuge water seal would be lost. As a


general rule, after centrifugation, fuel should not be heated
above 150C, since some chemical changes may occur, gases
may be given off, or water may vaporize to form steam pockets in suction piping. An increase in primary fuel p u m p pressure could be necessary to prevent water/fuel vapor from
forming the more volatile fuel components in the fuel returns
piping from the injection pumps. Additionally, all m o d e m fuel
systems should be closed (pressurized) systems with n o access
to atmospheric pressure in mixing or vent tanks. Older ships
with open mixing tank systems should be upgraded to closed
and pressurized fuel systems at the next yard period to better
cope with m o d e m , cracked, blended residual fuels [1,2].
Another important parameter would be the viscosity index
(VT) of the fuel, which is determined according to ASTM D
2270. The viscosity index is the linear relationship between
viscosity and temperature. As a general rule, the lower the
viscosity index the higher the fuel density for a given fuel viscosity because of the higher concentration of cracked residuals present. A m o d e m cracked residual fuel could have a VI
of 10-15, whereas the older straight-run residuals can have a
VI as high as 80. Many of the published temperature viscosity/temperature curves and tables are based on residual fuels
with a VI of 65-70. Care should be exercised w h e n using
these charts and tables since cracked residual blends can deviate widely from these data, since they are more viscous at
lower temperatures. It is very important that a viscosity monitoring and control system is used and calibrated periodically. By using these viscosity controllers, variations in viscosity indices from stem to stem will be automatically
compensated [3].
Density

(D

1298)

The density of a fuel is the mass-per-unit volume and is expressed as grams-per-milliliter (g/mL) for liquid fuels. In reality, density and specific gravity have very similar values
and, for approximate purposes, could be considered the
same. Originally, specific gravity at 60F was predominantly
used but, currently, meuine fuels will specify density at 15C
superceding specific gravity as the common usage. In 1977,
the Worldwide Marine Industry officially adopted SI units,
although it has tciken many years for the Marine Bunker Industry to adjust to the SI units.
Since all liquid hydrocarbon fuels expand their volume
when heated, their weight-per-unit volume decreases. Therefore, the density (and specific gravity) must be reported at a
standard temperature even though another temperature may
have been used in the test method. ASTM D 1550 contains
volume correction tables for reference.
The significance of fuel density revolves around the waterfuel separating technology, such as centrifugal separators or
settling tanks that operate on the difference of the densities
between the water and the fuel. Older centrifugal sepeirators
(purifiers) were limited to fuels at or below 991 density at
50C to control water removal efficiencies. The removal of
free water and salt water are important to control damage,
corrosion, and deposits in fuel injection systems; turbo
chargers and boilers in diesel; and gas turbine engines. The
more m o d e m centrifugal separators can efficiently remove
water u p to a fluid density of 1.012 at 50C.

TO MARINE

PETROLEUM

FUELS

149

A marine fuel with a high density indicates that the fuel is


heavily aromatic from being heavily cracked. Higher density
fuels are likely to possess poor ignition and/or combustion
qualities and could cause increased wear to the mechanical
components of the diesel engine.
Ignition Quality (D 613 for
Distillates)
(ISO 8217, Annex B for
residuals)
The ignition quality of all marine residual and distillate fuels
is most important for diesel engines, since combustion starts
each cycle of operation. This is not critical for continuous
combustion cycles, such as those used for steam boilers and
gas turbine engines. In a diesel engine cycle there is always a
delay between the beginning of fuel injection and the start of
ignition or the initial combustion of fuel. In a distillate fuel,
the ignition queJity is indicated by the cetane number/cetane
index. The ignition quality in a residual or blended fuel oil is
indicated by the Calculated Carbon Aromaticity Index (CCAI)
number. The lower the cetane number/index of a fuel or the
higher the CCAI number, the poorer the ignition quality of
the fuel. This translates into a longer ignition delay, a lower
period of time between the start of fuel injection and the beginning of fuel ignition, and the rapid pressure rise associated with fuel ignition. The results of poorer ignition quality
can be loss of power, poorer fuel economy, higher NOx emissions, and even diesel engine damage [4,5].
The characteristics of the crude oil and the degree of refinery cracking are largely responsible for the ignition quality of
a marine fuel. The combination of highly cracked fuels with
high densities and blended or visbroken fuels with low viscosities results in the highest CCAI numbers and the poorest
ignition qualities for diesel engines. These high CCAI n u m b e r
fuels can cause serious operational limitations on medium
speed and high speed diesel engines that have the greatest
sensitivity to ignition quality. Large, medium speed diesels
and slow speed diesel engines operating at less than 400 RPM
are m u c h less sensitive to the ignition quality of the marine
fuel. Although m e a n piston speed has been considered a
more precise method to categorize diesel engine speed, the
Marine Industry generally accepts a slow speed diesel engine
to operate below 249 RPM, a medium speed diesel engine between 250 u p to 899 RPM, and a high speed diesel engine
above 900 RPM.
The ignition quality of a marine fuel can be calculated by a
CCAI nomograph or an equation. Most people use the nomograph to derive the CCAI, which is found in Fig. 4. The International Mcirine Fuel Testing Laboratories calculate and list
CCAI based on analyzed viscosity and density from the fuel
analysis reports.
Heating

Value (D

4868)

Heating value is the quantity of heat produced by the combustion of a unit of marine fuel under specified conditions.
The gross heating value is the sum of the heat produced by
the total combustion of the fuel and the heat released by the
condensation of the water and SOx gases formed during combustion. This is primjuily applicable to a steam boiler power
plant. The net heating value is the gross heating value minus
the heat released by the condensation of the water (vapor)
produced during combustion and the sulfur and metals con-

150 MANUAL 37: FUELS AND LUBRICANTS


^1

800
820

HANDBOOK
^800
810

840
-820
860
830

-3

880
-840
900
-850
920
940

860

960

870

980

880

1000

890

1020
-900
1040
910

-920
5000
930
20000
50000

(added) test flame but before it will bum continuously (fire


point). The flash point is an important indicator of the fire
and explosion hazards associated with a marine fuel. The test
equipment and test procedure are very important in obtaining accurate test results. A carefully conducted test will not
miss light fuel contamination that can depress the real flash
point. For most marine fuels that require heating, a minimum flash point of 60C is a prerequisite for storage safety.
Even though marine fuels may test above 60C for a flash
point, after fuels are heated in storage tanks, vapors can collect in the head space of the storage tanks that can flash below 60C, which can cause safety concerns. Volatile vapors
can be produced at the surface of the hot heating coils so controlling steam temperature (and pressure) of the heating coils
and maintaining flash arrester screens on aJl tank vents are
critical for shipboard safety [6].
Pour Point (D 97)
Pour point is an indicator of the ability of a marine fuel to
flow at low temperatures. It is considered the lowest temperature at which the fuel will flow when cooled under controlled conditions. Pour point is not related to fuel quality but
depends on the type of crude oil, refining process used, and
the use of fuel additives. As the fuel temperature drops, the
wax components begin to crystallize and impede the flow
characteristics of the fuel. When stored, marine fuels should
never be permitted to reach their pour points, because once
the fuel congeals, pumping may not be possible until the fuel
is heated 10C above its pour point. If a fuel has congealed,
much more time must be allowed for heating since the congealed fuel will not naturally flow to the heating coils.

-950

FIG. 4Nomograph for determining tlie CCAI. International


Organization for Standardization (ISO). This material is reproduced from ISO 8217:1996 with permission of the American National Standards Institute on behalf of ISO. No part of this material may be copied or reproduced in any form, electronic
retrieval system or otherwise or made available on the Internet,
a public network, by satellite or otherwise without the prior
written consent of the American National Standards Institute,
25 West 43rd Street, New York, NY 10036.

tent. The net heating value is apphcable to a diesel engine. To


obtain the full net heating value from a marine fuel, the diesel
engine must burn the fuel completely. As marine fuels increase in density and carbon content, it becomes increasingly
difficult to completely "bum-out" the fuel. To achieve complete combustion ("bum-out"), all carbon must bum to carbon dioxide, all hydrogen must bum to water vapor, and all
sulfur must bum to sulfur dioxide.
The net heating value will be primairily influenced by density, water content, and sulfur content. As the fuel density increases, the carbon-to-hydrogen ratio increases, causing
there to be relatively less hydrogen with its higher heating
value per unit weight. This results in a decrease in the net
heat released during combustion. Water and sulfur also
cause the net heating value to be lower.
Flash Point (D 93)
The flash point is the lowest temperature at which a marine
fuel will support instantaneous combustion (a flash) from the

Ash (D 482)
Ash from the marine fuels includes the inorganic metallic
content, other non-combustibles, and miscellaneous contamination. Metallics can contain a mixture of aluminum, calcium, potassium, iron, vanadium, nickel, silicon, and
sodium. Ash deposits can cause localized overheating and
corrosion to the metal surfaces where they adhere, especially
to the exhaust valves. Excessive ash can cause abrasive wear
of the cylinder liners, piston rings, injection pumps, fuel
valves, and injection tips. Catalyst fines can result in just such
abrasive damage.
In marine fuels, some of the dispersed and insoluble metallic compounds can be removed onboard by settling, centrifugation, and filtration. However, fuel soluble metallics cannot
be reduced by shipboard fuel handling equipment [7-9].
Cat Fines (ISO 10478)
Catalyst (CAT) fines are small particles of aluminum silicate
used as a fluidic catalyst in the catalytic cracking units at
modem refineries. Cat fines can be carried over from the catalytic cracker and can be found in marine fuels. Cat fines are
very hard and abrasive and can cause excessive wear of engine components, particularly fuel pumps, cylinder liners,
piston rings, and piston ring grooves.
To prevent severe abrasive damage, cat fines must be limited by fuel specification restrictions or by shipboard removal settlement, centrifugation, or fine filtration of five to
seven micron control. Cat fine control can be monitored by
testing the treated fuel for aluminum/silicon levels [10,11].

CHAPTER
Water (D 95) (D

6: INTRODUCTION

4176)

Water is a contaminant that enters mEuine fuels during transport, usually when taken by tanker or barge over water. Salt
water can cause greater problems in marine fuels then fresh
water. Salt water has been considered the greatest single
cause of fouling, deposits, and corrosion, especially in the
higher temperature regions of the power plant. The presence
of water can initiate microbial growth in marine fuels. These
simple organisms must live in the water at the tank bottom
and feed on the marine fuel at the water/fuel interface.
Water in the marine fuels can cause large volumes of centrifuge sludge as a result of water-sludge emulsification during centrifugal separation.
Because of upcoming IMO and EPA exhaust gas emission
regulations, diesel engines may start using water in fuel
emulsions (made with potable water) to reduce oxidizes in
nitrogen (NOx), particulates and smoke. These water-in-fuel
emulsions can consist of u p to 50% additional potable water
and must be intentionally-made emulsions with a tightly controlled water droplet size and a control on all larger size
droplets. Lastly, whenever the diesel engine is shut down, all
emulsion must be purged out of the fuel system such that the
shut down diesel fuel injection system contains no water-infuel emulsion [12].

TO MARINE

PETROLEUM

FUELS

151

360

340

320
1500 P S I ,
900 P S I x

300

I1

300 F*SI

280

260

OPSI^

Fuel PropertiesChemical
Sulfur

(D

240

4294)

Sulfur is a nonmetallic element that is chemically bound into


the marine fuel. Sulfur originates in crude oil and is concentrated into the higher density residual fractions. The mEirine
residual fuel has capped sulfur content at 4.5 weight percent
to begin to control oxides of sulfur (SOx). When sulfur is
burned in the diesel engine it causes several problems, primarily in promoting corrosive wear of the piston rings and
cylinder liners and by causing deposits in the ring zone. During the combustion process, sulfur dioxide and sulfur trioxide form in the cylinder. These sulfur compounds then combine with water vapor to form sulfurous and sulfuric acid,
which can cause aggressive corrosion.
When sulfuric acid vapor leaves the cylinder and contacts
low t e m p e r a t u r e surfaces of the heat recovery boiler, the
gaseous sulfuric acid condenses and forms highly corrosive
(liquid) sulfuric acid. So, in addition to ring and liner damage, the sulfuric acid can attack valve guides, as well as the
cooler parts of the heat recovery boiler.
Diesel engines can be designed to prevent low temperature
corrosion by maintaining surface temperatures above the
sulfuric acid condensation temperature, as shown in Fig. 5.
Sulfur in marine fuels is normally neutralized by using an alkaline (TBN) lube oil additive. The fuel sulfur level should be
balanced against the lube oil TBN additives to just neutralize
the sulfur. If too m u c h alkaline additive (TBN) is used, a
harmful (abrasive) level of alkaline material is produced that
can increase the wear of the cylinder liner and the piston
rings. The average sulfur level in marine fuels today is 2.8-3.0
weight percent.
Carbon Residue

(D 524)

Carbon residue is the coked material that remains after the


marine fuel has been exposed to high temperatures under

220
0

Sulfur [%]
FIG. 5Acid dew point for diesel engine fuels. Reprinted with
the permission of the Society of Naval Architects and Marine
Engineers (SNAME). Material originally appearing in SNAME
publications cannot be reprinted without written permission
from the Society, 601 Pavonia Ave., Jersey City, NJ 07306.

controlled conditionsthe laboratory test for Micro Carbon


Residue gives an overall guide to the carbon forming tendencies of the marine fuel. As heavier crude oils are refined with
the more intensive, secondary cracking process, the carbon
concentration in the marine fuel can approach 18-20 weight
percent. Further, as the carbon content increases, the asphaltene content typically increases as well. Asphaltenes are
high molecular weight hydrocarbons that can adversely affect combustion, residue formation, a n d the compatibility of
marine fuels. These high Ccirbon content marine fuels have
poor combustion chciracteristics; increased carbon deposit
forming tendencies on injection nozzles; pistons and ports of
two stroke engines; increased ignition delays; and slow burning constituents that can increase the thermal loading of
diesel engine components [13].
The asphaltene content in marine fuels influences the compatibility of blends of light and heavy fuels and blends of marine fuels from different liftings. An increase in purifier sludge
discharge or filter fouling is an early indication of incompatibility of fuels being mixed and/or high asphaltene levels.
Therefore, fuels taken on-board in different ports should be
segregated in separate tanks (as on-board m u c h as possible)

152 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK

and mixing fuels from different tanks on a single vessel should


be avoided.
Compatibility (ISO 10307-2)
Compatibility is the ability of a fuel to form a homogeneous
mixture that is neither separated nor altered by chemical,
time, or temperature interaction. Marine residual fuel blends
can be considered a colloidal dispersion of high molecular
weight substances (asphaltenes) held in a chemical and/or
physical equilibrium in the fuel. If the equilibrium forces are
disturbed, the high molecular weight components (usually
asphaltenes) are precipitated and dropped out of solution to
form a sludge or sediment. This can result in rapid tank
sludge buildup, clogged strainers, fouled filters and purifiers,
and damaged viscometers. Once into the diesel engine, incompatibility can cause rapid fuel injection pump sticking,
fuel injector deposits, exhaust valve deposits, turbo-charger
turbine nozzle and blade deposits, and carbon fouled waste
heat boilers [14].
Vanadium and Nickel (ISO 14597)
Vanadium and nickel are metallic elements that exist as fuelsoluble organometallic compounds. Vanadium and nickel,
originate in the crude oil and are concentrated in the marine
residual fuels by the various refinery operations. Depending
on the origin of the crude oil, the vanadium and nickel levels
of the fuel can vary widely.
In the combustion process, vanadium and nickel can combine (bond) with sodium (from salt water contamination) to
produce very aggressive, low melting point compounds that
are responsible for accelerated deposit formation and high
temperature corrosion of diesel engine components such as
piston crowns, exhaust valves, and turbo charger turbine
nozzles. Figure 6 shows for the relationship between vanadium and sodium. In steam boilers, these contaminants, together with sodium, can cause accelerated fouling of the
screen tubes and the superheater tubes as well as serious
high temperature corrosion of the superheater tubes. Gas
turbine engines are the most sensitive to both contaminants
due to the very high temperatures of the turbine section.
These contaminEints are fuel soluble, therefore they cannot
be removed from the fuel on the ship. If they are troublesome
to a particular engine, they must be limited at the time of fuel
purchase. The effects of vanadium and nickel can be neutralized by using a metallic fuel additive such as magnesium or
calcium.

Fig. 7, which shows the critical ratios of metcdlic components


and the large effect upon the ash melting temperature. It is
the molten form of sodium, vanadium, and nickel that causes
the severe hot corrosion and deposits to form. No power
plant is beyond this problem since it affects steam boilers,
diesel engines, and gas turbine engines.
Oxidation (Storage) (ISO 3735)
Marine residual fuels are tjrpically stored in heated tankage
on shore and in the ship. The higher storage temperatures
and the presence of air in the head space above the fuel in the
storage tank both combine to age the fuel. As marine fuels
age, they oxidize and begin to polymerize, forming sludge,
gum, and resin that can foul heaters and filters as well as fuel
injectors, combustion chambers, and the exhaust system. Oxidation products can vary in form: some are soluble in marine fuels while others are insoluble and result in the formation of an organic sediment [11].
Sediment (ISO 3735)
The insoluble organic products that result from oxidation of
marine fuels can combine with inorganic insolubles, such as
rust, cat fines, and sand, to produce sediment. This sediment
1600

Sodium (ISO 10478)


Sodium is a metallic element that is extremely active chemically. Generally, marine fuels are essentially sodium free
when leaving the refinery. The vast bulk of the sodium in marine fuels originates through Scilt water contamination during
transport by tank ship or barge and can be removed by settling tanks or by centrifugal separator. Sodium or salt (NaCl),
if present in significant quantities, will become involved in
severe high temperature corrosion and deposit problems.
When unfavorable ratios of vanadium combine with
sodium in the fuel, they react during combustion (at high
temperatures) to produce eutectic compounds with ash melting points within the engine's operating temperatures. The
relationship between sodium and vanadium can be seen in

100

VA
ITO

55

'

B5

'

3D

~2!r

Mixture Proportion [%]

FIG. 6Bonding relationship for vanadium and sodium.


Reprinted with the permission of the Society of Naval Architects and Marine Engineers (SNAII/IE). IVIaterlal originaiiy appearing in SNAIVIE publications cannot be reprinted without
written permission from the Society, 601 Pavonia Ave., Jersey
City, NJ 07306.

CHAPTER 6: INTRODUCTION

TO MARINE PETROLEUM FUELS

153

1600

1500
/

3Na20*V205

1400
o

1300

vp^

Q.

NA20*V 2O/5V2O
O)

1200
N a j O-V^Os

w
<

2Na20*V205

1100
5Na zO-V^O/ 11V 2 0 \

1000

900
0

10

20

PRACTICAL FO ULING
ZONE

30
P

40

50

60

70

80

90

NajO, MOL Percent

INCREASED FOULING RATE


FIG. 7Phase diagram for sodium and vanadium. Reprinted with permission from ABS, Houston, TX.

can damage high-pressure fuel injection pumps and fuel injectors. Sediment can be removed by gravity settling, filtration, and by centrifugal separators.
Fuel Additives
A fuel additive can be any material that, when added to a marine fuel, changes its properties, characteristics or performance. As secondary refinery processing cracks fuels more
severely, the resultant meirine fuel quality becomes more difficult to handle, store, and combust efficiently. The increased
amounts of metallic components, ash levels, and carbon contents adversely affect the performance of the fuel treatment
system and the power plant itself. Fouling and corrosion of
engine components and increased tank, centrifuge, and filter
sludge levels can present costly challenges for the ship's engineers. As fuel cracking intensifies, the fuel density increases
and it can make the centrifugal removal of free and emulsified water more difficult.
In addition to the conventional methods of settlement, centrifugation, and filtration, a chemical (additive) approach
Cin sometimes offer a solution to a particular problem. The

chemical additives that have been the most effective are the
stabilizers and dispersants, ash modifiers, biocides, demulsifiers, and emulsifiers [14].
Stabilizers and Dispersants
Stabilizers and dispersants tend to control the formation of
new sludge and to aid in the dispersion of existing sludge. By
limiting sludge, more of the hydrocarbon content of the
sludge can be burned and there is less sludge to incinerate or
to offload in the next port. Asphaltenes can significantly contribute to sludge production. By dispersing the asphaltenes
into very small particles with dispersant additives, sludge can
be reduced. Some additives work by using surfactants to facilitate a surface film formation at the fuel/asphaltene interface to stabilize the asphaltenes. The additional surface tension reduction tends to break the asphaltenes into minute
particles and stabilizes the fuel.
Additive additions are typically known as "tank treatments." Usually, when this additive is first used, it dissolves/disperses existing sludge and organic sediment and it
places a heavy burden upon the centrifugal separators and
filters as it begins to clean up tanks, piping, etc.

154

MANUAL

Ash

Modifiers

37: FUELS AND LUBRICANTS

HANDBOOK

These ash modifying materials can react with corrosive elements of the fuel during combustion to raise the melting temperatures above the critical temperatures, thereby avoiding
high temperature corrosion. Magnesium compounds represent one of the more popular ash modifiers since they are
available in many forms and are relatively inexpensive. Prior
to combustion, these chemicals are added so that the magnesium combines with the vanadium (from the fuel) to form
harmless, high-melting compounds that no longer adhere to
and corrode the exhaust valves and seats, piston crowns and
turbo charger nozzles in diesel engines and the superheater
tubes in boilers. It is preferred to know the vanadium-plusnickel content of the fuel to determine the proper additive usage. Overdosing of ash modifiers could produce h a r d deposits within the cylinder of a diesel engine, which can lead
to abrasive wear of the piston rings and cylinder liners.
Demulsifiers
These chemical additives cause small water droplets to coalesce and separate more readily from the marine fuel. They
are typically added to the fuel storage tank before bunkering
fuel. They allow better water settling in storage, in the settling tank, and in the centrifugal purifier. These demulsifiers
are most effective when the water in the fuel exists as a fine
dispersion or as an emulsion.
Biocides
These chemicals are toxic to microbiological growth in marine fuels, tanks, and piping. This growth typically lives in the
water at the bottom of a fuel tank and feeds on the fuel at the
interface between the fuel and the water. Since this growth
must live in water, the goal of good housekeeping practices is
to keep the tank bottoms drained of water. This is a challenge
since fuel transport is usually by barge or tanker over seawater. A small quantity of biocide will keep the overall fuel system free of microbiological growth. Biocides should be selected carefully since some are fuel soluble a n d some are
water soluble.

F u e l Oil I m p a c t o n E x h a u s t E m i s s i o n s
There are several marine fuel properties that can impact exhaust gas emissions. Sulfur is the first fuel property to be regulated by international and domestic rules. The International
Maritime Organization (IMO) has limited sulfur to a maxim u m of 4.5%. Some localized regions, such as the Baltic Sea,
have imposed even lower sulfur levels.
The next emission to be regulated will be Oxides of Nitrogen (NOx). The IMO will restrict new marine diesels installed
after 2000 to NOx limits based upon the rotational speed of
the engines. Slow speed engines have the highest limits,
medium speed next, and high speeds have the lowest limits.
The nitrogen content of marine fuels does contribute to NOx
emissions, b u t to date, no organization has attempted to limit
fuel nitrogen.
Ignition quality, cetane for distillate fuels and CCAI for
residual fuels, has an impact on NOx produced in a diesel engine. Usually, the lower the ignition quality of the fuel, the
higher the NOx exhaust emissions.

Exhaust particulates and smoke b o t h relate to the ability of


the diesel engine to completely and efficiently b u m the marine fuel so little or no solid carbonaceous material remains.
Therefore, the higher the micro carbon residue and asphzJtene content, the higher the Ccirbonaceous pcuticulates and
smoke that can be expected.
Lastly, if stack opacity is regulated or if excessive smoking
is prohibited, the marine fuel should not contain used lube
oil (either supplied with the fuel at bunkering or as the result
of the disposal of used lube oil from the diesel engines on
board). Used lube oil in marine fuels results in a blue colored
haze in the exhaust gases that cannot be reduced until all of
the marine fuel with used lube oil has been burned.
P e t r o l e u m F u e l Oil T o x i c i t y
Marine fuel oils present a minimal health hazard when the
engineers practice high standards of personal and industrial
hygiene. A caution, however, is that extended exposure to
marine fuels can cause skin dermatitis and even skin cEuicer.
To minimize this possibility, these precautions should be
considered.
Minimize skin and eye contact with marine fuels by modifying work procedures, if necessary.
Always wear protective clothing, especially impermeable
gloves and eye protection.
If clothing becomes fuel soaked, remove it and thoroughly
wash the affected skin with soap and water.
Avoid carrying fuel soaked rags in pockets.
Do not use light hydrocarbon solvents for removing fuel
from the skin. Always avoid inhaling hydrocarbon solvent
vapors.
Avoid inhaling hot fuel mist or vapors since the fuel could
contain contaminants such as waste solvents, acids, and
strong base mixtures that can sometimes get dumped into
marine fuel tanks.
Avoid accidental injection of marine fuel into the skin during the testing of fuel injection equipment by following test
equipment directions and maintaining protective shields
in place.

PETROLEUM FUEL SPECIFICATIONS


When the combined requirements of the commercial and
military marine fuels are considered, marine fuels represent
a small fraction of the refinery capacity. Marine fuels and, in
particular residual fuels, are the end products of the major
shore side fuel producers' needs. Therefore, the refineries'
production is driven by shore side needs and the remainder
is delivered into the marine industry. It is little wonder that
the unique needs of the marine industry have little impact
upon the quality of marine fuels [15].
Commercial m a r i n e fuels range from gas oil to m a r i n e
diesel fuel, to blended marine diesel fuel, to blended residuals, to heavy residuals.
Gas oils are clean, high quality, 100% distillate diesel fuels
that are shipped and handled clean. If gas turbines are used
in commercial service, the specifications will likely cedl for
gas oil to maintain the very, very low trace metallic contamin a n t levels required for long life. Gas oils are typically used
for emergency and lifeboat diesels.

CHAPTER

6: INTRODUCTION

Marine diesel oils (MDO) can be two very different fuels.


MDO-light is similcir to gas oil but is handled in dirty barges
that carry residucd fuels. This produces a dark colored fuel,
which is essentially all distillate, with a little additional sedim e n t and a carbon residue below 0.2% (by mass).
MDO-heavy is roughly 85% MDO-light blended with 15%
residual fuel and handled dirty in a residual fuel barge. Since
MDO-heavy contains about 15% residual fuel content, this
should only be used in diesel engines that are designed to
have a blended residual fuel capability. The carbon residue of
MDO-heavy is typically above 1.5% (by mass).
Heavy Residual Fuels (HFO) have high viscosity and density and, in many situations, they must be blended to a lower
viscosity and a lower density to be used in marine vessels.
Most marine residual fuels are blends of different residual
fuel stocks with lighter stocks, such as MDO and cycle oil.
The blending process can r e d u c e sulfur, c a r b o n content,
vanadium and ignition quality, as well as viscosity and density. Residual fuels are still generally classed by viscosity,
however, m a n y other properties are considered before a
residual fuel selection is made.
International Specifications
The International Orgcinization for Standardization (ISO) has
written a basic International Marine Fuel Specification 8217
and revised it several times since the original document was
published in 1987. The most recent revision was published in
1996. The ISO relies on the guidance Eind advice of the International Council on Combustion Engines (CIMAC), Heavy Fuel
Committee, which consists of engine builders, major oil companies, bunker suppliers, treatment equipment builders and
consultants. CIMAC also publishes a distillate and residual fuel
specification but, since it is not voted upon by an international
membership, it truly doesn't carry an international importance.
The International Maritime Organization (IMO) has proProperty
Density at 15C, kg/m^
Kinematic viscosity at 40C, cSt *
Flash point, C
Pour point (upper), C"
Winter quality

Summer quality
Cloud point, C
Carbon residue on 10% bttns,
Ramsbottom, % mass
Carbon residue, Ramsbottom, % mass
Ash, % mass
Sediment by extraction, % mass
Water, % vol
Cetane number
Visual inspection
Sulfiir, % mass
Vanadium, mg/kg

TO MARINE

PETROLEUM

FUELS

155

duced a document called Annex VI of MARPOL 73/78, the regulations for the prevention of air pollution from ships, which
caps the sulfur level in marine fuels at 4.5 wt. percent and has
a provision that will restrict the NOx production from marine
diesel engines after Jan 1, 2000. As time moves forward, the
IMO will continue to regulate and restrict air pollution from
marine diesel engines. In some cases, as in the SOx emissions,
the air pollution control will be regulated by restricting fuel
properties. Therefore, although the IMO MARPOL regulations are not strictly fuel specifications, they will achieve
some of their regulation by restricting marine fuel properties,
as has already been done with a fuel sulfur cap.
ASTM Marine Fuel Specifications
The ASTM D 2069-98 Fuel Specifications are similar to the
ISO 8217 standard in many ways. Figure 8 shows the ASTM
detailed requirements for marine distillate fuels, and Fig. 9
shows the ASTM requirements for marine residual fuels.
Military F u e l Specifications
Military marine fuels consist of all distillate fuels that meet
an individual country's fuel specifications but most also conform to North Atlantic Treaty Organization (NATO) fuel
specifications as well. Military fuels place additional restrictions u p o n these distillate fuels to support the unique, multipurpose military requirements, as well as to provide for extended storage times. In the U.S. Mihtary, the MIL-F-16884
fuel specification requires a clean, stable distillate, somewhat
similar to marine gas oil, with additional properties and testing required before acceptance. Therefore, MIL-F-16884,
Diesel Fuel Marine (DFM), and NATO F-76 are the same fuel
that requires dedicated clean handling to prevent transport
contamination, which can cause the fuel to tail out of specification.
Limit
max.
min.
max.
min.
max.
max.
max.
max.
max.
max.
max.
max.
min.
max.
max.

DMX
a

1.40
5.50
43

DMA
890.0
1.50
6.00
60

DMB
900.0

DMC
920.0

11.0
60

14.0
60

-6
0

0
6

0
6

0.25
0.01
0.07
0.30
35

2.50
0.05

2.0

2.0
100

-16"
0.20

0.20

0.01

0.01

45

40

1.0

1.5

0.30

"There may be a maximum limit in some locations.


*lcSt=.lmm^/s
"Purchasers should ensure that this pour point is suitable for the equipment on board, especially if the vessel
operates in both the northern and southern hemispheres.
*rhis fuel is suitable for use without heating at ambient temperatures down to -15C.
TTiis fuel shall be visually clear and bright.
FIG. 8ASTM D-2069-98, Detailed Requirements for lUlarine Distillate Fuels.

156 MANUAL 37: FUELS AND LUBRICANTS

HANDBOOK
The U.S. Navy uses a ciistillate fuel, JP-5, for aircraft gas
turbine engines anci selected high speed diesel engines. This
fuel is lighter than MIL-F-16884. It differs from other aircraft
fuel primarily by its higher flash point requirements (60C vs.
38C). JP-5 fuel must be handled and stored clean.

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Environmental Considerations
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It is possible that localized environmental regulations could


place more stringent limitations, beyond the International
anci/or Domestic Regulations, on fuel specifications. As previously reviewed, limits on sulfur, carbon content, and ignition quality could be imposed to achieve a local regulation. If
a catalytic converter was installed, the use of a very low sulfur fuel would be prudent to preclude premature catalyst
fouling and poisoning.

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FUEL TESTING

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A known fuel quality has been determined to be fundamental


to reliable marine diesel engine operation. A comprehensive
fuel sampling and testing program is essential to ensure the
quality of the marine fuel lifted, and to ensure that the ship's
fuel treatment system can properly clean, heat, and pump
this fuel to the diesel engine for efficient combustion, good
fuel economy, and low exhaust stack emissions. Even if the
marine fuel is refined clean, shore side handling and storage,
as well as marine fuel movements, can and frequently do contaminate the fuel such that poor engine operation, accelerated wear, or serious exhaust gas violation can occur. It is
critical that the ship's fuel treatment system can properly
treat the bunkered marine fuel so that clean, high quality fuel
can flow to the diesel engines.

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Fuel Sampling
Fuel sampling is the critical first step in obtaining knowledge
about the newly bunkered marine fuel. For a fuel test and
analysis to be meaningful, it is critical that a representative
sample be taken during the delivery of the fuel. A representative sample requires continuous sampling throughout the entire bunkering operation, since marine fuels can stratify or
can vary the blending ratios during the delivery period. Most
marine fuel testing services provide detailed directions and
equipment to take a continuous, representative sample. Also,
ASTM D 4057 can provide detailed instructions on taking a
representative sample. The old practice of taking a "spot or
grab" sample is no longer acceptable.

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Sending the representative sample to a shore side laboratory


as soon as possible for accurate and complete analysis is
strongly recommended. In addition to a comprehensive analysis, a shore side laboratory can confirm that a fuel meets the
ISO purchase specifications and can alert the crew to contaminants, incompatibility, abrasives, excessive water content, and other damaging aspects of the bunkered fuel.
Lastly, since these independent shore side laboratories provide an unbiased analysis, they can facilitate the resolution of
disputes quickly and at low cost.

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CHAPTER 6: INTRODUCTION
On Board Testing
Since the shore side testing can take 24-72 h, some operators
prefer to supplement the shore side testing with quick, simple on board tests that are helpful in the short term. These
quick on board tests provide the immediate results often
needed to support decisions on fuel treatment system alignments, adjustments, and operations. The alignments and adjustments of the centrifugal separators can be effected by fuel
density, water content, compatibility, abrasive content, etc.
Typical on board tests include those for viscosity, density,
water, compatibility, and particle content.

FUEL STORAGE SYSTEMS


Steam, diesel, and gas turbine marine fuel storage, settling,
and transfer systems are very similar. Figure 10 illustrates a
steam propulsion plant with a 600 cSt residual fuel and diesel
oil fill, transfer, and storage system. A diesel engine propulsion plant with its fill, storage, transfer, and centrifuged purification system is illustrated in Fig. 11.
The marine fuel transfer system provides the following
functions:
To transfer marine fuel from any storage tank to any other
tank, such as to the settling tank.
To strip solids and water from the bottom of the settling
tank(s) through the stripping and drain connections.
The marine residual fuel and marine diesel fuels are
bunkered through deck fill connections that should have sampling connections installed to allow continuous, representative fuel samples to be taken as the fuel is taken aboard.
Heated tanks are used for storing marine residual fuels, and
unheated tanks for marine diesel fuels and gas oils. From the
residual fuel storage tanks, the transfer pumps forward the
fuel to the settling tank(s). The residual fuel settling tanks begin the fuel treatment process by settling gross water and
solids to the bottom. As soon as the settling tank is filled, it is
heated to 80C, but not higher than 10C below the fuel's flash
point. By heating the fuel, the viscosity is reduced, the gravity
settling process is enhanced, and the fuel deaerates as well.
Once settled, the fuel is forwarded to the boiler fire front,
after additional heating, as illustrated in Fig. 12. The settling
tank bottom drain connections permit the removal of settled
water, sludge, and solids to the sludge tank.
In the fuel transfer system, all piping should be traced,
heated, and insulated to prevent the marine residual fuel
from solidifying in the piping. The residual fuel storage tanks
all have heating coils to control tank temperature and to
maintain the fuel at 10C above the pour point until it is
transferred to a settling tank.
From the safety standpoint, experience has proven that explosive atmosphere can collect in the tank headspace even
though the fuel oil temperature is well below the flash point.
This condition exists when cracked marine fuels contact hot
heating coils that are significantly hotter than the bulk fuel
temperature. Further, if shore side petroleum waste products
have been mixed with the marine fuel, the lower flash point
of the waste products could greatly lower the flash point of
the bulk marine fuel. Even worse, this lower flash point may
not be reported if the shore side sample was taken prior to the
introduction of the waste. Therefore, the crew must fre-

TO MARINE PETROLEUM FUELS

157

quently inspect and maintain the condition of the flame arrester screens on the fuel tank vent lines, and careful and safe
use of the ullage equipment is imperative.
In a steam propulsion plant system, a duplex heater set
heats the fuel to the atomizing viscosity prior to the fuel
reaching the boiler fire front.
In a diesel engine propulsion system, the settling tank delivers heated residual fuel to the purifier heater set prior to
the centrifugal separator(s). It is important that the residual
fuel temperature to the separator stably remain at 98-99C to
maintain high separator efficiency and to prevent boiling of
the water (in the fuel) within the separator.
Service tanks or day tanks provide an additional opportunity to further settle water and solids from the heated residual fuel. The service tank can be filled by the centrifugal separators and provides additional time for deaeration.

FUEL TRANSFER SYSTEMS


The fuel transfer pump(s) is provided to move fuel from storage to settling tank(s). The positive displacement transfer
pump(s) is protected by coarse suction strainers, pressure relief valves, and pump bypass lines. The flow rate of the transfer pump is established by the engine's fuel consumption rate
and the capacity of the settling tank. The operational flexibility of the transfer system is provided by the arrangement of
the valves in the system. This valving can permit the fuel to
be pumped from any storage tank to any settling tank or to
other storage tanks.

STEAM PLANT FUEL SERVICE SYSTEM


The simplest of the service systems is that of a steam plant. It
consists of storage, settling, and service tanks; transfer and
service pumps; and heater sets (see Fig. 10). The treatment
system consists of a heated settling tank that allows solids
and gross water to fall to the bottom of the tank [4].
The service system is also very simple, consisting of a
pump, a heater, and a pressure (or flow) regulating controller. Most modern systems incorporate a quick-closing
fuel valve to shut down fuel flow if there is a flame out, loss
of combustion air, or loss of fuel pressure.
Two fuel service pumps, with one in standby, are provided
and each is capable of supplying the total fuel flow plus an
additional msirgin, with the excess flow diverted back to the
settling tank. Service pumps are typically of the positive displacement type that are fitted with a pressure relief bypass,
remote shut downs, and isolation valves (for servicing). The
pressurized fuel flows to the service heater sets where the
temperature is increased to provide for the proper fuel viscosity for atomization. The two heater sets (one in standby)
are steam heated shell and tube or plate type heat exchangers, each with the capability of increasing the fuel to 145C.
It is important to use properly sized heat exchangers and lowpressure steam supply to prevent overheating the fuel as it
passes through the heat exchanger. After the heater sets, the
fuel passes through duplex strainers, a viscometer, and a flow
meter and then to the burner management system at the
boiler Are front. All residual fuel piping must be trace heated
(usually by steam) and insulated.

158 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

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CHAPTER 6: INTRODUCTION TO MARINE PETROLEUM FUELS 159

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CHAPTER 6: INTRODUCTION
The marine diesel fuel storage (see Fig. 11) provides a separate fuel supply for cold boiler start up and for the emergency diesel generator. A small diesel fuel service tank is used
to provide clean fuel for emergency operation when neither
steam nor electricity is available. This diesel service tank is
located high in the machinery space so that gravity will supply enough fuel pressure to start the boilers and diesel generators in an emergency.

DIESEL PLANT FUEL SYSTEM


Diesel engine power plants require more intensive and complex fuel systems than those of steam plants. The contaminants, water, solids, and debris that may have been allowable
in a steam plant must be removed prior to diesel engine operation. When burning residual fuels in diesel engines, the
basic principles of settling, pumping, heating, and treating
are common to slow speed and medium speed diesels alike. A
typical residual fuel and diesel fill, transfer, storage, and
treatment system for diesel engine power plants can be seen
in Fig. 11. All residual fuel piping should be insulated and, if
the viscosity exceeds 380 cSt at 50C, trace heating should be
included under the insulation.
Whenever emergency shutdowns occur to a diesel engine
operating on residual fuel, the viscous fuel will remain in the
piping and heaters, and also in the injection pumps and high
pressure piping. If all piping and components have trace
heating and insulation, it is not a problem since the residual
fuel can be reheated and its temperature controlled by recirculation prior to restart. If the emergency will keep the engine shut down for a lengthy time, the residual fuel should be
purged from the piping with marine diesel fuel and this will
eJlow the trace heating system and the recirculating pump to
be secured. Additionally, if Einy maintenance is planned for
the fuel injection system, the work will be faster and easier
with marine diesel fuel in the piping system.
When bunkering residual fuel and marine diesel fuel, both
enter through sepjirate deck connections. Both deck connections must incorporate sampling equipment to permit continuous, representative sampling during the entire lifting.
This is considered the point of custody transfer and these
samples will be key should a quality dispute arise.
As was the procedure in steam plants, marine residual fuels for diesel plants are transferred to the settling tank(s) by
a transfer pump through a coarse strainer. The best practice
is to duplex transfer pumps to prevent pumping problems.
If a demulsifier chemical is to be used to aid in water or
particulate removal, the demulsifier should be metered into
the suction strainer ahead of the transfer pump. Demulsifier
chemicals work by facilitating the separation of water and
solids from the residual fuel, and this process begins in the
settling tank(s). After the settling tank(s), the centrifugal purifiers and clarifiers, from two to four centrifuges, are typically installed to treat the residual fuel. These units include
supply pumps, heaters, and automated controllers. Centrifugal separators, set up as purifiers and clarifiers, are widely
used. They are considered a reliable and efficient method for
treating and cleaning marine diesel fuel and marine residual
fuels if properly maintained and adjusted. Centrifugal purifiers have the clear advantage of being capable of removing
large quantities of water and particulates. The centrifuge ser-

TO MARINE PETROLEUM FUELS

161

vice pumps, fuel heaters, sludge tank, and interconnecting


piping must be designed to match and support the needs of
the centrifuge.
The piping system must be configured to allow centrifuge
operation in parallel or in series as either purifier/purifier,
clarifier/clarifier, or purifier/clarifier. The centrifugal processed residual fuel then passes through very fine duplex filtration units that remove abrasive catalytic particles (cat
fines) that pass through the centrifuges. After these fine filters, the residual fuel enters the service/day tank.
From the service tank, the residual fuel is forwarded to the
diesel engine through the residual fuel service system as seen
in Fig. 13. The service system raises the residual fuel temperature up to the fuel injection temperature as controlled by a
viscometer. An advanced service system will include a homogenizer to treat the residual fuel just prior to injection into
the diesel engine. The service system flows two or three times
the maximum fuel consumption of the diesel engine. Older
fuel service systems are atmospheric pressure mixing tanks,
while modem practice is to pressurize the entire system, remove the mixing tank, and add a mechanical deaerator to
eliminate gases and water vapor from the injection pump discharge flow.
The marine diesel fuel system moves fuel from storage to
the service tank by a transfer pump or by a centrifugal purifier. The fuel can be transferred from the service tank to the
emergency diesel generator service tank by either transfer
pump or centrifugal purifier.

DIESEL FUEL SYSTEM COMPONENTS


Centrifuges
The recommended centrifuge flow capacity is the quantity that
can be treated at the highest separating efficiency. This flow
capacity is based upon the d5Tiamic viscosity of the residual
fuel at the temperature of separation. The maximum separation temperature has an upper limit of 98C. There is a risk of
the loss of the water seal in the centrifuge due to the formation
of steam bubbles. A thorough review of each centrifuge manual will determine recommended maximum flow rates for any
given residual fuel. The rule is to reduce the fuel flow through
the centrifuge to slighfly above the fuel consumption of the
diesel engine. Avoid the temptation to rush the fuel through
the centrifuge and into the service tank so it overflows back to
the settling tank and is recentrifuged. Peak centrifuge operation efficiency occurs when the flow is reduced to increase the
residence time of the fuel within the centrifuge while maintaining a stable fuel temperature of 98C.
Two properly sized, correctly adjusted and operated, selfcleaning centrifuges are considered absolutely necessary to
provide a reliable diesel fuel treatment system. Most diesel
engine warranties become invalid if adequate centrifuges are
not used effectively. The following fundamental principles
are necessary to establish and maintain effective centrifugal
separator procedures for marine residual fuels.
The centrifugal separators are the foundation of the diesel
fuel treatment system.
To treat contaminated marine fuels, supplementary systems are required in addition to the centrifuges. These supplementary systems consist of fine filtration, demulsifier

162 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


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CHAPTER

6: INTROD

chemicals, combustion catalyst chemicals, and homogenizer/emulsifiers.


Each centrifuge must be supplied with a complete manual,
all necessary parts to operate as a purifier and as a clarifier,
a complete set of spare parts, seals, gaskets, etc., and a
complete set of specialized tools.
The combined centrifuge flow rate (for parallel operation)
and the single centrifuge flow rate (for series operation)
must not exceed the diesel engine demand by more than
10%.
All residual fuel centrifuges should be operated continuously, even in port. This reduces fuel contaminants and increases the effective time for fuel treatment.
To properly adjust and operate a centrifuge, these residual
fuel properties must be known:
1. viscosity
2. density
3. fuel oil compatibility
4. water content
5. ash content (or bottom sediment content)
6. catctlyst fines content (as measured by aluminum plus
silicon content)
With this residual fuel information, fuel treatment decisions can be made.
Whenever a residual fuel from a different bunkering is
transferred to the settling tank, a density check of this new
origin fuel should be made to determine if a gravity disk
change is needed in the purifier.
Since the centrifugal separator is the foundation of the
residual fuel treatment system, its reliable and efficient operation is critical to the durability and reliability of the diesel
engines. The operation of the centrifuge must be thoroughly
understood by all shipboard engineers so they cein immediately troubleshoot any problems. The following conditions
can cause mal-operation of the centrifuges.
Improper residual fuel handling such as improper or inadequate blending, incompatible residual fuels, and emulsified fuels.
Improper flow rate, such as varying flow rates, excessive
flow rates, or varying densities.
Improper temperature control, such as varying temperatures or temperatures below 98 C.
Improper water/fuel interface inhibiting a uniform flow of
fuel through all disks, usually caused by the installation of
an improper gravity disk. As the residual fuel properties
change, the gravity must be checked and changed (if necessary) to control the water/fuel separation zone for maxim u m efficiency.
Improper operation with a water-in-fuel emulsion blocking
efficient water and solids removal through the sludge zone.
Overloading the centrifuge with a n accumulation of
sludge, which is usually caused by extended desludging intervals or by incompatible residual fuels.
Another area of concern is the centrifuge valving to prevent
contamination from passing through the centrifugal separators during start up. Immediately after the separators, valving should allow the recirculating of residual fuel back to the
settling tank during the centrifuge start up process. During
start up, a considerable time must be given to allow the flow
rate and the fuel temperature to be increased and stabilized

UCTION

TO MARINE

PETROLEUM

FUELS

163

before the separator efficiency has optimized. If residual fuel


is recirculated to the settling tank during this time, no contamination will be passed on to the service tank. Once stabilized, the valving can be switched to allow properly centrifuged fuel to flow to the service tank.
Proper practice requires at least two centrifugal separators
to be properly sized, adjusted, and operated. When operating
at the recommended flow rate for m a x i m u m separating efficiency, each of the two separators must be capable of treating the maximum fuel rate of the diesel engine(s) plus approximately a 10% margin. For normal operation, the series
method of a purifier followed by a clarifier is the preferred
flow path. The first separator operates as a purifier to remove
sludge, sediment, a n d water. The second separator is arranged as a clarifier to remove any remaining sediment or
catalyst fines from the residual fuel. Additionally, the clarifier
provides a backup to the purifier should it malfunction.
Parallel centrifugal separator operation is recommended
when the residual fuel contains a high water content. The
parallel operation allows each sepsirator to operate as a purifier at one-half the normal fuel flow rate. By doubling the residence time in each purifier, the water removal efficiency of
each purifier is enhanced. In the parallel configuration, both
purifiers provide the highest cleaning efficiency and, therefore, the cleanest fuel to the diesel engine. There is just one
problem: if either purifier should malfunction, there would
be n o second stage of centrifugal separation to prevent contamination from directly entering the diesel engine.
The decision to operate in series or parallel is a judgment
that the ship's engineers must make based upon reviewing
the analysis of the representative sample taken during the entire bunkering operation. The fuel analysis must be examined
for viscosity, density, water content, sediment, ash, catalyst
fines, and compatibility in addition to the expected voyage
fuel flow rate.
Filters a n d Strainers
All marine residual fuel systems use coarse strainers to provide gross protection from very large fuel contaminants. But
in diesel power plants, fine filtration serves a major function
in controlling highly abrasive solids from reaching the engine. It is because of the high ash, sediment, and catalyst
fines content of marine residual fuels that supplemental fine
filtration is recommended. Even though the fine filtration is
considered as backup to the centrifugal separator system,
these filters are essential to ensure that the fuel delivered to
the diesel engine is free of damaging abrasive particles. All
fine filtration should be duplexed to allow cleaning and replacement of filter elements without a n interruption in fuel
flow. An effective fine filtration system can provide positive
protection from abrasive particles that would normally damage high pressure injection pumps, injection VcJves, injection
nozzles, cylinder liners, piston rings, and piston ring grooves
in the piston. Typically, these fine filters require the filter elements to be replaced at 2 0 0 0 ^ 0 0 0 h intervals under normal
operating conditions.
Additionally, fine residual fuel filters can be used with homogenizers to reduce the asphaltene and sludge removal by
filters. In fact, most of the matter collected in fine filters is
non-particulate, organic hydrocarbon material. The basic

164

MANUAL

37: FUELS AND LUBRICANTS

HANDBOOK

function of a homogenizer is to disperse the sludge and asphaltenes in the residual fuel to prevent the removal of these
hydrocarbons while passing through the fine filter. Therefore, the homogenizer can greatly increase the life of the filter elements as well as reduce the total quantity of sludge removed from the residual fuel. The reduction in sludge burden
reduces the problems and expense of sludge removal and decreases the wasted heating value of the lost sludge.
Some fine filters have the ability to remove trace quantities
of free water missed by the purifiers. Even though trace water removal might seem insignificant, shipboard testing has
shown a 100% increase in injection p u m p life after the addition of fine filters to remove the trace water from the marine
residual fuel. It is critical that the water sumps in fine filters
are drained daily to prevent water from rising above the
sump level and wetting the filter elements.
Self-cleaning or auto-flushing filters contain metallic
screens that automatically or periodiccdly back flush to clean
sections of the screen to allow for continuous operation. The
sludge and debris back flushed must be treated and finally
discarded. A problem can arise when filtering even a mildly
incompatible fuel since the increased sludge volume can require the filter to back flush u p to 400 times a day. This can
cause increased wear on back flushing components and on
the screen, as well as produce a Icirge volume of sludge for
disposal.
There are two t3rpes of replaceable, cjirtridge-type fuel filters: the surface type a n d the depth type. Surface elements
are similar to metal screens that have a limited thickness.
They can be made from cellulose, fiberglass, felt, or metal.
Surface filter elements are frequently pleated to increase the
filtration surface area within a given space and to increase
the element's life. A problem with surface filters is that organic sludge and/or asphtdtenes, together with solids, cEin accumulate on the surface of the filter and seal the surface. This
results in rapidly increasing pressure across the filter, which,
in turn, limits the useful filter life.
A depth filter is designed so that the entire depth of the element works as a progressive filter. This allows the contaminants to be controlled throughout the element's depth Eind reduces the buildup of contaminants on the surface that can
reduce filter life. This feature is especially important for fuels
with residual components that can cause problems for surface filtration.

Boost Systems and Deaeration


The boost or service system consists of two p u m p s (one running, one standby) providing fuel to the boost heater sets, the
viscometer, the homogenizer, the final filter, and to the diesel
engine injection system. Duplex strainers of 20 to 40 mesh
protect the boost p u m p s from tank and piping debris.
Modern fuel systems use deaeration units t h a t remove
gaseous bubbles from the return fuel from the engine. These
systems are closed and pressurized to prevent fociming and
frothing of the hot residual fuel. Older systems were open to
the atmosphere in the mixing t a n k where the r e t u r n fuel
mixed with the incoming fuel and the gaseous bubbles were
intended to dissipate within the tank. All older/boost systems
should be upgraded to closed, pressurized systems at a convenient yard period. Closed, pressurized systems should use

deaerator units to remove any gaseous or vapor bubbles from


the r e t u r n fuel before the fuel gets back to the injection
p u m p s . Closed, pressurized boost systems stre the best to prevent operating problems when operating on high viscosity
residual fuels, b u t they do require additional circulating
p u m p s to be effective.
Fuel Service Heaters
Two fuel heaters are needed in the service or booster system,
with one clean heater on standby. Steam is the normal heating m e d i u m for the t5rpical shell a n d tube or plate style
heaters. Frequently, duplex 20 to 40 mesh strainers protect
the heater sets from piping debris. The heater sets should
have the capability of heating the fuel to 150F without thermally stressing the fuel in the heater (and coking the heaters).
Heaters made from stainless steel, titanium, and aluminum
are preferable over copper-based materiEds. The temperature
control for the heater(s) should be the automatic viscometer.
Viscosity Control
The automatic viscometer continuously samples and measures the viscosity of the fuel and controls the steam to the
heaters to maintain a preset injection viscosity to the engine's
fuel injection system. This is critical since viscosity control is
a major factor in efficient fuel injection into the diesel engine.
Real time, accurate viscosity measurement is very important
because of the low viscosity index of m o d e m , highly cracked
residual fuels. Since the viscometer is critical to correct fuel
viscosity control, the units should be checked and ccdibrated
periodically. A valved bj^Dass line, together with isolation
vEdves before and after the viscometer, can provide the means
to service the unit without a main engine shutdown.
Fuel Supply Flowmeter
To accurately measure the engine's fuel consumption, a fuel
supply flowmeter is needed. A mass flowmeter or a positive
displacement type of meter that is reliable and accurate is
recommended. A corrosion resistant material should be used
on EJI oil wetted internal surfaces. Some fuel system arrangements require the use of a second fuel flowmeter to measure
the return fuel from the engine's injection system. In these
systems, the return flow must be subtracted from the fuel
flow to determine the fuel used by the engine. The return
flowmeter should be the same type a n d model as the fuel
flowmeter.
Fuel Final Filter
Since the high pressure injection p u m p s are sensitive to any
debris, the boost system should be fitted with a final simplex
10 micron filter located just before the supply to the fuel injectors. This filter should be fitted with a differential pressure
indicator. Some operators opt to use self-cleaning final filters
to minimize manpower.
B a c k Pressure Control
To minimize foaming, cavitation, and vapor formation in the
fuel returning from the fuel injections pumps, a positive pres-

CHAPTER 6: INTRODUCTION
sure of 350 kPa will be needed for high viscosity residucil fuel
that requires a high preheat for proper injection viscosity.
Homogenizer
As residual fuels become more dense with a higher viscosity
and higher carbon and asphaltene contents, homogenizers
will become more important to aid in the preparation of the
fuel for injection, complete combustion, and the reduction of
exhaust peirticulates cmd opacity (smoke). Very simply, a homogenizer disperses insoluble hydrocarbon clusters in the
residual fuel, completely disperses all free water and cem produce a stable, water-in-fuel emulsion (when potable water is
added to the fuel prior to the homogenizer). The homogenizer breaks up the insoluble hydrocarbon materials and
sludges into very fine particles that aid ignition and burnout
of the high boiling range, high molecular weight materials.
There are several different types of homogenizers available,
but the most effective operate on cavitation and shear principles, and require significant power to operate. Other units
operate on some ultrasoniccJly. As fuels become more heavily cracked, the use of homogenizers will increase. When
used regularly, homogenizers can reduce the unbumed fuel
particles that cause waste heat boiler fires (from unbumed
fuel particles).

TO MARINE PETROLEUM FUELS

165

engines operate at sustained metcJ temperatures over twice


those found in diesel engines, the cleanliness requirements of
the fuel are much more severe than those for diesel engines.
In gas turbine engines, it is criticcJ to control metallic compounds, insoluble and soluble fuel contaminants, dissolved
water soluble metallic contaminants, fire water, solids, and
sometimes microbial contaminants [16,17].
The gas turbine fuel treatment system is similar to the
diesel engine system except for the more intensive treatment
needed to all but eliminate metallic contamination in the
fuel. Where some metallics, such as vanadium and nickel
cannot be (practically) removed by fuel treatment, they can
be neutralized using fuel additives. For example, marine
diesel engines can operate well at hundreds of parts-per-million of metallic contaminants, whereas gas turbines must
have metallic contaminants in the single digit parts-per-million range, or less. This critical requirement places great emphasis on all aspects of fuel purchase, sampling, delivery,
storage, and treatment. The fuel treatment system must consistently and reliably control fuel contaminzmts without upsets or malfunctions. Additioneilly, most gas turbine manufacturers strongly recommend that starting, warming up, and
shutting down be done with a clean, contaminant-free, light
distillate fuel. Once the engine has been warmed up and stabilized, the residual/crude oil can then be introduced into the
fuel system.

Emulsifiers
Emulsifiers are units that produce a controlled, stable, waterin-fuel emulsion of residucd fuel. Emulsifiers can be homogenizers with the addition of potable water. The IMO has considered water-in-fuel emulsions as the most cost-effective
method to reduce NOx exhaust emissions for existing marine
diesel engines. If marine diesel NOx reductions ever mandate
the control of NOx on existing ships, water emulsion retrofits
will be the primary technology utilized.
Waste Heat Economizers
As diesel engines become more efficient and slower ship
speeds result in reduced diesel engine loads, the heavily
cracked fuels are not completely burned out in the diesel engines. The residue of unbumed cylinder lube oil added to the
organic fuel residue causes the waste heat economizer to experience a greater rate of tube fouling, soot fires, and major
economizer (iron or hydrogen) fires. Since the mid 1980s, the
incidence of economizer fires has steadily increased. The homogenizer Ccm minimize the unbumed residual fuel residues
and, if potable water is added to produce water in fuel emulsions, the economizer can be maintained in a cleaner condition. Chemical additives used in the residucd fuel can also
benefit the cleanliness of the economizer.
As a minimal precaution, waste heat boilers should instcJl
cind monitor the economizer exit temperature and the pressure drop across the unit to warn the engineers about an impending fire.

GAS TURBINE FUEL SYSTEM


Gas turbine engines can operate on gaseous and liquid fuels,
including limited residual fuels and crude oils. Since these

Tankage
The fuel treatment system actually begins with the fuel tamks,
since the initial settlement for free water and solids occurs in
storage. Gas turbine fuel tanks should be fitted with floating
suctions and fill line diffusers. The floating suctions draw the
cleanest fuel from the top of the tank continuously, allowing
more time for the settlement of contaminants in the mid and
lower regions of the tanks. A fill line diffuser reduces the velocity of the fuel and redirects it during tank filling to prevent
reentrainment of tank bottom settlement. Also, it all but eliminates currents in the tank that hinder settling.
Since metallic contamincmts are to be minimized, coating
the inside tank surfaces with an inert, non-metallic coating,
such as an epoxy, is recommended. Under no circumstances
should a zinc type coating be considered.
Fuel Treatment
As with all marine fuel treatment systems, the centrifugal
separator is the foundation and keystone of the system. But,
with gas turbine systems, this separator system becomes
much more comprehensive and complicated [18]. A modem
residual fuel or crude oil burning gas turbine usually requires
two stages of water washing, centrifuging at reduced flow
rates, the use of demulsifying chemical additives, and the use
of metallic neutralizing fuel additives (see Fig. 14). Demulsifying chemicals reduce the tendency of residual fuels to readily emulsify with water. Since these emulsions are difficult to
break in the sepjirator, the use of a demulsifier is recommended to prevent a problem during water washing of the
gas turbine fuel.
Figure 14 shows a typical two-stage water washing gas turbine system using a demulsifying additive. The staged water

166 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK


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washing system is used to reduce the sodium level to below


one part-per-million. The system operates by use of a metering pump that adds a demulsifying additive to the untreated
residual fuel. The in-line heater set increases the fuel temperature up to 97-99C. The demulsifier and heated residual
fuel are thoroughly mixed with 98C recycled wash water in
the first mixing tank before flowing to the first centrifugal
separator. Five to ten percent clean water wash water at 98F
is then metered into the discharge of the first centrifuge and
mixed in the second mixing tank. The residual and water
mixture then flow to the .second centrifugal separator for final water and solids removal.
To maintain an effective gas turbine treatment system, all
treated fuel must pass through a monitor that reads the water content in the residual fuel after the second separator.
The separators must also remove solid contaminants such
as catalyst particles, sand, rust, and debris from the fuel to
prevent damage and wear to the gas turbine fuel nozzles. Additionally, these aggressive solids can cause severe erosion to
the turbine blades and turbine nozzles.
The final step in the gas turbine fuel treatment process is to
inhibit/neutralize the vanadium and nickel with a chemical
additive. These additives are metered into the clean fuel
stream just prior to gas turbine usage. Oil soluble additives,
which are the easiest to use, are cost effective for vanadium
and nickel levels below 150 PPM.
Above 150 PPM, additive cost dictates more economical
water soluble or oil dispersable magnesium additives as an
alternative. These alternative additives have low operating
costs but higher capital costs.
(0
Heater sets for gas turbine residual fuels should be low
a
density designs to prevent heater deposits and to prevent
destabilizing of any additives used with these fuels.
Gas turbine treatment systems require filtration to remove
(5
all solids above five microns. This level of filtration of residual fuel requires a specialized filtration medium that is an all
organic, depth type, system. This is critical since gas turbines
have a lower tolerance than diesel systems for solid contaminants.
Lastly, a final filter, not necessarily a five micron unit,
should protect the gas turbine from any piping or system related debris.
In addition to using a clean distillate for starting and stopping the gas turbine engine, a fast acting bypass system
should be installed to allow the distillate to purge out the
residual fuel from the gas turbine's lines in case of an emergency shutdown, stall, or trip. If residual fuel solidifies in the
piping of the gas turbine, the engine will require disassembly
prior to restart.

I
I
2

CONSTRUCTION MATERIALS
In a typical gas turbine treatment system, iron-based materials, steel, and stainless steel are all valid material choices. It
is important that no copper, copper alloys, zinc or any of its
alloys (such as galvanized) be allowed to come into direct
contact with the fuel. Copper and zinc alloys or coating must
never be used in tubes or coils within heaters nor in any coating or cladding for fuel storage tanks. It is essential to avoid
the use of any galvanized piping or tank plating, as well as the

CHAPTER

6: INTRODUCTION

popular zinc-rich tank coatings. The preferred tank coating


would be an epoxy type coating.

TO MARINE

D396
D2880
(also see D 4418)

PETROLEUM

FUELS

167

Fuel Oils (Steam Plant Spec)


Gas Turbine Fuel Oils (G.T. Spec.)

Conclusions
The supply of marine residual fuels will experience pressure
from three eireas. Refineries will receive heavier crude oils,
which will result in higher density, higher carbon content
marine residual fuels. Then as refineries upgrade, there is
more pressure to increase the intensity of cracking that will
result in fuels with more ignition problems and higher carb o n contents. Lastly, the shore side (and to a lesser extent
marine) environmental regulations will require cleaner burning fuels with less sulfur and less aromatics. This will divert
more difficult, heavier fuels into the marine market. The net
result will be that more difficult fuels will increase in the marine market.
Then, from the engine manufacturers, come new diesel engines with higher Brake Mean Effective Pressure (BMEP),
higher fuel injection pressures, that are more demanding of
ignition quality and are more sensitive to fuel contaminants.
The combustion of the residual fuel supply quality and the
trend in m o d e m diesel engine design will demand larger,
more efficient fuel treatment equipment to be assembled into
more comprehensive fuel treatment systems to preclude operating problems and schedule interruptions. Older diesel
ships should upgrade fuel treatment systems to prevent problems caused when older fuel treatment equipment/systems
try to cope with m o d e m cracked fuels.
As gas turbine engines continue to grow in the military marine and in cruise ships, their fuel treatment systems must
maintain the highest fuel quality and least contamination of
any marine engine. Since gas turbine engines use only 100%
distillate fuels, the problems are initially easier, but one load
of contaminated fuel can cause severe hot corrosion damage,
so continued vigilance is needed to prevent fuel related problems.

ASTM STANDARDS
No.
D 445
D 1298
D 613 for Distillates
D 4868
D 93
D
D
D
D

97
482
95
4176

D 4294

D 524
D 2069-98

Title
Kinematic Viscosity of Transparent &
Opaque Liquids
Density by Hydrometer
Cetane N u m b e r of Diesel Fuels
Estimation of Net and Gross Heat of
Combustion of Petroleum Fuels
Flash Point by Pensky-Martens Closed
Cup
Pour Point of Petroleum Products
Ash from Petroleum Products
Water by Distillation
Free Water and Particulate Contamination in Distillate Fuels
Sulfur in Petroleum Products by Energy-Dispersive X-ray Fluorescence
Spectroscopy
Carbon Residue, Conradson,
of Petroleum Fuels
Marine Fuel Specifications

OTHER STANDARDS
ISO
ISO 8217, Annex B for Residuals: Calculated Carbon Aromaticity Index Calculation
ISO10478, Cat Fines: Digestion & Analysis of Catalyst Particles
ISO 10307-2, Compatibility: Total Sediment Potential of
Petroleum Fuels
ISO 14597,Vanadium and Nickel: Determination of Vanadium and Nickel in Liquid Fuels^Wavelength Dispersive
X-Ray Fluorescence Spectrometry
ISO 10478, Sodium: Sodium Content of Petroleum Fuels
ISO 3735, Storage Oxidation: Storage Oxidation of
Petroleum Fuels
ISO 3735/10307-1, Sediment: Total Sediment Existent of
Petroleum Fuels
ISO 8217, Petroleum ProductsFuels (Class F): Specifications of Marine Fuels
Military F u e l Specifications
MIL-F-16844: All Purpose Marine Distillate Fuel

REFERENCES
[1] Winkler, M. F., Residual Fuel Oil User's Guidebook, Volume 4,
Diesels; and Volume 3, Gas Turbines; Southwest Research Institute for Electric Power Research Institute, May 1988. EPRIAP-5826.
[2] Leigh-Jones, C, A Practical Guide to Marine Fuel Oil Handling,
The Institute of Marine Engineers, London, 1998.
[3] Winkler, M. F., The Influence of Fuel Quality on the Performance,
Operation, and Maintenance of Diesel Propulsion Engines, Maritime Administration, U.S. Dept. of Commerce, March 1979.
[4] Winkler, M. F., Relationship of Fuel Quality to Marine Boilers and
Diesel Engine Performance, The Society for Marine Port Engineers, NY, January 1978.
[5] Barnes, G. K., Liddy, J. P., and Marshall, E. G., "The Ignition
Quality of Residual Fuels," CIMAC Paper 25, International
Council of Combustion Engines, 1 Birdcage Walk, Westminster,
London SW1H911, UK, June 1987.
[6] The Flammability Hazards Associated with the Handling, Storage
and Carriage of Residual Fuel Oil, Oil Companies International
Marine Forum (OCIMF), 27 Queen Anne's Gate, London,
SWIH, 9BU, December 1989.
[7] Winkler, M. F., "Coping with Today's FuelsDistillate and
ResidualDiesel and Steam," Society of Naval Architects and
Marine Engineers, Jersey City, NJ. Presented at the SNAME
Chesapeake Marine Engineering Symposium, Washington,
D.C., January 1984; Society of Marine Port Engineers, NY,
March 1982; National Maritime Show, Baltimore, March 1982.
[8] Winkler, M. F., "Fuel Management: Coping With Future Fuels,"
Marine Engineering/Log Magazine, March 1983.
[9] Newbery, P. J., Davies, T. A. C, and Chomske, K. M., "Heavier
Residual Fuels for Marine Diesel Engines," MotorShip Magazine,
West Sussex RH16 3DH, UK. Presented at the 6th International
Motorship Conference, London, March 1984.

168 MANUAL 3 7: FUELS AND LUBRICANTS HANDBOOK


[10] Winkler, M. F., Systems Design for Future Fuels-Steam and
Diesel, Society of Marine Port Engineers, Avenel, NJ, 1983.
[11] Winkler, M. F., "Operational Problems and Marine Fuel Oils,"
Presented at the International Conference and Long-Term Storage Stabilities, San Antonio, TX, Jixly 1986; Society of Automotive Engineers Conference, Washington, D.C., May 1986.
[12] Winkler, M. F., "Shipboard Fuel Handling and Treatment For
Diesel Engines," presented at the ASTM International SjTnposium on Marine Fuels, Miami, FL, December, 1983; Society of
Maritime Arbitrators, NY, October 1983; Fort Schuyler Forum
sponsored by Society of Marine Port Engineers, NY, March 1981.
[13] Fisher, C. and Lux, J., BUNKERS: An Analysis of the Practical.
Technical and Legal Issues, Second Edition, 1994, Lloyd's of London Press, NY, 1994.

[14] Winkler, M. F., "Diesel Fuel Systems to Prevent Operational


Problems," presented at the S.A.E. Marine Propulsion Technology Conference, 14 May 1986, Washington, D.C.
[15] ISO 8216-0: Petroleum Products - Fuels (Class F) - Classification
- Part 0: General, International Organization for Standardization, Geneva, Switzerland, 1986.
[16] Winkler, M. F., "Management of Gas Turbine Fuel Systems,"
Gas Turbine International Magazine, March-April 1977.
[17] Winkler, M. F., "Management of Residual Fuel Systems for Gas
Turbines," Gas Turbine International Magazine, May-June 1977.
[18] Winkler, M. F., "Management of the Gas Turbine Fuel Systems,"
ASTM International, October 1973; Society of Automotive Engineers, Canada, August 1971; Society of Automotive Engineers,
Philadelphia, November 1970.

Section III: Hydrocarbons and Synthetic Lubricants:


Properties and Performance
Rajesh J. Shah, Section Editor

MNL37-EB/Jun. 2003

Hydrocarbon Base Oil


Chemistry
Arthur J. Stipanovic^

chemistry:
provide a brief overview of the base oil market and identify
emerging trends,
outline the refinery processing scenzirios typical of current
base oil production in the United States,
review the chromatographic and spectroscopic techniques
most commonly used to characterize base oil composition,
provide a com