NASA Technical Memorandum 79231

JET FUEL THERMAL STABILITY

William F. Taylor, Editor

Exxon Research and Engineering Company
Linden, New Jersey

A Workshop held at
Lewis Research Center
Cleveland, Ohio
November 1-2, 1978

1979
 FOREWORD

As the fuel availability problem becomes more acute,

additional attention is being focused on broadened-specifi-
cation and nonpetroleum-derived turbine fuels. These fuels,
with a higher aromatic and heterocompound content, have a
greater potential for forming deposits at elevated tempera-
tures than current fuels. Due to higher compression ratios
and staged fuel injection, newer engines will be operating
with higher fuel temperatures and longer residence times to
further complicate the problem.
In order to present a forum for discussion of the
various aspects of the thermal stability problem and to
identify critical areas for future research, the Lewis
Research Center sponsored the Jet Fuel Thermal Stability
Workshop. Dr. William F. Taylor of Exxon Research and
Engineering Company was the workshop chairman.
This report, edited by Dr. Taylor, presents the conclu-
sions and recommendations of each of four working groups.
In addition, the figures from a number of presentations made
during the introductory session are included, giving a synop-
sis of much of the work presently being conducted in this
field.

Stephen M. Cohen
Workshop Organizer

iii
 CONTENTS
Page
INTRODUCTION . . . 1
PROBLEM STATEMENT. 4
SUMMARY OF WORKING GROUP CONCLUSIONS AND RECOMMENDATIONS 6

BASIC RESEARCH . . . . . . . . . . . . 7

LABORATORY CHARACTERIZATION TECHNIQUES 7

APPLIED RESEARCH AND TEST SIMULATORS . 8

ENGINE SYSTEM TRENDS AND REQUIREMENTS. .. . 9

APPENDIXES
A - FIGURES FROM INTRODUCTORY SESSION 19
INTRODUCTORY REMARKS: CHANGES AND THEIR CHALLENGES -
William F. Taylor. . . . . . . . . . . . . . . 21
NASA JET FUEL THERMAL STABILITY ACTIVITIES -
Gregory M. Reck . . . . . . . . . . . . . . . . 31
AIR FORCE AVIATION TURBINE FUEL THERMAL OXIDATION
STABILITY R&D - Charles R. Martel. . . . . 41
SOME CHEMICAL ASPECTS OF DEPOSIT FORMATION -
Robert N. Hazlett . . . . . . . . . . . . . . . 53
REFINING JET FUEL FOR THERMAL STABILITY -
William G. Dukek. . . . . . . . . . . . . . . . . 79
FUEL THERMAL STABILITY/ENGINE TRENDS - Allyn R. Marsh 87
THERMAL STABILITY ACTIVITIES - Maurice Shayeson 99
THERMAL STABILITY EFFORTS - A. E. Peat. . . 109
AIRLINE STATUS REPORT - Walter D. Sherwood. 117
B - ADVANCE QUESTIONS . . 121
C - WORKING GROUP REPORTS 129
D - WORKSHOP PARTICIPANTS 151

v
 JET FUEL THERMAL 5T ABILITY

INTRODUCTION

The Jet Fuel Thermal Stability Workshop was conceived and

sponsored by the NASA Lewis Research Center as a means to bring together
various workers involved in the different phases of the aircraft turbine
fuel stability problem so as to share their results, conclusions and
plans and to interchange ideas for the planning of future work.
This report summarizes the findings and conclusions of the
workshop. Thirty eight participants met for two days. Included were
representatives from universities; various segments of industry including
petroleum refining, engine and airframe manufacturing, and airline
transportation; and a number of branches of government including the
Air Force, Navy and Department of Energy. A number of NASA personnel
were in attendance as working group coordinators and observers.
Participants are listed in Appendix D.
The workshop started with a plenary session during the first
morning. Welcoming remarks were made by W. L. Stewart, Director of
Aeronautics. The following presentations were then made:
1. Introductory Remarks: Changes and Their Challenges
William F. Taylor - Exxon Research and Engineering Company
2. NASA Jet Fuel Thermal Stability Activities
Gregory M. Reck - NASA Lewis Research Center
3. Air Force Aviation Turbine Fuel Thermal Oxidation Stability R&D
Charles R. Martel - Air Force Aeropropulsion Laboratory
4. Some Chemical Aspects of Deposit Formation
Robert N. Hazl ett - Naval Research Laboratory
5. Refining Jet Fuel for Thermal Stabil ity
William G. Dukek - Exxon Research and Enginering Company
6. Fuel Thermal Stability/Engine Trends
Allyn R. Marsh - Pratt & Whitney Aircraft Group
 7. Thermal Stability Activities
Maurice W. Shayeson - General Electric Company
8. Thermal Stability Efforts
A. E. Peat - Rolls-Royce Limited
9. Airline Status Report
Walter D. Sherwood - Trans World Airlines
The visual aid material which was employed in these presentations is
attached in Appendix A.
After the plenary session, the participants were organized
into four working groups as follows:
I. Basic Research
Chairman: Robert N. Hazlett - Naval Research Laboratory
II. Laboratory Characterization Techniques
Chairman: Charles R. Martel - Air Force Aeropropulsion Laboratory
III. Applied Research and Test Simulators
Chairman: Royce Bradley - Air Force Aeropropu1sion Laboratory
IV. Engine System Trends and Requirements
Chairman: lolalter D. Sherwood - Trans World Air1 ines
Working group participants first addressed the question as to
what is the present state-of-the-art for their respective topics and
proceeded from there to identify future trends and needs. To aid in
focusing working group discussions, some representative questions were
provided to members of each of the working groups prior to the meeting.
These questions are shown in Appendix B. In addition, to aid in the
state-of-the-art review, preliminary copies of the Coordinating Research
Council's "CRC Literature Survey on the Thermal Oxidative Stabil tty of
Jet Fuel" were made available to workshop participants. This report was
in preparation at the time and will be released when the study is completed.
Brief reports were prepared by each working group, and these
reports were presented to all attendees for discussion at the final
session of the workshop by the Working Group chairmen. The written
2
report of individual working groups' conclusions and recommendations
are attached as Appendix C. In addition, the proceedings of this
final session were recorded on tape and subsequently transcribed.
This transcription of the summary session was particularly useful
to the editor in preparing this workshop report.

3
 PROBLEH STATEHENT

As the U.S. and world's supply of recoverable petroleum is

exhausted. major changes will undoubtedly take place which will impact
in some, but yet undefined. way on the sources. refining methods.
properties and use of jet fuel. In June 1977. NASA sponsored a workshop
on "Jet Aircraft Hydrocarbon Fuels Technology" to discuss the implication
of such changes for aircraft turbine fuels. Focusing on the 1990 to
2000 time period. it was felt that petroleum crudes would still furnish
most of hydrocarbon fuel liquids. with a small but growing contribution
from synthetics such as shale oil and coal liquids. It was felt that
in addition to keen competition for petroleum per se there would also
be sharp competition for the distillate fraction currently used for
jet fuel production. This latter competition would probably be caused
both by increased jet fuel use itself and by competition from other
distillate uses such as for diesel fuel and petrochemical feedstocks.
Thus, the high quality petroleum distillates used to make current
specification jet fuels may not be readily available. Synthetics and/or
heavier petroleum fractions can be used to manufacture current specification
jet fuels but will probably require substantial boiling range conversion
and hydrogenation, both of which will increase cost and energy consumption
during fuel manufacture. This serious future situation indicates a need
for all concerned parties to begin now to reexamine the tradeoffs between
fuel composition and specifications and engine and aircraft design in
order to try to determine if a more optimum combination exists for future
a i rcra ft.

4
 One major problem area which must be addressed in order to use
either broadened-specification petroleum derived fuels or fuels composed
of, or containing, synthetic derived stocks is the question of fuel
stability. Fuel stability broadly refers to deleterious fuel-derived
sediments and/or deposits which form via chemical reactions either during
prolonged storage at ambient conditions (generally referred to as fuel
storage stability) or from exposure to higher temperatures while the fuel
is being delivered from on-board storage to the combustion section of
the engine (generally referred to as fuel thermal stability). The
question of fuel stability is complex and depends not only on the chemical
nature of the fuel but also on the environment to which the fuel is
exposed.

5
 SUMMARY OF WORKING GROUP
CONCLUSIONS AND RECOMMENDATIONS

Significant additional research and development is needed to

aid in coping with the fuel stabil ity probl ems which would be associated
with the potentially poorer qual ity fuel s of the future such as broadened-
specification petroleum derived fuels or fuels produced either wholly or in
part from synthetic sources. This problem could well be aggravated by poten-
tial trends in engine design leading to more severe thermal stress on the
fuel in the future. Although much is known about the thermal oxidative
stability of current specification petroleum derived fuels, our present
state of knowledge does not suggest easy solutions to this problem nor
does it allow detailed predictions to be made about the effect on stability
of future fuel related changes. Thus, the broad objective of research and
development activities should be to expand our current knowledge with the
aim of establishing a fuel stability technology base which can be used in
the future, for example, to identify feasible ways to ensure adequate fuel
stability and to help in the design of engines and airframe components
from the stability viewpoint. Ideally such a technology base could also
make an important contribution to an overall future jet fuel composition
and use optimization. Some important considerations relative to this
overall problem include (1) fuel availability, (2) total fuel related
costs of the SystffO, (3) overall system energy consumption, (4) engine
performance and durability, and (5) environmental considerations including
the influence of low emission combustion designs on fuel stability
requirements.

,,
i.

Iif, 6

lj
I,I"
 BASIC RESEARCH

The detailed recommendations of the Basic Research Working

Group are shown in Table 1. Basic research has an obvious major role to
play. Extensive fundamental studies of a number of areas critical to
dealing with the fuel stability problem need to be carried out. Some
major areas where fundamental work should be focused include:
Studies to determine if non-free radical reactions are
important in deposit formation.
Additional chemical and physical characterization of
deposits and their dependence on fuel type and
environmental factors such as solvent and metal surface
effects. In addition, deposits should be characterized
to see if they change in character with time and depth.
Studies to elucidate fuel compositional effects such
as those related to boiling range and heteroatom
content.
Further explore and investigate additive effects for
a number of additive approaches including "peroxide
decomposers", antioxidants and dispersants. Additive
interactions should also be studied.
Further investigate metal surface and dissolved metal
effects.
Studies to investigate storage and aging effects as
the fuel passes from the refinery to the aircraft
including the role of intermediate hydroperoxides.

LABORATORY CHARACTERIZATION TECHNIQUES

The detailed recommendations of the Laboratory Characterization
Techniques Working Group (Group II) are shown in Table 2. The group
concluded that the primary function of laboratory test techniques should
be to measure and/or rank the stability of various fuels. They considered
and rejected the need for drastically new laboratory techniques to measure
the thermal oxidative stabil ity of modified specification and/or synthetic
derived jet fuels. Further improvements in existing test methods are

7
 needed, however. The existing techniques were reviewed and analyzed in
detail and a number of specific recommendations made for further work to
improve these techni ques. Concern was also shown for important related
problems such as sampling and it was recommended that standard techniques
be developed to reduce data variability from this source. Similar concern
was shown for the difficult problem of relating small scale laboratory
test devices to actual use problem areas such as engine fuel nozzle plugging.

APPLIED RESEARCH AND TEST SIMULATORS

The detailed recommendations of the Applied Research and Test
Simulator Working Group (Working Group III) are shown in Table 3. The
group recommended two types of approaches be used for fuel system simulator
studies of jet fuel stability. The first approach involves parametric
studies in a general design type of simulator whose objective would be
to provide parametric design data under near real world conditions. Such
data could be used to predict fuel performance in a variety of aircraft
systems. The second approach would involve systematic studies in a
complex simulator constructed to reflect the specific conditions in a
single, given aircraft system. Parametric simulator studies will be
I particularly useful in bridging the gap between small scale laboratory

I" test devi ce results and performance in actual fuel systems. They will
also provide a predictive design variable data base for aircraft fuel

I/l
~,'
..

~,;".,j.
It
'1
.1.,'
system designers analogous to those routinely developed in the chemical
and petroleum industry via pilot plant process variables studies whose
results are used to establish commercial production unit process designs.
!l-~
~1
11
1
,jlJ

8
I,:,.

I
Traditional, specifically designed simulators would be used to demonstrate
individual aircraft fuel system designs and to study specific flight param-
eters in more detail where needed.

ENGINE SYSTEM TRENDS AND REQUIREMENTS

The detailed recommendations of the Engine System Trends and
Requirements Working Group (Group IV) are shown in Table 4. The group
concluded (1) thermal stability is a problem today and (2) trends in
engine design are potentially toward a more severe environment for the
fuel. Thus, they emphasized the importance of having fuels available in
the future with good thermal oxidative stability. In this regard. they
expressed a need for balance between concerns for aircraft emission
controls. energy efficiency. engine durability, and fuel cost. Shorter
term they recommended that the question of fuel thermal stability changes
from the refinery to the actual airport delivery point be investigated.

9
 TABLE 1
BASIC RESEARCH RECOMMENDATIONS

A. Deposits
1. Employ modern surface analysis techniques: ESCA, Auger,
Pyrolysis GC, ESR, CIDNIP and study deposit vs. depth
especially for actual engine parts but also JFTOT and
other test devices.
2. Check deposit chemistry and morphology for possible
changes with time due to temperature on the hot surface.
3. Compare filterable deposits and varnishes.
4. Investigate solubility effects on deposits - include
effects of fluid temperature, fluid and deposit
chemistry, and flow rate.
5. Study deposit morphology and chemistry as a function
of parameters: temperature, pressure, oxygen
concentration, aging and composition of fuel.
6. Employ photo-acoustic spectroscopy and/or attenuated
multiple reflectance IR to analyze gum and especially
solid thermal deposits.
7. Employ radioactive tagging of contaminants.
B. Metals
1. Compare 3 possible metal effects
Dissolved metals
vs. Metal surface
vs. Non-metal surface
Look for stoichiometric metai involvement by
analysis of deposits.
2. Investigate metal effects with and without 02 and peroxides.
3. Check the effects of nitrogen compounds on copper pickup
(especially in light of synfuels).
C. Storage and Aging
1. r10nitor thermal stability from refinery through supply system.
2. Aerobic aging - check peroxides and electron spin - initial
and with time.
3. Anaerobic aging - do peroxides account for all the aging.
10
 TABLE 1 (contluded)
D. Reactions
1. Test fuel and deposits with ESR and CIDNIP for free radical
reactions.
2. Follow disulfide decomposition with ESR.
3. Follow fouling reaction mechanisms/precursors in liquid phase
employing field ionization mass spectrometry and other
techniques.
4. Analyze oxygen concentrations in liquid and vapor pha~e in
storage and aircraft tanks and as a function of time through
flight conditions.
5. Examine effects of prevaporized/premixed fuel on deposition.
6. Explore MW in dispersions and in adherent deposits by light
scattering/Tyndall effect and/or gel permeation chromatography.
7. Test effect of bifunctional N, O. and S materials.
8. Study variations of thermal stability with boiling range of real
fuel s.
9. Analyze fuels for trace components and their effects on fouling,
using "specific detector" gas chromatography.
E. Additives
1. Investigate "peroxide decomposers" for controll ing deposition
(as used in the polymer industry. such as:
Ni diacetylacetonate
and non-metallic equivalents)
2. Explore antioxidant and dispersant thermal stability effects
in a variety of fuels.
3. Study inhibitor interactions in storage and fouling.
F. Miscellaneous
1. Investigate effects and mechanisms of various treatments -
clay, H2, separations - on thermal oxidation stability and
composition of fuels.
2. Examine deposition as a function of reaction mechanism or
deposition mechanism.

11
 TABLE 2
LABORATORY CHARACTERIZATION TECHNIQUES RESEARCH RECOMMENDATIONS

1. Existing Laboratory Technigues

A. Jet Fuel Thermal Oxidation Tester (JFToT)
a. Examine actual aircraft and engine fuel systems and determine
the actual temperatures, pressures, flow rates, etc. of the engine fuel nozzlE
that are experiencing plugging problems. Use these data to select more
realistic JFTOT test conditions (pressure, temperature, residence times,
prefiltration, etc.).
b. 'Recommend that ASTM be asked to re-examine the need for and
degree of in-line fuel prefiltration for the JFTOT.
c. Research is needed to identify and develop improved tube
deposit rating techniques that correlate with fuel heat exchanger fouling
and nozzle plugging.
d. Reference fuels such as pure hydrocarbons and concentrates
containing reactive species should be investigated for use as calibration
fl uids.
e. Temperature control of the JFTOT test (Dutch weave metal)
filter should be investigated.
B. ASm-CRC Fuel Coker
Reference fuels are needed so that instrument performance could
be checked peri odi ca 11y.
Information is needed as to the actual effects of trace elements
in the fuel on thermal stability, as trace elements are believed to promote
deposition. If this is of concern, the sample size and length of test
required may need to be increased in order to obtain useful data when the
trace elements are present in parts per billion quantities.
C. Research Fuel Coker
This instrumerilis a higher temperature vedion of the ASTM-CRC
Fuel Coker. The test filter is the same for both units and the preheater
tube is of stainless steel for the Research Fuel Coker. The users have
not reported any operational probl ems. Al so see JFTOT and ASTM-CRC Fuel
Coker discussions above.
D. Monirex Fouling Honitor
Research needs include further evaluation of the hot wire
method, and the differential fouling test method. Development of a
'I
H
reference fuel for better device precision and inter-device correlation
would advance the state of the art.
i1

I
.]
12
 TABLE 2 (continued)
E. Thermal Fouling Tester (TFT)
With the design of a new test section and an operating technique
specifically tailored to discriminate and rank jet fuels, this device
could possible equal or perhaps surpass the present JFTOT technique. In
this technique, rating of a fuel sample would be strictly based on heat
transfer characteristics of the deposits generated and expressed as a
maximum delta T attained. Such a rating system would be highly desirable
as it excludes the operator from having to make a rating judgment as is
now the case with the JFTOT visual method.
F. Thornton Flask Test
The method provides (1) a portable and easily conducted procedure
for field measurements, (2) field samples may be taken directly into the
test unit, thereby reducing sample container/shipping problems, and (3) the
procedure provides a measurement in 1 1/2 to 2 hours.
Further development is needed to (1) improve the repeatability
and (2) provide correlation with specification techniques.
G. Oxygen Uptake Measurements
Measuring oxygen uptake alone in a typical jet fuel under we11-
controlled temperature conditions is relatively simple but it would be
necessary to also measure oxygen products or sludge for a meaningful test.
The technique does not lend itself to quality control as does a rig such
as the JFTOT but is more useful for research studies into oxidation mechanism
and system variables.
H. Thermal PreCipitation
The thermal precipitation test is a specification requirement for
MIL-T-382l9 Grade JP-7 fuel. It is useful for fuels where cyclic heating
and cooling in the system may leave deposits which affect engine components.
The thermal precipitation test is similar in principal to the
Thornton Flask test described above.
II. Related Problems
A. Sample Containers
The results of poor sampling techniques and their effect on the
thermal stability test results have been documented both in these sessions
and in other technical meetings. It is this group's recommendation that
both sampling and sample containers be seriously considered in order to
maintain the validity and precision of the various thermal stability test
methods. Areas to be considered would include: (1) Sampling location and
method of drawing samples. (2) Types of sample containers and how the
containers would be used in sampling. If using epoxy-coated containers,
should the type of epoxy be specified and should the epoxy coating undergo
a fuel exposure period before using. If unlined sample containers are
to be used, how should they be treated or rinsed with fuel prior to
sampling. Also, sample container seals must also be considered.
13
 TABLE 2 (concluded)

This work will be valuable for other fuel tests where sampl ing is
important.

B. Peroxide Formation Test for Thermal Stabil ity of Jet Fuel

, Peroxide formation has not been widely applied to jet fuel thermal
stability testing and further investigations are required. The relative
importance of peroxides and fuel components to final deposits has not
been established and it is likely that this will vary markedly among
various fuels. Peroxide formation is suitable for research studies of
thermal stab'ility and probl ems with specific fuel s but is not recommended
for general thermals'tability:testing of all jet fuels.

14
 TABLE 3
APPLIED RESEARCH AND TEST SIMULATORS RECOMMENDATIONS

The need for a complete parametric study that will provide data
under a variety of steady-state conditions is evident. The study would
use a device consisting of an instrumented tube capable of being exposed
to the entire range of engine conditions and designed to give quantitative
data on the rate of formation and characteristics of fuel degradation products,
particularly deposits formed under these conditions. The results from
this effort could then be used by the designer to predict the performance
of fuel in an aircraft, the results could also be used to evaluate small-
scale test devices. The priority of the parameters to be included in a
program of this type differ depending on whether emphasis ;s in the
area of design or fuel studies. A list of these parameters and the
order of importance to the two areas are:

Parameter Design Fuel

Wall temperature 1
Inlet temperature 2 2
Velocity (Reynolds Number) 3 3
Residence time 4 4
Pressure 5
Surface/Volume Ratio 6
Naterials 7
Surface Finish 8
Cleaning 9
Dissolved Oxygen 10
Fuel type 5
Contamination 6
Additives 7
During parametric testing, the heat flux used in preconditioning the fuel
must be minimized to avoid unrealistic fuel deterioration in the precondi-
tioner. It is not yet known whether simulator testing can be accelerated.
The results of these parametric tests should indicate the possibility of
accelerating future tests both on this test device and on small-scale devices.
It is noted that by sufficiently reducing the pressure and/or increasing the
temperature in the test device the effects of two-phase flow and supercritical
conditions on thermal stability can be investigated. The fuel type can be
varied to include fuels from alternative sources in addition to currently
produced fuels.

15
 TABLE 3 (concluded)

It must be realized that the results of the parametric program

won't answer all questions regarding fuel performance in an aircraft engine;
e.g. steady-state results may not be additive in a dynamic system. However,
the parametric program should provide the best source of predictive data
for design purposes. Final confirmation may require a test program using
aircraft engine hardware for each specific aircraft of concern.
'!J.

" r;t 1'5 recOgniZ,e:d that the design of supersonic aircraft fuel
systems will requireaf\.iel tank ,simulator (akin to. that described above)
in wh; ch fl ightparameters "and th.e; r effect on thermal /oxidaUve stabil tty
~an be systematitallY' s~udi:ed.. Clearly the g.eometry will diff.r from the
eng; ne' s imul ator',aswill ,the seltectiori and range, of vari abJ .es. The
device shodi~d iri!~~~pora'!te'rtie~riS of studying th,e effects of tank insulation,
; nerti'ngand cl eahing teic'hrhqO!es:, .. Hi s further. recogni ;zed that the
engine' a~d '!aire~lii'ft 't1
a1hk'.s1muTatilonswi11 likely be, car~i:ed oUt independently
until such time as a system des'igh iis laid down; attnat point, tnte'grated
systems tests are indlcated.
\

16
 TABLE 4
ENGINE SYSTEM TRENDS AND REQUIREMENTS - RECOMMENDATIONS

1. NASA should sponsor or coordinate a survey of fuel thermal

sta~ility at airports. Precautions on sampling and transporting
samples are mandatory.
2. In view of the concern over fuel thermal stability problems and
in the national interest as well, NASA should determine the
realistically practical limits of aircraft emission control with
full consideration of all fuel property and cost objectives,
energy conservation, engine durability, consumer costs for
transportation and inflationary pressure.
3. It is recommended that the present thermal stability levels be
retained for any proposed fuel specifications in the foreseeable
future as long as it is cost effective.

17
 APPENDIX A

FIGURES FROM INTRODUCTORY SESSION

19
INTRODUCTORY REMARKS: CHANGES AND THEIR CHALLENGES

William F. Taylor
Exxon Research and Engineering Company

21
 CHANGES AND THEIR CHALLENGES

IN THE FUTURE JET FUEL WILL NO LONGER

NECESSARILY BE INEXPENSIVE~ EASILY
AVAILABLE~ AND TIME INVARIANT IN COMPOSIT
AND/OR PROPERTIES.

THESE FUEL CHANGES WILL CREATE CHALLENGES

FOR FUEL PRODUCERS~ ENGINE AND AIRFRAME
MANUFACTURERS AND USERS.

THERf1AL STABILITY WILL BE ONE OF THE

MAJOR PROBLEM AREAS.
 JET F UELI NAT RAN SIT ION PER I 0 D

- EVOL UTI 0 NARY CHAN GES J E. G. P0 0 RER

QUALITY CRUDES

- BROADENED SPECIFICATIONS

- I NT ROD UCT ION 0 F S YNTH ETIC CRUDES J

E. G. S HAL E 0 I L

23
 GROSS CHEMICAL PROCESS IN
LIQUID PHASE DEPOSIT FORMATION

SOLUBLE OXIDATION INSOLUBLE OXIDA!

PARENT FUEL PRODUCTS PRODUCTS i

JET FUEL HYDROCARBON, INITIAL OXIDATION EXTENDED OXI~

1. E.,C5 TO C, 5 PRODUCTS TION PRODUCTS
PARAFFINS, NAPHTHENES
AND AROMATICS O2 SOLUBLE IN JET FUEL O2 INSOLUBLE IN
JET FUEL
TRACE SULFUR AND LOW OXYGEN CONTENT,
NITROGEN CONTAINING
COMPOUNDS
1. E.,8 TO 12 HIGHER OXYGEN
CONTENT, I. E.
INCORPORATION OF 18 TO 25%
LOW LEVELS OF OLEFINS SULFUR AND NITROGEN
INTO PRODUCTS INCORPORATION
OF SULFUR AND
NITROGEN

MOLECULAR WEI
200 TO 600

GROSS PHYSICAL PROCESS IN

LIqUID PHASE DEPOSIT FORMATION

AGGLOMERATION IN LIQUID COLLECTION ON SURFACES FUSION ON SURFACI

AGGLOMERATION OF NICROSPHERICAL PAR- MICROSPHERICAL PART

j'INSOLUBLE" OXIDATION
PRODUCT MOLECULES IN
THE JET FUEL TO
MICROSPHERICAL PAR-
TICLES 500 TO 3,000
ANGSTROM UNITS IN
SIZE (TYPICALLY
1,000 A IN SIZE).
TICLES SETTLE TO
SURFACES FROM LIQUID
OR COLLECT ON SURFACES
AFTER IMPINGEMENT FROM
MOVING FLUID. LOSS
OF VOLATILE FUEL ALSO
CAN LEAVE NON-VOLATILE
PARTICLES ON SURFACES.
ON SURFACE UNDERGOE:
COLLESCENCE AND PLN
FLOW TO FORM VARNISI
LIKE SUBSTRATE UPON!
WHICH ADDITIONAL PAi
TICLES COLLECT. FUI
OXIDATION MAY TAKE I
TO FORM DARK, BRITTI
"COKE" LIKE DEPOSIT!
ENVIRONMENTS SUCH A!
"EMPTY" WING TANKS.

24
 AUTOXIDATIVE PRODUCTS ARE NUMEROUS

(1)
I 11

OOH

20:) -
n

ctJ+05
TIl IV
+ H,O + 1/2 0, (2)

OH
! 0._

ex)
0
10. '00 '00 <00
Tr:.:e: - r.!iItJ.iTES

ure 5. Re~ctant" :>nd liquid product ch:mges during

-->-
0) + H,O (3)
catalyzed oxidation of tetmlin at. 11.5". Other conditions: IV V
11 of tetmlin in 2 rd of chlorobenzene, 0.30 g of catalyst, aud
tm pres.3ure. Y, tetralin conaumed; _, oxygen
"umed (by volumetric change); 0, tetralin
lroperoxide (II) content; J.., ketone (III) content;
.lcohol (IV) content; 0, 1,2..dihycironaphtnalene
ltent; fI, naphthalene content.

0) --->-
0)
::::,.. Af'
+ H, (4)
V VI

SOURCE H. F. TAYLOR J J . PHYS. CHEM. 79

2250 ( 1 970 ) .

25
FUEL STABILITY REGIMES VARY WIDELY

LOW T E MPER AT URE L I QUI D P HAS E

J J

AUTOXIDATIVE REACTIONS

INTERMEDIATE

HIGH TEt1PERATURE VAPOR J PHASE J

PYROLYSIS REACTIONS

26
 ~10RPHOLOGY OF DEPOSITS

77 PPM 0')"-
( AI R
SATURATED)

6.4 PPM 02

0.3 PPM O2

SOURCE: FINAL REPORT "DEVELOPMENT OF HIGH

STABILITY FUEL" CONTRACT N00140-74-C-0618~
JANUARY 1975.
ALL SEM'S AT 10~000 X j SAME PURE COMPOUND JET
FUELj DEPOS IT LEVEL 25-29){G CleM 44 HRS.
27
 -~"-- - ..-.
~~==--~ ~-.,......",.~

FLOW FROM RESEARCH & DEVELOPMENT TO END USE

FUEL THERMAL STABILITY

BEN CH ENG I NE
BAS I C -.- SIMULATIVE
SCALE
~
~ -;:;-
AIRCRAFT
RESEARCH STUDIES c{-

- STUDIES USE
L-- ----- - -- - - L..-

N
co
CHE~~ICALAND PETROLEUM
PROCESS DEVELOPMENT
..- ... ,.

BEN CH LARGE P I LOT

LABORATORY
STU DIE S
- SCALE
-= -
-;;;- PLANTS - COr~MERCIAL

PLANT
STUDIES - -
- DE M0 NST RAT ION
UNIT S
 HORKING GROUPS

BASIC RESEARCH

LABORATORY CHARACTERIZATION
T E CHN I QUE S

I APPLIED RESEARCH AND TEST

SIMULATORS

ENGINE SYSTEf1 TRENDS AND

REQUIREMENTS

29
OBJECTIVES OF FUEL STABILITY WORKSHOP

REVIEW THE STATUS OF THERMAL STABILITY

RESEARCH

DISCUSS CURRENT AND ANTICIPATED FUTURE

PRO B L E f1 S

IDENTIFY RESEARCH NEEDS

30
NASA JET FUEL THERMAL STABILITY ACTIVITIES

Gregory M. Reck
NASA Lewis Research Center

31
,-,', ,"- <C'?,-_ 0, 4- j;t'_'''''"t''-'';W,'''.-, '-::~,:;.'_t; . ::~::~..:_J\;:~::'_~:;;':' ~'-.. _ -"";-r.M:_...<;~_

AEROW\UT ICS
DIRECTORATE
H. STEW\RT

AIRBREATHING
ENGINES DIVISION
R. RUDEY

W
N
FUELS TECHNOLOGY
BRANCI1
J. GMBMN

FUELS COMBUSTION FUELS SYSTEMS PHYSICAL CHEMISTRY

SECTION SECTION SECTION
R. NIEDZvlIECKI G. RECK S. GORDON

-- AIRCRAFT GAS TllRBINE -- AIRCRAFT FUELS SYSTEMS -- COMBUSTION ANALYSIS

COMBUSTORS ~- FUELS SYNTHESIS -- COMPUTATIONAL THERMO~
-- GROUND POWEq COMBUSTORS -- FUELS CHl\R,l\CTERIZATION DYNAMICS AND CHEMICAL
1/_'_.1"-""_' f'n
 ~ '"!f"

FUELS TECHNOLOGY BRANCH

FUEL TI1ERMAL STABILITY ACTIVITIES

OUTSIDE
EXPERIMENTAL STUDY CONTRACT - UNITED TECHNOLOGIES RESEARCH CENTER
GRANT HITH COLORADO SCHOOL OF MI NES - EFFECT OF NITROGEN COMPOUNDS
w
w
ON STABILITY
FUEL DEGRADATI ON STUDY (PLANNED)

IN-HOUSE
THERMAL STABI LITY STUDIES OF DOPED FUELS HI,TH JFTOT
STABILITY STUDY HITH SYSTEM SIMULATOR (PLANNED)
EFFECT OF HYDROPROCESSING SEVERITY ON STABILITY
MECHANISMS OF THERMAL DEGRADATION OF ALTERNATE FUELS (PLANNED)
 EXPERIMENTAL STUDY OF TURBINE FUEL THERMAL
STABILITY IN AN .AIRCRAFT FUEL SYSTEM SIMULATOR
UNITED TECHNOLOGIES RESEARCH CENTER

OBJECTIVES
1. PROV IDE A MEMIS-oF OBSERV ING THE EFFECTS OF FUEL THERMAL STAB III TY
ON THE SIMULATED FLIGHT BEHAVIOR OF ,l\N AIRCRAFT FUEL SYSTEM
2. PROVIDE.~ ~EANS OF .~CCELERATING THE FUEL THERM.A.L BREAKDOWN FOR OBTAINING
PARAMETRIC AND BREAKPOINT INFORMATION
W
-1::0

3. ESTABLISHING CRITERIA FOR THE QUANTITATIVE ASSESSMENT OF FUEL

THERMAL DEGRADATION
APPROACH
TASK I - DESIGN OF APPARATUS
TASK II - CONSTRUCTION OF APPARATUS &EVALUATION OF FUELS
TASK I I I - CALIBR.~TION AND B/\SELINE TESTS
TASK IV - COMPREHENSIVE TESTS OF FUEL THERMAL STABILITY
TASK V - REPORTS &RECORDS
 UTRC - EXPERIMENTAL THERMAL STABILITY STUDY
FUEL SYSTEr1 SIMllLATOR FEATURES:
INCLUDE SUPPLY TMJK PUMP MANIFOLD NOZZLL HEATING SYSTEM" AND DISCHARGE TANK
J J J

SATURATED OR DEOXYGENlHED TEST FUEL

INDEPENDENT HEATING OF FUEL SUPPLY AND MANIFOLD/NOZZLE
NOZZLE SPRAY CH.ARACTERISTICS WILL BE MONITORED

TEST FUELS:
w
U1

1. JET AJ BREAKPOINT TEMPERATURE ~ 2600 C

.I
2. BROAD SPECIFICATION (SIMILAR TO ERBS OR DIESEL
J 2).1 BREAKPOINT TEMPERATURE ~ 240C I
I
PRELIMINARY TEST CONDITIONS:
1. FUEL SUPPLY TEMPER.ATURES - AMB IENT TO IS00C
2. MANIFOLD &NOZZLE HALL TEMPERATURES - 240 TO 400C
3. FUEL FLOH - 10 TO 100 KG/HR
4. DEOXYGENATED AND AIR SATURATED FUEL
 NASA GRANT - COLORADO SCHOOL OF MINES

PRINCIPAL INVESTIG.l\TOR - DR. STEPHEtl DANIEL

OBJECTIVE: DETERMI"NATION OF THE MECHANISM OF INFLUENCE OF

ORGANIC NITROGEN COMPOUNDS ON FUEL INSTABILITY

APPROACH:
w
en

1. ISOLATION AND CHARACTERIZATION OF LEWIS-BASE

CO~PONENTS FROM SYNCRUDES

2. DETERMINATION OF THE EFFECT OF THIS EXTRACT ON THE

STORAGE ST.~BILITY OF PETROLEUM-DERIVED JET A
3. IDENTIFICATION OF INDIVIDUAL FUEL COMPONENTS
UNDERGOING ALTERATION DURING THE AGING PROCESS
4. MODEL SYSTEM STUDIES
 GRANT PROGRESS:
I, ISOLATIO~ &CH~RACTERIZATION OF LEWIS-BASED COMPONENTS FROM SYNCRUDES
LE~/ISBASE EXTRACT HAS BEEN PREPARED FROM SYNC RUnES
GC WITH SELECTIVE NITROGEN DETECTOR (AFID) IS BEING USED FOR CHARACTERIZATION
GC/MS USED FOR DETAILED CHARACTERIZATION

II, STORAGE STABILITY EXPERIMErlTS

~ JET A BASE FUEL HAS BEEN CHARACTERIZED
4CCELERATED AGING TESTS CONDUCTED AT 1210 C
AGING MONITORED BY TWO "GUM" TESTS
DISSOLVED GUf1 - VACUUM EVAPORATION WITH IR HEATING OF FILTERED
SM~PLE

FILTERABLE GUM - HE IGHT OF DEPOS IT ON GLASS COVER SLI P IMMERSED

I~ REACTION VESSEL

OF JET ,~ l~IITH JET A SPIKED IHTH EXTRACT TO 5 PPM NH.AS SHOWN

CO~1P,~RISO~~
INCREASE IN FILTERABLE GUM IN SPIKED SN1PLE
 ,::;r::;=,;:--=~,5,=,-"-'---~ .,,>-_~-_2.:-~;'':':':[~=- .:;';_J:::;'';;~':=':c:r:;':':::;t;;~.iRii'ii'WE5iiSii5S 'f' _~ -'-:~~~""-..;.;:
r
- --~-~---

r,R~NT PROGRESS:

III. ACTIVE COMPONENT IDENTIFICATION

GC AN.~LYSIS OF FILTEREDJ AGED JET A WITH UNAGED JET A SHOWS NO
OBVIOUS QUALITATIVE DIFFERENCES
SeRUIJ13HH,JETA vJITH H2SQ4 SIGNIFIC.lI.NTLY REDUCED FILTERABLE GUM
EV/\UI:f\TI NG THE EFFECT OF .1\ NU,fv1BER OF NITROGEN COMPQUNDS ON .l\G ING
w
(Xl
OF JET AJ SINGLY MID IN COMBINATION VlITH PEROXIDES.

IV. MODEL SYSTEM STUDIES

.AG ING STUD IES ARE BE'ING CONDUCTED HIT II SI~PLE FUEL MODELS - BLENDS
OF VARIOUS CO~PONENTS IN DODECA~IE
COMPONENT CONCENTRATIONS DURING AGING ARE BEING MONITORED
WEEKLY HIGHLIGHTS - DIVISION OF ENVIRONMENTAL SCIENCES - 10/25/79
Oil Shale Environmental
One hundred and twenty gallons of retort water have been collected from
the evaporation pond at Rock Springs Site 12 and have been placed in cold
storage. A detailed analysis is being run on the water, after which it will
be available for distribution to qualified researchers.

HOW YOU CAN SAVE BY

USING A WOOD STOVE
With all the talk about energy saving these days and many
homes putting in wood stoves to supplement their fuel sup-
ply, someone has come up with the following figures to
save on fuel bills. We thought it interesting (and entertain-
ing) and hope you will too!
Stove, pipe, installation, etc ................................. $ 458.00
Chain saw ................................................ 149.00
Gas and maintenance for chain saw ......................... 44.60
4-Wheel drive pickup, stripped .............................. 8379.04
4-Wheel drive pickup, maintenance .......................... 438.00
Replace rear window of pickup (twice) . . . . . . . . . . . . . . . . . . . . . . . . 310.00
Fine.for cutting unmarked tree in state forest .................. 500.00
Fourteen cases Michelob . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126.00
Littering fine .............................................. 50.00
Tow charge from creek. . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 50.00
Doctor's fee for removing splinter from eye. . . . . . . . . . . . . . . . . . . . 45.00
Safety glasses ............................................ 29.50
Emergency room treatment (~roken toes-dropped log) ........ 125.00
Safety shoes ............. "". . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49.50
New living room carpet ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800.00
Paint walls and ceiling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110.00
Worcester chimney brush and rods .......................... 45.00
Log splitter ................... .":C,' . . . . . . . . . . . . . . . . . . . . . . . .. 150.00
Fifteeri acre woodlot ....................................... 9000.00
Taxes on woodlot.......................................... 310.00
Replace coffee table (chopped up and burned
while drunk) . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . 75.00
Divorce Settlement ........................................ 33678.22
Total first year's cost. . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. 54922.81
Savings in "conventional" luel- first year. . . . . . . . . . . . . . . . . . . . . (62.37)
Net costs of first year's woodburning ......................... $54814.44
 INTERAGENCY TRAINING CALENDAR FOR JANUARY 1980 (continued)
COLORADO
Administrative Officers' Seminar $145 Denver Jan 2~31
Management Information Systems 150 Denver Jan 2~31
Advanced EEO Counseling 130 Denver Jan 2~31
Zero-Base Budgeting 100 Denver Jan 30-31

MONTANA
Introduction to Supervision 175 Jan 14-18

NORTH DAKOTA
Advanced Secretarial Techniques i10 Bismarck Jan 14-16

Basic M3nagement Methods and Skills 175 Jan 14-17

Processing Personnel Actions 160 Aberdeen Jan 15... 18

.l!!.@.
Advanced Secretarial Techniques 110 Salt Lake City Jan 7-9
Management Institute 195 Salt Lake City Jan. 7-11
Proofreading with Precision 90 Salt Lake City Jan 8-9
Basic EEO Counseling 130 Salt Lake Ci ty Jan 8-10
*upward Mobility: Planning & Implementation 130 Salt Lake CityI Jan 8-10
Personnel Management for Supervisors
and Managers 180 Salt Lake City Jan 8-11
EEO and the Federal Employee 50 Sal t Lake City Jan 11
Personnel ';\ssessment and Selection 180 Salt Lake City Jan 14-18
A Matter of Style 120 Salt Lake City Jan 15-17
Basic Management FUnctions 175 Salt Lake City Jan 21-25
Basic Position Classification 300 Salt Lake City Jan 21-Feb 1
Writing EnviroIl11ental Assessments
and ~pact Statements 155 Salt Lake City Jan 22-24
Introduction to ADP 145 Salt Lake City Jan" 23-25
Effective Interaction Skills 130 Salt Lake City Jan 2~31

The Rocky Mountain Region, U.S. Office of Personnel Management, has instituted the simplified intergovernment billing
and collection (STBAC) System. This is an automated billing process and will be the vehicle for all billing of
reimbursable training programs offered for Federal agencies by the U.S. Office of Personnel Management in this Region,
except-for Department of Defense agencies. Tt will not be used for State, County and Municipal. billings.

In order to ensure the proper functioning of the STBAC System,. it is essential that agencies exercise particular care
to include on the Optional Form 170 or other training request forms the Document/Purchase Order/Requisition Number
(Block 23 of OF 170) and 8 digit station symbol. (agency location code) (Block 24 of OF 170). If you have any questions,
please contact Sandy Gregory (FTS) 234-2129. (Use this number for billing questions only.)

The U.S. Office of Personnel Management makes every practical effort to assure that its training programs are readily
accessible to handicapped employees. Nominating officials:,should contact the training center in advance of nomination
to discuss any special provisions needed to accommodate a handicapped nominee.
 October 17, 1979
INTERAGENCY TRAINING CALENDAa FOR JANUARY 1980

(Note added and rescheduled courses)

COLORADO
Listening and Memory Improvement $ 90 Denver Jan 7-8
Budget Analysis Techniques 190 Denver Jan 7-11
*Intermediate Skills in Statistics 180 Denver Jan 7-11
Personnel Assessment and Selection (4'll days) 180 Denver Jan 7-11
Technical Writing ,for Engineers
and Scientists 150 Boulder Jan 7-11
Improving Work Methods 135 Denver JanS-l0
Methods of Enviroranental Impact Analysis 150 Denver Jan 8-10
Supervis.ion of Low Skilled Employees 120 Denver Jan 8.. 10
Effective English Workshop, 100 Denver Jan 9-11
Introducti~n to 'the Statistic,al
Package .in theSodal Sciences-SPSS 165 Denver Jan 9-011
Effective English Workshop 100 Denver ,Jan 9011
Introduction t,o, Flowcharting and
, Computer Programming Logic 100 Denver Jan 10-11
Shorthand Refl::esher 100 Denver Begins Jan
Report Writ.ingWorkshop 120 Denver Jan 14-16
Developing Contract Work Statements 190 Denver Jan 14--18
Instructor Training 200 Denver Jan 14-18
Program Evaluadoil Techniques 180 Denver Jan 14-018
Presenting Statist:l.cs USing Charts,
Graphs and,'Tlibles 145 Denver Jan 15-17
Understanding and Mknaging Human Behavior 135 Denver Jan 15-17
JoIanagerial D.:cision Milking
'0 155 Estes Park Jan 15-018
Economic Analysis for Decision JoIaking 150 Denver Jan 16-18
Introduction to ADP 145 Denver Jan 16->18
Team Building,for Organizational
Effectiveness "t, 250 Denver Jan 21.. 24
How to conduct a Hanagement Review 190 Denver Jan 21",25
Better Office Skills and Services 100 Denver Jan 22..,24
COunseling Techniques f9r Supervisors
and JoIanagers ' 130 Denver Jan 22,.,24
Basic Labor Relations 160 Denver Jan ,22",25
Agency Budgeting 150 Denver' Jan 23 .. 25
The Federal Budget Process 100 Denver Jan 28~29
Effective COmmunication Workshop 120 Denver Jan 28 30G

Goverranental Bookkeeping and Accounting

Phase II 175 Denver Jan 28-Feb 1
ROCKY MOUNTAIN REGIONAL TRAINING CENTER
U. S. OFFICE OF PERSONNEL MANAGEMENT, BLDG. 20
DENVER FEDERAL CENTER, DENVER 80225 (303)234-2304
 DOE 2100.1 Attachment
9-25~79 Page 1
c
GLOSSARY OF FINANCIAL TERMS

1. Accrual Basis of Accounting recognizes revenues in ~he period

earned and recognizes cost in the period incurred, regardless
of when payment is received or made.
2. Accrued Cost encompasses the concepts of accrued expenditures
and applied costs, both of which are defined below. It is the
formal recognition of the incurrence of cost when goods and
services are received, produced, consumed, or otherwise applied
to operations, programs,or projects, whether or not cash payment
has been made.
3. Accrued Expenditures. Expenditures accrue regardless of when cash pay-
ments are made; whether invoices have been rendered; or incases of
constructive receipt, whether goods or other tangible property have
been physically received. Accrued expenditures are accounting trans-
actions during a given period that reflect liabilities incurred and
the need to pay for: .
a. Services performed by employees, contractors, other Government
accounts, vendors, carri ers, grantees, 1essors, and other payees;
( b. Goods and other tangible property received; and
c. ,l\mountsbei ng owed under programs for whi ch no current servi ce
or performance is required (such as annuities, insurance claims,
other benefit payments, and some cash grants, but excluding the
repayment of debt, which is considered neither an obligation nor
an expenditure.

4. Applied cost is the value (purchase price) of goods and services

used, consumed, given away, lost or destroyed within a given
period of time, regardless of when ordered, received, or paid for.
For operating prograrr;s,-" applied costs represent the value of
resources consumed or used. For procurement and manufacturing
programs, app 1i ed cos ts represent the value of ma teri a1 recei ved
or produced. .For capita 1 outl ay programs, app 1i ed cos ts represent
the value of work put in place. For loan activities, applied cost
represents assets acqui red (even though no resource has been
consumed). In the case of appropriations for programs that are
essentially operating in nature, equipment is included in applied
cos t when it is placed in use. For a 11 programs, accrued annua 1
leave is included in applied cost when the leave is earned, rather
than when taken, even though it may be unfunded at the time; and
Attachment 1 DOE 2100.1
Page 2 9-25-79

depreciation cost and other unfunded costs are included

where appropri ate.
5. Allotment is an authorization by the head or other authorized
officer of an agency to the responsible heads of organizational
units or activtties toincur~bligations within a specified
amount pursuant to anappropr'i ati on or other statutory provi s i on.
6. Advice-of-AHotmentis the document used to officially record
allotments and is issued.to the head of a field office, an
Ass istarit Secretary, or the head of a Headquarters organization.
In accordance with an approved fi nanci a lplan, theadvi.ce-of-
allotment establishes organizational limits whi.ch may not be
exceeded. This document is the mechanism by. which DOE satisfies
the. requi
,
rements
. . '
of the Anti -Defi dency Act.
7. Ap{lOrtionmeiit is thedistr'ibution made to an agency by the Office
of Management and Budget (OMB)of. amounts. available for obliga-
tion tnan appropriation or fLind account ,into amounts available
for specified. time periods; for activities, projects , objects;
or, for combinations thereof: The amounts so apporti oned limit
the oblii'gatlonsthat may'bejnc:urred.
8. Appropriationlsthe legisrati~nwhich establishes statutory
authority for: Federal agencies ,to incur obligations and to make
payments out or the Treasury for specified purposes. An
appropriatlqo usua lly fo1J ow:;, '~nactment of authori zi ng 1egi s 1a-
tion.,Anapproprlatioriact6unt isestabUshed in the Treasury
by thi~ ,J~~qsHti9ntO:r~~ord amoun~savanab1e, for obl igation
and outl,ay..,+Each~uchaccol:lnt provldes" the framework for the
establi~hmeiH:! qf a set of balahce'd;, aycountson,the books of the
agency concerned whi ch include .not only those accounts to whi ch
money is di rettly appropriated but a1 so those accounts to whi ch
revenues are available for use without current congressional
appropriation'Oac,tion, suchA.S revolving funds and trust funds.
" (, ,'"
9. Authorization 15 the basic substantive le'gislation enacted by
Congress which sets up orcontinues the, legal operation of a
Federal progfamo;lag~ncyei ther i ndefini te ly or for a specifi c
period of time, or sa~ctiofl~ia particular' type ..of obl igation
or experid~turewithin'a,progt;'am .. Such legislation is normally
aprerequisHe;for subsequentappropriati'ons" or other kinds of
budget authof; ty to becO(l~a~ r:wcti napprdpria tjoo acts. It may
limit the amouY;lt of b~dget';:a~thority to. be prov; ded subsequently
or may authpf;z~ the appro,pr~aticinldLl'such ,sums as may be
neCE:SS a ry. " : 'Ina few 'trs tances ,biJdget' authorjty I may be provi ded
in the :authorization. ", ''.1' ;.,.:'! ' ,
 DOE 2100.1 Attachment 1
Page 5 (and 6)
( 9-25-79

24. Outlays are the dollar amounts of checks issued, letter of

credit withdr~wals, or other payments made (including advances
to others), net of refunds and reimbursements. (The terms
"expenditure" and "net disbursement" are frequently used
interchangeably with the term "outlay.")
25. Procurement Initiation takes place when the Office of Procurement
and Contracts Management accepts and begins action on a procure-
ment request which has been properly approved by the program
official authorized to allocate program funds and has been
confirmed and recorded by the appropriate field financial office.
For any individual procurement request, the dollar amount of the
program initiation and the dollar amount of the procurement
initiation will be identical.
26. Program Initiation is an administrative recording by the program
division or office that a procurement action has been requested
from program funds. The dollar amount of the program initiation
must equal the dollar amount on the procurement request.
( 27. Program Reservation. Program reservation is the measure of a
program staff's execution performance, and represents the completion
of program staff work necessary to get a project or concept to the
s "action" stage. Upon completion of internal programmatic staff
work on a proj ect or task, and upon fi na 1 approva 1 by the program
staff to initiate an effort, the program staff will request the
Office of Procurement and Contracts Management to initiate a
procurement acti on. Program reservati on is the do 11 ar amount of
allotted funds reserved by the program office for each particular
effort which is awaiting action by the Office of Procurement, the
Controller, or field offices.
28. Project is a major endeavor within a program with (a) firmly
scheduled beginning, intermediate, and ending-date milestones;
S' (b) prescribed peyC'Y'ormance requirements; (c) prescribed costs;
and, (d) close management planning and control. A project is
not constrained to any specific element of the budget or accounting
structure; i.e., operating or construction.
 EFFECT OF NITROGEN COMPOUNDS ON THE
THERr1AL STABILITY OF .JET FUELS
LEWIS IN-HOUSE ACTIVITY

OBJECTIVE:
TO DETERMINE THE EFFECT OF CONCENTRATION OF VARIOUS TYPES
w
~
OF NITROGEN CONTAINING COMPOUNDS ON THE THERMAL STABILITY
OF AIRCRAFT TURBINE FUELS

APPROACH:
VARlOUS nITROGEN COMPOUNDS <INCLUDING CARBAZOLE., PYRIDINES.I
PYRROLE.I INDOLE QUINDLIND HILL BE ADDED TO JET A.I SINGLY AND
IN COMBIN.~TION.I AT SEVERAL CONCENTRATION LEVELS

JFTOT BRE.t'lKPOINT TEMPERATURES WILL BE CORRELATED WITH

NITROGEN CONCENTRATION
AIR FORCE AVIATION TURBINE FUEL THERMAL OXIDATION
STABILITY R&D

Charles R. Martel
Air Force Aeropropulsion Laboratory

41
::-':-'--::-:-:'7 _~::::'7..:~_~' .:...-:-=:- -_--:--:;---
-~-:X:!7~-- ..-:_-F:- .--:::._-;....-;:-._'" ~~-_.~_ - ---- -:::-.:::-j:~;.. . ',~::r:- 7'._:- -_~:--.
.;;;.';.--

PREVIOUS THERf'1AL STABI LITY PROGRA~1S

ADVANCED AI RCRAFT FUEL SYSTEM SIr1U LATOR TESTS

JFTOT TEST METHOD DEVELOPf1ENT -CRClASH1
JFTOT HEATED RESERVOIR PROGRAM - CRC
PRESSURE EFFECTS ON JFTOT TUBE DEPOSITS
JFTOT TUBE DEPOSIT RATING COMPARISON

.J:>
COKER/JFTOT CORRELATION
N

i'1OGAS JFTOT TESTS

 CURRENT AFAPL/SFF THERMAL STABILITY PROGRAMS

"JFTOl r[ST FOR THER~1ALLY STABLE JET FUEL (JPTS)

JFTOT TEST FOR LOW VOLATILITY TURBINE FUEL (JP-7)

I,

' J-f9.FUELNOZZLE: PLllGGTNG"TESTS (GENERAL ELECTRIC) ,

~,
w

JP-8 SAMPLE CAN/FUEL DEGRADATION PROBL~1

I, i
I
I
.. 1

II
I
I
I,
.~

i
(

I
I
!
 -,;;,;.- ~;o;;;--',;;"

,'---:.',;;::.-.,.- ~;;;.=- -r'~-';"- ~..;;- _~.;- ~.. ;-.~;;. .:.::;;.::::.::- ~.:~~""_~

~~.-",'---~ -~';;"'-"';'--~------'

JPTS THERr-lALLY STABLE JET FUEL

PRESENT SPEC TEST:

ASTN/CRC COKER AT 4501550/6 TEST COf'i'DITIONS

f@
.
I
,11.

(~
PROPOSED TEST:
-ij!:.

~'.
li11
?i" \lfiTAff.'r:TEi'l[il\'rf'!5h,!7/iilutilijIR"S ,),,~IlI\J
, -.IF V'I""1 O'I"""'~ itlli ''l'IIi.1U
ll."r:;!t!tt\ 1"\i)'lI:J;,vtC.l'
' '1-Ell lP!LI\ TURE
rit'.it'h!1:U~FSTT'!fI"Mi:lttr1A- OF' ABOUT
"

335C (635F). USE MARK 8A TUBE DEPOSIT RATER.

,If)
1~T
I
,.l,
t Yf
p. J, i ~::~ )

REF: AFAPL-TR-73- ~ "THERMAL OXIDATIVE STABILITY TEST ~1ETHODS FOR

'?~,"l J,pitblcl'IE1i 5H".>' .,t-1
-I~ t) ~!'~r' lj,- Iho /'-1 'j Ci "
,;

t) ,,. '; j"""

if Ii
 JP-7 LOW VOLATILITY TURBINE FUEL

PRESENT SPEC TESTS:

THERMAL PREC I PITATI ON TEST PER APPEND IX BI MIL-T-3821SA
RESEARCH COKER TEST AT 500/600 PER APPENDIX AI MIL-T-38219A

PROPOSED TESTS.!
JFTOT TESTJljJiSJ~OURs)[!5~aJp<S\G O(f~1}r8,f~~RATURE OF ABOUT 350 TO
~ 370 C. VO~~~'!~A~k:\gAftGB{(tlk~6~~!f~At~R:';';jJJViCUJ:;lv;fi:HIE? t:OH 'H:U)j
0

nf) r
i' 1 \,~' j~,

; .,t,l
~">_

;- ~i'

J, l.

\i ']' 'Ii b' :'~;' ,

t
# J !I~.i 1.
~
.l.II
'I

f '1'
f "i ~

~'-1 .~ P't \ 7 ;-.

l~'\ ,,"

~l
j.
I
~\,
 ----"'-"'..,-~...".-=:: --,-,---------

ALCOR ~1ARK SA TUBE DEPOSIT RATER

PROPOSED FOR USE WITH JP-7 AND JPTS FUELS.

ANTICIPATED LH1ITS:

[<lAX. ~TDR = 12 (~TDR = ~1AXIMurJl POST TEST RATING MINUS PRETEST RATING)
REF: AFAPL-TR-77-53 J 'DETERMINATION OF THE EFFECT OF PRETEST RATING
OF JET FUEL THER~'IAL OXIDATION TESTER TUBES ON POST -TEST RATINGS
USING THE TUBE DEPOSIT RATER" J JUNE 1977.

"""
0"1 , i' AFAPC~rR:7:5-t1J;~- "1tffi-1PA:R~fSOU OF RATING TECH~ IQUES . FORJFTOT
,:''H8HER- TUBE:"IlEPOSI1s~i'}: OCTOBERHjtg.ls~';i;);-:!;:~"; .,.' ""'.,
'"
i~

-\ ',.
1

\;i . ,;t;.,

'-'

~,
 R&D NEEDS - mPROVED QUALITY CONTROL TEST

REEXArHNE PRACTICE OF FUEL PREFILTRATION

RUN AT REALISTIC TEST TE}1PERATURES. TRADE-OFF OF TEMPERATURE FOR TH1E
QUESTIONED
WHEN SHOULD HEATED RESERVOIR BE USED?
DEPOSIT RATI NG f1ETHODS QUESTIONED.
WHAT DOES COLOR OR OPTICAL REFLECTIVITY MEAN TO ENGItJE?
HEAT TRANSFER f1EASURENENTS CAN BE f1ISLEADING. REQUIRES TOO LONG A TEST
-l'>
'I OR TOO HIGH A'Ttl1PERATURE:' ,',' . I
;.<1 :.'
i
WHY DOES TEST PRESSURE AFFECT DEPOSITS? I
,'. NEED STANDARD SAf4PLECANSd1ADE OF. INERT f1ATERIALS.
,,'.,', '".~'.-.J'_: ,-, '< ,.. " .
QUESTWN NEED FOR INERT
~-'. ',: ' , __ \,

'.
ATMOSPHERE OVER SANPLE.
,f', 1 '
,;'\ Pi
1
I
J " '~

.,<-,
i : ," -..
I
I
i
, ".1 :,',;" , ;: \' n' .
1
dC' ~,' '.1
I

.;" r" ;,:~ .", ~:.:I_ .t:' ! '. '\ ;- , ~ ,

; .I ;,:
,.'
~ j'
'
t '
}~ .' .1':" I
i

I
I
~

II
,I
 ::c=:=:C~~~="",=s=:.:;i'C"='''E~=C~''2'''C~~'''''''''',"~,,'C~,'C,-~-, ,'""",' _', ,,'~~.~"
-----.-.

R&D ~1EEDS - ~lHAT ARE

EFFECTS o.F SUPERCRITICAL OPERATIQN?

EllEL CRITICAL TH1P C (of) PRESSURE AT CRITICAL TEMP (PSIA)

JP-4 \,;'J """,2as,\ I(SSQ)TO. 365

til' /r ',' hi!"
vi..' ,~'lN' '_..
(&9{)) SOo. TO. 40.0.
4;P-5 ')~'&2 r("72Q}1,)TQr'
\",:j ~~~J"I L
'4hl5",(7Qc\'hl I
>", ill/~ II ~';J\1LJL UL '1'ft;Cj,,),J~
'" r,3Qo;r,(l 220.", ,I
t}l H-:,{tJ. j :W1d lid:.. LV ,!

JP-7 j'~ ;- "'1 i " iii Ii'{ ,'" ll"'1:/t'ii'{'\'"

f.A;~i' . M"Ut:J:liJ t,,\,t~UU1' )~,
"1
i) J. 270
~ \-11: Pq 11 I ('~i4tr:"!~l !.Q.l{C
JP-8 ," ~" 57ar:t"l~Cj) "'ltI'4o.S (760.)
j
"[,,;'
3So. TO. 275
,\.\.1
I' "j,~ '1 ;-!
I ,\ V
r h ')"
till
ttl y
'l~i .t
R~
':-\~
q
fl II:~

,,~~
1 t, '" > rqiJr
\W "I., ,101:,(,,,,1, .,\.1 1, L JJ
(A~
\~ I ','6"" I
bL,}C1, ""'LIN!"
U,.~,.J.

II
p ,,'
" I)'
,
~
,.l
 U)
u
o
CO
.....
I-
U')
H o
c...
""" w
~
w
~
=>
I-
z
o
LJ
0::
::::>
U')
U')
UJ
c:::
c...
I-
~
I-
o OJ
U.
o
I-
u
W
u.
u.
w
0 0 0

0 0 0
0
~;::j a
",-.'-"', ,,'""-,
;".~o,.", ,-<,~"\
""-~, '~/

5Z OZ

49
 " --~~-=;;:;;:::"'-7'---~-;:c-~~~~ . '~- _,~ __ ~-=-'i'::::,~,~ '.~I~_"':.'" :...., .~.~...;:--~~_ .:..:-:.=-__

;,-, ,",
..,
"

,SAMPLE ,CAN PROBLEM

, -. < - ' - ,_ .\ ;".-,1_
! i',

JFTOT BREAKPOIHT DATA FOR JP-8

SA!~PLE 1.D. mo.' LABS) ',',; AVE B'.P. (0 ''',,", ,".,,,,.-.,, ,'- '.<
,. B. P. RANGE FAiLURE MODE
'1,(

AF LI NED CANS :(6) 295 ;~ -:c

270 TO 310 DEPOSIT (5/L liP(1)
GE LI NED CANS ,(1) '; ,285 DEPOSIT (1)
GE UNLINED CANS ( 7 ) " ,
" 1 ... '.,./
<250 220 TO <280 liP (7)
GE GLASS DOTTLE (1) 300 DEPOSIT (1)
t:,
JFTOT BREAKPO
! I NT,,., DATA FOR JP-4
~ {'IF LIriED CANS ;(5) 262 <260 TO 265 DEPOSIT (3)~ lip(4)
GE LINEn CANS (}) 265 DEPOSIT (1)
GE UNLINED rAN~ (7) 258 240 TO 765 nEPOSll (5)~ lip(5)

'-i
~: .-'

, ,.,
,t, ,~, ;;' ,l 'i, ' ! ~,' .{ 'f:
" ,
~;, .,;; f'.f .\ .'..,
V-i, '
 R&D NEEDS - SIMPLE BUT SENSITIVE FUEL SYSTEM SIMULATOR

SINGLE TUBE HEAT EXCHANGER:

USE TUBE FRO~1 ACTUAL AIC FUEL-OI L HEAT EXCHANGER
SACRIFICE TUBE AFTER EACH TEST
MEASURE FUEL-SIDE HEAT TRANSFER

NEED FUEL NOZZLE THAT SIMULATES CDt-mUSTOR CONDITIONS

0'1
~
SNALL SIZE TO REDUCE FUEL NEEDS

ACCURATELY SIMULATE TEMPERATURe PRESSURES, REYNOLDS NUf1BER

AUTOHL\TED TO PERMIT CONTINUOUS OPERATION

j
I
~
-"~~~
"';,-~<'; ,-1
.-r-!o
~()MECHEMICAL,ASP'ECTS"OFmEI?OSIT FORMATION:,,

Robert N. Hazlett

53;:
 The NRL work is attempting to give a chemical rationale for the reactions
which begin with that between dissolved oxygen and fuel molecules and end with
the formation of solid varnishes and/or suspended particulate matter. The
presentation will be divided into 3 parts: liquid phase reactions triggered
by oxidation, the relationship between liquid phase reactions and deposit for-
mation, and the characterization of deposits.

I. LIQUID PHASE CHEMISTRY

Figure 1 - The bulk of the NRL work has been done in a modified JFTOT which
can be used at more extreme conditions than the standard JFTOT. Further, fuel
samples can be directed to a gas chromatograph for real time determination of
oxygen depletion and product formation.

Figure 2 - GC features include a helium ionization detector which has excel-

lent sensitivity for low molecular weight gases.

Figure 3 - Con&ide:table research has "been conducted I1sing n-dodecane, a pure

hydrocarbon which is a major constituent of JP-5. Analytical considerations are
greatly simplified by this choice.

The initial product from 0Z/dodecane reaction is a hydroperoxide. This

product is formed in a free rad~caLreaction occuiring between 400 and 500F
in the JFTOT flow sy&tem. Decomposition of the hydroperoxide at higher tempera-
tures (550-750F) forms alcohols and ketones. Carbon monoxide also forms during
this regime.

Figure 4 - This Arrhenius plot depicts the production of scission products.

The various sections of the curves can be related to hydroperoxide decomposition
(600-750F), minimum reactivity (75Q-900F) and pyrolysis (above 900F). The
plots for CO and the n - alkanes exhibit similar slopes. n - Decane and hydrogen
exhibit unique behavior.

Figure 5 - Olefins are also produced from thermal oxidative stress of

n - dodecane. At lower temperature, paraffins predominate over the l-olefins,
but equal amounts were found at temperatures of 800F and above. The distribu-
tion pattern with carbon number is noteworthy.

Figure 6 - The sum of all ~ - alkanes and l-olefins is plotted in this

graph. The dissolved oxygen concentration significantly affects product yield,
particularly at lower temperatures (60 ppm is the amount of O2 dissolved when
n - dodecane is equilibrated with air at 1 atmosphere pressure).

Figure 7 - The 3 reaction regimes occurring in the n - dodecane/02 system

are:

(a) liquid phase oxidation - 400 - 500F

(b) hydroperoxide thermolysis - 550 - 750F

(c) pyrolysis - 900F and above

l' I
54
rt
I
It!
Regime (a) can be explained on the basis of well-established oxidat'ion chemistry
and will not be addressed in this talk. Regime (c) can be explained On the basis
of the Rice-Kossiakoff mechanism as 'developed by Fabuss, Smith, andSat:terfieId
and modified here for high pressure c o n d i t i o n s . , c ,

Figure 8 - Regime (b) can .be explained using an initial thermo+ysis of

hydroperoxide. The alkoxy radicals formed react primarily to form alcohols'in
the reducing environment but also decompose to ketones. A third path'affbrps
cleavage to smaller fragmants which .include primary alkyl radicals. These ':.
radicals :can participate in the chain 'propagation reactions shoWn inFig.f'
to fo:r;m similar products , small alkanes and olefins, found. in . the higher temper-
ature pyrolysis regime. Termination via secondary alkyl radicals appears to be
more important than beta-scission, however, at lower temperatures and the alkane
yield exceeds olefin yield ..

Figure,g - Product formation from n - dodecane is similar for 3 me-tals.usep

as heater tubes in the JFTOT. Thus these metals are not catalytic fort:he,oxida-
tion reactions examined.

_,."..;;;......o-=c::.. -'Some aromatics added to.n -'dodecarte inhibit the oxidation

Figure 11 - Fluorene is the best .inhibitor for the oxidation reaction. The
inhibitory action may be related to the strength of the pertinent C-H bond.

Figure 12- The aromatic compounds also affect the reactions

hydroperoxide thermolysis, reducing the yield of hydrocarbons.

Figure 13 - In addition, fluorene reduces the olefin/paraffin

800f and below.

II. RELATIONSHIP BETWEEN LIQUID

PHASE. CHEMISTRY AND DEPOSIT FOEMATION

Figure 14 - The deposits formed during thermal oxidative stress in the

modified JFTOT were evaluated using the Alcor Tube Rater. Since tubes (particu-
larly stainless steel tubes) usually had . an initial meter reading above zero , the
di:fference between the after and before readings (liTDR) have be.en ;utilized in the
plots. Thisfigure for n -dodecane Xlowing over 316 S,:s. indicate,sdepqsit fo,r-
mation coincides with hydroperoxide decomposition. In addition, the liTDR and CO
val1,!es exhibi t a remarkably similar rise as peroxide decays ..

Figure 15 - The Arrhenius plot illustrates further the parallel behavior

observed in .the different portions of the graph:

. ,.,

Figure16- .. For a cOlllplex. hYdrocarbon mixture (C.aC"fue,:lRAF..,l77)"t9.e pattern

is somewhat different but relationships .are stilLapparent.. In.this;case,, ,;d.ep()/?it
forms during the oxidation phase and also as hydroperoxide decomposes. ' Deposit
formation decreases some after all of the. peroxide is ,re~cted.

55
 a):8sd Figure 1/,'+sAm:a1uniinum neatea::tjrube usediw:LthlRAF-!l:i78E!xhfj,bit!i aGdifE!'ifeh~S
paftetn3altI!ough !!omE!ndepes.ili13ror:n\sbduringshydropE!roxidE!!udl!Eoniposmt31on_,.Li} 9!ij .10
,_ f; fl ~:,J: j 1.2;, {I Ci ~1 2. :3.9 'Jj>1 1: rf '1 G 1 ~{:r s::r I::; ;:.:Lt".ll b O~I!" b fIB
Figure 18 - The deposit maxima for 2 .f1uids with 3 metals are summarized
and compate4Iwtrh,lhydrpe:r;0xJi:degc6nceiltnatiqns. sdDepositi) fo~don IQ.l!::::J1H~":
stainl,essosfeeiL:s:ocoilncdes.switlr the'''tempe1taiiunes:)6i1iBma~imcirli-sROOH cefiaeiitlfafiioh'{d
and/irE oReElHr{deplet:idn . '\ Sine:.; the fhree~l:'~dicail: doric ewnj a e:ilon:n;ilS l reialI i\tE!lI:y8lii gti j
at thes e ",temperatures;; w~:;Jpr,opose~t4a threactidns:!f0111illi!ng2.solills .tare 8a~so ta;atMC:;
wi th f ree.tt'adicalnreaetiJ6rts-"s:1 The JnCidequate.l:evia1uEi tion 0 fsd6!pdiSit qqaandatil;;ft:r
~qliltnit'lt~e.r;applicatio;n:JO_f" t;hess;Lrellia-tienshl1ps to."s:;imgllle:;f,he1(Jmetial:mSysftems. en
1 <! O:2i
"JI_i~;iJd 'illi:l h:,;!",;::."::::;
III. CHARACTERIZATION OF DEPOSITS.t"{

03:oUFigure- 19:1:." :lNRL 1.has aa'tso ~!allP};oaChedil.tl1e:rIue-ill':deposit jmecha:nismi?J;t9J1),~tlie

dE!nd ,,,oy :;use 1:0 p,bofl1nqua:Hta.t:iive: anddquB.l1t:Lta tiVe'gbecliniqiies;l cluESCA::afid 2.13
~depo:s\i t
Aug~r analyses have not been very informative. E11ipsometry:iils:y,:questidfiaJ;;leDol::J
as a quantiattive tool because a deposit which adsorbs light requires an absorp-
tion cO"E:fj;cient:!:im ::tl:ie riti1l:i ekness Qcalc1!latibnb DlOPyrol}ts;i;s iSGCmwiLll ~,!L~tJ!'.9iin
the future. Elemental analysis is a marginal technique for the JFTOT tubes,~e4Z
cause of inadequate sample. However, this analysis has been useful when applied
tdTdepositls sfo'med) i;fi:J-.othei:! devicEls :'. :hiti ,,Or tmudhai[(mgE!r ~'tr:ilili@S; '1 - LL.'~:0 ji~~~_

Figure 20 - Tomcat (F-14) heat exchanger tubes have been used at NAPTC in
1ul)e o:iil.tfutiljhea.t,-excnang~::)teSt ].r; TneSe 2H!i1S 0:i1nh otn ;ill:fiiees rfflave_~15e~nl:i.eA~_ into
segments and c1eanedned::re1fi6,ij:E!:fafty jbbcicdepdsitr.tonbthe, e:l1:tetl!@r;djThe1:r,esllirt:thgii
stainless steel specimens have been analyzed for the elemental composition o.f the
organiC! fue]Pde.i'ii}ed"'d~p0s:i!t()bndthEPititerior!."I WI.[\ ,.n.t.:!lbbB r;I:':}~t~-;?-iS;ti I" 008

Carbon, hydrogen, and nitrogen can be determined simultaneously on a segment

but o~gen and sulfur require separate segments. An increasing trend is observed
for all elements going fr6m;}t1fe;IaoHliJ&ntUefu~1TicM;:rto, the hot end. The data also
indicate!! that with thi'i3'1e~eiiimeniWimJhgHd-epo'HN:JlsJl~idlEaown on those segments
to which fins had been welded. This latter phenomenon was observed in several
tests~1rlj J'1..l a2..3'lJ~ .0"\[- bb.L:<Cl l.Cii-:h~i.:;.;dj bsnrl'Oj: 2:3 ::.3rIT

cHl, OF:iigui'eOZll -errAtOIil'JratioSt f0i':itl'i~ segfiietits ffom'-'4 (tle!fcs were2ciH,eriill.i~a. '{.Tll~

Sddncen1;pationi:bfiSlietero:i at8i1\S Lin etliebdeposiE 9i!s btemai:'R);iB1e;!:! Tlie"ii:hi'ldufiefi6'EeiH:f!~0-
-ge'd :tii atlie' t:dS'p'Odl ;;11 . aMm (ldf; gi'ei:itet-l: f'6Iti e i:i(:ll'i :)OD~arhPjllli ttomsLf;i!n'ItlttEfe of afIle q
-gstos',' :iIl;'T$urptisil'n:gj[;}f;5~li~se ,pett6J!e'iim()8:etiveax:lHle:lls;bYIDh~:r<linotifittotfiiti'&gefim
in the total tube dep6s.:fies~ fibwevei'~ amoUllS to I 6flty Gl:QJi:>lpfimS0f5tnedO:Eare;fu~~EV
flow.

The o~gen/ carbon ratios are daJ?sB ve't'y 11ligllv i partlieu3!a::tiylfopifTub'e B;n':frne'o
hydrogen/carbon ratios indicate the deposit tends toward an aromatic structure.
Tube B again appears to be a maverfitQ(" clS'6Iifu itosorpt'ii8R-8f\waj;etc'ini1ticthe polar
organic deposit seems likely for Tube B. Organic dibasic acids, i.e., phthalic
c;ae:i!d~ liei've ;.iiir;QlGf~gt6mlJra&fa')of.'fQ15t'(f G0lisequefItlIy;;:"'dxy~enscofi'tefi:t.XpJL!!iR;i;s. .mag-
~,. ~ , '. . ~,~ '~'. . " " ~,.. ~ "" ,. r, , c. ", ", ~ " .. ' ." .'
~ .Lri':i2ffude ;maY"re:f!lilec,LareasGiialJlie.Ldeposit.Scompos:;t1?icHH'-"" :L,fej j5J1W;3m08 8,[
-" 9b.txO::t:3qc:rb\~I~ BJ~ DBLa b'DJc~ a.rr:r1:o1 .nol:jsbJ::XQ srJ:i
Figu):'e 22 ~ DeP'&si!-:::oi1,l:fiea:i!ixexenan~erlfubes stt'~se@O:En8tHe9AF0imiij;at0ifO!
have also been examined at NRL. For these analyses the fuel derived varnish was
removeq from the steel tube. Atom ratios found for 7 different fuel tests fell
in a narrow t:ange for H/c and N/C.The OIG .ratio was relatively high except for
AFFB.,.:U and .,.12, which are high stal>'tUty jp~7;C" The low H/c values indicate a
concentration of aromatic species in the deposit" . TheN/C and o/c values are
generally lower than those found fortheNAPTG heaiiexchanger deposits.

Figure 23 .,. coinpoundsifljet fue~s whiVehcdritairi heteroatoms make a major

contribution to deposit formation.

Further, these compounds appear to be highly aromatic. These two findings

are also characteristic of gumsformedfrom.fuels ..during low temperature storage.
The limited amount of dissolved oxygen available for reaction with a fuel in a
flow system is insufficient to form .the.e;lttensively .oxidized products found in
thermal deposits. Rather, the high oxygen content in deposits suggests that
partially ozidized compounds in a fuel are easily:; at.1:acked and fllrther oxidized
by dissolved oxygen as the fuel is thermally stressed .

.- I ,...
,";Ie., .

-'. ' .'E~;

""", ',_" 'c_~

.:....,-"-","
" ._l..<:~
 JFTOT MODIFICATIONS

'-, '. ~;~

, ,.. ;.'1000 ci=CAPp,.BI LilY

-;. ',." , " 1 " TSSJ ~S!,:CTI,oN-5.1 N,CH I:\EATED LENGTH

, , . ~

STAINLESS STEEL TUBES-316 AND 304

;'i,f'
.. i SAMPLE:fAKEOFFTOGC

IMPROVED TEST SECTION SEALS

TIC IN LIQUID AT TEST SECTION EXIT

STRAIN GAUGE PRESSURE TRANSDUCER

Figure 1

GAS CHROMATOGRAPH FEATURES

LIQUID SAMPLlNG-10 MICROLITERS

DUAL DETECTORS

-HELIUM IONIZATION (0 2, N 2 , H2, CO, CH 4 , C2 H )

S

-FLAME IONIZATION (HYDROCARBONS)

DUAL COLUMNS-SERIES OR PARALLEL

COLUMN BACK FLUSH

Figure 2

5'8
 L2
II A+K+HP I / /'
- - ........
,,--A HYDROPEROXIDES
\ /
\ /
-
VI
Q,)
\ .
\CO(x 5). /
I A

~O.8 I-

-E V\Z . / ,
.~V_",,, ~
r - ......... ~---v-. .. ' ...
... ""'-.......V./ .. p. ...
.,
..

l)~--'-.......~~._,;/ ~\\.
tTl
10

b
=>
c
o \\ALCOHOLS
g: 0.4

KETONES
o
o \. ,

i
/.3

." ., t'
I
i
!
Figure 3
I
I

I
I
 Tube Tempero ture (oj-)

1.0

-
Vl
Q.)

o
E
E
c.J
z
o
u
t;
::::>
Q
o
g: 0.1

1.3 1.4 1.5 1.6 1.7 1.8

IOOO/T (OK)
Figure 4

60
 PAXAFFI NS AND OLEHNS FROf'l N-DODECANE
'.-~-....,. --.--.,.
'-
I I I I I
--,C:.-PARAFFINS
--O-OLEFINS
_0-0---...
0---...
0,
-0
\
\
\
\
\ -I
o

-
V>
(])

o
I8--0--8--0--0~~--\
___0
E
E
u
I
z
o
u I ,~
t3
I
~
'~
:0
o
e::::
0...
0./
\
0 __ 0 \ 0

,
-- 0 --0 --
o~ "0--0
\

, I \
6.
I \
I \
o.or~____~~~~~~~ __~~I__~~__~I~~r __~
3 4 5 6 7 8 9 10 11
CARBON NUMBER
Figure 5

61
 EFFECT OF. OXYGEN
ON SMALL HYDROCARBON
PRODUCTION FROM DODECANE
I t
1000 0
900 0
' 800 0 ,. 700 0
TUBE TEM~ERATURE(OF)

100.0

I~

"-
til'
(])

0
E
E
(f)
z
0
CD
cr:
<c
0
0
cr:
0
>-
:c
H

1ppm
OXYGEN

1.3 1.5.
lOOO/T (OK)
Figure 6

62
 PYROLYSIS OF N-DODECANE
FABUSS-SMITH-SATTERFIELD MECHANISM
INITIATION R-H + X, ) R . (sec) + Xli

R (sec) ,B-scission) 1~OLEFIN + R/ (pri) .

PROPAGATION
R'I ( PrJ') + R-H hydrogen) R' .. H ( smaller) + R . (sec )
m
transfer n-afl<ane
w
NET 2 R~H +X . ) 1-0LEFIN+ R' -H + XH +R . (sec)

I
!
PREDICTIONS-EQUAL AMOUNTS OF INTERMEDIATE
SIZE HYDROCARBONS
-LOW YIELDS OF METHANE, ETHYLENE, I
I
N-DECANE, N-UNDECANE, AND 1-UNDECENE !
-SINGLE STEP PROCESS AND MINIMAL !!
RADICAL ISOMERIZATION BECAUSE
OF HIGH PRESSURE i
I
Figure 7
<l:P I
!
~- _'~~~'~"d;~'":~'-'- ~- ~'_'===--~_'_' ~w_~---=:-:,,"," "_.~,~"-,,,,~~,,::.i~:~ .. ~".::' ~--~. :;;;;;:.....~,;, ,..;,;."""'''';,~~ "-~ _ ~""",';;;;;::?J:;" ;;;;p-z=

HYDROPEROXIDE THERMOLYSIS
ROOR-; - ..

ALCOHOL KETONE

ALDEHYDE + R/ (pri)
. JRH
+ A" . (pri) I (smaller)
m
CO R H . n-alkane' +R . (sec)
"""
1Jl-SCiS~ion
i-OLEFIN + Alii' (pri)
PREDICTIONS~BQUAL AMOUNTS OF INTERMEDIATE
SIZE HYDROCARBONS
--LQW YIELDS OF METHANE, ETHYLENE,
N-UNDECANE AN-O 1.. UNDECENE
~,N!:"CiCANE FA-VORED OVER OTHER
., ::;--..:...--;:- _ :;- __ .. ; __ ! __ ,.c -.: ,.7_~" -_--;-. .:;.- :.,._ - '_ _' __ --:;: '_:'

N~~A[KANES -.
--N";ALKANES FAVORED OVER 1 .. 0LEFINS
~..; ,.,..... _ _ 0
 EFFECT OF METALS ON PRODUCT
FORMATION
0'>
U1
PRODUCT (MMOL/L)
MAX. TUBE
TEMP-OF (OC) METAL H2 CO C2H6
i

600 (316) 316 S.S. 0.005 0.020 0.046 I

304 S.S. 0.010 0.020 0.040 I
AI 0.005 0.023 0.062 I
800 (427) 316 S.S. 0.033 0.128 0.700
304 5.5. 0.030 0.130 0.740
AI 0.020

Figure 9
0.122 0.680
I
I
<@Y

I
i
I
 REACTION' WITH OXYGEN
-0- 5 MOLE % CUMENE IN n-DODECANE
--x-- 5 MOLE % I, 2,4-TRIMETHYLBENZENE
_.-<)-.- 5 MOLE % DIPHENYLMETHANE
........ 0 .. ...... 2.5 MOLE % FLUORENE
100 "i,'... ~ 'I:!

-
-

~
. \ .
0
........ \\ \.
0
w 80
.'-:
.' \ \.
l-
u
\. I \
<l:
w
., .
\\ \
0: 60 ~. ~\, \:' .

O'l
O'l z \I
\\
.
W
<..9 . \ \.
>- ~'. \ "X,
.

X 40
-1

0 ,.' .,
.
\ ! . .\...
20f- IJ!t
l
\
b.
1.5 1.7 1.9 2.1 2.3
1000/T (T lS TUBE TEMP IN OK)
I I I I I I I I I
750 700 650 600 550 500 450 400 350
M\KTUBE TEMP (OF)
 REACTIVITY WITH DISSOLVED OXYGEN

ADDITIVE" CONCENTRATION TEMPERATURe-

NONE 5.0 MOLE % 437F

CUM ENE " 434
INDANE " 435
N-PROPYlBENZENE " 436
CYCLOHEXYLBENZENE " 437
1-ETHYL-2-METHYLBENZENE H
440
1,2,4-TRIMETHYLBENZENE
.." 440
2-METHYLNAPHTHAlENE
.. 457
TETRAUN
DIPHENYLMETHANE .. 457
494
INDENE " 530
FLUORENE 1.0 MOLE % 532
FLUORENE 25 " 568

"DISSOLVED IN N-DODECANE
""TEMPERATURE AT WHICH 1/2 OF DISSOLVED OXYGEN (60 PARTS PER MILLION OR 1.S MILLIMOLESI
LITER) HAS REACTED IN THE NRL JFTOT; 51NCH 316S.5. TUBE

Figure 11

TOTAL HYDROCARBON
PRODUCTS FROM JFTOT'"
.
SAMPLE 650'F 700F 800F 900F

DODECANE 1.45 3.95 11.25 28.63

+ , MOLE % FLUORENE 0.50 1.18 2.21 30.55

+ 5 MOLE % DIPHENYLEMETHANE - 1.73 4.07 -

+ 5 MOLE % 2-METHYL NAPHTHALENE - 3.08 7.71 -
+ 5 MOLE % INDANE - 1.12 2.63 -
+ 5 MOLE % TETRALIN - 1.11 2.59 -
"MILLIM;JLES/LITER
DISSOLVED OXYGEN CONTENT-l.S MMOLES/L
316S.5. TUSES (5 INCH)

Figure 12

67
 EFFECT OF TEMPERATURE ON
OLEFIt-l/PARAFFIN PRODUCT RATIO

RATIO OF OLEFIN TO PARAFFIN

TEMP. (cF)
DODECANE + 1 MOLE % FLUORENE

650 0.44 0.16

700 0.62 0.25

750 0.71 0.34

800 0.77 0.48

850 0.79 0.79

900 0.86 0.87

-3165.5. TUBES (5 INCH)

Figure 13

68
 (I)

01
0- z
w l.!..I
o
-;j- <i
U 0

W t;'
00
o !Jl
OlO
I -
ctf")

I
.....lw
1
Wrn
:::>:::> en- ..-..
u.}-
- ""
-'-
o
C
'-

!-
o
x
"oo
to-
o
~

-_0
r<)

,_ - --o=--
co (D .
6 0
(I/salOw W) 'JNOJ IJnam:ld
69
 I
900 800 700 600F

-Vl
(1)

o
E
i
-<.J
E
40 ,...
0::
o
z I-
o <l
.......
u
C)
t3
:::::>
20 Z
o I-
o et
e::: 0::
a..
I-
0.1 (J)
o
0-
W
a

O.OI~ ____~____~____~__~-J_ _ _ _~~_ _ _ _~~

1.2 1.5 1.6 1.7 /.8
1000/T (OK)
Figure 15

70
 ux y(jt.r~ A I t. Ul-l HUUUc...; I ~ AND I Ufjl:. UI::JJU~rl S
TUBE TEMPERATURE (OF)
800 750 700 600 550 500 . 450~_ _.t!...!..rOrO~_ _ __
,.--:-::;-, \1 I
650
I I I -I' r I
i\ FUEL- RAP-177
TUBE - 316 s.s.

A H2,(x 100)
X CO (x5)
o C2 H<:; (x5)
o C~Hc; (X/O)
--
VI
Q)

~
E
0.9'-
~ ROOH
40J ~ <r
0::.
...... u
...... :2:
ou 0.6'- 30-1 I-
(f)
t) 0
:::J
o 0..
o w
e:::
a.. 20-1 0
W
en
:::::> i
10..,-J
l-
I
t
1.5 !
"
I!
Figure 16
I
!
 ~........,.... _
"_~ ~~_ .. --,-----,-,". ;::;;<::r=:::':"=~~,~.
~~~.'"-- ~~,...,;:;:;;;.:;.'

JFTOT REACTIONS
600 0 500 0 400 0 F
I I

FUEL --RAF-177 -tr- O2

-'0'- ROOH
TUB E--Aluminum --x-- CO

/'0" IIIIIII A TOR

x t. / \
\ ' .
-- " " ..x_--.... x /
/'
\.\
VI
~I " . . 80
o
~ i-O.e
~ "\)( I \ w
- ~
E
\ r \ l-

~~
I.)
U

\i \
-.J Z
N 81-0.6
W
6 0=-t
30
0:::
Cl
t; 0:: ~
"l, \
~'1,
::::> C\I
Cl o
!1\\ '\
o
0:::

~~
CL ~ 40
-0.4
/ \ \\ 20
/1 .... I' \\ \
20
-0.2 -'10

IIIf//JflI/I!;;/!;;;JiI, "\''- ~
O'I-:'...-a --16 I.7 1.8 KJ 2.1
IOOQ~TlIb~ TelllJ2
1.3 1.4 2.2
1.5 . (
 DEPOSIT MAXIMA FOR
HEATER TUBES

NDODECANE RAF-177
ALUMINUM 70QOF(?) 70QOF
> 800 > BOO
;j 304 ST AI N LESS 700 560
> 900 710(?) I,
I!
870 I
I

316 STAINLESS 720 560 I

1000 710 t

ROOH - MAXIMUM 500 .. 525 550

I
DEPLETED 700 700 II
Figure 18
I,
 DEPOSIT EXAMINATION TECHNIQUES

METHOD INFORMATION COMMENTS

ESCA ELEMENTS PRESENT MARGINAL

CHEMICAL STRUCTURE SENSITIVITY

AUGER ELEMENTS PRESENT INTERPRETATION

DEPOSIT THICKNESS DIFFICULT

CARBON, ELEMENTAL COMPOSITION MARGINAL

HYDROGEN QUANTITATIVE ESTIMATE SENSITIVITY

ELLIPSOMETRY DEPOSIT THICKNESS EXAMINE SMALL AREA

PYROLYSIS GC CHEMICAL STRUCTURE INCOMPLETE

REACTION?
Figure 19

~."

74
 C-H-N ANALYSES OF NAPTC HEAT XCHGR TUBE C
(No Blank Tube SubtracTed)

o NITROGEN
A HYDROGEN

-E--COOL END, FUEL IN

FINNED SEGMENTS ~
~1500
CO
0:::
<t CARBON
tJ

CI)
::::E
<t
~500
o
0:::
o
~

OL---~~----~~----------~2~O----------~3~O~~33
NUMBER

Figure 20

75
 "'------'-.- ,;";"-- -~.:. -

NAPTC HEAT EXCHANGER DEPOSITS

ATOM RATIO
FUEL TEMP
TUBE of-IN/OUT H/C N/C O/C S/C
- '
A 286/366 0.7-1.7 0.08-0.13 0.3-0.7 0.02 -0.04
B 250/330 1.4-2.4 0.08-0.11 0.8-1.2
.......
C 260/340 1.1-1.5 0.11-0.18 0.3-0.5 0.04-0.12
O'l
0 260/340 0.5-0.B 0.03-0.04 *

* LIMITED DATA FOR SIC

DATA NOT RELIABLE
Figure 21

~
 AIR'FORCE HEAT EXCHANGER DEPOSITS
ATOM RATIO
FILM TEMP
FUEL (OF-CALC.) HIC N/C OIC
AFFB-10 512 0.60 0.053 0.28
AFFB- 9 544 0.48 0.019 0.20
AFFB- 8 550 0.52 0.027 0.25
'-.I
AFFB-16 554 0.53 0.017 0.23
'-.I
AFFB-13 564 0.45 0.006 0.22
AFFB-11 665 0.57 0.005 0.09
AFFB12 688 0.62 0.011 0.10
Figure 22
@.f9
 .... .._-----,------
..." ""

IMPLICATIONS FROM ELEMENTAL ANALYSIS

OF JET FUEL THERMAL DEPOSITS

HETEF10ATOMSCONCENTRATED IN DEPOSITS
.....,
co
H:IGH 0XYGENCONTENT DERIVED FROM OXYGEN
COMPOUNDS IN STARTING FUEL

LOW HIe RATIO INDICATES AROMATICS IN

DEPOSITS

OXIDATION REACTIONS TRIGGER INVOLVEMENT

OF HEfEAaAT6M~COMP6'UNDS
Figure 23
<t-l~
REFINING JET FUEL FOR THERMAL STABILITY

William G. Dukek
Exxon Research and Engineering Company

79
 Routine testing of jet fuel for thermal stability evolved in the
50's when it had become evident that older tests such as Potential or Existent
Gum did not predict the tendency of fuels in the high temperature environment
of the engine fuel system to produce deposits. Refiners equipped themselves
with the eRC ERDCO Fuel Coker subsequently standardized as ASTM 01660 to test
fuels for thermal stability. In the early 70's, the scaled-down version of
the Fuel Coker, the Alcor Jet Fuel Thermal Oxidation Test (JFTOT) was
developed by CRe and standardized as ASTM D324l. Many, but not all, refiners
replaced Fuel Cokers with JFTOT's because the latter was a shorter test that
used less fuel and less manpO\~er. ~'oreover, it appeared to exhibit better
test precision. Specifications for U.S. commercial fuel offer the refiner
the choi ce of either teslt.trlethod. Abroad most specifications have dropped
the Fuel Coker and refiners have generally installed JFTOT testers.
The most significant fact to note about the thermal stability test
is that the refiner does not tailor his processing steps to meet it (VG-l)
His experience tells him that ifherneets other critical specification re-'
quirements as dictated by the type of crude he will usually meet the
pass/fail criteria of the thermal stabil ity test. Knowing that deposits in
the stabil tty test resul t from traces. of reactive species that occur either
naturally or in basic processes such as distillation or cracking, the refiner
does not make a stabil ity rating in his crude assay cuts but instead checks
refinery fuel blends prior to shipment. If one fails the test -- which is
seldom -- he does not reprocess but ships the product as No.1 fuel 011 or
blends it into other fuel oils. His finishing processes for jet fuel com-
ponents are dictated by the needs to improve odor(i .e., remove mercaptans)'
to lower total sulfur (sour crUde), to reduce acidity, to upgrade color or
color stability (for dual purpose jet fuel/kerosene) or to remove or react
aromatics and olefins (for smoke point imprcwement).
Refining experience with finishing processes has supported the
findings of researchers in the field of oxidation stability. The marginal
lti;-LI processes in terms of thermal stability convert thiols (mercaptans) to di-
I"
Iii
!j I
sulfides rather than remove them (VG-2). For this reason, among others,
if: the worst of these processes -- doctor sVleetening -- has largely disappeared.
,} i
Instead there remain conversion processes such as air svleetening (which uses
antioxidant as a catalyst), MEROX (which uses a fixed bed cobalt catalyst)
and copper sweetening (which uses c~pric chloride solution). Processes
which actually remove mercaptans from the fuel tend to upgrade thermal
stability. Chemical treating methods involve caustic waShing usually fol-
lowed by water washing and clay filtration. t4ercapfining is a trade name
for a mild catalytic hydrotreating step that only removes thiols leaving
other sulfur compounds untouched. Operated at a somewhat higher temperature
and pressure, the catalytic process is called Hydrotreating and. in fact, will
remove sulfides as well as thio1s.

80

> I
Ii '
 The most severe of these finishing processes lnvolves removal of
aromatics as well as sulfur compounds and results in the greatest improve-
ment in thermal stability. Acid treating is still employed by some refiners
for this purpose. However, refiners are more apt to use extraction processes
to remove aromatics. Sulfur dioxide is the usual extraction media. Alterna-
tively, the aromatics can be hydrogenated to naphthenes by higher pressure
hydrogenation.
Typical processing sequences carried out on Jet A fuel at four
different refineries show application of various finishing methods on blend
components (VG-3). Refinery A typically processes sour crude and employs both
hydrotreating-and extraction to meet mercaptan and smoke point levels. Refinery
B usually processes sweet crudes and uses chemical treating methods to meet
acidity. Refinery C processes Alaskan Crude and must defulfurize; aromatics
are usually critical. Refinery 0 is usually mercaptan limited and uses both
chemical and hydrogen methods. In no case is thermal stability the_ limiting
property.
The only examples of refinery processing dictated by thermal stability
derive from special purpose military fuels (VG-4). JP-4 is usually mercaptan
1imited and processed by both chemical and hytlT5'gen methods. JP-7, on the other
hand, requires considerable additional processing such as aromatics extractton
to meet the Luminometer Rating. In so doing, thermal stability is upgraded
from a 260 c C JFTOT breakpoint to an estimated 370C JFTOT breakpoint (JP-7 re-
quires a Research Coker Thermal Stability Test}. One special fuel called
Thermally Stable Kerosene is manufactured to an estimated 320C JFTOT break-
point (the specification requires a 0 1660 Fuel Coker Test) by blending a
highly processed component with a conventionally processed fraction. It turns
out to be the only product that is specifically limited by its thermal
stability requirement.

81
=:-,~_~=~-, ,- __
~:--'''''=_:~: ~'::=~'''~:;;;;~~:::='=":~:'''7~'-:::,:;;C--:''::~::~~:=~~,",:~=:.:'::~:~~--::::~-:S-:'~-t--:-~:tt.~L':t7Z.:;r::~~~'F:XF:;n;:=-~=->'"", -"-=;;"'"TW'C:;-=, ~-~~ ..;--:..= -,.;;;-

THERMAL STABILITY IS THE BY PRODUCT OF

TYPICAL REFINERY JET FUEL PROCESSING
STABILITY RATING IS NOT ABASIC ASSAY TEST
OXIDATION INSTABILITY RESULTS FROM REACTIVE SPECIES
- ~1ERCAPTANS (SOUR CRUDES)
- DIOLEFINS AND OLEFINIC AROMATICS
- NJ SJ OR a COMPOUNDS
PROCESSING IS CARRIED OUT FOR SPECIFIC REASONS
- ODOR IMPROVEMENT (MERCAPTANS)
OJ
- SULFUR REDUCTION
N
- REDUCE ORGANIC ACIDITY
- REMOVE COLOR BODIES
- SATURATE OLEFINS (GUf1)
- AROMATIC REMOVAL
MOST PROCESSING UPGRADES OXIDATION STABILITY
EXCEPTION: MERCAPTAN COVERSION TO DISULFIDES
BLENDS THAT FAIL JFTOT OR COKER TS TESTS ARE SOLD AS NO. 1 FUEL OIL
 -

COMPARISON OF REFINERY FINISHING PROCESSES FOR JET FUEL

(LISTED ORDER CORRESPONDS TO fNCREASING STABILITY IMPROVEMENT)
PROCESS PRINCIPLE ADVANTAGE DISADVANTAGE
MERCAPTAN CONVERSION (RSH~ RSSR) e CONTROL
I. AIR SWEETENING O2 AND NAOH LOW c EFFLUENTS
2. MEROX OXIDATION WITH LOW COST NO S REDUCTION
CO CATALYST NEW-SIMPLE
3. COPPER SWEETENING OX IDA TI ON WITH LOW COST Cu CARRYOVER
LI QU ID CuC1 2
MERCAPTAN REMOVAL
co
w
fl. CAUST I C WASH RSH-) NA SR-L, LOW COST EFFLUENT
5, MERCAPFINING RSH + H~-> H2st Lm~ TEMP HIGH CAPITAL COST
(CATAL ST) AND PRESS.
6. HYDROTREATING RSH + RSR +HT~ H2 st ~10D. TEMP. e EXPENSIVE
(CATALYST) AND PRESS. H2 SUPPLY
AROMATICS REMOVAL ,
@+ H2 S04 -). SLUDGE REMOVE MOST REACTIVE EXPENSIVE I
7. ACID TREATING
SPECIES AND COLOR BODIES fJ SLUDGE
EFFLUENTS I
8. EXTRACT! ON @+S02 ~ EXTRACT REMOVES AROMATICS AND 0 EXPENSIVE l'
S CPDS REGENERATION I
9. HYDROGENATION @+ H2 ~ 0 HIGH TEMP AND PRESS. EXPENSIVE I
(CATALYST) H2 MFG ROAD I
I
!,
 TYPICAL REFINERY PROCESSING FOR JET AFUEL

REFINERY A B C D
CRUDE SOURCES DOM SOURIIMP DOM SWT/IMP N SLOPE
I DOM/IMP
STREAMS 1 2 3 4 1 2 3 1 1 2
- - - - -
JET FUEL
FINISHING
PS X
CH-WW-CF X X X
co
.f>o
HT -CV1-CF X X X X X (MF)
AT-CF X
EX-CF X
LIMITING AROMATICS ACIDITY SULFUR RSH
PROPERTIES RSH AROMATICS AROMATICS

CW = CAUSTIC WASH AT = ACID TREATING

WYI = WATER WASH EX = AROMATICS EXTRACTION
CF = CLAY FILTRATION PS = PARAFFIN SEPARATION
MF = MERCAPFINING
HT = HYDROTREATING
 PROCESSING OF MILITARY JET FUELS

FUEL GRADE JP-4 JP-7 KEROSENE

mL SPEC 5624K 38219 25524B
THERMAL STABILITY
REQUIREMENT 260 (370) (320)
AS JFTOT BREAKPOINT) C
PROCESSING 1 2 1 1
-
2
-
-
CW-WH-CF X
EX X X
00
<.n
HT X X X X
RD X X
AD X X
LIMITING PROPERTY RSH LN OIl
CW-\~W-CF = CAUSTIC/WATER HASH - CLAY FILTER
EX = AROMATICS EXTRACTION
HT = HYDROTREATING
RD = REDISTILLATION
AD = ADDITIVES

--~'."' ,---".'-------
FUEL THERMAL STABILITY/ENGINE TRENDS

Allyn R. Marsh
Pratt &Whitney Aircraft Group

87
 ,~-";:;;;::-~"'"';C_;';::- --:-C
"';=,'-'.~';':',," -'~ --~~:::; :-:-;~_:;"';-"':;:--=---="":::''::~::?:':';;:-:-::;~- ~~::'~~----;;<h~_'~;;:;;=~~-'";';:;;:'- :i;~ <:"'~;;:'.2" ~:.:=::.:..:: _-~:...c ~ --.:.': .-;;;,~, -.-=;-

FUEL THERMAL STABILITY AFFECTS

Fact MAINTENANCE COSTS
The aviation gas turbine "Hot Section" is:
Costly to manufacture
Costly to maintain
Vulnerable to premature:'deterioration due to
00

inadequacies in jet fuel thermal stability

00

Inadequate thermal stability causes engine fuel system

fouling/ coking which disrupts normal fuel distribution
and engine hot section temperature profiles.

Conclusion
Thermal stability is the most important jet
fuel property considering impact on engine
mai nten () nce _ cg st. _.______ J20003-4
 AVIAllUN IURBINE ENlilNI:

.....

(Xl
\0

HOT SECTION PARTS SUBJECT TO

FUEL PROPERTY EFFECTS
Fuel nozzles and supports
Burners and transition ducts
Turbine foils, seals and disks

J20003-3
781210
PRATT & WHITNEY ;j'V,<_
AIRCRAFT GROUP VI'm':......
'~-=-:-----~~=::--.:.,~:...~-=--::~====~-. -.~'-.--- . .,.-.----.-,-,-.;-=~. ~--.,-'-_+~,~~k::_::J =

EVOLUTION/TREND IN AVIATION
TURBINE ENGINE DESIGN AND PERFORMANCE
(Com par ed at aIt it ude max. cr ui sec 0 ndi t ion s)

Fan to core Core Relative Compressor

Engine by compression fuel discharge
model Time pass ratio ratio consumption temperature

JT4-11 (1958) 0/1 12.5/1 1.000 555F

~ JT30-7 1.38/1 14.8/1 0.848 568F
0

JT80-9 0.9,5/1 17.4/1 0.856 668F

JT80-17 20 years
I 0.99/1 17.7/1 0.888 688F
JT90-7 A 5.13/1 24.7 /1 0.706 771F
JT90-7F 4.99/1 25.6/1 0.693 784F
JT90-70A ( 19l8) 4.65/1 27.6/1 0.698 811F
JT 100 12 years 6.15/1 30.9/1 0.642 848F
E3 ( 19 90)
t 6.55/1 38.6/1 0.586 898F
J20003-11
PRAn & WHITNEY
AIRCRAFT GROUP
C m:=-.... 781810
--- - - --
 TREND IN HOT SECTION TO TOTAL
ENGINE MANUFACTURING COST

Burner, trans. High & low pressure

duct, fuel nozzles turbine w/ 0 cases Total-Hot
&supports and shafts Section

JT30-7 5.B% 15.4% 21.2%

....
~

lTBO-9 3.7% 17.6% 21.3%

JTBO-17 4.3% 20.8% ' 25.1%

lT90-7 2.5% 23.9% 26.4% ~

i
II
27.0% 29.6%
JT90-7F 2.6% II
JT90-70 2.9% 28.9% 31.8%
i;
I
PRATT & WHITNEY C mw'--.." J200035 Ii
AIRCRAFT GROUP 781810 I

I
ltt,,~ ,';:',~~~,:;,:,,::,~ ::-": - _ -- ~--~ --- ::.;~:~:~~:.r.::...:~_~::;;:.:,~,:::-~~~;;,~,~--- ,,"_-~-r-' ~' --~-"'.- - -~;;i,,~~s>il:iig..jgiliiO;az";"::;;.,.,~"~ ,t~_-', ," --------'- ------'---"."-,,--"- -----

TREND IN HOT SECTION

MAINTENANCE COST
(Shown as % of total engine maintenance material cost) /

High & low Total-Hot

Engine model Burner section turbine section section
1.0
N

JT30 1.2% 13.5% 14.7%

JT8D-7,-9 1.2% 19.8% 21.0%
JT80-17 1.1% 26.3o/n 27.4%
JT9D 3.4% 46.6% 50.0%

Pft!\JT~Y'[HIT"!EY 1""' ___ J20003-6

------
 P& WA COMMERCIAL ENGINE EXPERIENCE BASE
Operating Years of Engine hours
engines * 1 experience *2 per year *3

JT4 600 20 2,200,000

FT 4(1ndustrial) 1,070 15 6,300,000 hrs
1.0
(total-all years)
w

JT3D 4,200 17 15,000,000

JT8D 7,750 14 17,000,000
JT9D 1,300 8 4,800,000
Totals 14,920 39,000,000
*1 Installed active engines - excludes military
* 2 Commercial & Industrial
* 3 Commercia I engine hours-current annua I rate ex cluding industria I J2000J7
781810
PRATT & WHITNEY 0
AIRCRAFT GROUP \':".::.::........
 >'';' ~,,--~,.; '~:~,""=&li'-- "':-,,;t;;;:t;: __.,.2:J;;:~~;,;;.,t,~~.:...:.._' .. _-'~\- -"-i...- ....;:;:.'~,,~"_._~A"' .. ,A,, _ _' _._~ ....- - -_ _ _

,/

, '

FACTORS INFLUENCING AVIATION TURBINE ENGINE

HOT SECTION LIFE
Design maturity

Engine maintenance/engine condition/component efficiencies

Engine operational variables

\D

""" Fuel thermal stability

Actual stability level at airport

Specification pass"fail test level at refinery

Abnorma I or un f avorab Ie variat ion s in te mper at ure leve I

and/or pattern is a principal common denominator to all
fa ct or sin flu enci ng hot sec t ion Ii f e
J2000:l8
PRATT & WHITNEY ~I"
 Cost of golf match
played to principle of
Arrhenius law

-
, .'0-

l.- _ ..-.................. .
~
U1 ......... -. ~'- .. ,

I
I
.......-.
------- -._
.. -.... .... ..

-.. . v_. . -. . .
-~'-t.._ ........ .
~
I
... ' .. -.....

.
.' .
I
I
....
. ...... -.
~. '

J20003- 2 i
PRATT &. WHITNEY }"'"- '
AIRCRAFT CROUP 'V'm1.'.::..oo.o
A7B3010

iI
 =_=-__ ._.__._._" _. ____
OZ:::=_ ~ "-----.--h:,,-:~.---~- "'~ . ~..l.-; .,_ ",_. ,;~", ...."-:;;:.";',W;;-,,,,- =~.,..~===~~'''-,--.,-,-~"

EFFECT OF TEMPERATURE ON TURBINE LIFE

(Principle of Arrhenius law applied to turbine life)
Indianapolis racer
500 miles + 10-0 __
(19th hole)

Military combat engine-----..

(18th hole)
Rate of
turbine
~ life loss .
Transport turbine engine - -
($l/golf hole
(17th hole)
won or lost)

Turbine temperature
(Golf holes)
J20003-1
PRATT & WHITNEY ~\I/",
AIRCRAFT GROUPV~. 781210
 ".

HOT SECTION COMPONENTS ARE SUBJECT TO

FOUR MODES OF THERMAL DETERIORATION

Creep/stress rupture

low cycle fatigue

U)
.......

Oxidation

Corrision

I
All modes are destructive, subject to the principles of II
Arrhenius law, and tend to accelerate by self I
I
generating mechanisms
J20003-9
PRATI & WHITNEY ;jill",
AmCRAFTGROUPV~.. 781810
~~~,~-~~-:~,~~",;.~~_~~"o::::l'7~:::=~....:.:;,j\.:,.~ :-"'.':~:;:~;:,:,;,,;: ::"~~1..:..:;:t~; ,"!' ...
".~:::::::::.t "':~.z; ',,'''' 'Yjm7ii3l1\"lO'>"crif,j,~,j,.-,;;,-~:;"~;..:;ru":,,,"":,.=-:~t:._~

AVIATION TURBINE ENGINE TRENDS

VERSUS AVIATION FUEL TRENDS
Engine trends
By passratio. _______ ---:-' ___ .__ .,..,...... ____ ~ ___ ~~ _____ 'ncreasing
Compression ratio ___________________________ 'ncreasing
Fuel efficiency ___________________________ Increasing

Severity of fuel thermal enviornmentin hot s(lction _______________ Increasing

Cost of hot section___________________________ 'ncreasing

Maintenance cost of hot section _______________________ lncreasing

\0
00
Allowable exhaust emissions _____ .,.-- _________________ Decreasing

Fuel trends
Cost 0-- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Increasing
Combustion quality __________________________ Decreasing
Thermal stability ____________ - ______________ Decreasing

Conclusions
Fuel qualitylrends -are not fully compatabJe wHhengine trendsaqduser expectations

Adequate fuel thermal stability is vital to the attainment of engine design, J20003-10
performance and cost objectives and to user expectations 781810

DDATT.,WU.'Yuev "\\11,,
THERMAL STABILITY ACTIVITIES

Maurice W. Shayeson
General Electric Company

99
 THERMAL STABILITY RATINGS OF TEST FUELS

FUEL JFTOT
NUMBER COMPOSITION BREAKPOINT, c
JP-4 260 + 15
2 jp-8 303 28
3 jp-8 + WHITE OIL 303 8
4 jp-8 + NAPHTHALENES 280 20
5 jp-8 + XYLENE 285 25
......
0
0
6 jp-8 + MORE XYLENE 275 35
7 JP-8 + LESS NAPHTHALENES 300
8 jp-4 + NAPHTHALENES 265 + 15
9 jp-4 + LESS NAPHTHALENES 250 10
10 jp-4 + XYLENE 280
II jp-4 + LESS XYLENE 275 5
12 jp-4 + XYLENE AND WHITE OIL 270
 --< --<-

UJ
~
N
o
Z

0...
:::> -l
tw
V>
0l..W
l..L.J:::>Vi ~
I--u.._ ~
I--
<C (!)' 0
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l..L.J;- m 00
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101
"""'"""-.~- '"",~""'-1~-;" "'"',""""","~,' ,--;~.~~::-:--
~-----

EFFECT OF FUEL THERMAL STABILITY RATING ON J79 FUEL NOZZLE FOULING TENDENCY

\.2
w
I-- w 0 JP-4 BASED FUELS
<C I--
0::: <C
0::: 0 JP-8 BASED FUELS
3:: ~
9 TA I LED SYMBOLS, XYLENE BLENDS
u.. 9
u..
w w /
f'l 1.0 ~0->-- 0- 0 - 0 ElfB-
N ~ ---- --,. - (9"---, - - -- _.- -
N , ,-- .'.
0 0
~ z z
N >-
>-
Gf
0:::
0:::
<C <C
:2: :2:
0::: -0:::
0...
0... 0.8 [ STANDARD ENG.INE FUEL NOZZLES
I-- I--
V')
w V') TEST DURATION: 5 HRS
w
I-- I--
I
I-- WI
FUEL TEMPERATURE: 478 K
V)
0:::
0
,
0...
0...
,
0.6 I J s I
SOD 520 540 560 580 600

ESTIMATED JUELTHERMAL STABILITY RATING, K

(ASTM MEtHOD D3241 BREAKPOINT TEMPERATURE)
E.:Axi*--;:J~Vt>ik-:-.'~:;-!,;;;~.1i:.~-""~':::;"-,,,~. i~":;;;~""''':""';':.i';".;: 7 _-::-'-::-,j. ';"~;.< . , t,"_;::;:o;r,-'-. --"-11--- - ..". ;;I:~ - ...... c"'" .","~.",.,;,~w:::::t;:;J:::&&:::::!:LiZ::J ~_u ---.~----,-"-- ----

JP-4 SAMPLES FROM W-PAFB

FA I LURE
BREAKPOINT MODE

TEXACO 265C TUBE

EXXON NO SAMPLE

-'
0
ALCOR 260C ~P
.j:>o

DUPONT 265C TUBE & ~P

NRL < 260C, 265 c TUBE, ~P

ASHLAND 260C ~P
 JP-8 SAMPLES FROM GE

FA I LURE
BREAKPOINT MODE
TEXACO <260C .DoP

EXXON <260C .DoP

--'
0
(J'1
ALCOR 220 c L\P

DUPONT <260C L\P

NRL 230C .DoP

ASHLAND 250 c .DoP

W-PAFB (UNLINED SAMPLE <280 c .DoP

CONTAINER)

W-PAFB (LINED SAMPLE >280 c,<290 c TUBE

CONTAINER)
 .'.:.--.-.:.:.:::.-~<::'.

0;:;."'

JP-8 SAMPLES FROM W-PAFB

FA I LURE
BREAKPOINT MODE
TEXACO <310C TUBE

EXXON NO SAMPLE

ALCOR 290 c TUBE

-'
a
0'1 DUPONT 300C LlP

NRL > 270 C,<285C TUBE

ASHLAND 295C TUBE

W-PA~B (U NED SAMPLE 300C, 310 c TUBE

CONTAINER)
 rlul rUELNULLLt IVItltKll\lG VALVt GUIVIIVIII\lG It~1 t<1:.~ULI~, HUI I-UI:.L ~YCLl~ II:~I t<1t;

VALVE SiN 22 1,6 SiN 2241 SIN 2272 SiN 2260

JP-4 @ "36 K JP-', @ 436 K Jp-B @ 436 K Jp-8 @ 1136 K

1.0r::~
1.0 ~L\Pf
0.8 E al L1f-'iCJ
r~f f"'~J!c'
._,,,,OJ,!
.... ('~ 4:';~,,;"r::G':;;
rro~tt"GOa1l .~,,~t\.,,:.~.f

0.8
=2.28 MPJ
,-'- - ' - - - -

~'f.l1?Pi ~~l;i'\!f.ri~l .......r;h-w..!'::1

:~Htr~d V
~o;
1.0
til
E-< 0.8 OIl'
cz
til
E-<
3 l 1:2~l MPil ~
cz ,r.., 0.6 L I
0
'-I
3
r..,
~
til
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,~. ';r
!l...-!:1
[:]..:J 't.!:iD
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~ I 0
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Ir
til
til (
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~ ., L..o,-:q~ ~ I
p.. o.B ~":"~'E i

0.6

0.4
II,~)
\ I
II'
o
~I
(.
"L~CENDING
\~leJ
I r.> ."

PRESSURE
0.2
CALIBRATION
I
0 r
0 1000 50 100 0 50 100 0 50 100
I
CUMULATIVE CYCLIC TEST HOURS
II
!
THERMAL STABILITY EFFORTS

A. E. Peat
Roll s~Royce Limi ted

109
 .
___ , -;~, ___ c_,~ -~_--".:.;' """"" ,~~-::":"";"'~-~_~,.,~,~=...r",,,,"",,<~-"""'-. --~ ...... _"'::'~""""'" ____ '''_~ ,-__ ___ ~_~~_c

'

/ r~()IlS Date
OCT 78
JEI THERMAL STABILITY-TYPICAL ENGINE DATA Chart No.
t

COMPRESSOR FUEL FLOWS

D TEMP. oK (0 C) ft /sec

........
a
AVON
I
590 (317 )
l 2 -"3 IDLE

~
, 4-35 TO.
* I

211-22 880 (607)

J
ONSET OF DEPOSITS Ex AVTUR Approx 175 o K :!: 25
(502)
\. j
 Date "'\
HIGl-t FUEL TE~I1PERATURE RESEARCH
i
IRdYCT
TEST CIRCUIT Charto.

~
----c--~~.- TE 5 Tel R.c. U I T
5ClO-GAL
C;Lt>..S':;'
C.[NTRI~UGA.L Tz
Pt..:MP
STE.1\1;1 LINED

~
PRE. - I
+--lHtATEf<
TA.t~K -tJ-IFLCW~~t~HHS;:1~~ I II ~fll1ERII--~ HP
PUMP I-
!,
II
~

I
f

~ FLOW , I
TO DUMP .. IFILT:;"~ I B(~.RNER.
A~., I:.M8l.'f
.. Isoc IC.ONTROL~I~lOWMETERI-4r:COC
U~ IT
I- I
I
T3 t
~

l
j
I
!

~ /
 . --~----

i~j. rUEL TE~/1P[R..ATUR RESEARCH

Da te ""\
r 111\\: HIGH
Chart No.
~Qlgj TEST TEMPERATURE LEVELS ~ND FUEL DI\TA :3

.'

~
TE.ST DtJRt>JION. FlJE.L TE PE p.:, UR 0c. \KROSINE FUEL THE.RMt>.L C.OKt::R JfiOT
N H:)URS SUPPLY HP PuMP FFR 8( .TR(~TMNT 56 oTA.BILlTTHRt.~HOLD nt~~110LD
TNtK IN 6URNEK 15/.5 "C b.,p INCHlS H'j 0<:;. OC

~ 12 "S
.....
..... 100 75 lie I~O A(.ID 0791 O'ISt()O'~
N

2. 100' 75 12>0 150 ACID 07<10 O-IS lo 0'2 IQO

3 100 100 140 175 MEROX 0'7<14- 0'051:,,0'2205/175 275/20.0

4 5: 110 170 200 ME-ROX o 7q2 u'05 to 0'1 175 270

 /',
l~~
HIGH FUEL TE.MPERt\TURE RESEARCH
NOMINAL TEST- CYCLE COt\IDITIOt\!S
Date

Chart No.
4

DUR.ATION E.NGINE'. ~o r: UE-1.. HP PUMP PRESSURE MAIN eURNE.R

r: L.O',,/ PSIG INLET PRES!lURE
CONDITION RPM GPH INLET DLlVr:P"I P~Ic;.

--'
5 MIN5 IDLE 00 II0 '10 300 30
w

I'
5 M\N~ MAX 100 400 eo 570 2. 90

2 HR. &> lv'\INo CR.UISE. qs 400 80 .;:. -II"

..;., f ,,,) 300

5MIN5 IDLE. 100 110 gO ~OG 30

15 MINSl STATIC o

--------------------------------------------_/
- ,-~- - -- --~----------
 ------.~~ ...

/ .. --~ Date '. ~

1
,,
j'UR SCHEMATIC DIAGRAM OF COMBUSTION APPARATUS Chart I
:. . ~ ". i I
- , No. 12 I
COMPRESSED ..... DRYING "- CO 2 ."-, OIL ,
,
AIR SUPPLY " TUBE ABSORBER "
ABSORBER

., ~

"-"

"'"
NONDISPERSIVE CATALYTIC TUBE FURNACE
..,

r
... INFRARED CO 2
ANALYZER
..,
"
900 0 C , ..:: ... .:.....-t-~
.,
",
OXIDATION FURNACE 500 C
0 I
I
.. '

q
(.)* \JFTOT TUBE
''-----0

--_.. _ . . -
RECORDER
GAS .__/ \.. ,.___ J,
METER
INTEGRATOR
 dJ
r-- 0
Cl' z
......
QJr-- s..
..... u '"
2 6

H'i'DROFINED
WITHOUT
ANTI-OXIDANTS
200

100 "-
"-
"-
"'-
"-
"-
"'-
"-
50 "-
"'-
GRAMS "- MEROX
OF
"'-
"'-
CARBON "-
X10- 6 " HYDROFINED PLUS
ANTI-OXIDANTS

COMPARISON OF THREE TYPES OF AVTUR.

NB. HYDROFINED WITH AND WITHOUT
ANTI-OXIDANTS.

115
Tc" 7""""--::-~:--" '-~"",,"'-- -,- '-; '-,--.-",",...". -''--.-~"."" -"-,,-
-~~-~-~-~~~-~"-""-"-"" ~". -----<~-"--~~ -~~---

I' ibm Date "

~rffi Ocr 7B. .
FUEL DEGRADATION - BURNER ARM char No.
~
14
BURNER Av. Wt. per. CARBONACEOUS TYPI CAL SPEC.
BORE mgm 0/0 ANALYSIS
MAJOR ELEMENTS

SPRAY 1- 0 50 - 90 Fe , Ni , Cr , Al ,
-'
( 100 hrs ) Si
-'
0'1 "

AIR BLAST 200 60- 85 Na , Pb , Fe , Ag ,

(2000 hrs av.) Si

(513 hrs) 16 0 85 Cu., Fe

--- - .
J
AIRLINE STATUS REPORT

Walter D. Sherwood
Trans World Airlines

117
 Many of us recall the birth of the subject of turbine fuel
thermal stability - back in the mid 1950's. The earliest problems
that I personally can recollect related to the P&W J-57 engine which
was the predecessor to the JT3 and JT4 series engines used on 707/0C8
aircraft at the onset of US Commercial Airl ine jet service. Because
of the seriousness of the problem, a shotgun approach was taken by
the engine manufacturer. Along with redesign of the fuel manifold
and nozzle arrangement, pressure was brought to bear on the industry
to develop a test to classify fuel as to its tendency to decompose
and form gum deposits under heat conditions. As you all know, the
"Erdco Coker" was conceived as an early answer to the determination
of fuel thermal stability. I relate this history only to set the
stage for the "history repeats itself" message I'm trying to convey.
Over the years since the mid 1950's, the coker test became more
sophisticated and engine fuel system designs were made less critical
of fuel thermal stability characteristics. Today, the somewhat contro-
~1
:-1
'J versial JFTOT tester, is being used more widely as a more sophisticated
I
j
tl
l device to determine the elusive thermal stability precipice for turbine
I. ~

H
,) fuels. At the same time, pressures for more efficient engine coupled
,.,1
1
i with over concern about aircraft engine contributions to air pollution
I'H
,;,i"
,;1
are driving the industry toward the return of the thermal stability
problems of 20 to 25 years ago. Witness the JT8D "low smoke" combustor
II"j designed to improve the esthetics of 727/737/0C9 airport operations.
Although I speak only of TWA exoerience, I have confidence that TWA's
problems are common with all JT80 operators experience.

118
 The JT8D "low smoke" combustor has accomplished the goal of de-
creasing visible smoke at the expense of increased maintenance cost.
,
Uneven flow patterns of JT8D fuel nozzles are the direct result of
fuel decomposition causing nozzle clogging which in turn results in
downstream hot section damage and deterioration of engine reliability
and performance. The fuel decomposition I refer to is the direct
result of the increased heat input to fuel in the fuel nozzles of the
"low smoke" combustor as compared to earlier JT8 combustor designs.
p.,s a means of combatin 9 this JT8D problem, TWA has developed an

"in-sitJ' flushing procedure for JT8D fuel manifolds and nozzles.

A concentrated solution of detergent and water is injected into the
primary and secondary fuel manifold connections at the P&D
valve. This solution is allowed to soak in the system for 30 minutes
and then a large quantity of detergent under high pressure is pulsated
through the sys tem fo 11 owed by a purge of high pressure air. TWA
experience with this procedure shows that high time nozzles (2000 to 2600
hours of service) are restored to within 90~~ of ne.w nozzle flOl'l rates.
HJA is presently flushing JT8D rlOzzles every 1000 hours as this best
fits its maintenance program and prevents excessive deposit build-up.
TWA estimates that this flushing procedure results in over $1 per engine
flight hour savings in hot section maintenance costs.
Although the JT8 engi ne is not a "new technology" des i gn, it will
be around for many years to come and at a high population density.
Looking at the newer technology designs leads one to the conclusion
that thermal stability and its characterization will be of increased
concern in the next decade and beyond. Wtih the emphasis on fuel
efficiency and ecology, future engine designs could increase thermal
119
stress on fuel and the need for a better definition of thermal
break points.
Although engine maintenance is a very important cost area in
commercial airline operation, the increased cost of fuel today over its
cost in 1973 makes fuel" the dominant portion of direct operating cost.
(35-40% of direct). It may come as a shock to those whose life has
been devoted to reducing engine maintenance cost to learn that fuel
consumption has become more important (2t to 3 times) than engine
ma i ntenance cost. However, to reassure the power plant engi need ng
fraternity, there is a strong bond betl~een fuel consumption and engine
maintenance. As Al Marsh pointed out earlier, engine cold section
condition can contribute to the health of the hot section and therefore
the end result - fuel consumption.
Maintenance of satisfactory fuel nozzle flow rate and spray pattern
will minimize turbine distress which greatly influences average ipecific
fuel consumption (pound~ of fuel per pound of thrust). Because of the
increasing importance of fuel consumption to the direct operating cost
picture, increased maintenance effort on engines susceptible to fuel
thermal stability problems must be thoroughly evaluated. Such increased
maintenance effort is a "band-aid" approach and design improvement
efforts are mandated for the long term solution to the airline cost
squeeze problem.
In summary, airlines today are faced with the return of thermal
stability problems of the past!

120
 APPENDIX B

ADVANCE QUESTIONS

121
GROUP I. BASIC RESEARCH

1. More information is needed on the effect of trace elements and com-

pounds on the decomposition of liquid fuels.

a) What is rate and mechanism of heterogeneous decomposition of

liquid fuels by trace C~ or 6ther element~ that might be picked
up in fuel linei?

b) Are there any foreign materials that could act the opposite way,
as stabilizers for liquid fuels?

c) What are heterogeneous catalytic effects Qn autoxidation reactions

of fuels?

d) What is the effect of temperature and pressure on all these sur-

faces or heterogeneous reactions?

2. Phenol is a "known antioxidant

a) What is effect of phenol on the stability of various liquid fuels

and the kinetics and mechanism of the reactions?

h) Would any products of the reaction Cause problems in"combustlon

such as increased emissions?

c) Is phenol stable in the gas phase: What is kinetics and mechanism

of phenol-fuel gas phase reaction?

3. What is the kinetics and mechanism of decomposition of certain organic

sulfides, phosphides and aliphaticamineswhich are known inhibitors
of oxidation reactions? Study'both in liquid and gas phase.

4. Mo~t organic sulfur and hrtrrigen compounds accelerate fuel decomposition.

But some, like certain a"mines, diphnyl sulfideanddibenzothiophene do
not accelerate fuel decomposition. What is key difference in reaction
mechanisms that"accounts for this effect?

5. What is mechanism of liquid fuel oxidation by dissolved peroxides?

Explanation of observed alcohol and ketone concentratioh prof(les would
help understanding of peroxide effects. How important is peroxide
reactions in the fuel stability problem.

6. How does me'chanism of decomposition of deoxygenated fuels differ from

that of 02 containing liquid fuel in the presence of various organic

123
 nitrogen and sulfur compounds? Usually deoxygenation helps fuel stabil
but not always. Mechanism of these reactions needs to be better under-
stood.

7. Are there synergistic effects when certain organic sulfur, nitrogen and
oxygen compounds (peroxides) are present together in an olefin fuel?
Some inpurities may be harmless alone but bad when present together.
We need to study the mechanisms of such interactions probably both in
liquid and gas phases.

8. Is the gas phase pyrolysis of hydrocarbons catalyzed by copper or other

trace liquid or solid impurities? Is pyrolysis of olefins and aro~atic
hydrocarbon mostly homogeneous or heterogeneous?

9. What is mechanism and rate of gas phase pyrolysis and oxidation of

various hydrocarbons in the presence of various organic.nitrogen and
sulfur compounds?

10. What is the stability in the gas phase of the 2 compounds diphenyl
sulfide and dibenzothiophene which db not promote hydrocarbon liquid
phase decomposition? How are their liquid or gas phase thermal decom-
positions different from that of other compounds that promote decompo-
sition of the hydrocarbon? (Combine with #4).

11. Propylene is a well known inhibitor of gas phase free radical chain
reactions. What effect would it have on rate and mechanism of pyrolysi
of a paraffin or aromatic hydrocarbon with and without the presence
of var i ous organ it nitrogen and sulfur compounds that promote free
radical decomposition? It might be interesting to find out also what
effect propylene has on the oxidation of paraffins. Usually olefins
are quite susceptible to oxidation, but a study of this system might
give some useful mechanism information.

12. What are typical quantities of oxygen dissolved in fuel and what
factors control this?

13. What are the actual molecules which are the building blocks of deposits
How can the structure and properties of these molecules be characterize

14. How do physical processes interact with chemical kinetic processes?

What is the role of solvent effects in liquid phase systems, volatility
effects in vapor phase systems and fluid mechanics effects in general?

15. How do microspherical deposit particles form from individual compounds?

How can these particles be more clearly characterized?

124
16. What is the mechanism of microspherical deposit particles collection
and agglomeration on surfaces and in pores of filters?

17. How should the effects of fuel composition on sediment and deposit
formation be elucidated? How can mechanistic kinetics studies and
basic research studies on the effect of fuel composition on deposit
formation be integrated?

GROUP II. LABORATORY CHARACTER I ZAT I ON TECHN IQUES

1. In the evaluation of deposits on JFTOT tubes

a) Should it be done by combustion?

b) Should non-carbon deposits be determined?

c) Is the TOR value of 13 acceptable for breakpoint temperature

determination?

d) Are color(ful) deposits indicative of incipient failure?

2. What are the needs for establishing reproducibility and precision

criteria in the JFTOT test?

3. To what extent should the deposit profile be considered? How should

the problem of the "solvent effect" be addressed?

4. What are the needs for uniformity of handling of fuel particularly in

regard to filtration? Is the 0.45 ~ filter realistic when considering
engine conditions?

5. What is the status of potential JFTOT replacement instruments or

methods?

6. Should there be a peroxide formation test?

7. What has been the experience with the heated reservoir modification
of the JFTOT tester?

8. Should there be an evaluation of the fuel just prior to injection

into the aircraft? If so, how should this be done?

9. There seems to be an ongoing effort in ASTM to correlate JFTOT data

with eRC Co1<er data. Is it really important to consider this?

125
 GROUP I II. APPLIED RESEARCH AND TEST SIMULATORS

1. What,simulators' are being or have been used.?, What are the results?
l,t", , " ' Are the reports available?
"": :::":'

2. What problems have been observed In p~actice?

3. What are the major causes of therm~l stability ~roblems?

dissolved 02
trace compounds of S, N2, 02, or metals
hydrocarbon composition & amount
metal surfaces
additives
interactions
storage time
other

4. Where would a thermal stability problem initially manifest itself,

in the ,injection nozzles, in the manifold, or on heat transfer
surfaces?

5.~hat area of an engine system would be the first to be adversely

affectedb'y,a stability problem?

6. Should a simulatIon attempt to simulate that portion of the engine

that s,hows" the fi rsts ign of the prob.!en,or the most 'cri tical area?
Can both be done? '

, ,

7. What scale of testing would be meaningful and would allow extrapolatio

to a real engine?

"'- 8, "What is a real,iStic,and practical temperature and pressure profile,

and cycle, for a simulator? '

9.' How shouldstab'ility bedeterinined in a simulator?

" 0 ' ': ':"

spray characteristics
LIP
change' in heat tran~fer coeffici~nt
amount 'of 'depos'i ts '
composition of deposits
amount of carbon in deposits
I other
, I

126
I
10. Isit necessary or desirable to fully identify deposits?
,

11. Are all the parameters scalable?

12. Can the tests be accelerated?

13. Would any trends or projections of future fuels or fuel systems change
any of the above?

14. How would an SST simulator differ from one designed for subsonic
flight?

GROUP IV. ENGINE SYSTEM TRENDS AND REQUIREMENTS

1. Are there any problems, borderline situations, or sensitive areas

with respect to thermal stability for present specification fuels?
Is there adequate statistical overhaul data to pinpoint these problems?

2. What wi II be the trends in the near future wi th respect to thermal

stability requirements? Will the low emission combustor designs make
increased demands on thermal stability and, if so, in what respects?

3. How well do the present specifications, such as JFTOT, relate to

actual fuel degradation behavior in engines? Is there a predictable
relationship between JFTOT and actual thermal breakdown in the field?

4. What trade offs are there between stringent requirements for fuel
thermal stability, and engine time between overhaul? How Iowa thermal
stability fuel can be tolerated? Can reduction in engine efficiency
with operating life be linked in some respects to fuel deposits?

5. What are the effects of fuel degradation or fuel nozzle performance?

Can nozzle designs be made less sensitive to fuel deposits?

6. What effects may fuel degradation have on heat exchange surfaces in

the engine system?

127
 7. Are these critical areas with respect to thermal stability in the fuel
system, outside the engine? Will fuel heating systems, such as for u~
of high-freezing-point fuels add more thermal stability stresses to
the system?

B. Is the fuel delivered to the user the same, in terms of thermal

stability, as that specified at the refinery? D6es storage instabilit
contribute to thermal instability? Would point of del ivery, quick te~
be of benefit?

9. What is the feasibility of using fuel purging, fuel cooling, or

insulation to minimize fuel temperatures?

r
[

It~
~
~1
!]
:. i.
il

[. 1 .1

tl
il
II
[,].1
',':.'
..

fi
[I
128
tl
["I
~~
 APPENDIX C

WORKING GROUP REPORTS

129
 GROUP I. BASIC RESEARCH
Chairman; Robert N. Hazlett

PART I

WHAT DO WE KNOW ABOUT THE BASIC CHEMISTRY AND PHYSICS

OF THERMAL OXIDATION STABILITY?

A. Mechanisms of Deposit Formation

1. Oxidation is the trigger

2. Chemistry is largely tree r~dical but condensation

reactions may also be important (e.g., aldehyde
condensations)

3. Reaction is temp. dependent - start'\, 200F

4. Metals influence deposit formation

a) heterogeneous (SUrfaCeS)} different

b) homogeneous (dissolved) mechanisms

Copper is most deleterious metal - effect may

depend on fuel composition

5. Solvent effects important but still poorly understood

6. Deposits form in both liquid and vapor phases - in wing

tanks worst situation exists when both phases are present

B. Characteristics of Deposits

1. Most are rriicrosph'erical but other .morphologies are

observed (plates, rods)

2. Temp. and dissolved O influence morphology

2
3. Other characteristics include

a) Hie ratio is lower than original fuel

b) Oxygen level is greatly enhanced in desposits
c) Other heteroatoms are concentrated

C. Effects of Fuel Compositions

1. Hydrocarbon types

a) benzene derivatives less deleterious than napthalene

b) some olefirisdeieteriou~
c) acetylenes greatly promote instability

2. Oxygen and nitrogen containing species can be deleterious -

also sulfides - aldehydes

131
 3. Interactions between fuel components are important

4. Dissolved 02 content critical - is typically 50-75

ppm in air saturated fuels at sea level.

D. Effects of Storage and Handling on Thermal Stability

1. Handling and sampling may be more important than com-

position effects

2. Storage effects variable - some fuels show improved

stability - others worsen

3. Erratic storage effects may be related to peroxide

content of fuels - these decompose on standing

4. Recommended storage procedures

a) Deoxygenate fuel before storage

b) Avoid light
c) Keep metals out
d) Preferred containers - Pyrex glass or Epoxy-lined
metal cans
e) Decompose peroxides prior to storage via heat or
by chemical reduction

E. Use of Additives

1. No "universal" additives - effectiveness depends on

fuel composition

2. Anti-oxidants useful in enhancing storage stability -

probably not thermal oxidation stability

3. Other potentially useful additives:

a) Metal deactivators - especially for copper

b) Dispersants - keep deposits dispersed - but tend
to disperse H as well
c) Metal passiva~ors

I
[1
4. Lubricity additives may adversely affect thermal
stability
11 5. Additives can interact in as yet unknown ways - have
n
II to be aware of possible problems
n 6. Market for additives not developed - inhibits research

[I 7. Future developments - e.g., synfuels may require additives

p trade-offs between hydrogenation costs and additive usage
will be needed
II, 132
 PART II

WHAT SHOULD WE KNOW TO ADEQUATELY DEFINE AND/OR

RESOLVE THE PROBLEM?

A. Deposits

1. Using ESR on solids formed from fuels, can one see

evidence for radical reaction pathways?

2. We need more detailed information on gum deposits,

preferably from actual engines or storage tanks.

3. What happens to deposits on JFTOT tubes or actual

engine parts as it remains on the hot surface?
Does it pyrolyze? Do the earliest deposits differ
greatly from later adherent materials? How does
the composition change with depth for deposits on
both real-life engine parts and JFTOT tubes?

4. How does a microspherical deposit particle form?

Is it via a second liquid phase which forms a sphere
due to surface tension?

5. What is the molecular weight distribution of soluble,

insoluble, and adherent gums and deposits?

6. What is the difference between surface varnishes

(adherent gums) and filterable deposits?

B. Metals

1. What is the importance of dissolved metals versus

surfaces? (e.g. would inert surface show similar
effects?)

2. What happens to the rate of deposition after surfaces

become coated, thus probably eliminating exposed
metallic surface effects?

3. How do dissolved metals catalyze fuel deterioration?

Is it non-radical chemistry?

C. Storage and Aging

1. When obtaining fuel samples for testing, where in the

fuel stream does one sample? - At the refinery, from
a tank car, from a fuel tank in a vehicle? What con-
tainers do we use for samples?

2. If one removed all dissolved oxygen and peroxides, would

there be any storage stability problems?

133
 3. The thermal stability has been observed to improve,
degrade, or remain constant after storage of various
fuels- why? What is hapPl'lning? What is the differ-
ence between the fuels that improve and those that
degrade?

D. Reactions

1. Aside from free radicals, what reactions are taking

place and what is their relative significance? (e.g.,
conq,ensation of ketones and aldehydes)

2. Is it possible to stop the initial oxidation reaction?

3. What happens to di-olefins? Are they found in jet fuels?

4. What is the significance of bi-functional compounds, as

well as hetero-atom compounds where neighboring carbon
atoms tend to be more reactive? '

5. What are the mechanisms of diphenyl sulfide, diphenyl

disulfide, and dibenzothiophene reactions in a clean
system?

E. Additives,

1. Could dispersants decrease the severity of problems

from gum formation? Can dispersants play a useful
role in stabilizing fuel and what are their effects
on other properties?

2. Is the need for different additives for different

fuels because of trace contaminants or fuel hydro-
carbon composition? or both?

3. How is additive performance affected by boiling range

of,fuels?

4. Are there any peroxide decomposers, radical scavengers,

or combination of both, which are both effective and
reasonably priced? (must be non-metallic)

F. Miscellaneous

1. Hhy does pre-treatment (clay, H , chemical separations)

2
improve stability of some fuels and not others?

2. How much oxygen is dissolved in fuel at various ,stages

during flight?

134
 3. What is the relationship betwe'en thermal stability
and boiling range of fuels?

4. Will pre-vaporization pose any new thermal stability

problems?

5. Solubility effects are unknown, but too complex for

immediate attack. This may become a critical area
when synfuels begin to be blended in. '

PART III

WHAT EXPERIMENTS WILL GIVE THE INFORMATION WE NEED?

A. Deposits

1. Employ modern surface analysis techniques: ESCA, Auger,

Pyrolisis GC, ESR, CIDNIP and study deposit vs. depth
especially for actual engine parts but also JFTOT and
other test devices.

2. Check deposit chemistry and morphology for possible

changes with time due to temperature on the hot surface.

3. Compare filterabledesposits and varnishes.

4. Investigate solubility effects on deposits - include

effects of fluid temperature, fluid and deposit
chemistry, and flow rate.

5. Study deposit morphology and chemistry as a function

of parameters: T, P, O , aging and composition of
2
fuel.

6. Employ photo-acbustic spectroscopy and/or attenuated

multiple reflectance IR to analyze gum and especially
solid thermal deposits.

7. Employ radioactive tagging of contaminants.

B. Metals

1. Compare 3 possible metal effects

Dissolved'metals

vs. Metal surface

vs. Non-metal surface

Look for stoichiometric metal involvement by

analysis of deposits.

135
 2. Investigate metal effects with and without 02
and peroxides.

3. Check the effects of nitrogen compounds on copper

pickup (especially in light of synfuels)

C. Storage and Aging

1. Monitor thermal stability from refinery through

supply system

2. Aerobic aging - check peroxides and electron spin -

initial and with time

3. Anaerobic aging - do peroxides account for all the

aging

D. Reactions

1. Test fuel and deposits with ESR and CIDNIP for free
radical reactions.

2. Follo,v disulfide decomposition with ESR.

3. Follow fouling reaction mechanisms/precursors in liquid

phase employing field ionization mass spectrometry and
other techniques.

4. Analyze oxygen concentrations in liquid and vapor phase

in storage and aircraft tanks and as a function of time
through flight conditions.

5. Examine effects of prevaporized/premixed fuel on

deposition.

6. Explore MW in dispersions and in adherent deposits

by light scattering/Tyndall effect and/or gel per-
meation chromatography.

7. Test effect of bifunctional N, 0, and S materials.

8. Study variations of thermal stability with boiling

range of real fuels.

9. Analyze fuels for trace components and their effects

On fouling, using "specific detector" gas chromatography.

E. Additives
1. Investigate "peroxide decomposers" for controlling
deposition (as used in the polymer industry, such as:

Ni diacetylacetonate
and non-metallic equivalents)

136
 2. Explore antioxidant and dispersant thermal stability
effects in a variety of fuels.

3. Study inhibitor interactions in storage and fouling.

F. Miscellaneous

1. Investigate effects and mechanisms of various treatments -

clay, H2 , separations - on thermal oxidation stability and
composiEion of fuels.

2. Examine deposition as a function of reaction mechanism or

deposition mechanism.

137
 GROUP II. LABOAATOR':I CHARACTERIZATION TECHNIQUES
Chairman: Charles R. Martel

I. OBJECTIVE

To determine the status of existing laboratory techniques suitable for

determining the thermal oxidative stability of aviation turbine fuels; to define
the problems and shortcomings of these techniques; and to iqentify recommended
research and possible improvements in these techniques.

II. EXISTING LABORATORY TECHNIQUES

The laboratory techniques available for characterizing the thermal

.oxidative stability of fuels are listed and discussed below.

A. JET FUEL THERMAL OXIDATION TESTER (JFTOT)

The JFTOT is a relatively new test method now in use for aviation turbine
fuel quality control per ASTM D3241. The test fuel is flowed past a polished
aluminum heater tube and then through a 17 micron filter. Plugging of the
filter or the formation of deposits on the heater tube darker than a light tan
are the test criteria used to characterize fuel thermal stability. Test
temperature, test time and test pressure are variable.

1. Status - The JFTOT is widely used as the quality control check for
aviation turbine fuels. Normal pass/fail operating conditions are 260C
heater tube temperature, 500 psig operating pressure and a 2 1/2 hour test
time. For commercial fuels a waiver to 245C heater tube temperature is
available.

Work is underway by the AF to select suitable JFTOT test parameters for

speciality jet fuels JPTS and JP7.

2. Problems-

a. Choice of test parameters - The choice of JFTOT test parameters

!~ has been based largely on the older ASTM-CRC Fuel Coker, as the JFTOT is
::j1 basically a minaturized coker. A better understanding of the deposit formation
conditions in actual aircraft engines would likely improve JFTOT accuracy
..
I
(i.e., the ability of the JFTOT to predict the deposit forming tendencies of
fuels). Specific parameters of concern include:

(I) Test pressure selection - Presently the JFTOT is operated

above the critical pressure of typical jet fuels. The quantity of heater tube
deposits can be increased by operating the JFTOT at a lower pressure near the
boiling point of the fuel. Also, deposits appear to differ significantly
between single and two-phase flow. The ideal or most realistic test pressure
has not been established.
(2) Fuel prefiltration - Currently the fuel to be tested in the
JFTOT is filtered through Whatman filter paper of 17 micron nominal pore'size.
within the JFTOT a 0.45 micron filter is used immediately prior to the heater
tube to improve test precision. This high degree of filtration is unrealistic
as compared to actual aircraft fuel systems. The degree of prefiltration is
knovm to affect the amount of deposits formed with some fuels.
 (3) Test filter temperature - In the JFTOT the temperature of
the test filter is not directly controlled. The test filter in the JFTOT,
being downstream of the heater tube, is supposed to simulate engine fuel
nozzles. By not controlling the temperature of the test filter the accuracy
"c:>f ,the simulation undoubtedly suffers, but the effect of this factor on the
accuracy of the JFTOT is unknown.

b. JFTOT Calibration - There are no absolute standards that can be

used to calibrate the performance of the JFTOT (or of any other thermal stability
test device.) The use of standard reference fuels has been proposed to improve
the precision of the JFTOT.

c. Tube deposit rating - Currently, deposits are rated by visually

comparing deposit color to color standards. This method is highly subjective,
has poor precision, and is of unknown accuracy (i.e., the deposit color ~ay not
correlate with heat exchanger fouling and engine fuel nozzle plugging). The
Alcor Hark 8A Tube Deposit Rater (TDR), an optical reflectance device having
improved precision but not necessarily improved accuracy, is available but is
not in widespread use. Research has been done on various alternative deposit
rating methods including beta ray backscatter, deposit combustion with sub-
sequent measurements of the carbon dioxide formed, l1uger spectroscopy, and
ell,ipsometry. None of these al ternati ves has been, ,developed to a point sui table
for laboratory use.

3. Opportunities:

a. Deposit Profile - The heater tube deposit profile vs. tube length
and test temperature may provide useful information such as the prediction of the
breakpoint of the fuel, unusual solvent characteristics of the fuel, two-phase
flow, etc. Deposit colors may indicate the presence of undesirable trace metals
such as copper.

b. Since additives are known to reduce deposit formation or modify

their character, their effects on JFTOT ratings should be more widely investigated.

c. Heated reservior - The heated reservoir now available provi,des a

significant increase in time for free oxidation reactions at a controlled temp-
erature ahead of the test section. It may prove to be highly useful for
determining thermal oxidation stability problems with certain types of fuels.
It has the possibility of turning the JFTOT into a miniature fuel system simulator
suitable for research programs.

d. }letal Catalysts - By using heater tubes of varying composition the

effects of different metals on deposit formation can be determined.

e. Long Term Tests - By using a larger reservoir or an external source

of test fuel, extended JFTOT tests can be run for ten's to hundred's of hours
to examine, deposit formation vs. time and test temperature.

4. Reco~~ended Research:

a. Examine actual aircraft and engine fuel systems and determine the
actual temperatures, pressures, flow rates, etc. of the engine fuel nozzles that
are experiencing plugging problems. Use these data ,to select more realistic
JFTOT test conditions (pressure, temperature, residence times, prefiltration,
etc. ) .
139
 b. Recommend that ASTM be asked to re-examine the need for and degree
of in-line fuel pre filtration for the JFTOT.

c. Research is needed to identify and develop improved tube deposit

rating techniques that correlate with fuel heat exchanger fouling and nozzle
plugging.

d. Reference fuels such as pure hydrocarbons and concentrates containin

reactive species should be investigated for use as calibration fluids.

e. Temperature control of the JFTOT test (Dutch weave metal) filter

should be investi~ated'. "

ILB. ASTH-CRC Fuel Coker

AHSI/ASTI1 D 1660

1. status:

These instruments have been used successfully for over twenty years to furni
thermal stability characteristics of aviation turbine fuels. Many laboratories
outside of Eastern Europe and'Western Asia have ohe or more units. The fuel
coker is still in production to meet a continuing world-wide demand. The manu-
facturer of the coker, Erdco Engineering Corporation, will continue to furnish
the components required for test and maintenance.

The allowed manufacturing tolerances for the test filter and inner tube are
being tightened, and the fuel pump capacity will be increased to provide greater
bypass and to further reduce the possibility of pulsations in fuel flow. ~hese
charges have yet to be evaluated by ASTH, but are hoped to improve test precisio

The instrument cabinet is being redesigned to utilize lower cost enclosures

to reduce 'the need for higher prices with declining instrument shipments.

Usage of the ASTM/CRC Fuel Coker declined for five years based on shipments
of test filters and inner tubes. During the last two years, demand has increase
I, with an even more marked growth during the last year. This has caused inventory
!' outages which are' being corrected.

2. Problems: (a ttributed to users)

1. Sample size limits ease of shipment

2. Intermittent pump effects

3. Precision of filter
i!

4. Repeatability of test results

I,
I 5. visual rating of tube deposits (See ILA.2.C., above).
, ,
, I 3. Opportunities:
"

Work is underway to tighten test component tolerances and to reduce the

pump effects to improve precision.

140
4. Research Needs:

Reference fuels are needed so that instrument performance could be checked

periodically (See II.A.4 .. d., above).

Information is needed as to the actual effects of trace elements in the

fuel on thermal stability, as trace elements are believed to promote
deposition. If this is of concern, the sample size and length of test required
may need to be increased in order to obtain useful data when the trace elements
are present in parts per billion quantities.

II.C Research Fuel Coker

1. Status:

Approximately fifteen of these instruments .are available worldwide. Due to

their ability to test at higher temperatures, improvements in the thermal stability
of fuels such as JP7 have been obtained.

2. Problems:

This instrument is a higher temperature version of the ASTM-CRC Fuel Coker.

The test filter is the same for both units and the preheater tube is of stainless
steel for the Research Fuel Coker. The users have not reported any operational
problems. Also see JFTOT and ASTM-CRC Fuel Coker discussions above.

II.D. Monirex Fouling Monitor

1. Status:.

Monirex jet fuel testing has been done on a differential hot wire device
using two different fuel samples which are, in every way possible, subjected to
the same. test conditions. Hot wire sensors are used to collect foulant deposits.
Results are based on the difference in the rates of change of the heat transfm:
coefficient for the two fuels. The Monirex Fouling Monitor is presently in
product development. Delivery and costs are not available at this time. The
original Monirex device using a singl~ hot wire has been used for refinery
fouling tests and is also in product development.

2. Problems:

The Monirex hot wire Fouling Monitor is still in development.

3. Opportunities:

The problem of interpreting JFTOT and coker tube deposit data can be eliminated,
as the Honirex unit outputs heat transfer data about the deposit fouled wire
surface.

The Monirex device capability to test at one specific wire temperature pro-
vides an opportunity to evaluate in greater detail the mechanisms of fouling.

141
 4. Research Needs:

Research needs include further evaluation of the hot wire method, and the
differential fouling test method. Development of a reference fuel for better
device precision and inter-device correlation would advance the state of the
art.

II.E. Thermal Fouling Tester (TFT)

1. Status:

The TFT, a derivative of the JFTOT, is presently in wide use as a

laboratory device to evaluate the effectiveness of antifoulant additives in
refinery feedstock.

In its basic function the TFT maintains a preset fluid discharge temperature,
and the rise in heater tube temperature is indicative of fouling or deposit
build-up on the heater tube.

2. Problems:

From recent CRC work it '.;as established that in its present configuration, th,
TFT is not too well suited for establishing thermal stability characteristics of
turbine fuels.

3. Opportunities:

with the design of a new test section and an operating technique specifically I
tailored to discriminate and rank jet fuels, this device could possible equal
or perhaps surpass the present JFTOT technique. In this technique, rating of a
fuel sample would be strictly based on heat transfer characteristics of the
deposits generated and expressed as a maximum delta T attained. Such a rating
system would be highly desirable as it excludes the operator from having to
make a rating judgment as is now the case with the JFTOT visual method.

Disadvantages of the TFT would in all probability be an increased test time

in order to generate a significant delta T.

II.F. 1~ornton Flask Test

1. status:

This portable test device is used for rapid field measurements of the thermal
stability of aviation turbine fuels. The procedure uses alSO ml sample in a
250 ml Pyrex flask (which is open to the atmosphere) immersed in a 150C controlll
temperature bath for 60 minutes. Fuel degradation is assessed by either
measurement of the reduction in light transmission using a spectrophotometer or
more simply by assessing the extent of color change using available standards.

2. Problems:

tj A rough correlation has been established with a 1/2 scale simulator and
H laboratory test methods. However, the repeatability of this test is in the
order of + 10% when used for field measurements.

142
3. Opportunities:

The method provides (1) a portable and easily conducted procedure for field
measurements, (2) field samples may be taken directly into the test unit, thereby
reducing sample container/shipping problems, and (3) the procedure provides a
measurement in 1-1/2 to 2 hours.

4. Research Needs:

Further development is needed to (1) improve the repeatability and (2)

provide correlation with specification techniques.

II.G. Oxygen Uptake Measurements:

Oxidation mechanisms of liquid hydrocarbons are usually studied by

researchers in laboratory glassware. Typically oxygen is bubbled into a pure
hydrocarbon such as tetralin dissolved in a solvent .. The mixture is well-
stirred and held at a specific temperature. The amount of oxygen absorbed is
measured as a function of time, and frequent samples of liquid (and gaseous)
products are taken to measure hydroperoxides, complex intermediates, acids,
ketones, etc. Frequently metal salts are introduced.to catalyze oxidation, and
sludge products are measured by filtration and weighing. Many variations of this
technique are employed - air for oxygen, reflux, metal strips, highly sophisticated
techniques to measure oxidation intermediates, etc.

Measuring oxygen uptake alone in a typical jet fuel under well~controlled

temperature conditions. is relatively simple but it would be necessary to also
measure oxygen products or sludge for a meaningful test. The technique does not
lend itself to quality control as does a rig such as the JFTOT but is more
useful for research studies into oxidation mechansim:and system variables.

II.H. Thermal Precipitation:

The thermal precipitation test consists of heati~g the fuel to 300F for two
hours. After cooling, the fuel is filtered through a 0.45 micron Millipore
filter and the color compared to a standard color ch~rt.

The test was developed after sluggish response and sticking was observed in
close tolerance parts subjected to hot Jp-7 fuel. R~search coker tests of the
Jp-7 fuel did not identify this aspect of therma.l ins:tabili ty.

The thermal precipitation test is a specification, requirement for

MIL-T-38219 Grade JP-7 fuel. It is useful for fuels where cyclic heating and
cooling in the system may leave deposits which affect l engine components.

The thermal precipitation test is similar in prink::ipal to the Thornton

Flask test described above.

143
III. RELATED PROBLEMS AND RESEARCH NEEDS

A.' SAMPLE CONTAINERS

The importance of sampling procedures and sample containers was discussed

during the Plenary Session. The Coordinating Research Council has a small
program underway to investigate this problem. Suppliers and consumers are to
submit their sampling techniques which will be compiled and evaluated by the
Thermal Stability Group of the Coordinating Research Council.

The results of poor sampling techniques and thei:r effect on the thermal
stability test results have been documented both in these sessions and in other
technical meetings. It is this group's recommendation that both sampling and
sample containers be seriously considered in order to maintain the validity
and preci~sion' of the various thermal "stabili ty test methods Areas to be con-
sidered would, ,i.nclude : (1) Sampling' Idca tion and method, bf drawing samples.
(2) Types ,of sample containers and ,how the' containers would be used in
sarnpli'ng. If using epoxy-coated containers, should the type of epoxy he, specified
amlshould, the epoxy coating undergo, a fuel exposure period before using. If
unli,nedsample contners are to beused,how should they be treated or rinsed with
fuelpripr to ,sampling. Also, sample container seals must also be considered.

This work will be valuable for other. fuel tests where sampling is important.

III.B. PEROXIDE FORMATION TEST FOR THERMAL STABILITY OF JET FUEL

Peroxide formation has been proposed as a test to assess thermal stability

based on an autoxidation mechanism for deposit formation. (See CRC Literature
Survey-Jet Fuel Thermal Oxidation Stability, Chapter IV). Peroxide compounds
are found in the propagation steps and in the termination step products.

Peroxide formation has not been widely applied to jet fuel thermal stability
testing and further investigations are required. The relative importance of
peroxides 'and fuel components to final deposits has not been established and
it is likely that this will vary markedly among various fuels. Peroxide
formation is suitable for research. studies of thermal stability and problems
with specific fuels but is not recommended for general thermal stability testing
of all jet fuels.

IV . GENERAL COl-L.'1ENTS

A. FUEL THERMAL OXIDATION TESTS

All of the existing laboratory techniques discussed in Section II, above, are
fuel oxidation tests. oxidation tests, being rate and time dependent, are non-
equillibriumtests, ,and by their nature have poorer precision thanequillibrium
tests such as gravity. Tightening mechanical test variables such as temperature,
flow rate, and pressure can afford only limited benefits, and a point is soon
reached where little or no further improvement in test precision will be realized.

144
B. RELATION OF SMALL SCALE TESTS TO FIELD PROBLEMS

The Applied Research and Test Simulator Group and the ~ngine System Trends and
Requirements Group both reported that engine fuel nozzle plugging was. the most
critical thermal stability problem in today's and tomorrow's engines. Engine fuel
nozzle types in current use include the pressure atomizing type, the pressure
atomizing-air assist type, the slinger type, .and the airblast atomizing type. The
various types of engine fuel nozzles differ significantly in their susceptability
to deposits and to the nature of the deposits. For example,the hard lacquer
type of deposit may cause malfunction of nozzle valves that switch fuel flow from the
primary to the secondary nozzles, while the formation of thick, flaky "deposits can
result in the sudden blockage of small orifices.

Existing small scale tests do not attempt to differentiate among deposit types.
Furthermore, to obtain sufficient deposits for detection the test is significantly
increased in severity to obtain test results in a matter of a few hours with a
small quantity of test fuel. The test condition used with the JFTOT, Cokers,
Monirex, .and the Thermal Fouling Test are selected to obtain detectable deposits
in a matter of a few hours. These test conditions differ significantly from the
actual engine nozzle conditions that may result in deposits aft~r several hundred
or several thousand hours of operation.

145
 GROUP III. APPLIED RESEARCH AND TEST SIMULATORS
Cha;rmanl Royce Bradley

1. Several simulators are in use or have been in use to evaluate fuel thermal
stability. Two simulators, Shell-Thornton's half-scale rig and the USAF's
advanced aircraft fuel system: simulator are both large scale rigs and involve
complete fuel systems. Other simulators such as the USN's single tube heat
exchanger and General Electric's and Pratt &Whitney's nozzle simulators
only consider one portion of a fuel system, At 1east two additional simulators
are planned, one by United Techriology Research Center (UTRC) and the other
oy Rolls-Royce. BothDf the proposed simulators are primarily concerned with
thermal stability in the engine fuel system. Both programs are parametric
efforts with the UTRC program being somewhat more limited in scope tryan the
Rol:l s-Royceprogram. ..
2. Reports are or will be available delineating the results obtained on each
of the simulators. Published reports are listed in the thermal stability
literature 'survey that will be published by the Coordinating Research Council.
3. Problems experi enced in opera t i on are i ni ti ally encountered in the nozzl e
area; i.e., nozzle plugging due to deposits in the discharge orifice and
other small passages or gum formation between moving components. These problems
are equally likely in both subsonic and supersonic aircraft. Long residence
time in certain locations (e.g., divider valves) and high heat flux are the
primary contributors to the problems. Performance degradation problems are
also experienced in heat exchangers, however, the effects are much different
than in nozzles. Heat exchanger performance degradation is gradual and can
often be delayed by oversizing the heat exchanger. In contrast, deposit
flaking may cause plugging of individual fuel nozzles and subsequent performance
problems; design changes to reduce this problem are much more difficult.
4. It is difficult and expensive using aircraft type hardware, to design a
simulator that will provide the necessary conditions found in a given aircraft
engine. It is even more difficult to design a simulator that will generate
data relating to fuel performance in a variety of different aircraft. This
latter difficulty is due to the tremendous variation in aircraft environmental
conditions and hardware.
5. The need for a complete parametric study that will provide data under a
variety of steady-state conditions is evident. The study would use a device
consisting of an instrumented tube capable of being exposed to the entire
range of engine conditions and designed to give quantitative data on the rate
of formation and characteristics of fuel degradation products, particularly
deposits formed under these conditions. The results from this effort could
then be used by the designer to predict the performance of fuel in an air-
craft, the results could also be used to evaluate small-scale test devices.
The priority of the parameters to be included in a program of this type
differ depending on whether emphasis is in the area of design or fuel studies.
A list of these parameters and the order of importance to the two areas are:

146
 PARAt~ETER Dt:SIGN FUEL
Hall temperature 1
Inlet temperature 2 2
Velocity (Reynolds Number) 3 3
Residence time 4 4
Pressure 5
Surface/Volume Ratio 6
Materials 7
Surface Finish 8
Cleaning 9
Dissolved Oxygen 10
Fuel Type 5
Contamination 6
Additives 7

During parametric testing, the heat flux used in preconditioning the fuel
must be minimized to avoid unrealistic fuel deterioration in the precondi-
tioner. It is not yet known whether simulator testing can be accelerated.
The results of these parametric tests should indicate the possibility of
accelerating future tests both 9n this test device and on small-scale devices.
It is noted that by sufficiently reducing the pressure and/or increasing the
temperature in the test device the effects of two-phase flow and supercrit-
ical conditions on thermal stability can be investigated. The fuel type can
be varied to include fuels from alternative sources in addition to currently
produced fuels.
6. It must be realized that the results of the parametric program won't
answer all questions regarding fuel performance in an aircraft engine; e.g.,
steady-state results may not be additive in a dynamic system. However, the
parametric program should provide the best source of predictive data for
design purposes. Final confirmation may require a test program using air-
craft engine hardware for each specific aircraft of concern.
7. It is recognized that the design of supersonic aircraft fuel systems
will require a fuel tank simulator (akin to that described above) in which
flight parameters and their effect on thermal/oxidative stability can be
systematically studied. Clearly the geometry will differ from the engine
simulator, as will the selection and range of variables. The device should
incorporate means of studying the effects of tank insulation, inerting and
cleaning techniques. It is further recognized that the engine and aircraft
tank simulations will likely be carried out independently until such time as
a system design is laid down; at that point, integrated systems tests are
indicated.

147
 GROUP IV. ENGINE SYSTEM TRENDS AND REQUIREMENTS
Chairman: Walter D. Sherwood.

INTRODUCTION:
This group took note of the importance of fuel efficiency, en9ine
durability, and emissions. Some reasonable balance is necessary because
gains in some areas cause degradations in others. The group examined
the impact of fuel properties, particularly thermal stability.

SUMMARY OF CONCLUSIONS:
1. There are problems and sensitive areas in engine fuel systems
with respect to deposits with today's fuel. The relative influence
of factors (i.e. fuel system design, operational procedures
or thermal stab;l ity per se) cannot be defined.
2. Trend~ in engine desiqn are toward a pbtentia1ly more severe
environment for fuel, however today's thermal stability levels
will be the tarqet.for new engine designs. Low emission combustor
desians could make increased demands on thermal stability and
therefore care must be exercised to ensure that nozzle and
manifolding design caters to the problem. Reco~mition of the
practical limits of emission control must be achieved by all
regulatory agencies acting in concert.
3. Relationship between thermal stability test methods and
actual fuel degradation behavior in engines is unknown. The
predictable relationship between JFTOT and actual behavior
in the field is only directional in nature.
4. Fuel cost at today's prices is several times the total engine

maintenance cost in the direct operating cost picture.

148
5. The effect of fuel degradation on fuel nozzle performance is to accel-
erate turbine performance degradation and increase fuel consumption and
engine maintenance. Fuel system/nozzle design or redesign to achieve
less sensitivity to fuel deposits is possible in some cases.
6. For subsonic commercial engine operations, fuel degradation effects on
heat exchangers (fuel/oil coolers) has not been a signiflcant problem
to date and does not appear to be a future design problem with fuels
meeting present specifications. For potential supersonic commercial
applications, research on effects of fuel with various thermal stability
levelS should be conducted .for heat exchanger system designs.
7. With today's commercial aircraft designs, there are no areas outside
the enginec:onsideredcritical from a thermal stabil i.ty standpoint.
Properly designed .fuel heating systems will not add more thermal sta-
bility stresses to the fuel on subsonk commercial aircraft.
8. Thermal stabil ity at airport del ivery points is a potential question
to be resolved (see recommendations). Storage instability contribution
is not of concern in commercial operations due to the relatively short
time between production and consumption of the fuels involved. Point
of delivery, quick tests for thermal stability are not considered of
sufficient benefit to merit development at this time.
9. Need for purging, cooling or insulation is highly dependent on applica-
tion of the engine. Feasibility of any of the foregoing is completely
design sensitive.

149
RECor~MENDATIONS :

1. NASA should sponsor or coordinate a survey of fuel thermal

.stability at airports. Precautions on sampling and transporting

samples are mandatory.
2. In view of the concern over fuel thermal stability problems
and in the national interest as well, NASA should determine
the realistically practical limits of aircraft emission control
with full cons i derati on of a 11 fuel property and cost obj ecti ves,
energy conservation, engine durability, consumer costs for trans-
portation and inflationary pressure.
3. It is recommended that the present thermal stability levels be

retained for any proposed fuel specifications in the foreseeable

future as long as it is cost effective.

150'
 APPENDIX D

WORKSHOP PARTICIPANTS

151
General Chairman: William F. Taylor Exxon Research and Engineering Co.

Working Group I - Basic Research

Chairman: Robert N. Hazlett Naval Research Laboratory

Dennis W. Brinkman DOE Bartlesville Energy
Technology Center
Frank Mayo SRI International
Stephen R. Daniel Colorado School of Mines
John W. Frankenfeld Exxon Research and Engineering Co.
Howard Maahs NASA Langley Research Center
Hyman Rosenwasser Naval Air Systems Conmand
Ri chard Braun Universal Oil Products Inc.
J. Santoro Princeton University
Cyrus P. Henry E. I. du Pont de Nemours &Co.
Coordinator: David Bittker NASA Lewis Research Center

Working Group II - Laboratory Characterization Techniques

Chairman: Charles R. Martel Air Force Aeropropulsion Laboratory

William G. Dukek
Elliot Nesvig
Perry Kirklin
Henry Buschfort
Robert T. Holmes
Harold W. Poulsen
Stephen Boni fazi
W. A. Sutton
Coordinator: Albert C. Antoine
Exxon Research and Engineering Co.
Erdco Engineering Co.
Mobil Research and Development Corp.
. Al cor Inc.
Shell Oil Co.
Un i versa 1 Oil Products
Pratt &Whitney Aircraft Group
Ashland Oil
NASA Lewis Research Center

Working Group III - Applied Research and Test Simulators

Chairman: Royce Bradley Air Force Aeropropulsion Laboratory

Alexander Vranos United Technologies Research Center
Maurice W. Shayeson General Electric Co.
Kurt H. Strauss Texaco Inc.
Clarence J. Nowack Naval Air Propulsion Center
A. E. Peat Rolls-Royce Limited
Fred F. Tolle Boeing Commercial Airplane Co.
Frank Stockemer Lockheed-California Co.
Coordinator: Stephen M. Cohen NASA Lewis Research Center

153
 Working Group IV - Engine System Trends and Requirements

Chairman: Walter D. Sherwood Trans World Airlines

Charles Delaney Air Force Aeropropulsion Laboratory
Clifford Gleason General Electric Co.
A. J. Pasion Boeing Commercial Airplane Co.
Allyn R. Marsh Pratt &Whitney Aircraft Group
Tom Peacock' Douglas Aircraft Company
FrankLSalb Detroit Diesel Allison Div.
Jack Sweet Avco Lycomi ng Div.
N. Andersen P'an',Arnerican World Airways Inc.
JackA. :Be,rt Chevron Research Co.
Coordi nator: Robert Frfl~dman NASA. Lewis Research Center
, '

Other NASA Attendees

Everett Ba i 1ey
Charles Baker
Theodore Brabbs
Daniel Gauntner
Sanford Gordon
Jack Grobman
John Haggard
Friink Humeni k
Jo~eph Lamberti
Joseph Notardonato
George Prok
Gregory Reck
Gary Seng
Arlthur Smith
Daniel Sokolowski
Warner Stewart
Gary Wolfbrandt
Edgar Wong
Frank Zeleznik

154
 1. Report No. 2. Government Accession No. 3. Recipient's Catalog No.
NASA TM-79231
4. Title and Subtitle 5. Report Date
August 1979
JET FUEL THERMAL STABILITY
6. Performing Organization Code

7. Author{s) 8. Performing Organization Report No.

E-109
10. Work Unit No.
9. Performing Organization Name and Address
.

11. Contract or Grant No.

13. Type of Report and Period Covered

12. Sponsoring Agency Name and Address
Technical Memorandum
National Aeronautics and Space Administration
14. Sponsoring Agency Code
Washington, D. C. 20546
15. Supplementary Notes

Editor, William F. Taylor, Exxon Research and Engineering Company, Linden, New Jersey.

16. Abstract
This report is the result of a workshop on jet fuel thermal stability held at Lewis Research CenteI
on November 1 and 2, 1978. The state of the art is reviewed and the status of the research being
conducted at various laboratories is presented. Discussions among representatives from univer-
sities, refineries, engine and airframe manufacturers, airlines, the Government, and others are
presented along with conclusions and both broad and specific recommendations for future stability ,
research and development. It is concluded that significant additional effort is required to cope
with the fuel stability problems which will be associated with the potentially poorer quality fuels
of the future such as broadened specification petroleum fuels or fuels produced from synthetic
sources.

17. Key Words (Suggested by Authorls)) 18. Distribution Statement

Fuel; Aviation fuels; Turbine fuels; Jet fuels; Unclassified - unlimited

Hydrocarbon fuels; Thermal stability; Storage STAR Category 28
stability; Deposits; Sediments; Hydrotreating ;
Aircraft fuel system
19. Security Classif. lof this report) 20. Security Classif. (of this page) 21. No. of Pages 22. Price*
Unclassified Unclassified 157 A08

'For sale by the National Technical Information Service, Springfield, Virginia 22161
*USGPO, 1979 - 657-059/5206