2nd INTERNATIONAL

2nd INTERNATIONAL CONFERENCE

CONFERENCE ONON
STORAGE STABILITIES
STORAGE STABILITIES OF
OF LIQUID
LIQUID FUELS
FUELS
San Antonio,
San Antonio, Texas,
Texas, USA
USA
July
July 29
29 - August
— August 1,I, 1986
1986
STORAGE STABILITY
STORAGE STABILITY OF
OF RESIDUAL
RESIDUAL FUEL
FUEL OILS[1]
OILS[l)
By
By
Raymond P.
Raymond P. Anderson,
Anderson, Dennis
Dennis W.
W. Brinkman,
Brinkman,
John 14.
John W. Goetzinger,
Goetzinger, and
and James
James 14.
W. Reynolds
Reynolds
National Institute
National Institute for
for Petroleum
Petroleum and
and Energy
Energy Research
Research
P.O.
P.O. Box
Box 2128
2128
Bartlesville,
Bartlesville, OKOK 74005
74005
(918)
(918) 336-2400
336-2400

ABSTRACT
ABSTRACT
The Increasing
The increasing use
use of
of low
low quality
quality heavy
heavy crudes
crudes inin refinery
refinery feedstocks has
has
been paralleled
been paralleled by
by increasing
increasing problems
problems inin both
both processing
processing andand product
product quality.
quality.
Lower product
Lower product quality
quality Isis evidenced
evidenced byby increased
increased problems
problems with
with product
product stability
stability
compatibility. The problems
and compatibility. problems are particularly
particularly severe with residual materials
which contain the highest levels of problem componentscomponents such
such as asphaltenes or
heteroatom compounds. Problems with stability
Problems stability are increased as the refiner
resorts to increasingly severe processing to increase distillate yields as the
demand for residual fuels decreases. Experience has shown that conventional fuel
oil analyses are inadequate to allow prevention or prediction of handling
difficulties due to problems with instab11ity
instability or incompatibility.
Incompatibility. A A number of
"problem"
“problem” and "nonproblem"
“nonproblem” fuel o11s oils have been analyzed in an attempt to
understand the reasons for the reported problems. In addition to chemical and
physical characterization, these and additional fuels and blends have been
subjected to baseline tests for measuring stability. These baseline tests have
been used as a basis for initial evaluation of rapid tests which might be used for
the prediction of potential problems.
INTRODUCTION
Recent years have seen a drastic decline in the quality of residual fuel oils
available to the electric utility industry. Concern with this decline in quality
and
and the
the inadequacy of of current
current specifications
specifications to prevent
prevent or
or predict problems in
handling and burning these oils was recently voiced
handling and burning these oils was recently voiced by by the utilities
utilities participating
In an EPRI-sponsored workshop on Fuel Oil Utilization (1). Problems
in an EPRI-sponsored workshop on Fuel 011 Utilization (1). Problems with
with fuel
fuel
quality are in no way limited to residual fuels but are also being observed in
quality are in no way limited to residual fuels but are also being observed in
distillate
distillate fuels
fuels with
with discoloration
discoloration and and the
the formation
formation ofof insoluble
insoluble gum
gum and
and
sediment
sediment on
on storage
storage (f-~)'
(2-4).
-The
The -decline
decline inIn residual
residual fuel
fuel oil
oil quality
quality isIs due
due to
to aa combination
combination of of factors
factors
which
which were
were recently
recently reviewed
reviewed by by Mueller (5). Foremost
Mueller (~). Foremost among
among these
these factors
factors is is the
the
decline
decline in crude 011
in crude oil quality;
quality; i.e.,
I.e., the
the increased
increased use
use of
of heavy
heavy crudes.
crudes. This This is is
shown
shown by
by the
the declining
declining API
API gravity
gravity ofof U.S.
U.S. refinery
refinery feedstocks
feedstocks and
and the
the increased
Increased
level
level of
of heavy
heavy crudes;
crudes; i.e.,
i.e., crudes
crudes ofof API
API gravity
gravity <20.
<20. Although
Although the
the consumption
consumption
level
level for
for heavy
heavy crude
crude remains
remains low,
low, it
it has
has been
been estimated
estimated that
that as
as Jauch
much asas 30%
30% of
of
the
the petroleum
petroleum refined
refined in the U.S.
In the U.S. already
already contains
contains aa heavy
heavy crude
crude component
component (6).(6).

25

\
The heavy crudes, which are generally of high heteroatom content, high metals
content, and high asphaltene content, are particularly deleterious to both
processing and product quality.
A second factor responsible for decreased residual fuel oil quality arises
f rom
r om changes in refinery processing. While refinery feeds were becoming heavier,
product demand was shifting toward lighter products and away from heavy residual
fuels. Residual fuel oil consumption decreased by 50% from 1977 to 1983 (~), and
the decrease has continued (7). This has led the refiner to more severe
processing in trying to converf the bottom of the barrel to distillate products.
As will be discussed later in this paper, more severe processing can lead to
increased problems with
wi th stabil
stabi 1ity.
i ty. Other factors, such as growth of the spot
market at the expense of long-term supply contracts with refi ners, have also
contributed to the decline in fuel ~il quality.
A residual fuel is usually m~d~ of two components~ ,& resid {the bottoms from
either an atmospheric or vacuum distillation} ".; boning
boiling above about 650 F 0

(atmospheric resid) or about 950 F {vacuum

0
(vacuum resid}
resid) ; and a 1ighter
'lighter flux component
boiling above about 350 F which is used to control visC9S)ty
0
visc9s~ty and, to a lesser
extent, to adjust sulfur content. The residual mat:erial
mat:e rial may be .either straight-
straight­
run or cracked. Residual fuels produced from the smaller", simpler refineries
(many of which are now closed) were typically straight-run bottoms made from
relatively high-quality crudes; this source of high-quality residual fuels has
largely disappeared. Stability problems are generally more significant with
cracked materials than with straight-run materials, and are generally more severe
with thermally cracked material than with catalytically cracked material. In this
t ime of low . demand for residual fuel and high demand for distillate, the · refiner
may resort to visbreaking (thermal cracking) to decrease the viscosity of the
resid, thereby lowering the requirement for addition of more valuable distillates
to lower the viscosity.
This paper is concerned primarily with instability of residual fuels on
storage, and secondly, with incompatibility. Both phenomena lead to difficulty in
handl ing; i.e., formation of solids or sludge which may solidify in tanks, foul
heater s , plug strainers, cause pumps to fa il, or plug lines. The traditional
definitions of instability and incompatibil i t y are as follows:
InstabilitY--The
InstabilitY- -The tendency of a fuel to produce a deposit in storage or
on heating. Instability may
may also be .observed
observed via other changes in the
fuel; e.g., via increases in viscosity.
Incompatibility--The tendency of a fuel to produ~e a deposit on
dilution or on blending with other fuels.
The distinction between the two phenomena may be clear cut in some instances;
how
however,
ever, in other instances it may not be readily apparent whether a problem was
due to instability or incompatibility. Examples di.scussed in this paper provide
instances where the problem was clearly instability, where the problem was clearly
incompatibility, and where it was not clear which phenomenon was responsible for
the reported problem.
The overall objective of this research is to provide rapid practical tests
wh iich
ch utilities can use to predict whether use of a particular fuel or blend is
l i kely to lead to problems during its utilization. A general change in the
di rrection
ection of the project has taken place. The initial approach was to perform
26

detailed analyses
detailed analyses ofof problem
problem andand nonproblem
nonprob1em fuels;
fuels; learn
learn the
the type
type ofof components
components
which were
which were responsible
responsible forfor instability
instabil ity or
or incompatibility;
incompatibil ity; and,
and, based
based on
on that
that
information, develop
information, develop rapid
rapid practical
practical tests
tests for
for utility
utility usage.
usage. Emphasis has
Emphasis has
shifted from
shifted from detailed
detailed chemical
chemical analyses
analyses initially
initially undertaken
undertaken towards
towards more
more general
general
chemical characterization
chemical characterization of utility supplied
of utility supplied “problem”
"problem" and
and “nonproblem”
"nonprob1em" fuels
fuels
and, most recently,
and, most recently, toward
toward evaluation
evaluation ofof simple
simple empirical
empirical tests
tests which
which may
may
correlate with
correlate with instability
instability oror incompatibility
incompatibility and
and which
which can
can be
be utilized
utilized in
in utility
utility
laboratories.
laboratories.
EXPERIMENTAL AND
EXPERIMENTAL AND RESULTS
RESULTS
Residual Fuel
Residual Fuel Oil
Oil Data
Data Base
Base
One part
One part of
of this project
project encompassed encompassed the the establishment
establishment of of aa residual
residual fuel oil oil
base. Nine
data base. Nine residual
residual fuel oils, oils, most most of of which
which were were supplied
supplied by by utilities
utilities and and
were generally
were generally not defined
defined as problem problem fuels, were were subjected
subjected to to aa set set of of analyses
analyses
elemental composition, ash composition,
including elemental composition, distillation
distillation (both ASTM D0 1160 1160
and simulated distillation by GC), GC). carbon residue, asphaltene aspha1tene content content (by several
methods), viscosity versus temperature, temperature, flash point, point, and burning profile (a
Babcock and Wilcox thermogravimetric method). These results will not be discussed
in detail here, but some some analyses will be provided provided to indicate the range of
compositions observed
compositions observed in today’s
today's commercially commerCially available available residual residual fuels. AA summary
of the analyses is provided in table 1.
AA wide range of
product qualities is
readily apparent. For Sel. JOf 11M IMI ...
, 1954
Table I -Residual Fuel Oil caaeeie
1964 IteO 2033 2035 2041 2103

.....
~ 308 1768 1861 1953 1980 2033 2035 2041 2103
'API Gra .. tty 16.2 11 •• 12.2 20.5
asphaltene
example, asphal tene AP! Gravity
flntal~
16.2 37.8 32.2 20.5
14.1
34.7
11,3
11.3
10. 6
30.6
5.5
5.5 10.0
10.0
f1.-nt&l. .,t wt S"
content ranges from c....
Carbon ~ 84.79
14.19 86.70
86.10 65.94 86.40 86.68 54.32 84.74 88.63 85.98
It1drogen
Hydrogen 11.82
11.82 11.'
11.94 . 85.9.
10.60
16. 40
12.".
12.44 11.30
14.32
10.52 84""
10.34 ".63
9.32 85.9'
10.11
as little as 1.3% to
..
10.60 11.lO 10.52 10.34 9.32 10.17
Ilitrogen.
MU'OI,n, KJeldahl
Kj"dllli 0.45
0.45 0.34
0.3. 0.47
0.47 0.26
0.26 0.38
0. 38 0.45
0.45 0.53
0.53 0.25 0.45
lZ.l%, API
as high as 12.1%, Sulfur.
Sulfur,lA:co
LaCO 1.02
1.02 0."
0.34
2.47
2.47
0.35
0.35 '.00
1.00 "
4.34
2.51
2.5)
0. 25
0.98
0.98
0.41
1.35
1.3$
gravity from as low Carbon Resioue, wt
Conradson 12.97
12 .91 11.10
11.10 17.94
11.M 7.38
1.1' 12.99 .....
11." 18.09 It." 39.25 13.60
n.1O ZLU 21.33
as 5.5 to as high as
ZO.5,
20.5, hydrogen from
rFuel
.... l A$,,,,lt_.
..
Aspi’.Itene. wt
o0 3279
"t.....
Penta
vt "
3.78
1.1.
7.14
1.14
4.05
6.16
6.16
....
10.35
10.l5
15.44
15.44
..29
1.29
1.94
1.9.
....
4.69
7.35
1.15
13.96
11.96
17.84
17.14
12.12
12.12
17.42
11.42
5.60
5.60
10.04
10,04
....
9.64
14.58
14.58
9.3 to lZ.4%,
12.4%, and Ash Content. wt 5 00.045
. 045 0.043
0.043 0.076
0,015 0.0)0
0.010 0.030
0.031) 00.066
.... 00.086
.... 0.053
0.063
0.020
0.020
sulfur from 0.34 to Ash Co~osition
AsI'I eo.posttlon
4.34%. The level of I—ray. .,,,l1t.th.
I-rll, qualitative C.,V. Nile V•Ki, f.,
Fe. ItNi v,r ••• ,
vje,NI V,.t
~ V,lIt
V.11 C.,V,IIt,
~ V,NI,
V.11,
Ni Jo Fe.Pb Fe.Pb,Zn Fe
".'b,ln f.
nondisti1lab1e
nondistillable residue Viscosity, SFS. SF5. 122'f
l2tF ZlS 235 330 .st ,,.
..
Yhco,lty. "0 159 59.6
59.1 112
lIZ 465
465 338 120 238
(boiling point Residue, lit
"Sl_. WI ,S (0 HIO)
1160) 55
SS 61 53 38 '" 120 50
>1000·
>1000° F) ranges from " " " " 50

Z8
28 to 61% and the
viscosity from 60 to
SF5 at lZZ·
465 SFS 122° F. Strong correlations between many of these properties are
apparent, but these are beyond the scope of this paper.
ANALYSIS OF UTILITY SUPPLIED PROBLEM/NONPROBLEM
PROBLEM/NONPROBLEN RESIDUAL FUELS
Utilities have provided a number of samples characterized as ·prob1em"
“problem” or
"nonproblem"
“nonproblem” samples. In most cases, a utility supplying a problem sample also
supplied a companion sample with which the problem was not experienced. A A general
description of utility supplied samples and their designation as "problem"
“problem” or
"nonproblem"
“nonproblem” is
Is provided in table Z.
2.

27
 Analysis of
Analysis of the
the first
first problem
problem Tibia 2- UtilIty Supplied 9robi....ndwaonprooI..ns..pln
sample (strainer plugging) has
sample (strainer plugging) has been been
reported previously
reported previously (8)
(8) and
and will
will Id..tIflcatio~

not be discussed in detail here.

not be discussed in detail here. In In "'.'.-,-111
‘~‘‘ ~flprobI..tC~panion ~,.._I_"~IQII

.....
that case, the problem appeared
that case. the problem appeared to to 1761,..2
“‘~ Strainer PIuf&ng
be due to addition of used motor
be due to addition of used motor oil oil "
,1964
to the
to the residual
residual fuel;
fuel; the
the material
material ",.
‘956
lllll PlugglnSi Dwrllli
LIn.PIs.gginfl.ring

...
--....
CyCliC 1011.,- OpoM-;ltlOtI
plugging
plugging the strainer appeared
strainer appeared to to ,,,~ ,~
f ....1 MM'.,. Ph,"I",
consist primarily of a polymeric Viscosity Instability
f._It,llIstlOl,lt,
material which was believed to be a
viscosity index improver from the motor oil.
The next sample set is identified
Identified as the "line-plugging"
“line—plugging” problem set. In
this case.
case, a row of burners in a boiler was operated in a cyclic manner. Flow of
fuel1 through the 11
fue line would
ne wou 1d be stopped.
stopped, and the burners
burners wou
would
1d not be operated for
about an eight-hour
eight—hour period. On trying to restart the burners.burners, it would sometimes
not be possible to reestablish flow through the lines. A A sample taken at a time
when flow was difficult to reestablish constitutes the problem sample. sample, and the
nonproblem
nonprob1em sample was taken at a time when problems in reestablishing flow were
not evident.
is identified
The next sample set 1's Identified as the "heater-plugging'"
“heater—plugging” problem set. AA
heater used to heat the fuel to atomization temperature would plug to the extent
that flow through the heater could not be maintained. A A sample believed to be
associated with the plugging behavior was provided as the problem sample; another
residual fuel purchased to the same specifications was supplied as the nonproblem
sample.
The final sample set of the problem/nonproblem fuels is identified as the
“viscosity
"viscosity instability°
instabil ity" problem set. In this case,
case. three samples associated
associ.ated with
aa shipment of fuel which exhibited severe viscosity instability were provided.
Only in this case could the problem reported by the utility
util ity (and the lack of the
problem in the companion sample) be verified in the laboratory.
Some of the more conventional
convent i ona 1 analyses
ana lyses for the above samples
samples are summarized
sUlllT1ari zed
in table 3.
3. The fuels were also subjected
subjected to thin—film
thin-film distillation to provide aa
flb’. 3 — 9.nral
rebl.]- .,..... 1 Analysas
AMI,",.f of 07111
Utili"

,....
?y S~pp’
,....
lad Probl..Aionp.obIaa
S","'I"
....'yt,...,-
1'rob1_~I_ Foe’ 0’’~

,
0111

Cr641 Vy,••• WI
Gr, .. It, API
1768,
11M,

16.2
16.2
. ,-
Honprobie.
I'''.
‘9%.
Probla
.... COI_

21.6
11.'
"'" . ,- -'-
1964,
Hoaprobla.

,..,
20.5
‘954,
Probi..

n .•
75.4
1960.
Idonprobi..

14.7
'4,1
-,-
,."
202’
Problee

17,5
17.5
'01'
1661

"'" ,-
Noe’probla.

‘7.8
17.8

Viscosity.
Yi.~It,. (CSt I 122
122' F) 499.2 ....
68.5 124.2
124.2 426.1
426.1 237.’
2]7.1.
''''.
1299. 275.3
215.3

...
(cSt. • 99.2

... ... ...

F)

Pour
PoYr Point. 1
Pol lit • or 65. 65.
IS. 90. 90.
".
55. os.
65. 90.

Ela..nt.I,
EI_"tll, at

"'-
Carbon
.t SS
64.79 66.50
... 50 .....
66.40 86.60
...lIO .....
6646 .....
86.00 66.70
16.70

,...
' •• 79
H,O'."
Hydrogen 11.62
11.12 72.53
11.$) 12.44
12.'4 11.50
11.50 11.30
11,:10 11."
71.55 11.94
11.94
Sulfur,
S",lfur, (taco)
Nitrogen,
(LIto'
~ltrooell. (KJeIdai,i)
(l(J.ldefl')
'.02
‘.02
0.45
0.4'
0."
0.35
0.23
0.2)
0.35
0,15
0.26
0.26
0.93
0.93
0.35
0.'5
1.00
0.38
0.38
0.4’
0.4'
0.50
0.50
0.34
0."
0,34
0."

.
Asphaltenes, at S
~"""'
n—Psntane
lI~t_
.."

........ f_.
n-tbpfene, by 110'1' Atm
A$nI 03279
Dl279
7,'"
7.14
S.,.
3.78
'.U
1,56
o.n
0.77 '."
‘.94
'.29
1.29
‘‘.92
11.91
t.'.
9.84 ....7."
7,75
4.69
n.70
17.70
13.65
1).65 ....
6,76
6,16
4.05

Carbon
c.rbo<\ bald.., att SI
. .sICl .....
(Conradson)
(Conr,dlOll ) 12.91
12.97 6.16
6.1' 1.18
7.18 4.06
14.06 12.99
12.99 15,06
15.06 ‘7.70
11.10

A.14 at - ·
AIFI;.tS 0.05
0.05 0.019
O.Olt 0.0)0
0.010 0.053
0.053 0,030
0.030 0.073
0.013 0,042
0.047

Residue,
Ani4 .... . .7
(Thinfil.
. t 5S
IT~II'IIII. distillatIon)
"stlll,tlon) 65.5
65.' .,
47.6 .. ".'
49.7 ....
49.4 50.3
50.'

28
28
distillate
distillate and
and residue
residue for analysis.
analysis. Thin—film
Thin-fill'A distillation was
was used
used to
to minimize
minimize
the
the thermal
thermal stress
stress to which
which the
the sample
sample was
was subjected.
subjected.
conventional analyses do not provide aa definitive
In general, the conventional definitive explanation
for the problem
problem versus nonproblem
nonprob1em behavior. The two samples in the line—plugging
line-plugging
set (1956—1964)
set (1956-1964) were quite similar; both of these low sulfur (0.35%)(0.35%) fuels would
be considered high—quality
high-quality residual fuels. They are of high API gravity and low
viscosity. They are high In in hydrogen and low
low" in sulfur, nitrogen, asphaltenes,
aspha1tenes,
and ash. The samples
s'amp1es are of high pour
pour point, and the distillates are waxy. It is
conceivable that if if" sufficient
sufficient cooling In
in the lines took place, the problem with
reestablishing flow could ' be related to the waxiness of the fuels.
reestablishing .flow High wax
contents were apparent from the physical
physical appearance of the distillates and from
the presence
presence of high molecular weight n—paraffins
n-paraffins in the simulated
simulated distillation
chromatogram. This does not account
account for - the reported variation
variation between
between the
problem
problem and nonproblem
nonprob1em samples,
samples, however, unless the problem
problem is strictly
strictly related to
environmental conditions
conditions at the time of ' sampling.
sampling.
The next set
set of samples
samples (heater—plugging
(heater-plugging set, 1954 and 1980)
1980) are 1%
1% sulfur
fuels. The lower quality of these fuels is shown by their higher sulfur content,
lower API gravity, lower hydrogen, higher nitrogen, higher asphaltenes,
aspha1tenes, higher
carbon residue, and higher ash. In this case, the problem sample is of higher
viscosity and higher asphaltene
aspha1tene content than the nonproblem
nonprob1em sample. With the
available information, it is not possible to know if the heater plugging problem
is associated with the higher asphaltene
aspha1tene content of the problem fuel. It was not
possible to reproduce the plugging problem in an Alcor
A1cor Thermal Fouling Tester.
Other than the high viscosity itself, there is nothing in the data from the
viscosity instability set (2021 and 1861) to indicate a stability problem with the
problem sample. Asphaltene
Aspha1tene content is high, but this alone is not indicative of
instability.
It is apparent that 'the
the conventional analyses (and a number of other analyses
which are beyond the scope of this paper) fail to allow the prediction of problem
behavior for these fuels. Other analyses of the above fuels, Including
including stability
testing and various methods of determination of sediment, are discussed in the
following sections.
STABILITY TEST METHOD
METhOD DEVELOPMENT

Baseline Stability Test

Some uncertainty exists with the samples discussed above as to whether the
problem samples are inherently "bad"“bad” fuels and the nonprob1em
nonproblem samples are
“good” fuels or whether other factors are of overriding importance.
inherently "good" Importance. As
the problem or nonprob1em
nonproblem behavior reported by the utility is dependent on
mechanical and physical considerations unique to a particular situation, a fuel
which is not a problem in one situation may become a problem sample in another
application, and vice versa. Consequently, it was decided that the development of
predictive tests for instability or incompatibility must be tied to a baseline
test which will definitively demonstrate, in the laboratory, whether or not a fuel
exhibits instability (or incompatibility on blending).
As a baseline determination of stability, residual fuels were subjected to
long-term aging at elevated temperature and changes in the fuel were monitored.

29
Aging was
Aging was carried
carried outout for
for periods
periods upup to
to 24
24 weeks
weeks atat SO·
800 CC (equivalent
(equivalent toto
approximately 22
approximately 22 years
years atat 25·
25° C.
C, assuming
assuming doubling
doubling of
of reaction
reaction rates
rates with
with every
every
100 C
10· Increase in
C increase in temperature).
temperature). Changes in
Changes In viscosity.
viscosity, asphaltene
asphaltene content.
content,
sediment via
sediment via hot
hot filtration.
filtration, and
and .carbon
carbon residue
residue were
were monitored.
monitored. Changes in
Changes in
Conradson carbon
Conradson carbon (carbon
(carbon residue)
residue) were
were quite
quite small
small and
and will
will not
not be
be di
discussed
scussed
further.
further.
The technique used
The used for
for determination
determination of of sediment
sediment formation
formation during aging aging at
at
elevated temperature
elevated temperature is
is based
based onon the
the new
new method
method of of the
the Institute
Institute of of Petroleum.
Petroleum,
Test for Total Sediment 1n in Residual Fuel Oils, IP-375. IP—375. This method involves
filtration of the fuel at 100· 1000 CC through a glass fiber filter paper, washing the
solvent, drying.
sediment with an aliphatic solvent. drying, and weighing. At the time our work
was initiated, the method had not been formally adopted. adopted, and two variations (using
single or double filter papers) were under consideration. Our initial work used
the single paper method which was subsequently found to be inferior Inferior to the double
paper method in which the bottom filter paper is used as a blank.* Results for
the first two problem sets are shown in In figure 11 (single filter paper method).
Initial sediment levels are low «(< 0.1%). lO.0
10.0 r : - - - - - - - - - - - - - - - - ,
several weeks
Results through the first several-weeks
of aging are erratic, probably due in
part to inaccuracies in the sediment deter-
deter
mination method at low levels of sediment.
However, after long periods of aging.
aging, the
levels of sediment do become quite large.
At 24 weeks, sediment levels ranged from 1110 Noftptobl . . Co.""ion to It54

0.2% to over 2%. SyBy eight weeks, the

levels of sediment for the four samples
were in the same order as at 24 weeks; 1.0
1.0
i.e., the sample showing the highest
i.e., the sample showing the highest
level of sediment at 8S weeks also showed I~
the highest level of sediment at 24 ••
weeks,
weeks. etc.
The sediment
sediment formation on long—term
a
I ....
80· CC aging
800 aging did
did not
not correlate
long-term wa"
correlate with
with the
the a ...
problem/nonproblem
problem/nonproblem
the utilities.
behavior reported
utilities. For the heater—plugging
heater-plugging
by
ii
C
Ia
..
0.I
0 .1
set,
set. the nonproblem sample
sample (#1980,
(119S0. 2.2%
sediment)
sediment) showed
showed aa much
much higher level
level of
sediment
sediment formation than the problem
than the problem
sample
sample (#1954,
(11954. 0.28%
0.2S% sediment).
sediment). ForFor the
the
line—plugging set, the problem
line-plugging set. the problem samplesample v
did
did show
show aa higher
higher level
level of
of sediment
sediment for
for-
mation
mation (1956,
(1956, 0.96%
0.96% sediment)
sediment) than
than the
the
nonproblem
nonproblem sample (11964. 0.23% sediment).
sample (#1964, 0.23% sediment).
Sediment
Sediment could
could not be determined
not ·be determined for
for the
the
viscosity
viscosity Instability
instability samples
samples (#2020—22)
(#2020-22) 0.01
0.010oL--!--'----',_~---------:'.
as
as they
they were
were not
not filterable.
filterable. 22 44 6• C•
WEEKI At
WEEKS AT SO .c
10·C
24
24

Figure -1 SedIment
Figure —1 Sedt~t formation
fOrlllt1on on eo- CCaging.
on 8O~ aging.

*Sediment
*Sediment by
by hot
hot filtration
filtration for
for the
the unaged
unaged samples
samples was
was rerun
rerun by
by the
the dual
dual filter
filter
method.
method. AsAs expected,
expected, these
these values
values are
are lower
lower than
than those
those from
from the
the single
single filter
filter
method.
method.

30
 Viscosity changes
Viscosity changes are
are shown
shown In in 1000.----------------..,
boo
figure 2.
figure 2. InIn addition
addition toto the
the samples
samples
discussed previously,
discussed previously, samples
samples ofof aa
visbroken Mayan resid
visbroken Mayan resid and
and aa hydro
hydro-
cracked residual
cracked residual fuel oil sample
fuel oil sample areare
included. wide range
included. AA wide range of
of stability
stability
behavior is
behavior is noted.
noted. FarFor example,
example, the the
utility fuel sample
utility sample exhibiting
exhibiting thethe I.
~

viscosity instability (sample

viscosity instability (sample #2021)
'2021) •
0
a~
;
increased by 290%
increased by 290% (from
(from 140
140 to
to 540
540 I
centistokes atat 1800
180· F)
F) in
in two
two weeks.
weeks. 10
centistokes i 100
'00
Although substantially
Although substantially less
less severe,
severe, !
other samples which
other samples which showed
showed high
high vis
vis- ,:
instabil ity include
cosity instability include the
the vis—
vi s.- •
F
a;;
00
hydrocracked
broken Mayan resid, the hydrocracked 0
u
a~
nonproblem utility
sample (#2103) and nonproblem
samples all under
sample #1768. These samples
increases of about 50—
went viscosity increases
under-
50-
•
- ,_- - T-'-----------------
' .• , . Lin. 1"'."'_'
75% during four weeks of aging at 80° 80·
stability was
C. Very high viscosity stability _________
problem set
noted by the line-plugging problem set IC
ot...
'oL-~-i_L-~

0 2 4 6
~.

‘4
1:4
('1956 and #1964)
(#1956 '1964) which increased by WEEKS AT 60C
less than 10% during four weeks of Figure
figure —2
-2 Viscosity change
cMnge on 80~
SO- CC aging.
Ig1ng.
aging. This would follow from the fact
that they are both low sulfur, higher
gravity fuels.
It should be noted that there is not a correlation between instability as
It
noted by viscosity increases and instability as noted by sediment formation. For
example, the sample showing the highest degree of viscosity stabil ity (11956,
stability (#1956,
whose viscosity increased only 20% on 24 weeks of aging) had the second highest
amount of sediment formation.
Changes in asphaltene content on 80·
80° C
C aging are shown in figure 3. There is
a rough correlation between increases in
In viscosity and increases in
In asphaltene
.0

-
..
I

.za
~
hi

z 20 ~ ~O .. VI,O,.". Mo, ••
SU

.
;;
0~
N
N
F- lOll VI" •• It, Inslobillt,

e
n
~

.. -;/
.
C

hi
za
w
hi
L2IO' H,4racroc'"
/1954 HMt., "I~I",

~ ~- ---- LIT ••
----- --
4 10
'0 No",robl,,,,
I
%
a
~
~
~-

..
44
It80 NOli".",,,, e....,onlo.. to It54
/~" flit. NO"Drebl,,.. C.... 'onlon to 1t5.

- ---- -----
I I
-- I
--I
--"";1t5. Lift, 1'1'11"1"1
I
o0 22 44
•
6
•
6
WEEKS AT
"(IKI ataoc
10·C
24
24

Figure -3
Figure —3 Asphalt.ne
Asphaltene content
content change on eo-
change on 80 cC 191"9.
aging.

31
31
 content. The
content. The following
following ca.parlsons
comparisons are are .ade
made forfor the
the asphaltene
asphaltene content
content Increases
increases
for the first four weeks of aging. Significant increases in
for the first four weeks of aging. Significant increases in absolute asphaltene absolute asphaltene
contents were
contents were observed
observed for
for the
the visbroken
visbroken Mayan
Mayan resld
resid (12032,
(#2032, from
from 16.6
16.6 to
to 20.5%
20.5%
asphaltenes), the viscosity instability sample (#2021,
asphaltenes), the viscosity instability sample (12021, frOM 13.6 to 16.5% from 13.6 to 16.5%
asphaltenes), and nonproblem sample #1768 (from 3.6 to 7.3%
asphaltenes), and nonproblem sample 11768 (from 3.6 to 7.3% asphaltenes). These asphaltenes). These
samples also
samples also exhibited
exhibited significant
significant increases
increases in in viscosities.
viscosities. Small Small increases
increases in in
absolute asphaltene contents were observed for the line-plugging
absolute asphaltene contents were observed for the l1ne-plu9ging samples (11956 samples (#1956
and #1964,
and #1964, from
from 1.3
1.3 to
to 1.9
1.9 and
and from
from 0.8
0.8 to
to 1.3,
1.3, respectively).
respectively). These These latter
latter two
two
samples also showed only small increases in
samples also showed only s.all Increases in viscosity. viscosity.
Rapid Test
Rapid Test Methods
Methods for
for Prediction
Prediction of
of Instability
Instability
The IllE!thods
The methods discussed
discussed above
above indicate
indicate the
the stability
stability of
of aa fuel
fuel on
on long-term
long—term
aging at elevated temperature. These methods, all requiring long aging
aging at elevated temperature. These methods, all requiring long aging times, are times, are
obviously not suited for routine usage but should be considered
obviously not suited for routine usage but should be considered baseline tests baseline tests
against which
against which rapid
rapid predictive
predictive tests
tests cancan be
be compared.
compared. Tests
Tests which
which have
have been
been
considered as possible predictors for long—term instability include
considered as possible predictors for long-term instability include electron spinelectron spin
resonance spectroscopy (ESR), coke content, the Shell accelerated dry
resonance spectroscopy (ESR), coke content, the Shell accelerated dry sludge test,sludge test,
and acid-base
and acid—base contents.
contents. These
These will
will be
be discussed
discussed inin turn.
turn.
Electron Spin
Electron Spin Resonance
Resonance SpectroSCOPy
Spectroscopy
Samples which
Samples which have
have been
been severely
severely treated
treated during
during processing
processing are
are more
more likely
likely toto
exhibit instability problems. A possible indication of severe
exhibit instability problems. A possible indication of severe processing is the processing is the
presence of
presence of free
free radicals.
radicals. Free
Free radicals
radicals (a (a che.ical
chemical species
species containing
containing anan
unpaired electron) may
unpaired electron) may be
be produced during the
produced during the severe
severe temperature
temperature conditions
conditions used
used
in refinery
in refinery cracking
cracking processes.
processes. Free Free radicals
radicals are
are unstable
unstable and are generally
and are generally
short lived. However,
short lived. However, duedue to
to the low mobilities
the low mobilities ofof large
large species
species found
found in
In resids
resids
and
and the opportunity for extensive electron delocalization, long-lived free
the opportunity for extensive electron delocalization, long—lived free
radicals
radicals maymay exist
exist in
in residual
residual materials.
materials. The The concentrations
concentrations of of free
free radicals
radicals may
may
be
be expected
expected toto show
show aa correlation
correlation with
with severity
severity of
of processing
processing and
and with
with instability
instability
of
of aa sample.
sample. SuchSuch aa correlation
correlation hashas been
been observed.
observed. ThisThis correlation
correlation is is most
most
readily
readily evident
evident inin the
the correlation
correlation of of free
free radical
radical concentrations
concentrations with
with viscosity
viscosity
instability.
instability.
ESR
ESR data
data are
are summarized
summarized inin table
table 4.4. The The carbon
carbon free
free radical
radical concentrations
concentrations
are
are in arbitrary but self-consistent units. The increase in carbon free
in arbitrary but self—consistent units. The increase in carbon free radical
radical
concentration
concentration which
which may
may occur
occur during
during processing
processing is is shown
shown by by the
the Mayan
Mayan resid
resid
visbreaking run; concentration in the feed (#1735) was 13.4,
visbreaking run; concentration in the feed (11735) was 13.4, while concentration while concentration
in
in the
the visbroken
visbroken product
product (#2032)
(#2032) was was 22.5.
22.5. This
This sample
sample andand the
the viscosity
viscosity
instability
instability sample (#2021) had the highest free radical concentrations and both
sample (#2021) had the highest free radical concentrations and both
showed
showed significant
significant increases
increases inin viscosity
viSCOSity on on aging.
aging. Intermediate
Intermediate concentrations
concentrations
of
of free
free radicals
radicals (and
(and intermediate
intermediate levels
levels ofof viscosity
viscosity instability)
instability) werewere noted
noted for
for
samples
samples #1768, #1954, and the hydrocracked sample #2103 (free radical
#1768, #1954, and the hydrocracked sample #2103 (free radical
concentrations
concentrations of of 15.9,
15.9, 16.2,
16.2, and
and 15.8,
15.8, respectively).
respectively). The The samples
samples which
which had
had the
the
greatest
greatest viscosity stability on aging (the line-plugging set, #1956 and #1964)
viscosity stability on aging (the line-plugging set, #1956 and #1964)
also
also had
had the
the lowest
lowest free
free radical
radical concentrations
concentrations (7.7 (7.7 and
and 9.3,
9.3, respectively).
respectively).
Although
Although there
there does
does appear
appear to
to be
be aa correlation
correlation between
between instability
Instability and
and
concentration
concentration of carbon free radicals, ESR spectroscopy is not aa technique
of carbon free radicals, ESR spectroscopy Is not technique
regarded
regarded as
as suitable
suitable for
for use
use in
in utility
utility quality
quality control
control laboratories;
laboratories; hence,
hence, aa
more simple method of predicting instability was sought.
more simple method of predicting instability was sought.

32
Coke lietennination
Coke Determination
Another method
Another method which
which maymay indicate
indicate aa history
history of
of severe
severe processing
processing and,
and, hence,
hence,
the potential for instability is the presence of insoluble
the potential for instability is the presence of insoluble coke—like material. coke-like material.
Hot filtration
Hot filtration methods
methods as as discussed
discussed above
above determine
determine the the presence
presence of of material
material
insoluble in the residual
insoluble in the residual fuel. fuel. These insolubles may be largely precipitated
These insolubles may be largely precipitated
asphaltenes which
asphaltenes which are
are insoluble
insoluble in in the
the residual
residual fuel
fuel butbut soluble
soluble inin anan aromatic
aromatic
solvent.
solvent. ASTM D 473, Sediment in Crude Oils and Fuel Oils
ASTM 0 473, Sediment in Crude Oils and Fuel Oils by the Extraction by the Extraction
Method, determines
Method, determines the the amount
amount of of material
material which
which is is insoluble
insoluble in in anan aromatic
aromatic
solvent (toluene). The insolubles could include inorganic
solvent (toluene). The insolubles could include inorganic contaminants as wellcontaminants as well as
as
coke-l i ke materi
coke—like material. a 1. Determi nat ion of sediment by extraction
Determination of sediment by extraction followed by followed by
determination' of carbon and hydrogen contents of the
determination of carbon and hydrogen contents of the toluene insolubles can toluene insolubles can
provide an
provide an indication
indication of of the
the level
level ofof coke—like
coke-like material.
material.
AA comparison
comparison ofof thethe viscosity
viscosity instability
instability samples
samples (#2020-2022) and their
(#2020-2022) and their
companion
companion nonproblem sample showed a high level
sample (#1861) showed a high level (0.4—0.8%) of toluene
(#1861) (0.4-0.8%) of toluene
insoluble material
insoluble material (via
(via Soxhlet
Soxhlet extraction)
extraction) in
in the problem
problem samples
samples compared
compared to
to aa
very low level
very low level (0.04%)
(0.04%) for the companion
the companion nonproblem sample. The high carbon
sample. The high carbon and and
low hydrogen contents
contents (88%
(88% and 5%,
5%, respectively, for sample
sample #2021) showed
showed this to
be primarily aa coke—like
coke-l ike material. In comparison, hydrogen contents
contents of vacuum
excess of 10%,
resids have run in excess petroleum asphaltenes
10%, and hydrogen contents of petroleum
run about 8%.
8%. AA correlation
correlation of high coke content and viscosity
viSCOSity instability
instability was
also observed for the visbroken Mayan resid.
Due to this potential correlation between the presence of coke and viscosity
instabi 1ity, a number of additional samples were subjected to determination
instability, determi nati on of
toluene insolubles by ASTM 0D 473. Results are summarized
sunrnarized in table 5. Only the
samples discussed above (12021,
(#2021, the viscosity instability sample, and #2032,
12032, the
visbroken Mayan resid) show large amounts of coke-like
coke—like material.
,Tabi.
.. , ...4 -— E
E l«trOll
lactron S,.n AII_.IlC.
Spin Raonanc. TabI• 5 — sad lasot by E.trsctlon and Viscosity Stability
, •• , 5 - s.dl_t b, btrect'OII .11/1 V'$C:05itr St,blllt.,

Carbon
CM_
'1'.coalt,. C..ti.ttea. .t
Vluco.l,y, CeII'f'UoIIM at

s.,.
sql. ,I Duer,,'i_
D.scr Iption
F ra.
fr Rad cal
.. llMiul
eo.c..U"'0011
Concentration
sql.
,-"
I .0. 0 Weeks
,to',
‘601 ,tt.,.
•ttsi ~I~
Aqia It .t I2'C
arc
CF.ang.
S.diasnt
SMi_t
by [stract Ion
-!&.L ~ ~ ~ /)1 hfr«:fI_

,.,.
17)5
1"5 Haydn
... Ratio
".., Ret'.
1iII.,." ...,,,
‘3.40
1].40 2021
202'
39.3
139.3 921.4
921.4 ,..
560 0.44
0 •••
20)2 "hllraql!
VIsbroiin iiaysn Rabid 27.50
22.~
,."
2035 97.8
91 •• 245.9
2.5 •• 151
'",."
0.0)
0.01

,."
,.,
2021 't,,,otoU,
VIscosity '"$t,b"It,
instabIlity 22.10
20,.
2032
766
86.2
116.2
82.'
82.7
325.0
143.6
141.6
75
74 .,"
0.59
0.00
'.00
1561 ~.'_~aftIOlll
idonprobl.. Csnion 15.61
15.6' ""
,."
2Q35
....".'
1)4.9
200.'
200.7 ~5 0.00
'.00
.,.,""
1}4.'
2103
210) 69.6 104.9 5) 0.02
0,02
954
''''
",.
1950
Heater
HMt plogging ~l'
... """";"
,.,...._'_~I-
sa.pl.
Honprobla. Co.paaion

5..,.,
16.20
16.20
11.80
11.80
204)
204'
1953
""
",.
2120
....
39.1
66.4
42.2
<1'.2
57.3
n.]
97.)
91,1
57.2
57,2
47
47
,.
36
0.02
0.01
0.0)
0.o,
'0.0'
.06
0.06
110)
2)03 Hyclroc:rec:ke4
Hydrocrackad Sd.9la ‘5.80
15.eo
,.,.
1980 47.5
50.'
58.3 23 0.01

...
47.5

,""
"197
764
"60
,.,.
Ido..proolaa 5Sa.ple
NOnprQO'" ...... ‘5.90
15.90
954
1864
,.,.
1956
....
65.6
'5.6
30.3
25.6
76.0
18.0
32.5
12.5
24.4
24.4
" 3
0.0’
0.0.
0.0)
0.01
0.0’

...
21.' 0.01
‘956
'
U.. """"'IIIc::..,ealoa
'.....
tine plugging td.pIa 7.70
'.70
964 ~I_
)ionpeobla. cp.aIon t."
9.29

In conclusion, the presence of a large amount of coke-like coke—like material in a

residual fuel may be an indicator of viscosity instability. However, the absence
of a ssignificant
i gni fi cant amount of coke-1 i ke materi
coke-like a 1 does not necessarily iindicate
material ndi cate that
there will not be problems with viscosity instability. For example, sample 12035 #2035
(a
(a high
high asphaltene
asphaltene content
content fuel
fuel from
from the residual
residual fuel
fuel oil
oil data
data base,
base, table 1)
1)
underwent
underwent aa 150% 150% increase
increase in
in viscosity during
during four
four weeks
weeks of
of aging
aging at 800 C
at 80' C but
but
contains
contains only 0.01% sediment
only 0.01% sediment by
by extraction.
extraction.

33
 Shell Accelerated
Shell Accelerated Dry
Dry Sludge
Sludge
Shell has
Shell has recently
recently reported
reported on on an
an accelerated
accelerated test
test for
for the
the detern1nat10n
determination of of
potential dry sludge content (8). This test (5145 2696—83, Accelerated
potential dry sludge content (8). Th1s test (SMS 2696-83, Accelerated Dry Sludge Dry Sludge
Content of
Content of Res1dual
Residual Fuel
Fuel Dlls)"
Oils~ 1nvolves
involves the
the add1t10n
addition ofof aa ssmall amount of
.. ll aJIOUnt of poor
poor
solvent (10 parts residual fuel, 1 part cetane) and aging at 1000
solvent (10 parts res1dual fuel, 1 part cetane) and ag1ng at 100' C for one hour C for one hour
followed by the determination of sediment by hot filtration.
followed by the determinat10n of sediment by hot flltration. The techn1que for The technique for
determination of
deteminat10n of sediment
sediment after
after the
the cetane
cetane add1t10n
addition 1s is s1.llar
similar to to the
the IPIP method
method
for sed1ment
for sediment byby hot
hot f11tration
filtration but
but d1ffers
differs 1n
in aa number
number ofof .1nor
minor respects.
respects.
Preliminary results
Pre11m1nary results indicated
indicated aa corre1at10n
correlation between between sed1111ent
sediment fonaat10n
formation on on
long—term ag1ng
long-term aging and and the Shell
Shell accelerated
accelerated dry dry sludge
sludge test.
test. figure 4,
In f1gure 4, the
the
sediment present
sediment present after
after 2424 weeks
weeks of of ag1ng
aging at
at 80' 800 C C (IP
(IP s1ngle
single f1lter
filter method)
method) 1s is
compared w1thwith our 1n1tial
initial results
for the
the Shell
Shell accelerated
accelerated dry dry sludge
sludge 0
0.09. 0 0 . - - - - - - - - - - - - , ' -ItlO -----,
for
test. These 11mitedlimited data show a
correlation between the two methods.
correlat10n
A further
further eva1uat10n
evaluation of of the
the corre1a-
correla— .08
A .09
tion between
t10n between sediment
long-term aging
long-term
sediment format10n
aging andand the
formation on
the Shell
Shell accel-
on
accel— •e
.
.07
erated dry
erated dry sludge
sludge testtest was
was recently
recently :. .07

completed. A
completed.
between the
between
A general
the Shell
general correlation
correlation
Shell accelerated
accelerated dry dry
.
:0
• ..
•..; .0'
.06
sludge test
sludge test and
and sediment
sediment format10n
formation oo
on aging
aging continued
continued to to hold.
hold. WhenWhen
on
the sample
the sample was
was unfi1terab1e
unfilterable in in the
the
""
..
oJ
.05
accelerated Shell test or
accelerated Shell test or the accel- the accel—
erated
erated dry
than
than 0.06
dry sludge
sludge content
content was
wt %, significant
0.06 wt
was greater
significant amounts
greater ..
;"a: .04
of
of sediment
sediment formed
formed during
during four
amounts
four weeks
weeks ....
.04
oJ
of
of aging
aging at
at 80°
80' C. C. This
This correlation
suggests that simple precipitation
correlation
precipitation or ..
U
U

flocculation
flocculation of of asphaltenes
aspha1tenes Is is aa con—
con-
trolling factor in sediment
trolling factor in sediment formation formation
on
on long—term
long-term aging.
aging. This This conclusion
conclusion .02
.02
is based on the assumption
is based on the assumption that the that the
addition
addition of of the
the poor
poor solvent
solvent would
would 1t14
accelerate
accelerate aspha1tene flocculation but
asphaltene but .01 ~----!_---___:~---__:! 2 3
not chemical reactions such
not chemical reactions such as oxida- as oxida— 0 2 '
SEDIMENT IN .GEO SAMPLE, .,19M .,.c."t
SEDIMENT IN AGED SAMPLE. wii~htpnc•nt
tion,
tion, condensation,
condensation, or or polymerization
po1ymer1zation
which Figure -4 correlation
Correlation Shell
Shill accelerated
accelerated dry
dry sludge
sludge with
vith
which would
would lead
lead to to material
mater1a1 of of reduced
reduced sedt~"t on 80- C Igtng.
solubility.
so 1ubll ity.
Acid—Base
Ac1d-Base Contents
Contents
Residual
Residual fuels
fuels in in the
the original
original problem/nonproblem
prob1em/nonproblem sample
sample sets
sets were
were subjected
subjected
to
to separation 1nto strong acids, weak acids, strong bases, weak bases,
separation into strong acids, weak acids, strong bases, weak bases, andand
neutrals
neutrals via
via aa nonaqueous
nonaqueous ion ion exchange
exchange technique
technique developed
developed atat NIPER
NIPER (10.
(10. Where
Where
sufficient
suff1cient size
size samples
samples were
were available,
available, the
the separation
separat10n waswas conducted
conducted on on the
the
distillate and residue fractions following thin—film
distillate and residue fractions following thin-f11N d1st111ation. distillation. Where
Where
adequate
adequate samples
samples were
were not
not available,
avallable, the
the separation
separation was
was carried
carried out
out on
on the
the whole
whole
residual fuel.
residual fuel. Differences
Differences between various fuels were markedly lower for
between various fuels were markedly lower for the
the
whole
whole fuels,
fuels, butbut these
these areare the
the results
results which
which will
will bebe compared
compared asas they
they are
are
available
avaflable for
for all
all ofof the
the fuels.
fuels. Complete
Complete results
results have
have been
been reported
reported previously
previously

34
34
 (11), and
(11), and selected
selected results
results are
are plotted
plotted in in figure
figure 5.5. Strong
Strong acids
acids have
have often
often been
been
implicated in
implicated in problem
problem behavior.
behavior. For For this
this data
data set,
set, the
the strong
strong acidacid contents
contents ofof
the problem fuels
the problem fuels are
are higher
higher than
than the
the strong
strong acid
acid contents
contents ofof the
the companion
companion sample
sample
(problem and
(problem and nonproblem
nonprob1em samples
samples fromfrom one
one sample
sample setset are
are connected
connected by by lines
lines in
in
figure 5).
figure 5). It It was
was also
also found
found that
that the
the weak
weak base
base contents
contents of of the
the nonproblem
nonprob1em
samples were
samples were higher
higher than
than those
those forfor the
the corresponding
corresponding problem
problem samples
samples (figure
(figure 5).
5).
It may
It may be
be coincidence,
coincidence, but
but many
many ofof the
the commercial
commercial antioxidant
antioxidant additives
additives are
are basic.
basic.
Separation of
Separation of fuels
fuels into
into fractions
fractions as as described
described aboveabove is is beyond
beyond thethe
capabil ities of
capabilities of utility
uti 1ity quality
qual ity control
control laboratories.
laboratories. ASTM ASTM DD 664
664 potentiometric
potentiometric
titrations have
titrations have proved
proved to
to be
be unsatisfactory
unsatisfactory for for correlation
correlation withwith residual
residual fuel
fuel oil
oil
problem behavior.
problem behavior. Some
Some more
more sophisticated
sophisticated nonaqueous
nonaqueous titration
titration methods
methods developed
developed
at NIPER
at NIPER were
were evaluated.
evaluated. The The data
data base
base was
was not
not large
large enough
enough toto warrant
warrant aa general
general
conclusion, but
conclusion, but itit was
was found thatthat oils
oils high
high Inin both
both acids
acids andand bases
bases tended
tended toto
produce higher
produce higher sediment
sediment levels
levels on on aging.
aging. ThisThis area
area has
has not
not been
been further
further pursued
pursued
because the
because the difficulty of of either
!!ither thethe titration
titration or or ion—exchange
ion-exchange methods
methods preclude
preclude
their ready
their ready adaptation
adaptation as ,.
as aa quality
quality control
control test.
test.
... ......
....".. ,...
SI, •• , Acidi
Strong Ac le. 4~0k ectot

·
:
C

I •
".81-
Problon,

"III""
•nnpI~i
Nonproblon
"."M
•ompl•s
ProbItn~
" •• , _
,•• "..
.ompI..
Nenproblso
N • • " .....
"IIII"M
somplos
•.11'"
TSP

."~
2021
ia
a
1'1'
1 tOII~I"4
““4
S.; 1010

•• •
=
•1
S
C IOIO,:?' /
S
IOtt tOIl
••
4
w
1. . 0

• •
I..

~
a~
4—
1'54~
'111

•C0
S

4
S
a;;
•
• ,
1950
I.,.~t"o
In,
1.14
....
2a 2
0a I’S,,
c
•• .'7"
I
S •I7S5

•a
Ftgure
Figure -5 -5 Strong acid and weak base content for
far
probleis/nanproblem fuels.
pl"Oblea/nonprobleil

INCOMPATIBILITY
It is recognized that the subject of this conference is long-term
long—term storage
stability. However, with residual fuels the subject of incompatibility needs some
consideration. As noted in the Introduction, instability is the tendency of a
fuel to produce a deposit on storage while incompatibility
Incompatibility is the tendency of a
fuel to produce a deposit on dilution or blending with another fuel.
fueT. In practice,
a residual fuel may contain a deposit and it may not be evident whether this is a
manifestation of instability or of incompatibility.
Instances of severe problems of incompatibility on blending of residual fuels
have been noted in the literature. In one example (12), after fuels were blended
for transport, a tar-like
tar—like precipitate formed, settled, and partially solidified.
A
A very similar incident
Incident was experienced by a utility during the course of this
project. Unfortunately, samples from this incident were not available.
Incompatibility usually results
Incompatibility results from
from blending
blending one
one fuel
fuel of
of high
high aspha1tene
asphaltene
content
content with
with another
another fuel
fuel or diluent which
or diluent which isis of
of tootoo low
low solvent
solvent power
power
(aromaticity
(aromaticity too
too lOw)
low) to
to keep
keep the
the aspha1tenes
asphaltenes in in solution.
solution. Thus,
Thus, it
it should
should be
be
possible
possible to
to predict
predict incompatibil ity by
incompatibility by consideration
consideration of
of two
two factors:
factors: first,
first, the
the

35
35
aromaticity of the solvent fraction of the residual fuel and, second, the quality
In solution.
of solvent required to keep the asphaltene fraction of the fuel in
Griffith and Siegmund of Exxon have developed a compatibility test (13,14)
based on the Scatchard-Hildebrand equation of solubility behavior and the
solubility parameters for asphaltenes and nonasphaltenes. The solubility
parameters of asphaltenes were determined from the solubility of the resid
fraction of the residual fuel in mixtures of toluene and heptane (toluene
equivalence, reference 15), and the solubility parameter of the nonasphaltenes was
found to correlate with the aromaticity as determined by the Bureau of Mines
Correlation Index (BMCI, reference 16). BMCI is used as a measure of an oil'soil’s
solvency, in particular its aromatic content; high BMCI is indicative of a highly
aromatic oil, and low BMCI indicates a more paraffinic oil. Toluene equivalence
resid’ss "solvent
(TE) is a measure of a fuel or resid' “solvent requirement,"
requirement,” or the amount of
aromatic character required of a diluent to completely dissolve the asphaltenes in
a fuel/solvent mixture. Toluene equivalence is expressed as the percent toluene
hexane—toluene mixture to completely dissolve the asphaltenes. The
required in a hexane-toluene
Exxon workers applied the test to the resid fraction while we have applied it to
the total residual fuel, as a utility will generally not have access to the resid
fraction alone.
We have evaluated techniques to predict incompatibility based on
characterization tests which: 1) determine the quality of solvent required
(solvent quality demand) to dissolve the asphaltene fraction of the residual fuel
and 2) the aromaticity (i.e., solvent quality) of the overall blend. Toluene
equivalence was found to be a satisfactory measure of solvent quality demand.
Solvent quality measurements attempted besides the BMCI included determination of
saturates and aromatics by high performance liquid chromatography (HPLC) and
detailed structural information by a combination of proton and C-13 C—13 nuclear
magneticc resonance (NMR) spectra.
magneti Although these methods may provide
significantly more information
Information than the BMCI, they are significantly more complex
and do not appear to be better predictors of incompatibility than the BMCI.
We determined the BMCI and TE of 27 oils Ta,. 6
Table 6 —· ":1,
SCI, n.
Th, Ifill S.dl.~nt by
886 SecU_t by tot
Hot FIltr,tlOli
F! ltr~tlo
and blends and determined the level of S.dl.8t by
Sedl_t b,
sediment via the IP hot filtration method Ibt FII,.,...tlon
Hot Flltratio..
9i1S.
..
Oil No. !!!!£!. It !!!:!.=If Vt. Pet
Itt.
(dual filter). Results of this work are SC SC-TE Pet.l

summarized in table 6. The utility of the "

..... .... ..,.
766 54 24 30 0,00
',00
BMCI and TE measures for predicting ,",.
956 46
••
6 40
40 0,02
',02

,... ..
‘964 46 4 44 0,0’
0,01

,. ,
incompatibility is apparent by evaluation ‘954
1954
" • 61 5 56 0.00
',00
of these data. We have set a standard
of satisfactory compatibility as a hot
1910
1161
1953 ." .. ."""
65
OS
52
S2
69
46

44
5
‘9
47
25
0.05
0.05

0,00
',00

.." ." •,
2033
lOll 73 24 49 0.00
',00
sO.1 wt %
filtration sediment value of sO.l % 2035
20"
2103
210]
77
71
7$
61
66
‘6
16
9
0.02
',02
0.27
and a (BMCI - TE) of >10 as a predictor
— 2032
20)2 84 ‘00
'00 -16 U
U
exami
of satisfactory compatibility. In exami- 2113
2111 55 54 I

..." .""
U
2114 52
S2 76 —24
-24 U
nation of these data, one finds 11 oils 2115
2116
65
OS
66
67
63
—2
-2
3
.57
1.57
3.41
with (BMCI - TE) <10. Of these 11, 10
.
— 2117 55 66 .11
-II 3.24
of them have sediment values >0.1 wt %. 2114
211'
2119
85
OS
105
27
2'
37
56
SO
66
0.02
',02
0.02
Of the 16 samples with (BMCI) >10, all 2120
2'20 '"
74
"
"65
OS —II
-II
0.02
0.16
0.16

but two have sediment values <0.1%.

..,
2122 76 100 —22
-22 13,12
" '00 13,12

..
2133
2111 50 43 7 0.31
2134
2114
SO
56
SO "‘0
10 46 0,00
',00
2)35
2115
2136
55
"34
34
21
2'
20 ',"
0.30
0•07
2']6 54
" 0.07
2137
2131
213$
2'"
2)39
2139 .
54
56
SO
69
52
S2
)2
32
54
26
15
"
2

.,..
',0'
0.0’
0.00
',00
0.50

Ii • Wltllt.ralli.
U. .~tlItsr.0I.

36
 In conclusion,
In conclusion. measures
leasures of
of solvent
solvent quality
quality and
and solvent
solvent quality
quality demand
demand can
can
be used
be used to
to predict
predict problems
problems of
of incompatibility
incompatibility for
for potential
potential blends
blends with
with aa high
high
probability of
probability of success.
success.
CONCLOS IONS
CONCLUSIONS
oo The connuonly
The commonly used
used tests
tests for
for characterization
characterization of
of residual
residual fuel
fuel oils
oils
are inadequate
are inadequate to
to allow
allow prediction
prediction of
of instability
instability or
or incompatibility
incompatibility
problems.
problems.
oo Problems with
Problems with fuel
fuel oils
oils experienced
experienced by
by utilities
utilities could
could inin some
some cases
cases
be reproduced
be reproduced in
in the
the laboratory
laboratory and
and correlated
correlated with
with fuel
fuel properties.
properties.
I n other
In other cases,
cases. the prob 1em reported
the problem reported by
by the
the utility
ut il i ty could
cou 1d not
not be
be
reproduced or
reproduced or satisfactorily
satisfactorily explained.
explained.
oo AA baseline
baseline test
test for determination
determination of of stability
stabil ity of
of residual
residual fuels
fuels
involving long—term
involving long-term aging at 800
aging at 80· CC was
was developed;
developed; this
this test
test involved
involved
monitoring changes
monitoring changes inin sediment
sediment determined
determined by by hot
hot filtration,
filtration.
asphaltene content,
asphaltene content. and
and viscosity.
viscosity.
oo of carbon free radicals
Concentration of detenlined by
radicals as determined by electron
electron spin
correlates with viscosity
resonance spectroscopy (ESR) correlates viscosity instability.
instability.
oo significant levels of coke may exhibit
Residual fuel oils containing significant exhibit
however. the absence of coke does not assure
viscosity instability; however,
wi 11 not undergo 1large
that the sample will arge increases in viscosity
vi scos i ty on
aging.
oo There is a general correlation between sediment fonnation
formation on aging
and the Shell accelerated dry sludge test.
oo In most cases, incompatibility of residual fuel oils can be
predicted by consideration of two factors: the solvent quality and
the solvent qual i ty demand. So
quality 1vent qual
Solvent i ty is adequately deter-
quality deter
mined by Bureau of Mines Correlation Index and solvent quality
demand by toluene equivalence.
o There is a potential correlation between acid-base
acid—base contents and
problem behavior.
ACKNOWLEDGMENT
This paper is based on work jointly supported by the U.S. Department of
Energy
Energy under
under Cooperative
Cooperative Agreement
Agreement DE-FC22-83FE60149
DE-FC22-83FE60149 and
and the Electric
Electric Power
Power
Research
Research Institute
Institute under
under Agreement
Agreement RP2527-1.
RP2527—1. The
The authors
authors would
would like
like to
to
acknowledge
acknowledge the
the assistance
assistance of of the
the EPRI
EPRI Program
Program Manager.
Manager, Dr.
Dr. William
William C.
C.
Rovest i • and
Rovesti, and the
the DOE
DOE Project
Project Manager
Manager for
for Advanced
Advanced Process 1ng and
Processing and
Utilization.
Utilization, Alex
Alex Crawley.
Crawley.

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38