Copper catalysis of polymerization of sunflower oil diesel fuel
by Stephen John Jette
A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in
Chemical Engineering
Montana State University
© Copyright by Stephen John Jette (1985)
Abstract:
The role of copper catalyst in the oxidative polymerization of contaminant sunflower oil fuel in
commercial lubrication oil was investigated in laboratory apparatus simulating engine crankcase
conditions.
Sunflower oil mixed at 5.0 percent in Phillips HD II SAE 30 lube oil was exposed to various forms of
copper in catalytic quantities at 150°C for periods of 15 to 72 hours. Oil mixtures were contacted by
percolation with both nitrogen and oxygen to provide agitation and/or an oxidizing environment.
Polymerization was monitored by oil mixture viscosity, and both mixture acidity and dissolved copper
concentrations were measured in selected experiments.
Dissolved copper species as opposed to metallic surface appear to be of primary importance in catalysis
of the triglyceride addition polymerization. The impact of varying metallic copper surface seems to be
largely due to effects on rate of copper solubilization.
Copper dissolves and becomes catalytically active in oil mixtures in both the presence and absence of
oxygen. Oxygen does seem to accelerate copper dissolution but may somewhat deactivate dissolved
copper. Sunflower oil appears to have little effect on copper dissolution phenomena.
A theory of dissolved copper and oxygen combining to yield free radicals which initiate triglyceride
polymerization is supported by experimental results. Copper does not appear to catalyze the
propagation phase of polymerization, as copper has little impact on a reaction system supplied with
excess initiation free radicals. COPPER CATALYSIS OF POLYMERIZATION
OF SUNFLOWER OIL DIESEL FUEL
byStephen John Jette
A thesis submitted in partial fulfillment
of the requirements for the degree
of
Master of Science
in
Chemical Engineering
MONTANA STATE UNIVERSITY
Bozeman,Montana
December 1985
MAV
N3?9
Ts /
c<3p. oL-
ii
APPROVAL
of a thesis submitted by
Stephen John Jette
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College of Graduate Studies.
3W
. 23. mes
Date
p, X .
______
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Date
Approved for the College of Graduate Studies
7; / 78-6
Date
Graduate Dean
iii
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iv
TABLE OF CONTENTS
Page
APPROVAL...................................
STATEMENT OF PERMISSION
±i
TOUSE......................
iii
TABLE OF CONTENTS...................................
iv
LIST OF TABLES........... ..........................
v
LIST OF FIGURES.....................................
ABSTRACT..........................
vi
vii
INTRODUCTION.............. ........................
I
RESEARCH OBJECTIVES..........
5
THEORY........
6
Oxidative Polymerization.......................
Copper Metal.......... .........................
Copper Catalysis...............................
6
11
14
EXPERIMENTAL........................................
17
Equipment.......................................
Materials.......................................
Experimental Procedures.........................
17
21
23
RESULTS AND DISCUSSION..........................
27
SUMMARY.............................................
59
CONCLUSIONS.................................
63
SUGGESTIONS FOR FUTURE RESEARCH.....................
65
BIBLIOGRAPHY...........................
67
APPENDIX........
70
V
LIST OF TABLES
Tables
Page
I. Atomic emission results for Run 6 ..............
II.
34
Atomic emission results for. ................
Runs 10 and 11.
4^7-
III.
Total Base Number for Runs 10
and 11... *......
48
IV.
Total Base Number for Runs 17
and 18..........
56
V.
Successive spectrographic analysis of used....
oil from a diesel locomotive crankcase.
70
VI.
Atomic emission data for copper and..........
common additive metals for selected runs.
71
VII.
Operation parameters for oil bath runs.......
72
Total Base Number in mg KOH/g Oil......... .
for several runs.
73
Limits for trace metal concentrations........
in used crankcase oils.
74
VIII.
IX.
vi
LIST OF FIGURES
Figures
Page
1.
Single cell apparatus..........................
18
2.
Oil bath.......................................
20
3.
Operating diagram........................
22
4.
Viscosity versus exposure time for standard....
conditions of Rewolinski C43 and the current
work.
28
5.
Viscosity versus exposure time for varying.....
copper surface and sunflower oil concentration.
30
6.
Viscosity versus exposure time with copper.....
foil removal at 18 hours.
32
7.
Viscosity versus exposure time for two.........
samples of Phillips 66 HD SAE 30 at
standard conditions.
36
8.
Viscosity versus exposure time with copper.....
foil removal and nitrogen gas changed to
oxygen at 24 hours.
38
9.
Viscosity versus exposure time with oxygen.....
and copper foil for initial 48.5 hours.
Copper foil removed and 5.0 percent sunflower
oil addition at 48.5 hours.
42
10.
Viscosity versus exposure time with oxygen......
and copper foil for initial 48.5 hours.
Copper foil removed and 5.0 percent sunflower
oil addition at 48.5 hours. Time zero
at the point of sunflower oil addition.
43
11.
Viscosity versus exposure time with nitrogen....
and copper foil for initial 48.5 hours.
Copper foil removed, nitrogen changed to
oxygen, and 5.0 percent sunflower oil
addition at 48.5 hours.
45
vii
Figures
Page
12.
Viscosity versus exposure time with nitrogen....
and copper foil for initial 48.5 hours.
Copper foil removed, nitrogen changed to
oxygen, and 5.0 percent sunflower oil
addition at 48.5 hours. Time zero at the
point of sunflower oil addition.
46
13.
Viscosity versus exposure time with cupric.....
and cuprous oxides at standard conditions.
50
14.
Viscosity versus exposure time for varying.....
levels of cupric acetylacetonate at standard
conditions.
52
15.
Viscosity versus exposure time with nitrogen....
or oxygen and cupric acetylacetonate for
initial 48.5 hours and 5.0 percent sunflower
oil addition at 48.5 hours. Nitrogen changed
to oxygen at 48.5 hours for Run 18.
54
16.
Viscosity versus exposure time with nitrogen....
or oxygen and cupric acetylacetonate for
initial 48.5 hours and 5.0 percent sunflower
oil addition at 48.5 hours. Nitrogen changed
to oxygen at 48.5 hours for Run 18. Time zero
at the point of sunflower oil addition.
55
17.
Viscosity versus exposure time using Lupersol...
130 as a free radical initiator.
58
viii
ABSTRACT
The role
of
copper
catalyst
in the oxidative
polymerization of
contaminant
sunflower
oil fuel in
commercial lubrication oil was investigated in laboratory
apparatus simulating engine crankcase conditions.
Sunflower oil mixed at 5.0 percent in Phillips HD II
SAE 30 lube oil was exposed to various forms of copper in
catalytic quantities at 150 C for periods of 15 to 72 hours.
Oil mixtures were contacted
by percolation with both
nitrogen and oxygen to provide agitation and/or an oxidizing
environment. Polymerization was monitored by oil mixture
viscosity, and both mixture acidity and dissolved copper
concentrations were measured in selected experiments.
Dissolved copper species as opposed to metallic surface
appear to be of primary importance in catalysis of the
triglyceride addition polymerization. The impact of varying
metallic copper surface seems to be largely due to effects
on rate of copper solubilization.
Copper dissolves and becomes catalytically active in
oil mixtures in both the presence and absence of oxygen.
Oxygen does seem to accelerate copper dissolution but may
somewhat deactivate dissolved copper. Sunflower oil appears
to have little effect on copper dissolution phenomena.
A theory of dissolved copper and oxygen combining to
yield
free
radicals
which
initiate
triglyceride
polymerization is supported by experimental results. Copper
does not appear to catalyze the propagation phase of
polymerization, as copper has little impact on a reaction
system supplied with excess initiation free radicals.
I
INTRODUCTION
Petroleum
fuel stocks
are
among the most important
energy sources available to modern society.
of the early 1970s
on worldwide
for
emphasized the United States' dependence
petroleum production.
suitable
The oil embargo
alternative
alternative fuel with a
properties similar to
fuels
chemical
has
intensified.
An
structure and combustion
petroleum
for petroleum products.
As a result, the search
could logically substitute
A further advantage to a chemically
similar alternative fuel
would
be the minimal modification
of existing power-producing systems.
One
of
the
key
fuels
in
both
agriculture
and
transportation is diesel oil.
Rudolf Diesel, in the search
for
invention, successfully used
suitable
fuels
vegetable oils as
for
fuels
his
in short-term evaluations. Diesel
chose not to promote vegetable
of
economics
and
drastic increase
engine
in
the
oils as diesel fuels because
design
cost
considerations
of
petroleum
CU. The
has begun to
remove the economic prohibition.
However, the engine design
problems remain
considerations
research.
as
important
in current
2
Factors favoring vegetable oils as diesel fuels include
heats
of
combustion
similar
potential widespread
and the fact that
oils
present
introduced
they
are
diesel
However, vegetable
difficulties
When
used
conditions for diesel engines,
under
vegetable
when actually
normal operating
oil fuels tend to
injectors, varnish build-up on pistons
and rings, and thickening of lubrication oil C23.
vegetable oils and conventional
to cause
still
lesser
void
oils,
portability as liquids,
renewable.
major
fuel.
cause coking of fuel
standard
availability,
several
as
to
problems,
warranties
Blends of
diesel fuel have been found
but
without
engine
manufacturers may
further
research
on fuel
mixtures C33.
Prior research at this
thickening
of
laboratory
lubrication
contamination [4,53.
contaminant in a
oil
If the
lubricating
viscosity may occur.
due
vegetable
system,
has focussed on the
to
vegetable
oil
oil is present as a
an excessive rise in
A 375 percent increase in viscosity is
considered a failure in lubrication oil tests [63.
The
lubrication
oil
of
an
engine
can
become
contaminated by incompletely combusted fuel passing from the
combustion chamber to the
lubricating oil is
more
crankcase.
pronounced
This dilution of the
under loaded operating
conditions when unburned fuel residue is most likely present
3
in the combustion chamber.
diesel oil or
vegetable
normal oil change
oil can be
Dilution takes place when either
oils
intervals
severe
with
are
used
thickening
vegetable
as
fuels.
Under
of the lubrication
oil
fuels but not with
diesel oils C73.
Lubrication
eliminating
fuel
oil
thickening
could
dilution
or
possibly
Changes
in
engine
lubrication oil.
dilution would be costly,
chemical makeup of
the
even
if
be
by
reduced
modifying the
design to eliminate
possible.
lubrication
by
Changing the
oil may, therefore, be
more feasible.
If the thickening
is
the lubrication oil, the
fuel
stocks
for
eliminated
vegetable
current
by the alteration of
oils become more viable
engines
(and
hence
a suitable
alternative fuel) without costly design modifications.
The thickening is a
of
the
unsaturated
result of oxidative polymerization
vegetable
oil
triglycerides.
The
polymerization is known to be catalyzed by transition metals
C83, some of
which
are
present
lubrication oil (Table V in
iron are found to be
et.al C93
produced
found
the
that
the
as
wear metals in diesel
Appendix) [63.
Copper and
common wear metal contaminants.
a
copper
and
thickening
effect
when
designed to simulate the crankcase
iron
used
Bauer
mixed catalyst
in
environment.
a
system
Rewolinski
4
C4] has demonstrated in
can
catalyze
Copper,
the
therefore,
a
similar manner that copper alone
thickening
was
polymerization
selected
as
the
reactions.
catalyst
for
continued experiments in this laboratory.
This particular
the
investigation
form(s)
of
copper,
contributing
to
the
reaction.
future
As the form(s)
research will be
was
dissolved
catalysis
of
designed to reveal
or
the
solid
surface,
polymerization
and role of copper are clarified,
aimed at modifying the lubrication
oil to eliminate the catalytic affect.
5
RESEARCH OBJECTIVES
This research was conducted
to characterize the role of
copper catalyst in the polymerization
lubrication oil system.
to determine
the
of vegetable oil in a
Specifically, the research sought
dominant
active
form(s)
of
copper and
clarify their function in the polymerization mechanism.
The interaction of
the
system variables was also
variables
included
composition, and the
active
an
time
copper forms with other
object
of
presence
of
this work.
exposure,
and
level
These
contact
gas
of vegetable oil
contamination.
A further
course
for
goal
future
was
the
research
catalytic effect of copper.
identification
aimed
at
of a suitable
eliminating
the
6
THEORY
Oxidative Polymerization
Vegetable
oils
triglycerides.
glyceral
are
predominantly
Triglycerides
esters
of
triglyceride is
are
fatty
typical diesel fuel
component
acid roughly the same
A
three
times
fuel molecule.
While a
straight and branched
vegetable oil is
best
with
molecular
vegetable
larger
oil
than a
each constituent fatty
weight as a typical diesel
diesel
chain
of
the common reference for
acids.
approximately
composed
fuel is largely composed of
paraffins with some aromatics,
described
as
a reaction product of
glycerol and fatty acids 1103.
CHL-OH
HOOC-R1
I
CH-OH
+
HOOC-R0
—
> 3H0H
+
I
I
CH2-OH
HOOC-R3
Glycerol
Fatty Acids
Sunflower
CH0-OOCR1
I
CH-OOCR0
oil,
CH2-OOCR3
the vegetable
investigation, characteristically has
linolenic fatty acid
carbon fatty acids
structural
with
one,
Triglyceride
Water
oil
in
this
oleic, linoleic, and
components.
two
used
These are 18
and three double bonds.
7
respectively.
T h e ' actual
ratio
and
composition of fatty
acids in a particular oil Can vary with climatic conditions,
soil conditions, geographical
even location of the seed
genetics may be used to
many factors that are
location, plant maturity, and
within the flower itself.
modify
Though
the extent of unsaturation,
not readily controllable affect fatty
acid content.
The unsaturated elements
autoxidation,
the
Autoxidation with
of
direct
sunflower
chemical
polyunsaturated
oil can undergo
attack
vegetable
by
oxygen.
oils, such as
sunflower oil, frequently results in addition polymerization
[103.
Rheimich and Austin
C113
have
given
the major stages
that occur during oxidative polymerization.
1.
An induction
period,
the oxidative chain
reaction,
physical or chemical
assumed that
proceeding the initiation of
during which no visible
properties
natural
are
changed.
It is
antioxidants are consumed during
this induction period.
2.
The interaction of oxygen with double bonds to form
hydroperoxides.
coincides
with
A
considerable
the
polymerization reaction.
beginning
uptake
of
a
of
oxygen
perceptible
8
3.
A
stage
of double
where polyunsaturates undergo conjugation
bonds
and
isomerization
of
cis
to trans
forms.
4.
Decomposition
of
hydroperoxides resulting in free
radicals which in turn contribute to auto-catalysis.
5.
Production
of
high
molecular weight cross-linked
polymers and low molecular weight carbonyl and hydroxyl
compounds
via polymerization
The work of Rheimich
Farmer
and
Sutton
C123
product identification
and scission reactions.
and
Austin
was substantiated by
who
also
demonstrated through
that
an
alpha to the oxidation site.
intact
double bond exists
The reaction was proposed to
be:
-CH2-CH=CH- + O2 -- > -CH-CH=CHOOH
Bolland
quantities of
and
Gee
C133
established
hydroperoxides
were
formed
that
substantial
in
the initial
stages of autoxidation. The hydroperoxides were shown to be
conjugated 90
involved C143.
percent
To
of
produce
equation would require
a
the
the
source
time
when
linoleates were
hydroperoxide by the above
of
alpha-methylenic carbon-hydrogen bond.
energy to rupture the
This bond, which has
a strength of approximately 80 kcal/mole, can conceivably be
9
broken when hydrogen
radical ClBIl.
indicate
The
that
abstraction
high
free
energy
is
performed
via a free
requirements would seem to
radical
formation
must
precede
hydroperoxide formation.
The purported formation of
hydroperoxides
almost
prompted
simultaneously,
free
several
to
radicals prior to the
investigators [16,17,18],
postulate
that
the
initial
oxidative attack occurred at
the
double bond and not alpha
to the double bond.
and
Gee 0 6 3
Holland
proposed that a
small quantity of diradical, formed
by oxygen attack on the
double bond,
to
would
be
sufficient
initiate
the chain
reaction.
The
reaction
mechanism
would
then
be
described as
follows 093.
-CH0-CH=CH-
2 I
.
;
-CH2-CH-CH-(O-Oo)|
- CHL-CH=CH-
. w
2
-CHL-CH-CH-(OOH)-
I
I
W
-CH-CH=CH-
-CHL-CH=CH2
CH2-CH-(OOH)- + -CH-CH=CHCH7
+
I
V
Chain
Reaction
W
-CH=CH-CH-(OOH)+Ho
|
V
Chain
Reaction
-CH-CH=CHOOo
V
Chain
Reaction
10
As free
radicals
polymers may also
be
are
formed,
produced
high
molecular weight
by an additional mechanism,
vinyl polymerization:
HH
HH
I I
Ro +
I I
C=C
----- > R-C-Co
I I
I I
R1R2
HH
R1R2
HH
I I
I I
I I
I I
ROOo + C=C
r
------> Higher polymers
----- > R00—C—Co------> Higher polymers
Ir2
R iR2
Hydroperoxides, the main
autoxidation, can react
by
initial
other
product generated by
pathways when present as
conjugated hydroperoxides of linoleate.
are saturated and unsaturated
other
bifunctional
constituents
hydroperoxides of
aldehydes, ketones, acids and
oxygenated
are
less
compounds.
reactive,
linolenic
and
catalyze the oxidation of oleic
induction period,
a
Oxygenated products
Though
readily
oleic
formed
linoleic constituents can
species.
considerable
After the initial
amount of polymerization
can occur ElOIl.
The
initial
attack
at
thermodynamic probability as
trace metal contaminants
radicals
by
electron
the
argued
such
as
transfer
double
by
Uri E83.
copper
and
bond
has
low
However,
may produce free
thereby
initiate
11
autoxidation.
Thus, trace metal contaminants (or additives)
and their radical-producing
factors in
the
mechanism
ability
of
may
become
oxidative
important
polymerization as
discussed later in this review.
Copper Metal
Copper is
element in
table.
a
the
first
The first
metal
transition
transition
are progressively
electrons.
transition
filling
Copper has a
and
series
of
the periodic
series contains elements that
their
third
energy levels with
completely filled 3d shell and one
4s electron when in a neutral state.
of d electrons is
is the completing
responsible
The ready availability
for the transition character
of copper.
Transition
metals,
and
hence
copper,
have
three
characteristic properties C203.
1.
Unpaired
electrons
are
readily
elevated from d
' energy levels to higher energy levels by visible light.
The unabsorbed light results in a characteristic color.
2.
The high catalytic activity of transition metals is
thought to be
related
to
the ease by which electrons
are gained, lost, or moved between shells.
12
3.
Transition metals
coordination
neutral
participate
compounds.
compounds
in the formation of
Coordination
formed
between
a
compounds are
complex
ion
(transition metal here) and other ions or molecules.
Most transition elements exhibit
states; copper
is
not
an
a number of oxidation
exception.
prevalent oxidation states Cu*1"1 ,
Copper
has three
Cu"4"2 , and Cu"4"3. A fourth
state, Cu+*, is known in Cs2CuFg but is quite rare. Though
+2
Cu
is the most common oxidation state, it is usually
difficult to predict from
the electronic configuration of a
transition element which is the most stable state [20,213.
The copper cation will readily
groups
containing
Though copper does
temperature, if
nitrogen
not
and
react
exposed
to
form a complex ion with
sulfur
as
appreciably
higher
donor
atoms.
with Og at room
temperatures,
it will
react to form copper oxide (CuO).
The
stereochemistry
complexes can involve
diastereometric
pyramidal,
and
[21,223.
copper
linear,
octahedral,
diastereometric
of
by
various
authors
These diverse
environment in which
compounds
and
its
planar, tetrahedral, square,
octahedral,
Brief descriptions
inorganic texts
of
pentagonal
bi-
dodecahedron geometries.
geometries
such
geometries
are
given in
as Cotton and Wilkinson
may
be modified by the
they are present [20-243.
13
The lubrication oil used
II
SAE
30,
contains
an
detergents, antioxidants,
contents
trade secrets and
thus
analyses
additive
and
are
revealed
in
These metals are
the
lubrication
composed
of
and dispersents. The
their
unknown
phosphorus and zinc present
oil.
package
surfactants
specific additive
Chemical
in this research, Phillips HD
chemical nature are
factors in this work.
boron,
magnesium,
calcium,
as additives in the lubrication
in complexes specific for their role
oil.
lubrication oil may be
Copper
introduced
into
the
Complexed by existing additives, the
extent of which is unknown.
A well-known
can be
used
lubrication
to
copper
complex,
introduce
oil system.
a
cupric acetylacetonate,
soluble
copper
The general formula
form into a
follows C233:
CH--C=CH-C-CHI
I
0
0
V
o' \
CH3-C-CH=C-CH3
Acetylacetonates are
soluble in
also
has
most
the
relatively
organic
ability
solvents.
to
simultaneously altering its
coordination
number
is
the
complex
non-volatile
and are
Cupric acetylacetonate
additional
molecules,
coordination
number E233.
number
non-metal
of
surrounding the central metal ion or atom E203.
The
atoms
14
The
coordination
number
complexed copper to participate
modification
allows
the
in the catalysis similar to
metallic copper, as described in the following section.
Copper Catalysis
Autoxidation addition
polymerization
is believed to
occur via a free radical mechanism, as discussed earlier.
radical, represented by Io,
hydrocarbon
producing
a
removes
new
propagation or termination
A
a hydrogen atom from a
radical
reactions.
which
may undergo
These polymerization
steps are outlined below C83.
RH + Io
----- > 'Rcffj + IH
Initiation
Ro + Og
----- > RO^
Propagation
RO3O + R H ----- > ROOH+ Ro
Ro + R'o ----- > RR'
Termination
Ro + R'02o ---- > RO2R'
RO2O + R'02o
---- > RO2R' + O2
Vinyl polymerization using the Ro (triglyceride radical) may
continue in the formation of higher polymers.
There
is
propagation and
uncertainty
as
considerable
termination
to
the
agreement
sequences;
formation
of
concerning
however,
the
radical, 19.,- necessary for the initiation [163.
the
there is
original free
15
The catalytic activity
shift valence states
in
of
copper,
which can readily
oxidation-reduction reactions, may
involve several alternate pathways CS,103.
1.
Trace hydroperoxides
may
shift the metal valances
and produce free radicals.
Cu+1 + ROOH ---- > Cu+2 + OH-1 + ROo
2.
The oxygen and metal ion may react directly. The
-i
resulting Og
then readily reacts with a proton to
form HO^.
Cu+1
+ O2 ---- > Cu+2
O2*1
3.
+ H+ ---- >
A metal/oxygen
forms the HO^
+
HO2Q
complex may form which subsequently
radical.
Cu+1 + O2 ---- >
Cut )1 02
+ O2"1
Cu+O1 O 2
X H --- -> Cu + 2
Electron transfer
to
+
the
X"1
+
h o 2®
metal ion may result in
the oxidation of the alpha methylenic group.
Cu+2 + RH ---- > Cu+1 + H+1 + R o
The radicals can
oxidation or the
initiate
the
chain reaction of aut-
propagation step producing hydroperoxides.
These hydroperoxides
can
rapidly decompose monomolecularly
16
or bimolecularly,
substantially
increasing
the
number of
free radicals for initiation CIO].
R O O H ---- > ROo
+ HOo
Monomolecular
ROO + HOOR
> ROO...HOOR
I
---- > HOH + ROo + RO^
I
H
2
H
Bimolecular
The copper is shown in ionic
a complexed ion
at
that
form.
It may actually be
respective oxidation state within
the complex.
According
probabilities
catalyzed
to
for
Uri,
"the
formation
initiation
kinetic
of
free
reactions
are
favorable than the Holland
and
and
thermodynamic
radicals
by metal-
considerably
more
Gee proposals of diradicals
by direct oxidation of a double bond" ClOIl.
17
EXPERIMENTAL
Equipment
The primary experiments in this research were conducted
in a single cell reactor
impact
of
multiple
experimental error.
apparatus designed to minimize the
sample
removals
and
It
referred
to
because each run was
is
completed
other
inherent
as a single cell
using the contents of one
cell, where in previous research C43 two to four cells of 50
ml samples were required.
The
500 ml reaction kettle fitted
(Figure I).
Each
entrance
single cell consisted of a
with a four post entrance lid
was 24/40 standard taper ground
glass to insure gas-tight seals when greased.
The center lid opening and one side opening were fitted
with Ace threads to provide
exiting gas tubes.
The
entering
mm diameter glass frit.
the bottom
airtight seals for entering and
The
tube terminated with a 30
glass frit was positioned in
and center of the kettle to provide maximum gas-
to-liquid contact. The exiting
oil surface providing a gas
tube remained well above the
flow
escape.
The gas flow was
then passed (via tygon tubing) to a soap film flow meter.
18
Gas Dispersion Tube
Gas Exit Tube
Glass Stopper
Ace Thread
Reaction Kettle Lid
Reaction K ettle
Copper F o il —
F itted Disc
Gas Dispersion
Head
-j.l.L.
Figure
I.
Single cell apparatus.
19
Thin copper foil, 0.125 mm
cut in 5.0 cm lengths
and rolled end-to-end.
cylinder of copper was
and supported by the
thick, used as catalyst was
placed
The resulting
over the gas dispersion tube
fritted
glass surface.
This provided
intimate gas, metal, and oil contact (Figure I).
The reaction kettle was
2) capable of holding
maintained at a
two
placed
test
temperature
cells.
of
Model 73 immersion circulator.
in an oil bath (Figure
150
minute.
approximately
The oil
bath
13
was
C using a Polyscience
The Polyscience Model 73 has
automatic temperature control with a
circulates
The oil bath was
precision of 0.2 C and
liters
also
of
heating
oil
per
fitted with a sheet metal
cover and side panel insulation to minimize heat losses. The
oil bath
was
situated
in
a
venting
hood
to remove any
noxious vapors.
Gas was
provided
outside the hood.
equipped
pressurized
Nominal
was plumbed from the
header
via
with
permanent headers were
secured
1/4 inch stainless steel tubing
tank
a
cylinders
regulator
0-30
psi
employed,
for oxygen. Tygon tubing was
to a precision needle valve.
to a four- position
pressure
one
gauge.
Two
for nitrogen and one
used to link a header position
The
valve
was connected by
stainless steel tubing to a preheating coil submerged in the
oil bath.
Insulated teflon
tubing was employed between the
20
Gas Lines
/4. Immersion
Circulator
D. Thermometer
B. Insulated
Gas Line
C. Gas Line to
Preheating Coii
E . R e a c tio n
K e t t le
F . Gas P re h e a tin g
C oit
Figure
2.
Oil bath.
21
preheating coil and the
glass
An overall
the
diagram
of
tubing
tubing
of the fritted disc.
and
control valves is
illustrated in Figure 3.
Viscosity of lubrication oil samples was measured using
calibrated
capable
serial
of
350
measuring
and
400
120-500
and
respectively. Viscometers
were
maintained at 40 C
0.2
(within
Cannon-Fenske viscometers
500-1200
mounted
centistokes,
in
a water bath
C) by another
Polyscience
Model 73 immersion circulator.
Initial scouting experiments were conducted in a multi­
cell
apparatus
Samples were
as
described
exposed
temperatures and
as
2,000
50
by
Chance
ml
ml/hr
Rewolisnki
aliquouts
gas
flow.
to
E43.
150 degree
Procedures were
followed according to Rewolsinki's work.
Materials
The vegetable
sunflower
mill
oil
Culbertson, Montana.
oil
used
from
throughout
Continental
It had
an
sunflower oil was centrifuged,
for 20
minutes
processes.
to
remove
iodine
when
visible
Lubrication oil was
the
research was
Grain
Company
value of 140.
of
The
necessary, at 5000 rpm
solids
left from mill
provided by Phillips
under
22
Gas cylinder
Pressure regulator
Shut-off valve
Stainless steel tubing
Four position header
Tygon tubing
Needle valve
Hood
Insulated teflon tubing
Heater circulator
Tygon tubing
Soap film flow meter
Oil bath
Figure 3.
Operating diagram.
23
the label of Phillips
Oil.
The
Petroleum
lubrication
oil
refineries, but both met
0.125 mm thick
foil
or
was
the
Phillips 66 HD II SAE 30.
but
was produced by Amoco
produced
at two separate
requirements to be labeled as
Copper catalyst was available as
powdered
forms
of Cu3O, CuO, and
cupric acetylacetonate. All powders were reagent grade.
free
radical
initiator,
Lupersol
130,
was
provided
The
by
Lucidol Pennwalt Corporation of Buffalo, New York.
Experimental Procedures
Samples of lubrication
oil
were
placed
in
the
individual sample size
reaction kettle was
accommodate 1,000 ml.
was
labeled
This
oil contaminated with vegetable
500
500
as
ml
reaction
ml
500
of
oil
kettle.
The
mixture.
The
ml but would actually
provided room for expansion and
possible foaming of the mixture, thereby preventing overflow
losses.
The 30
mm
gas
dispersion
tube
was
centered in the
bottom of the reaction kettle approximately 8.0 cm below the
Oil mixture surface.
2 cm x 5 cm
Copper foil was cut in I cm x 5 cm and
strips
and formed into cylinders approximately
1.5 cm in diameter.
The foil was then centered over the gas
24
entrance tube while supported
dispersion tube.
Mhen
the foil was not
present.
stirred into the
oil
by
the
fritted glass of the
powdered copper compounds were used,
Powdered forms were thoroughly
mixture
before
sealing the reaction
kettle.
The ground glass
surfaces
of
the reaction kettle and
lid flanges were then
greased
with Dow Corning high vacuum
grease.
placed
over the reaction kettle with
The lid
was
the stem of the
gas
dispersion tube protruding through the
center opening.
The lid
was
pressed and rotated to insure
an air tight seal between reaction kettle and lid.
The four ground glass
lid
Ace thread stoppers were used
around the stem of
the
gas
openings were also greased.
to. provide an air tight seal
dispersion
length of 1/4 inch stainless steel
exit.
tube
and a 5.0 cm
tubing was used as a gas
The remaining openings were sealed using ground glass
stoppers.
The
sealed
reaction
kettle
sample was placed in an oil
oil bath level
was
bath
containing
the prepared
maintained at 150 C.
approximately
one
The
inch above the test
mixture level to insure 150 C temperatures in the mixture.
The temperature
assumption
that
temperature is
a
of
150
diesel
approximately
C
was
engine
150
C.
chosen
based
crankcase
on the
operating
This assumption is
25
supported by the
Oldsmobile
evaluates an oil for
III
D
test
C63.
This test
its resistance to oxidative thickening
at oil sump temperatures controlled at 150 C.
Immediately after immersion in
lid was positioned
above
flow tube was attached
tube.
the
to
the
oil bath, the bath
reaction
kettle and the gas
of the gas dispersion
3
adjusted to 120 cm /min as measured
The gas flow was
by a soap film flow
meter
percolation through
the
the
stem
adjacent
oil
to
mixture
the oil bath.
sample
Gas
was visually
checked for problems of surging or excessive foaming.
Periodic samples were
time
intervals
removed
between
samples
experiment being performed.
was removed and 8 ml
the test cell. The
of
8
ml
One
used motor oil as
C63.
Following the
to
run.
The
by
the
dictated
the test mixture was pipetted from
sample
was then transferred to a
the
evaluate
discussed
water bath.
excess
The 40 C
viscosity rise in
in the Handbook of Lubrication
viscosity
prepared for Total Base
were
each
of the glass stopped ports
viscometer maintained at 40 C in
temperature is used
during
Number
determination the sample was
(TBN)
titrations, returned
to the reaction kettle, or discarded where appropriate.
TBN indicates
the
acid
neutralization
power
of the
lubrication oil. TBN values were determined potentiometricly
using ASTM Standard D 2896-73 C63.
This is a back titration
26
method where excess standard HClO4
solution
prepared sample.
then
The
excess
is
standard sodium acetate solution.
for
used
motor
oils
because
is added to a
back titrated with
This method is preferred
inflection
points
may
be
difficult to determine by other TEN procedures E253. Iodine
values are a
relative
These values
were
1959-69.
This is
indication
determined
the
of unsaturation present.
according
to
ASTM Standard
Wijs
procedure for determination of
unsaturation in drying oils.
It is applicable to vegetable
oils and their fatty acids C263.
27
RESULTS AKfD DISCUSSION
The purpose
of
several
establish a set of baseline
least a
hours.
375
percent
initial
was to
conditions which would yield at
increase
These conditions
experiments
in
would
viscosity
then
within sixty
be used as a standard
for comparison when operating parameters were varied.
Preliminary
conducted by
studies
Chance
related
Rewolinski
Rewolinski used
differed
current work.
Rewolinski
hours.
A
first
goal
differing
this
project
were
The apparatus that
that
used
in
most of the
established standard conditions
viscosity
of
this
Rewolinski's results, allowing
the
C43.
from
which gave a significant
to
apparatus.
rise in less than sixty
work
was
to approximate
for valid comparison between
If
comparable
results
were
achieved, work could then continue from Rewolinski's base of
experiments.
Figure 4 shows plots
exposure time for Run
line
represents
Rewolinski.
results
These
percent sunflower
4
of
of
the
at
standard
oil,
presence of copper wire.
oil mixture viscosity versus
2000
Run
current work.
standard
conditions
ml/hr
conditions
were
oxygen
The dashed
150
flow,
for
C, 5.0
and the
4 shows viscosity rising at a
28
- Rewolinski C43
VISCOSITY, cSt
O Standard Conditions (Run 4)
T I M E , hr
Figure 4.
Viscosity versus exposure time for standard
conditions of Rewolinski C4] and the current
work.
29
comparable rate to
Rewolinski's
it was performed
in
the
new
conditions of Run
4
were
single
cell
were 500 ml sample,
percent
oxygen flow, 150 C , and
cell apparatus.
therefore
conditions in the single
5.0
standard conditions though
2
selected for standard
apparatus.
cm
The
These conditions
sunflower oil, 120 cc/min
x
5 cm of copper foil using
Phillips HD II SAE 30.
Previous research
copper surface area
rise.
demonstrated
would
increase
that
the
an
increase in
rate of viscosity
It was also established that an increase in vegetable
oil concentration would
rise.
yield
an
increase
in the rate of
These results were also verified in early runs in the
single cell apparatus.
Results of Runs I,
2,
4) are given in Figure 5.
3 and standard conditions (Run
Run
I had no copper. Run 2 had I
cm x 5 cm copper foil and Run 3 had 2 cm x 5 cm copper foil.
Runs 2 and 3 had
target
level
of
4.7
5.0
percent
sunflower oil instead of the
percent.
This
was
due
to
a
1
calculational error which was eliminated in subsequent runs.
All
four
runs
used
oxygen
conditions are shown as a
at
120
cc/min.
Standard
dashed line and will be presented
as such in future figures when referenced.
Two
trends
are
evident
in
containing the same copper levels,
Figure
5.
The
runs
3 and 4, confirm that an
30
Standard Conditions (Run 4)
(Run I)
O I cm x 5 cm Cu Foil, 4.7 %
Sunflower Oil (Run 2)
O 2 cm x 5 cm Cu Foil,
Sunflower Oil (Run 3)
300
VISCOSI
>-
T I M E , hr
Figure 5.
Viscosity versus exposure
copper
surface
and
concentration.
time for varying
sunflower
oil
31
increase in vegetable oil
Run 4
contained
contained 4.7
5.0
increases rate of polymerization.
percent
percent.
sunflower
This
is
oil
while
Run 3
consistent with earlier
research by Rewolinski.
The second trend is
of greater relative importance to
the object of this research.
that
increased
copper
polymerization rate.
oil mixture.
surface
results
in
a
rise
in
The copper surface could be serving as
a site for the actual
source of catalytic
Runs I, 2, and 3 demonstrate
reaction,
metal
If the
or
the surface could be a
species
former
migrating into the bulk
is true, then the reduction of
polymerization might begin with reducing active surface area
or permanently coating such
surfaces.
This appears to be
infeasible based on current engine designs.
surface is acting
as
a
source
another preventive measure may
species
may
be
rendered
selective for these
surface is
species.
important.
of
However, if the
soluble metal species,
be available.
inactive
The
However,
by
Soluble metal
an
oil
additive
presence of the copper
the
exact
role
of the
surface needs clarifying.
Run 6 was conducted to see if it was necessary to have
copper surface
rise.
At
present
eighteen
following
hours,
approximately 30 percent
at
the
the
the
onset
viscosity
standard
of viscosity
had increased
conditions.
At
32
Standard Conditions (Run 4)
VISCOSITY, cSt
O Run 6
TI ME , hr
Figure 6.
Viscosity versus exposure
foil removal at 18 hours.
time
with copper
33
this point, the copper foil was removed.
6 in comparison to
the
feature is the fact
after the
copper
removal
surface
standard conditions.
that
of
The important
viscosity increase continued even
copper
may
Figure 6 shows Run
he
foil.
This indicates that
necessary
for
initiating
the
polymerization, or the surface
may have released sufficient
copper species to catalyze the
reaction.
these differing speculations
might
be
It was felt that
resolved if a metal
content analysis was performed on the oil mixture.
Oil samples at the beginning
were analyzed
by
atomic
tests were conducted by
Indianapolis,
emission
Case
Indiana.
atomization technique
means of two electrically
of the results is within
(AE).
Atomic emission
Lubricant Analysis Service in
This
where
and completion for Run 6
the
service
sample
uses
a
is volatilized by
heated graphite plates.
about
non-flame
20 percent.
Accuracy
The results in
Table I represent the oil mixture before the copper foil was
added and at 48 hours,the completion of Run 6.
The rise in copper content in the oil mixture supports
the speculation that
copper
into the mixture but
does
is not involved.
is
migrating from the surface
not prove that surface catalysis
34
I
I
I Run No. I Time of Sample
I
I
I
I
I
6
I
I
|
6
I
I
Table I.
I
Copper Level
0.0 hour
0.0 ppm
48.0 hour
2.0 ppm
I
I
I
I
I
I
-I
Atomic emission results for Run 6.
The viscosity
rise
in
Run
6
higher than standard conditions.
Run 6 was taken from a larger
is conceivable
that
the
was actually somewhat
The
oil mixture used in
batch mixed for two runs.
mixing
of
vegetable
It
oil in the
lubrication oil was incomplete, resulting in a vegetable oil
variation in the batch mixture.
Hence, the resulting level
of vegetable
may
oil
contamination
greater than the desired 5.0
conducted
using
single
have
percent.
batch
been slightly
Future runs were all
mixtures
to
avoid
this
potential problem.
Having established that
present to sustain the
begin using a second
referred to as
sampley was
new
scouting trials.
viscosity
sample
of
Phillips
exhausted
the
in
copper
rise, it was necessary to
Phillips
66.
Runs
foil need not be
66 HD II SAE 30,
The original, or first
I
through
6
and earlier
35
Atomic emission
data
indicated
differed substantially between
66 (Table VI in Appendix).
contacting the technical
the
the
additive metals
two samples of Phillips
This difference was confirmed by
representative
for
Amoco who had
supplied the two samples.
The
samples
had
been
shipped
from
two
separate
sources.
One was from a Wyoming refinery, the other from an
Oklahoma
refinery.
Each
of
these
refineries
used
a
different additive package based on its source of crude oil.
Though the packages were
engine
specifications
different,
for
findings, the standard
the
oils met the same
operation.
conditions
Based
were
on
these
repeated using the
second sample of Phillips 66.
Figure 7 shows that viscosity rise in Run 7, standard
conditions and new
Phillips
66,
standard conditions using the
The viscosity rise in Run
expected.
varied significantly from
original Phillips 66 (Run 4).
7 occurred much more quickly than
Identical conditions
were
repeated
in Run 8 to
obtain more data points and confirm the results of Run 7.
comparison of Runs
7
and
variability in viscosity
Runs 4 and 7 and Runs 4
variability. It was
themselves were
the
8
rise,
shows
A
there is some inherent
but the disparities between
and 8 are well beyond this range of
concluded
primary
that
the
additive packages
contributing
factors
in the
VISCOSITY, CSt
36
Standard Conditions (Run 4)
A New Oil (Run 7)
O New Oil (Run 8)
T I M E , hr
Figure 7.
Viscosity versus
exposure
time for two
samples of Phillips 66 HD SAE 30 at standard
conditions.
37
differences
between
new
and
original
standard condition
results.
The
fact
that
atomic
emission
spectra
revealed
different quantities of additive metals may tempt the reader
to draw conclusions
concerning
additive metal compounds
pointed
out
various
literature
complex
by
the
forms
on
Amoco
(unidentifiable by
complex
that is varying may
as
not
the
other
can
However, as
representative
[32,33],
means)
different circumstances.
activity.
technical
well
our
efficacy of individual
copper
references
as
in more than one
the
and
coordinated
organometallics
act
differently under
The additive metals may be present
form.
be
Also, the additive metal
the
actual
causal factor.
A
metal that appears to be constant in amount may vary greatly
in activity based
Amoco
on
representative
present
nor
a
difference
would
indicate
not
the
Speculation concerning lube oil
in
complex form.
specify
intended
the
The
metal forms
action
of
each.
additive metal activity was
therefore left for future research efforts.
Experiments were continued using
A new standard as determined by
Runs
the new Phillips 66.
7 and 8 was thus used
for comparison in further experiments.
The next
objective
being solubilized, perhaps
Run 9 was
conducted
by
was
to
confirm
that copper was
as catalytically active species.
initially
using
nitrogen as the
38
— Standard Conditions (Run 8)
VISCOSITY, CSt
O Run 9
TI ME , hr
Figure 8.
Viscosity•versus exposure time with copper
foil removal and nitrogen gas changed to
oxygen at 24 hours.
39
agitating gas, otherwise
using
standard
percent sunflower oil and 2
cm
x
running the experiment
24
hours,
for
removed and the nitrogen
gas
conditions of 5.0
5 cm copper foil.
changed
After
the copper foil was
to oxygen.
Figure 8
shows the resulting viscosity rise.
The results of Run 9 allow three important conclusions
to be drawn.
appreciable
earlier
First
plant
work
oxygen
oil
is
clearly necessary for any
polymerization
E43.
If
oxygen
polymerization would have occurred
standard conditions.
Secondly,
as
demonstrated in
were
within
copper
unnecessary,
15 hours as with
surface (as foil)
need not be present for polymerization initiation as long as
the oil mixture has been exposed to copper foil.
indicate that the copper is
dissolved form.
The
This would
dissolving and is active in the
third
point
is
that,
if copper is
dissolving, it will dissolve with or without oxygen present.
The copper that is
however, may only
Thus oxygen may
dissolved
become
be
in
active
necessary
to
the presence of nitrogen,
upon
exposure to oxygen.
convert dissolved copper
into a catalytically active state.
As discussed previously oxygen and copper can react to
form free radicals.
Run 9 supports the idea that copper ion
participates in
oxidation-reduction
oxygen as
the
an
electron
acceptor.
reaction involving
Atomic
emission data
40
indicated a rise in copper
at the point of copper
foil
and
oxygen
This
are
from 0.0 ppm to 2.0 ppm
removal.
This shows copper is
that
oxygen
is necessary to begin
supports
the
taken into solution but
polymerization.
content
primarily
assumption that copper
responsible
for
forming
the
original free radicals necessary for initiation.
At
this
vegetable
oil
solubilization.
help
clarify
phenomena
point
was
the
possibility
a
causal
existed
factor
in
A
series
of
experiments
the
impact
of
vegetable
incidental
to
actual
experiments were also used to
that
the
the
copper
was designed to
oil
presence
polymerization.
further verify the
on
These
catalytic
form of the copper.
The experiments in the following series have in common
the fact that
sunflower
lubrication oil
until
containing the lube oil
bath.
This
oil
contributing factor in
to addition
vegetable
introduced into the
hours
after
the reactor cell
had
been
placed
in the 150 C oil
time
time required for significant
Thermal
not
48.5
pretreatment
conditions.
was
period
viscosity rise under standard
exposure
any
was well beyond the
is
eliminated
is
not
a
predisposition of vegetable oil
polymerization in these experiments.
oil
as
present
to
aid
in
Also, the
the
copper
solubilization nor is the vegetable oil being exposed to the
copper surface (foil).
41
Each
run
lubricating oil.
began
with
500
ml
of
uncontaminated,
The lubricating oil was placed in the test
cell and the appropriate catalyst
initially either nitrogen or
48.5 hours in the hot
oil
added.
oxygen.
The gas flow was
At the completion of
bath a 5.0 percent contamination
of sunflower oil was added to the lubrication oil.
accomplished without removing
the
In certain experiments copper
foil
was removed just before
the addition of the sunflower
oil.
The gas flow was never
interrupted
adjustments.
for
If
longer
from the oil bath.
than
5
minutes
during
was
the
initial
gas, this was
nitrogen
changed to oxygen
cell
This was
immediately
following
these
the vegetable oil
addition.
The first run in
this
series.
using new Phillips 66, 2 cm x
was oxygen for the entire run.
at 48.5 hours and a
added.
5.0
sunflower
5 cm copper foil, and the gas
The copper foil was removed
percent level of sunflower oil was
The plot of Run 10
hours without
Run 10, was performed
is
oil
given in Figure 9.
shows
a
slight
The 48.5
increase in
viscosity, 31 centistokes, which is negligible in comparison
with the viscosity rise for contaminated oil.
after the sunflower oil
Several hours
addition a significant rise begins,
exceeding 375 percent within 18 hours.
42
- Standard Conditions (Run 8)
O Run 10
>-
300
T I M E , hr
Figure 9.
Viscosity versus exposure time with oxygen
and copper foil for initial 48.5 hours.
Copper foil removed and 5.0 percent sunflower
oil addition at 48.5 hours.
43
Standard Conditions (Run 8)
O Run I0
Figure 10. Viscosity versus exposure time with, oxygen
and copper foil for initial 48.5 hours.
Copper foil removed and 5.0 percent sunflower
oil addition at 48.5 hours. Time zero at the
point of sunflower oil addition.
44
Figure 10 is a plot of the standard conditions and Run
10 using 48.5 hours as time
rise
in
Run
10
sunflower
oil.
viscosity
has
standard
begins
At
zero for Run 10.
quickly
4.0
hours
increased
conditions
after
it
20
has
the
following
over
The viscosity
addition
the
addition.
centistokes
increased
of
while at
less
than
5
centistokes.
The
next
experiment
in
this
series.
Run
11,
was
performed using nitrogen gas flow prior to the vegetable oil
addition, with all other factors the same as in Run 10.
11 shows a viscosity rise result
as seen in Figure 11.
When
Run
similar to that of Run 10,
zero time is taken as the time
of vegetable oil addition and plotted with the standard case
(Figure
12)
it
is
seen
that
the
curve
for
Run
11
approximates the standard even more closely than Run 10.
The
atomic
emission
(Table
II)
reveals
a
copper
content of 28 ppm at 48.5 hours for Run 10, well above the 2
ppm measured at 24 hours
in
vegetable oil was
present
This demonstrates
that
factor in copper
Run
from
9.
Recall that in Run 9
the
beginning of the run.
vegetable
solubilization.
soluble copper level at 48.5
oil
It
is
not
the causal
also shows that the
hours may be greater than that
throughout a standard condition run.
45
- Standard Conditions (Run 8)
O Run 11
>
300
T I M E , hr
Figure 11. Viscosity versus exposure time with nitrogen
and copper foil for initial 48.5 hours.
Copper foil
removed,nitrogen
changed to
oxygen, and
5.0
percent
sunflower oil
addition at 48.5 hours.
46
Standard Conditions (Run 8)
O Run 11
TI ME , hr
Figure 12. Viscosity versus exposure time with nitrogen
and copper
foil for initial 48.5 hours.
Copper foil removed, nitrogen changed to
oxygen, and
5.0
percent
sunflower oil
addition at 48.5 hours.
Time zero at the
point of sunflower oil addition.
47
I Run No. I Time of Sample
I
I
10
I
I
48.5 hours
28 ppm
I
I
I
11
I
I
48.5 hours
14 ppm
j
Table II.
Atomic emission results for Runs 10
and 11.
The differences between Runs
10
complexity of the present system.
of the lubrication
slight
oxidative
This is
Copper Level |
based
oil
to
initial 48.5 hours
the
data also shows that
in
the
TBN
and
of
heat is leading to
the
lubricating oil.
rise
in
viscosity over the
absence
of
the vegetable oil.
with
oxidation
place in Run 10, probably
the
oxygen
small
This rise does not occur
III shows that
It appears that exposure
polymerization
on
and 11 emphasize the
nitrogen.
of
the
Total Base Number
lube oil is taking
at points of unsaturation.
(at
48.5
hours)
Table
for Run 10 with
oxygen flow throughout is far less than TBN for Run 11 using
nitrogen.
48
I
Run No.
I
I
I
I
I Initial TBN
I
I
10
I
I
I
7.0
I
I
7.7
TBN at 48.5 hrs
I
I
6.0
I
Total Base Number for Runs 10 and 11.
lubrication oil and its
may
to
It
copper,
as
to
the actual
thereby increasing the copper
in
copper
content
lubrication oil additives may
way that the soluble
The chemistry involved
is conceivable that oxygen
complexing
explain the higher
directly affecting the
speculate
components being oxidized.
may be oxidizing the
be
additives.
difficult
availability for
I
I
2.6
I
Oxidative degradation
very
I
I
I
11
Table III.
makes it
I
the
of
react
copper
system.
Run
with
This might
10.
Also the
oxygen in such a
activity is altered, resulting
in a change in viscosity rise.
The important results
copper dissolves in lube oil
from
Run
10
and
11 are that
with either nitrogen or oxygen
present and that vegetable oil
is not necessary to dissolve
the copper.
lead
These
soluble copper
is
runs
also
probably
the
to the conclusion that
active catalytic form(s).
49
requiring only an
copper surface.
initial
It
is
exposure
also
not necessary for dissolving
of
lubrication oil to
noted that although oxygen is
copper, oxygen may enhance the
rate of dissolution.
Having tentatively concluded
of copper catalyst was
could be verified if
dissolved
a
known
yield similar results.
in
later
research
that
the active form(s)
species, it was felt this
soluble form of copper would
This soluble form could then be used
to
minimize
polymerization
rate
by
limiting soluble copper levels.
Cupric and cuprous oxides were tested at approximately
20 ppm copper by
weight
Runs 12 and 13.
The
as
substitutes for copper foil in
other operating parameters for these
runs were at standard conditions.
fine powders,
making
it
possible
mixing action of the oil
suspension.
However,
The oxides were tested as
13
using
the
viscosity and
to maintain the oxide particles in
it
is
possible
particles agglomerated and settled.
Runs 12 and
for
the
two
that
some
of the
Figure 13 is a plot of
copper oxides and standard
conditions.
The copper oxides
show
catalytic
activity less than
that of the standard conditions using copper foil.
indicate poor solubility.
copper
oxides
are
less
It
This may
might also indicate that the
active
forms.
These
unknowns
50
Standard Conditions (Run 8)
O CU0O (Run 13)
(Run 12)
VISCOSITY, cSt
A CuO
T I M E , hr
Figure 13. Viscosity versus exposure time with cupric
and cuprous oxides at standard conditions.
51
prevented the use of
these
oxides
as
a copper source for
future experiments.
Another copper
source
coordination complexes.
The
acetylacetonate.
As
acetylacetonates
systems.
be
was
are
chosen
complex
from
very
group of
selected was cupric
discussed
generally
a
earlier,
soluble
in
metal
organic
An additional advantage is that, should the copper
released
by
decomposition
of
the
complex,
the
acetylacetonate fragments will evaporate C303.
Run 14 was conducted
using
5.0
ppm copper by weight
with cupric acetylacetonate as the source.
ppm was chosen based on
condition runs.
appears to be
The
a
The value of 5.0
atomic emission results in standard
viscosity
close
rise
as
seen in Figure 14
replication of standard conditions.
The experiment was repeated using 1.0 and 10.0 ppm copper as
cupric
acetylacetonate.
These
were
Runs
respectively, also plotted in Figure 14.
10.0 ppm are quite
variability
of
similar
this
and
system
trend
decreases
the
However, the
that
rate
as
of
similarity
the
as
16,
Results at 5.0 and
determined
(Figure
amount
viscosity
of
and
easily within the inherent
experiments at standard conditions
definite
15
results
indicates that the dissolved copper
of
rise
at
7).
by
repeated
There is a
dissolved Copper
also
5.0
decreases.
and 10.0 ppm
may be reaching a point
52
>- 300
— Standard Conditions
□ I ppm Cu (Run 15)
A 5 ppm Cu (Run 14)
O 10 ppm Cu (Run 16)
TIME, hr
Figure 14. Viscosity versus
levels of cupric
conditions. -
exposure time for varying
acetylacetonate at standard
53
where its
concentration
is
no
longer
the
rate limiting
factor.
The cupric
next used in
used oxygen
nitrogen.
acetylacetonate
48.5
flow
The
hour
pretreatment
throughout
overall
parallel the results
at
while
results,
for
10.0
experiments.
Run
as
ppm copper was
Run 17
18 initially used
shown
in Figure 15,
previous pretreatment experiments
with copper foil.
The
confirmation
of
soluble copper catalyst is
cupric
a significant finding.
these pretreatment experiments
between runs exposed to
48.5 hours.
acetylacetonate
again
oxygen
as
a
However,
revealed a difference
or nitrogen for the initial
Figure 16 plots standard conditions (Run 8) and
Runs 17 and 18 where time zero is the point of vegetable oil
addition
(48.5
hours).
As
lubrication oil is being
hour
period.
before,
slightly
However,
due
to
addition, equal amounts of copper
it
appears
the
degraded during the 48.5
control
of
the
copper
were present in both runs
and did not depend on rate of copper dissolution.
The curve
for the oxygen run has a profile similar to that for a lower
copper catalyst level, while the
is similar to a copper
conditions.
the catalytic
level
This indicates
activity
of
curve for the nitrogen run
of
10.0 ppm and standard run
that
the oxygen may deactivate
the
dissolved copper species.
54
A O2 Initially (Run 17)
O N2 Initially (Run 18)
>
300
T I M E , hr
Figure 15. Viscosity versus exposure time with nitrogen
or oxygen and cupric acetylacetonate for
initial 48.5 hours and 5.0 percent sunflower
oil addition at 48.5 hours. Nitrogen changed
to oxygen at 48.5 hours for Run 18.
55
— Standard Conditions (Run 8)
A 0„ Initially (Run 17)
O N9 Initially (Run 18)
5
IO
15
20
25
T I M E , hr
Figure 16. Viscosity versus exposure time with nitrogen
or oxygen and cupric acetylacetonate for
initial 48.5 hours and 5.0 percent sunflower
oil addition at 48.5 hours. Nitrogen changed
to oxygen at 48.5 hours for Run 18. Time
zero at the point of sunflower oil addition.
56
This deactivation is not
as
evident
when vegetable oil is
available for oxidative polymerization.
Total Base Number
data
similar to those of Runs
48.5 hours the oxygen
value when
oxidation
compared
of
the
10
run
to
lube
in
Table IV indicate results
and
had
11
At
a significantly reduced TBN
nitrogen
oil
with copper foil.
at
to
48.5
acidic
hours.
species
Again,
probably
accounts for the difference in TBN.
I
I
I
I
I
Run No.
I
17
I
I Initial TBN
TBN at 4B.5 hrs
I
I
I
7.0
1.54
I
I
I
18
Table IV.
It was
I
I
I
I
I
I
7.0
6.47
I
I
I
Total Base Number for Runs 17 and 18.
speculated
earlier
in
this
thesis that the
copper catalyst might be primarily involved in initiation of
the polymerization reaction.
confirmed
free
speculation.
radical
Lupersol
known to initiate
Scouting
initiator
130,
addition
tend
experiments with a
to
support
this
a commercial hydroperoxide, is
polymerization by spontaneously
decomposing into free radicals.
Lupersol 130 was added in
57
periodic
additions
intervals.
original
of
Two runs
0.48
(19
lubrication
and
oil
ml
Lupersol
20)
were conducted with the
with
catalyst, respectively.
Nitrogen
the run.
are
The
results
compared with the standard
oil.
without
copper
given
in
Figure
and 20 are similar.
propagation
If copper
phase. Run 20 containing
the lack
indicates
increased
rate
involved in propagation but initiation.
theoretical concept that
providing the initial
are then capable
double
bond
and
of
the
free
copper
hence
polymerization reaction.
a
copper
However,
is not
This reinforces the
catalyst
radicals.
abstracting
foil
case for the original
viscosity rise.
an
hour
17 and are
copper should have an accelerated
of
1.5
flow was used throughout
condition
The curves for Runs 19
were important in the
and
at
is a key in
These free radicals
hydrogen
initiating
the
alpha to the
free
radical
58
A Lupersol 130 with Cu (Run 19)
VISCOSITY, cSt
O Lupersol 130 without Cu (Run 20)
T I M E , hr
Figure 17. Viscosity versus exposure time using Lupersol
130 as a free radical initiator.
59
SUMMARY
This research demonstrated
oil polymerization in
Any review of the results
the multiple possible
drawn.
It
the
is
highly complex chemical system.
of
this
work must be mindful of
interactions
among system components
care
evident
with
which
that
any
mitigate the activity of copper
tested widely.
catalysis of sunflower
commercial lubrication oil containing
unknown additives creates a
and, therefore,
that
New additives
conclusions must be
additive
developed to
(or other) catalyst must be
must be fully compatible with
other additive formulations present for other reasons.
Copper foil was
copper
catalytically
vegetable
exposed
found
oil.
to
oil
active
The
polymerization, but
it
of
in surface area would
copper
is
dissolved.
solubilization
polymerization.
amount
mixture
related to the rate
to
would
was
contribute
in
of
the
soluble forms of
polymerization
metallic
important
appears
to
copper surface
in
have
the
been
copper solubilization.
logically
The
then
of
rate
of
primarily
An increase
increase the rate at which
increased
give
an
rate
of
copper
increase
in
60
A series
of
pretreatment
experiments
was designed to
demonstrate that the copper
was
indeed dissolving and that
contaminant
was
not
solvation.
vegetable
These
oil
experiments
responsible
verified
for that
that copper slowly
dissolved in oil mixtures at simulated crankcase conditions.
They also revealed
rate at
which
that
copper
deactivating the copper
oil is not present.
oxygen
appears
dissolves,
but
as
to accelerate the
that
oxygen may be
well, especially when vegetable
Vegetable
oil contamination seems to
have little if any effect on the rate of copper dissolution.
Though metallic copper
source of dissolved
foil
copper
dissolved was difficult.
in the areas
of
point of
catalyst
species,
It
poisoning
benefit if the amount of
had
determined as a
control of the amount
was felt that future research
or sequestering additives would
copper
could be quantified at the
addition.
conducted with materials
been
Experiments
that
would
were therefore
be sources of readily
dissolved copper.
Cuprous and cupric oxides
but gave polymerization rates
were tested as copper sources
far
below those expected for
the levels of copper chosen.
These compounds apparently had
only minimal
test
solubility
copper compound,
levels
of
cupric
catalytic
in
oil
mixtures.
A third
acetylacetonate, demonstrated high
activity
at
standard
conditions.
61
Results parallel those
exposure.
achieved
identified
as
a
achieved, cupric acetylacetonate
source
for
Precise amounts of copper can
mixture,
metallic copper foil
Based on the chemistry of the acetylacetonate and
the polymerization results
was
with
providing
control
soluble
therefore
of
this
active copper.
be added to an oil
system
variable
in
subsequent research.
Experiments in a
multi-cell apparatus indicated soluble
copper species were of
primary
importance in initiation of
the triglyceride polymerization reaction.
were conducted using
radical initiators
Lupersol
with
and
130
to
without
These experiments
provide excess free
copper
present.
No
enhancement of polymerization rate was given by the presence
of copper
as
would
be
expected
propagation phase of reaction.
if
copper catalyzed the
Theory for copper catalysis
suggests that copper and oxygen can function together in the
production of free radicals.
These
initiate addition polymerization.
radicals provided by
the
of
forming
free
Without the initial free
combined
oxygen, energy constraints
free radicals in turn
presence
of copper and
associated with other mechanisms
radicals
might
limit
the
overall
poIymerization.
The results of viscosity rise experiments were supported
using
atomic
emission
spectroscopy
and
alkaline reserve
62
experiments.
conclusions.
Both
tests
Viscosity
initial indications often
used as a whole the
viscosity data
helpful in developing valid
rise
without
experiments
being
had
provided
conclusive.
When
atomic emission. Total Base Number, and
reinforced
experimental results.
were
each
other
and
helped clarify
63
CONCLUSIONS
1.
Soluble copper species appear to be of primary catalytic
importance in the
oil
in
free
lubrication
radical polymerization of sunflower
oil
at
simulated
engine
crankcase
conditions.
2.
It appears that copper and
form the initial free
radicals
polymerization of contaminant
not
seem
to
oxygen act in combination to
catalyze
necessary for the oxidative
sunflower
the
oil.
propagation
Copper does
phase
of
the
polymerization mechanism.
3.
Oxygen
lubrication
is
oil
not
required
system.
however that oxygen does
to
dissolve
Preliminary
copper
evidence
in
a
suggests
enhance
the rate of dissolving of
The presence of sunflower oil
is not a governing factor
copper.
4.
in the rate of solubilization of copper at the conditions of
this research.
64
5. Oxygen may deactivate dissolved copper over long exposure
times,
present.
especially
where
When vegetable
reaction may
proceed
vegetable
oil
too
oil
is
not initially
is present the polymerization
rapidly
for
the
provides
a
source
copper
to be
deactivated.
6.
Cupric acetylacetonate
of soluble,
catalytically active copper which parallels results given by
metallic copper foil.
The
compound
provides
a means to
control concentrations of soluble copper in subsequent
experiments.
65
SUGGESTIONS FOR FUTURE RESEARCH
1.
One of the
key
approaches
to
seeking
an additive to
limit copper catalytic activity may be the comparison of the
two additive packages used in
the two different Phillips 66
batches of lubrication oil.
It is obvious that the additive
package in the
oil
lubrication
more readily inhibits
examination of these
the
rise
additive
from
in
the Wyoming refinery
viscosity.
A detailed
packages may reveal specific
additives effective in limiting polymerization.
2.
Additional
research
other engine oil wear
should
metal
include
the
contaminants.
screening of
If these other
metals, which are known to include iron, chromium, lead, and
silver,
produce
catalytic
polymerization, it may be
effects
on
triglyceride
necessary to develop more general
additives or mixtures of additives.
3.
The research in this
of oxygen may be
thesis indicates that the presence
influencing
the solubilization of copper.
It also indicates that in some instances oxygen may actually
be reducing the activity of the dissolved copper.
phenomena should be reviewed in
These two
greater detail as there are
66
other possible
results.
mechanisms
There
may
deactivation effect
to
which
be
the
an
could
yield the observed
possibility
advantage
or
of
of
using
using
the
it in
conjunction with a particular additive chemistry.
4.
There are prescribed
concentrations
in
used
advantageous to work at
acceptable
limits for trace metal
crankcase
oils.
these
It
would
contamination levels.
be
Table
IX in the Appendix lists trace metal contaminants at maximun
recommended limits in parts
oils would
normally
those listed.
maximum
metal
If
per
million.
Used lubrication
be
discarded
if
metal levels exceed
the
additives
are
effective at these
levels.
the
additives
will
effective at lower metal contamination levels.
probably
be
67
BIBLIOGRAPHY
1.
Nitske, H.R., and Wilson, C.M., Rudolf Diesel, Pioneer
of the Acre of Power, 1st ed., University of Oklahoma
Press, Norman, (1965).
2.
Pryde, E.H.,
Overview," J.
(1983).
3.
Peterson, C.L.,
Wagner,
G.L., and
Auld, D.L.,
"Vegetable Oil Substitutes Diesel Fuels," Power and
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4.
Rewolinski, C., "Vegetable Oil Dilution of Diesel
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Lubricating
Oil,"
Thesis,
Montana State
University, Bozeman, MT (1984).
5.
Dutta, A., "Polymerization of Lubrication Oil Base
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6.
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7.
Bruwer, J.J., Boshoff, B.V.D., Hugo, F.J.C., Fuls, J.,
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Duplessis, A.,"The Utilization of Sunflower Seed Oil as
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8.
Uri, N., Autoxidation
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(1961).
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"Vegetable Oils
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Oil Chem.
as
Soc.
Diesel Fuels:
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10.
Sonntag, N. 0. V., Bailey's Industrial Oil and Fat
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Rheineck, A. E., and Austin, R. O., "Treatise on
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68
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Farmer, E. H., and
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Bolland, J. L., and
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Privett, 0. S., Lundberg, W. 0. , Khan, N. A., Tolberg,
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15.
Formo, M. W., Bailey's Industrial Oil and Fat Products,
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Wiley & Sons, Wew York (1979).
16.
Bolland, J. L., and Gee, G., Trans. Faraday Soc. 42:244
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17.
Farmer, E. H., Trans. Faraday Soc., 42:228 (1946).
18.
Gunstone, F. D.,
1022 (1946).
19.
Swern, D., Fatty Acids, 2nd ed., Part 2, Markley, K. S.
Ed., pp. 1387-1436, Interscience Publishers, INc. New
York (1961).
20.
Bailar, J. C., Moeller, T., Kleinberg, J., Guss, C. O.,
Castellion, M. E., Metz, C., Chemistry, Academic Press,
Inc., New York, pp. 804-836, (1978).
21.
Cotton, F. A., and Wilkinson, G., Basic Inorcranic
Chemistry, John Wiley & Sons, Inc., New York, pp. 379416, (1976).
22.
Cotton, F. A., and Wilkinson, G., Advanced Inorcranic
Chemistry. 4th ed., John Wiley & Sons, New York, pp
798-821 (1980).
23.
Huckel,
W.,
Structural
Chemistry
of
Inorganic
Compounds, Volume I , Elsevier Publishing Co., INc., New
York, pp. 47-148 (1950).
24.
ColIman, J. P.,
Hegedus,
L. S., Principles and
Applications of
Qrcranotransition
Metal Chemistry.
University Science Books, California: (1980).
25.
"Total
Base
Number
of
Petroleum
Products
by
Potentiometirc Percholoric Acid Titration," ASTM D
2896, 1974 Annual Book of ASTM Standards, part 24,
ASTM, pp. 870-875 (1974).
Sutton,
and
Gee,
D.
G.,
Hilditch,
A.,
J. Chem. Soc. 119
Trans.
T.
Faraday Soc.,
P., J. Chem. Soc*
69
26.
"Iodine Value of Drying
1959-69, Annual Book of
PP. 283-286 (1979).
Oils and Fatty Acids," ASTM D
ASTM Standards, part 29, ASTM,
27.
Jennings, P. W., Personal Communication, Montana State
University, Bozeman, MT (1985).
28.
Hexler, H., "Polymerization
Reviews 64(6):591 (1964).
of
Drying
Oil,"
Chem.
Sample Mo.
Engine miles
(km)
Miles since last sample
(km)
Miles since last oilchange
(km)
2
4
5
6
7
501,000' 509,000 516,000 533,000 538,000 547,000
554,000
(806,281) (819,156) (830.422) (857,780) (865.827) (880,311)
(891,577)
4.000
8,000
7,000
17.000
4.000
9,000
7,000
‘ (6.437) (12.875) (11,265) (27,359)
(6.437) (14.484) (11.265)
4.000
12.000
19,000
36.000
4.000
13.000
20,000
(6.437) (19,312) (30,577) (57,936)
(6.437) (20,922) (32.187)
17
21
14
1.0
0.3
18
24
16
1.8
0.4
Note: Oil changed at 534,000 mi (859,390 km).
Table V.
3
20
31
17
2.0
0.5
39
59
36
51
2.1
12
11
12
4.3
0.3
19- •
17
16
2.9
0.4
-
Successive spectrographic analyses of used
oil from a
diesel locomotive crankcase.
(CRC Handbook of Lubrication 161)
23
24
21
1.4
0.5
APPENDIX
Iron (ppm)
Lead (ppm)
Copper (ppm)
Chromium (ppm)
Silver (ppm)
I
71
T
I
I
M
A
C
B
P
H
C
0
P
G
N
E
A
L
C
A
R
I
0
S
P
I
I
I
I
N
I
6
P
S '
I
U
H
I
C
I
6
I
U
M
U
M
I
I
I
I R
I u
I N
I
I
\
I N
I
I
0
I
E
I o
I
U
I
R
I
I
R
I
S
I
0.0
I
I
I
J _
I
I
H
I
I
I
I
I
I10
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
6
I
7
_1_
I
|11
I
I
113
I
0.0
I L
6
6
I
I
I
410
X
I
I
I
I
I
I
I
I
I
X
I
I
I
I
I
I
I
I
I
I
5
\
0
576
148
'550
1539
507
890
0
0
0
1039
I
682
1210
I
1230
2
162
530
0
871
I
517
I
24.2|
2
1280
7
0
1157
I 1118
I
I
I x I
X
I
I
X
I
I
I
I
I
I
I
I
I
I
I X
I
I
I
I
I
I
I
I
I
28
48.5|
990
5
0
986
I
1212
I
14
1172
4
0
890
I
1078
I
I
X
I
I
i
38.0|
I
I
I17
I
I
I
5
485
1490
4
0
0
0
882
1270
I
I
960
1280
I
I
I X
I
I
I
X
I
I
.5
I
I
I
I
0
I
.5
I
I
I
I
I
I
I
I
S
L
I
I
H 4
I
M
I
I
I
I
I
I
I
I
I
I
U
I
I o
I I
I
I N
I A
I
I
I
I
I
O
I
0
R
I
I
I
I
I
I
72.0|
CD
I
I
-
Z
I 0
I R
I I
I G
I I
1227
Ln
I 6
4
I
.P"
CO
I
I
I
I
I
I
I
I
I
I
I
I 4
J _
I
I
M
E
I N
I E
I W
I
9
I
Table VI .
1058
6
0
1088
I
1208
I X
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
Atomic emission data for copper and common
additive metals for selected runs.
I
I
I
I
I
I
I
-L
I
-L
I
I
I
I
I
L
I
L
I
I
Run I Nitrogen I
No
Time
I
Exposure I
I
None
I
2 I None
I
3 I None
I
4 I None
I
6 I None
I
7 I None
I
8 I None
I
9 I 0.0-24.0 I
10 I None
I
11 I 0.0-48.5 I
12 I None
I
13
None
I
14
None
I
15 I None
I
16
I None
_L
17 I None
I
18 I 0.0-48.5 _L
Table VII.
Oxygen |
Time
Exposure I
0.0-90.0 I
0.0-70.0 I
0.0-60.0 I
0.0-60.0 I
0.0-48.0 I
0.0-24.0 I
0.0-17.0 I
24.0-64.01
0.0-70.5 I
48.5-64.51
0.0-48.0 I
0.0-48.0 I
0.0-18.0 I
0.0-30.0 I
0.0-15.0 I
0.0-78.0 I
48.5-60.51
Copper I
Added j
I
None I
IcmxScm I
2cmx5cmI
2emx5cmI
2cmx5cmI
2cmx5cmI
2cmx5cmI
2cmx5cmI
2crnx5cm I
2cmx5cmI
CuO
I
Cu0O
Cu AcAc I
Cu AcAc I
Cu AcAc I
Cu AcAc I
Cu AcAc I
Copper Foil|
Time
Exposure
None
_L
0.0-70.0 hr I
0.0-60.0 hr I
0.0-60.0 hr I
0.0-18.0 hr I
0.0-24.0 hr I
0.0-17.0 hr I
0.0-24.0 hr I
0.0-48.5 hr I
0.0-48.5 hr I
None
I
None
I
None
I
None
I
None
I
None
I
None
I
Time of I % Sun
Sun Oil I Oil
I
Addition Added
0.0 hr I 5.0
I
0.0 hr I 4.7
I
0.0 hr I 4.7
I
0.0 hr I 5.0
I
0.0 hr I 5.0 _ 1
0.0 hr I 5.0
I
0.0 hr I 5.0 _ L
0.0 hr I 5.0 _ L
48.5 hr I 5.0
I
48.5 hr I 5.0
0.0 hr I 5.0 _ L
0.0 hr I 5.0 _ L
0.0 hr I 5.0
I
0.0 hr I 5.0 _ L
0.0 hr I 5.0
I
48.5 hr I 5.0 _ L
48.5 hr I 5.0
I
Operation parameters for oil bath runs
73
Run
No
I
Time
I
I
2
I Time
2
I
3
j Time
3
TSN
6
Time
|
7
, Time
7
TEN
j Time
10
j
Time
11
TBN
14
Time
14
TEN
15
Time
15
TBN
16
Time
16
TSN
Time
18
13
Ac
A
I
hr
hr
hr
0.0
10.0|
40.0
0.6
20.0
30.0
40 . 0 |
50.0
60.0
70.0
4.5
3.3
2.1
1.0
1.0
0.0
0.4
0.0
10.0
20.0
30.0
40.0
50.0
—
6.7
3.4
2.2
1.0
0.4
0.0
10.0
18.0
28.0
38.0 I 48.0 I
3.7
2.2
0.9
1.1
48.6
52.5
56.5
I
hr
j
hr
hr
hr
hr|
hr
TEN
Table VIII.
I
5.2
7.6
|
j
j
J
10.0
20.7
5.5
2.8
24 . 0 |
48.5
6.1
2.6
1.5
1.1
0.9
0.3
0.0
24.0J
48.5
48.6
52.5
56.5
60.5
64.5
7.7
6.2
6.0
6.0
6.4
3.4
0.9
1.5
0.0
6.0
9.0
12.0
15.01
18.0
7.2
5.8
4.6
2.8
2.0
2.2
0.0
10.0
14.0
17.0
20.0
6.8
—
3.4
— --
2.8
0.0
6.0
9.0
12.0
15.0
6.2
4.0
4.3
4.0
1.9
60.3
.
0.0
j hr
I
30.0
6.5
hr|
20.0
1.6
0.0
TBN
Time
11.0
8.7
---- I
TSN
Time
0.0
----
5.6
TBN
11
I
hrj
TSN
10
17
I
T3N
6
17
hr|
TBN
I
I
0.0
48.5
48.6
—
1.5
1.5
0.0
48.5
48.6
56.5
60.5
— --
6.5
6.5
3.4
2.2
0.0
10.0
20.0
30.0
6.7
5.9
3.7
1.5
j
0.8
66.5
-
Total Base Number in mg KOH/g oil for
several runs .
* This run had no copper, 5.0 percent Sunflower Oil,
and was performed in new Phillips 66 lube oil.
74
Table IX.
Metal
Diesel, dual-fuel, and gas engines
Max cdnc (ppm)
Aluminum
BoronChromium
Copper' •
Iron
Lead
Potassium
Silicon
Silver
40
20
40
40
100
100
. 50
20
6
Limits for trace metal concentrations in used
crankcase oils.
(CRC Handbook of Lubrication C63)
MONTANA STATE UNIVERSITY LIBRARIES
CO
7
OC>1457C
CO
CM
CO
I! IIII 111IlIIIIIIII
Vain
N3T8
J51
cop.2
DATE
Jette, Stephen John
Copper catalysis of
polymerization of...
ISSUED TO
Main
N378
J51
cop.2
I