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Патент USA US2404871

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Patented July 309 lgd? 4
UNITED STATES PATENT OFFICE
I
2.404.811
LUBRICATING COMPOSITIONS
Paul R. van Ess, Berkeley, Forrest J. Watson,
Oakland, ‘and Gary M. Whitney, Piedmont,
Calif., assignors to Shell Development Com
pany, San Francisco, Calil’., a corporation of
Delaware
No Drawing. Application July 28, 1943,
Serial No. 496,678
12 Claims. (Cl. 19.6-13)
1
This invention relates to sulfur-containing ad
ditives used to produce improved lubricants and
stabilized organic compositions, to methods of
preparing concentrates of naturally-occurring
sulfur-containing additives for lubricating oils
and greases, and to improved methods of inhibit
ing oxidative decomposition and lubricating in
ternal combustion engines, particularly those
containing corrosion~i5ensitive alloy bearings. ,
2
is to obtain superior aviation and Diesel engine,
heavy duty lubricating oils. A still further pur
pose is to produce novel sulfur-containing petro
leum fractions which contribute valuable anti
corrosive, anti-oxidant, anti-wear, high ?lm
strength and/or other advantageous properties
to organic compositions in which they are incor
porated. Other objects will be apparent from the
following description.
I
It was quite generally; believed heretofore that 10 It has been determined that the anti-corrosive
and anti-‘oxidant properties of the desirable nat
relatively high boiling sulfur compounds natur
ural petroleum sulfur compounds are associated
ally occurring in petroleum crudes were good in
vwith the availability or activity of the sulfur in
hibitors for lubricating oils, imparting to them
them.’ If the compounds or mixtures thereof,
anti-corrosive properties and oxidation stability.
As a result, several high sulfur-content lubricat 15 such as those obtained from petroleum by the
hereinafter described methods have low sulfur
ing oils have appeared on the marketfor which
certain superiorities are claimed. However, in ' availabilities, they are themselves'substantially
non-corrosive to bearing surfaces but may fail to
many cases such claims cannot be veri?ed by
inhibit other types of corrosion. If, however,
laboratory and engine tests. Moreover, it was
found that as a rule these high sulfur lubricating 20 their sulfur availability is above a certain mini
mum, they will inhibit against both bearing cor
oils have a very strong and dangerous tendency
to form lacquer, sludge ‘and carbon on pistons
and piston rings, particularly in high tempera
ture operation.
rosion and oxidative decomposition and may also
contribute other valuable properties to the lubri
eating oil to which they are added. Some of these
It has now been discovered however that 25 additives may produce a brown or colored ?lm
on metal bearing surfaces in engine operation.
among the naturally-occurring sulfur com
pounds in petroleum oils there are bene?cially
active as well as inactive and even detrimental
With others, (notably the hereafter described
Utanol ra?lnates) this discoloration of copper‘
surfaces may be substantially absent, but the an
varieties and that the bene?cially active com
30 ti-corrosive and anti-catalytic properties which
pounds can be extracted from the oils in which
the sulfur compounds contribute to the lubri
they occur to produce concentrates of relatively
eating oil are still prominent. Some of these sul
high non-corrosive sulfur content, which, when
furcompositions (e. g. the Utanol ra?inates) also
added to well re?ned lubricating oils, impart to
possess material anti-wear properties and/or the
properties without materially increasing their 35 ability to enhance or prolong the anti-wear prop
erties of other anti-wear agents.
tendency to form lacquer, sludge and carbon.
them good oxidation stability and anti-corrosive
It is accordingly an object of this'invention to
produce from crude petroleum, sulfur concen
trates which, when added to refined lubricating 40
oils and the like, act as oxidation and corrosion
inhibitors without materially increasing the lac-.
quering and sludge depositing tendency of the
base oil. A further purpose is to provide lubri
cating compositions having decreased tendencies 45
to attack modern alloy bearings. Another object
The reactivity or availability of the sulfur in
various compounds is de?ned as the percent sul
fur (calculated on the total sulfur content in the
compound or mixture) which will react with me
tallic copper under certain conditions. It is de
termined by heating at various temperatures
samples of the compositions with an excess (over
the amount equivalent to the sulfur content) of
?nely divided metallic copper for a standard pe
2,404,871
riod of time, here taken at 16 hours. The cop
2,315,131, sulfuric acid treatment, solvent extrac
per sul?de formed is then determined quantita
tion, selective hydrogenation, etc., or a combina
tively as by oxidizing the sul?de with bromine
tion of such treatments, preferably under condi
and precipitating the resultant sulfate with bar
tions not to reduce the sulfur content of the con
ium chloride. If the percent of sulfur reacted is
centrate excessively, i, a. so that not more than
plotted against the reaction temperatures for
about 1/3 of the total sulfur content is lost. In
various sulfur compounds or high sulfur content
other Words. our concentrates are “rai?nates,”
oils, a family of curves is obtained which at rel
“raiilnates” as commonly understood in the petro
atively low temperatures are quite close together.
leum industry being relatively para?lnic petro
However, at temperatures of say 300° C. the 10 leum fractions from which naturally associated
curves separate widely and the availability of the
aromatics have been removed. Whether the
sulfur as determined at this temperature gives
sludging tendency is the result of over-activity of
a reasonable correlation for various petroleum
certain sulfur compounds (as might well be) or
derived sulfur compounds with their inhibiting
is due to the presence of other associated com
e?icacy when incorporated in re?ned lubricating 15 pounds, is not known at this time. However, this
oils. At this particular temperature, compounds
is immaterial, as it is sufficient that a treatment
having sulfur availabilities below about 15% (for
adapted to remove aromatics from hydrocarbon
example those in West Texas high-sulfur lubri
mixtures will achieve the desired result.
cating oil extracts) are of little if any effect,
In general, crudes which contain the active sul
while certain other natural petroleum sulfur 20 fur compounds in concentration su?lclent to re
compounds of higher availability, 1. e. above
cover them in relatively concentrated form. are of
about 15% and preferably above about 20% (for
highly asphaltic nature such as certain California
example, those in Utanol ra?inates) are highly
(particularly Mount Rose, Coalinga, Santa Maria)
effective.
and Venezuelan crudes.
The availability of these sulfur compounds has 25
Outstanding is an oil known to the trade as
been correlated with their anti-corrosiveness in
“Utanol" which is an asphaltic petroleum crude
lubricating oils, for example by determining the
obtained from snallow wells in the Great Salt
comparative weight losses of copper-lead bearings
Lake area and southern Idaho. The oily fraction
subjected to the action of lubricating oils contain
separated from this material is known as “Utah
ing standard amounts of these sulfur additives 30 on.” Utanol varies in sulfur content from about
plus a commonly used detergent, which, although
10% to 1.5%, has a spec?c gravity of about 1.0 to
contributing other valuable properties, causes or
1.1, a saponi?cation number of around 10 to 20,
increases corrosiveness of the lubricating oil.
naphtha msoluoles of 10% to 15%. and contains
Thus various blended oils have been tested and
about 40% to ‘10% asphalt as determined by pre
compared by a procedure known as the Thrust 35 clpitation with about 0' volumes of n-butane at 60°
Bearing Corrosion test, which was described in
to 11500" C. It has no appreciable content of phe
the National Petroleum News, September 17, 1941,
pp. R 294-296.
Fractions or concentrates of active sulfur com..
no
.
Methods for obtaining an oil fraction having
the desired concentration of active sulfur com
pounds may be obtained by various methods from 40 pounds from crudes having a sulfur content above
5%, such as Utanol, are relatively simple. One
tain them. In most crudes, the concentration of
such method speci?cally applied to Utanol is as
these compounds is quite low, and special methods
follows:
(which are described later) are required in order
The crude is ?rst de-asphalted by any of the
45
to recover them in relatively high concentration,
standard de-asphalting methods. This may be
so that they may be added to re?ned lubricating
achieved by asphalt precipitation or distillation,
oils in eifective amounts without materially
or
both. The precipitation method is preferred
changing the desirable properties of the latter.
because of the extremely high asphalt content of
As a rule, it is poor practice to add to a well re
?ned lubricating oil more than about 10% of any 50 ‘the Utanol which may interfere with the proper
distillation and result in cracking of the asphalt
addition agent. The effective amounts of sulfur
and the inclusion of harmful cracked material in
which must be added to various re?ned lubricat
the distillate.
ing oils in the form of active sulfur compounds
various high sulfur petroleum crudes which con
The precipitation may be carried out by mixing
usually are on the order of 0.1% to 0.3% by ~
55 the Utanol with several volumes of a liquid light
weight of re?ned oil, although quantities of be
tween 0.02% and 1% may be useful. In a semi
plastic composition such as a grease, higher
amounts may be employed. Therefore, it is de
sirable, if not essential, that the. sulfur content
of a concentrate of active compounds be at least 60
2% and preferably 5% or higher.
As previously indicated, the indiscriminate ad
dition of natural petroleum sulfur compounds
tends to cause an increase in lacquering and
sludge depositing tendencies of the blended oils.
This however can be minimized by properly re
?ning either the oil from which the active high
sulfur concentrates are produced or the concen
hydrocarbon oil comprising predominantly or
consisting of C: to C6 hydrocarbons, preferably at
a temperature within about 75° to 100° C. of the
critical temperature of the latter. Thus propane
or propylenes at normal room temperature, bu
tanes or butylenes at temperatures of 60° C. or
above are well suited. Dissolving in benzene and
precipitating with isopentane also proved suc
cessful. If desired. the crude may be dissolved
in a liquid 04 to Cu hydrocarbon, naphtha. light
kerosene, etc., and gaseous methane. ethane, nat..
ural gas, propane, fuel gas. water gas, CO, CO: or
other cases may be introduced at high pressures
to effect or complete the asphalt precipitation.
trates themselves before they are added to lubri
cating oils. Such re?nement includes substantial 70 Moreover, selective so-called “naphthenlc” sol
elimination of asphaltic materials and a treat
vents may be present. such as liquid 80:. furtural,
ment capable of separating aromatic from non
nitrobenzene, beta,beta'-dichlor-diethyl ether.
aromatic hydrocarbons, for example, by precipi
phenol, cresylic acids. aniline, methylsulfolane,
tation with gas, such as methane under high pres
dimethylsulfolane. or a large number of others
sure as described by Pilat in U. 8. Patent 75 or their mixtures.
, 3,404,871
If the crude oil contains relativelyv low boiling
components, as gasoline, kerosene, etc., they may
be ?ashed from the crude prior to the precipita
tion or else may be separated later by fractional
distillation of the deasphalted ra?inate oil.
Ability of Utanol raillnates to decrease wear
. was determined on a. Multiple-Four Bali machine
similar- in‘ principle to ‘the Boerlage apparatus
described in themagazine vEngineering, volume
'
» 136, July 14, 1933. This apparatus comprises four
The supernatant liquid layer, 1. e. the ra?‘inate
steel balls arranged in pyramid formation.‘ The
phase resulting from asphalt precipitation and
top ball is rotated by a spindle against the three
containing the desired oil, is now separated from
bottom balls which are clamped in avstationary
the precipitated asphalt. This oil must be further
ball holder. All balls are immersed in the oil to
re?ned to reduce its lacquer-imparting tendenq 10 be tested. The tests are run for two hours at ,700
R.- P. M. under a '7 kg. loadfand at a controlled
Depending on the conditions of the precipita
temperature of 130°_ C. Diameters of the wear
tion, the nature of the solvents employed and the
scars worn on the three balls forming the base of
nature of the crude itself, one of several ways may
the pyramid are then measured, and the average
cies.
-
~
'
be followed. Obviously the more drastic the pre
cipitation conditions are, the less ‘drastic need
be the second treating step which involves (as
previously indicated) a treatment adapted to re
move aromatic hydrocarbons. Solvent extraction
may be employed with any one of the well known
selective “naphthenic" solvents previously men
tioned. Treatment with strong, i. e. 93 to 100%
sulfuric acid is usually desirable and effective.
Amounts of sulfuric acid ranging anywhere from
5 to 100 pounds per barrel of the ra?inate oil may
be employed.
taken as the true indication of wear. Results
were as follows:
Scar
Lubricant
'
diameterin
millimeters
1
Re?ned aviation lubricating oil,‘
PI gravity
2
Oil #1 containing clay treated Utanol. Pilat
3
Oil #1 containing clay treated Utanol Pilat
'
about 26, S0 at 210° F. about 115-125 ________ __
0.7
raiilnate, AS=0.10% ......................... ._
0. 47
raii‘lnate, AS=0.30% __________________________ -_
0.36
Oxidation tests were made with the same oil
_
Several treatments may be combined and the
second re?ning treatment may be carried out in,
the presence or absence of the light hydrocarbon
liquid employed in the precipitation; generally 30
its presence may be helpful in the second step.
The undesirable components, if any (which may
be in the form of sludge, extract, etc), produced
in the second re?ning treatment, are now sepa
to determine the time required for the absorption
of 1800 cc. of oxygen by 100 g. of oil in the pres
ence of 1 cm.2 of copper surface/gram of oil at
150° C. The following data are typical:
Hours
Oil No. 1 (as above) ____________________ __
9.3
011 No. 2 (as above)? _____________ ...'- ____ -_ 48 1
rated. Solvent, if present, is removed in the usual "
manner as by distillation or washing with water
or wash solvent, and the recovered-‘high sulfur oil
may be given a ?nishing treatment‘ with clay
(such as fuller’s earth, acid activated clay, etc.),
bauxite, zeolite, silica gel-or other adsorbents.
The speci?c dispersion of the treated high sul
fur rafiinate oil is often a fair indication of its
lacquer imparting tendencies. ' It is desirable
This Utanol rai?nate was also tested in the
Thrust Bearing Corrosion test, referred to earlier,
employing. a compounded heavy dutytruck and
bus or Diesel lubricating oil. It contained ineach
case 1 % of the magnesium salt of lauryl salicylate
which has been a widely used lubricating oil de
tergent. but which. although otherwise bene?cial,
imparts corrosive properties to the lubricant. In
20 hour tests at 125 lbs. thrust and 2400 R. P. M.
with this oil, the copper-lead bearings showed a
weight loss at 130° C. of 15 mg./cm.2. When test
that the specific dispersion be below about 160,v
ed with this same oil, to which had'been added a
more preferably below about 140 or 145. Also, 45 clay treated Utanol Pilat ra?inate, AS=0.10%,
the bearings showed no weight loss at 160° C.
the color may be an indication if taken together
with the speci?c dispersion. Preferably, the color
v
Chevrolet engine tests using procedure L-4—243 ‘
of the Cooperative LubricantsTest Program were
should be better than 6 (A. S. T. M. or National
Petroleum Association Scale).
also made using a corrosive S, A. E. reference oil.
- .
Samples of treated Utanol railinate oils from 50 Results were as follows:
Varnish
mung
Used voil properties
gang's:
_
mgJcm.’ 1 Sail)‘. No.
Neut. No.
Sludge
mung
,
Base oil _____________________________________ ._
105
73
.'
.
’ 106. 5
109. 5
70- 5
72
Base oil + Utanol rai?nate AS=0.30%.__ _ ___
104. 5
i 73
Base oil + Utanol ra?lnate AS=0.10¢7.
Base oil +. Utanol raf?nate AS=0.1 ,7.
General
range
Gravity‘,o ........... ..
Viscosity at 100° F...
Viscosity at 210° F.
34-39
Viscosity index.._..
--.
40-55
. _ _ _ _ . _ _ _ __
130-145
Color _______________________________ __
4-7. 5
Saponi?cation number, mg.KOH/"_--
Ultimate analysis:
__
Carbon ________ -_per cent weight“
I
Hydrogen _________________ _.do__._
Sulfur ................. ..do.._.
‘ Nitrogen... ............... -_' .'.-_
0-8
65
0. 9880
' 1,018
'
34. 7
53
132
i
1
4%
1 ° 0. 9
A‘ clay treated
.Pilat ra?inair
‘
I
f 33:4
2i. 7
‘3. 2
mg. KOH/g. v
_22. 2
91's
4- 6
4. 2v
2. 8
' 25-1 ‘
26.8
: 9. 98,
salt of methylene bis p-i'sooctylphenol, may be
seen from the following‘ data of piston ringweight
loss _in a CFR-Diesel engine. _Test conditions:'
1400
P. M.;'load,v 68 155.1111? brake mean‘ effec
‘ tive pressure; jacket-temp.‘- 100° C.; voil tempera-J
70
compression ratio ‘1631;114'7 =ceta’ne"
number commercial Dieselffuel;~ baseioilt','com-,-_
76. 27
10. 90
12. 7- V
0.14
84. o
'
OH/g.
I the e?lciency of ananti-Wear agent, the calcium
one acid
treated Piiat
railinate
0. 98-1. 0
950-1400
mg.
The action of a Utanol-railina'te in increasing
di?erent batches had the following properties:
Speci?c dispersion . . . _ _
I
-
l"
11.9
' 0.06
mercial Diesel. lubricating on s. AYE‘. amiss;
length, 4, runs of lit-hours, 'resultsreported for:
overall period.
Megan
8
relatively high speci?c dispersion or content of
aromatics, the former often being considerably
above 160, unless the solvent extraction and ad
P weigh-its‘
Additive
loss, mg.
ditional treatment preparatory to the solventex
13.4
31.6
radinate
NJ
‘ The Utanol ra?lnates‘also possess other desir
r
able characteristics when incorporated in a lubri
cating oil, such as anti-scu?ing and anti-scratch
ing properties in Diesel engines. Their bene?cial
activity may also be enhanced’ by utilization in
the presence of small amounts of synthetic or
ganic sulfur-containing ‘anti-oxidants, e. g. di
benzyl sul?de or disul?de, wax disul?de, diphenyl
sul?de, sulfurized sperm oil, sulfurized ole?n
polymers, sulfurized wax ole?ns (obtained in the
cracking, or by chlorination and dehydrochlori
traction was very drastic. If the speci?c dis
persion of the sulfur concentrate is above about
145, the concentrate may ‘ again be solvent-ex
tracted or sulfuric acid treated, etc., to further
reduce its 'aromaticity and speci?c dispersion to
below about 140 in order to produce an addition
agent for lubricating oils which has the least
lacquer imparting tendencies.
the oxidation‘ st‘ability (Domte type oxygen ab
sorption apparatus at 150° C.) in the presence of
1 square‘ centimeter of copper per gram of oil of
an S. A. E. 60 lubricating oil when added thereto
in amounts to raise the sulfur content by 0.1%:
Bpre?c. die;
,
Source of petroleum material
>
In the table below, ‘a comparison is made of
the e?ect of the several sulfur concentrates on
pc
on o
'
sulfur eon-
Method of obtaining sulfur cone.
Tim; fgm
"mm"
m 0’ M00
mxme
11
I. 011
Hours
None
Utanol ......................................................... __
” "
0. 2
Asphalt precipitation-acid treating ........ ._
132
47, 7
Mt. Poso lubricating distillate, furiural railinate, 55 V. I _______ -_ Mercurlc acetate in acetic acid ............ _.
120
52,0
SbClr-AlCln .............................. ..
143
32, 1
Mt. Peso lubricating distillate, iurfural ramnate, 65 V. I _______ __ Aluminum chloride ....................... ..
West Texas distillate
‘
Acid treat-i-extractlon with HgAer in HA ..
‘17min lubricating distillate, acid treated iurtural railinate,
15B
19d
21, a
13
D0
*
_____
Duosol extration followed by acid treat .... .-
200+
0.8
The method of concentrating sulfur com
nation, of para?ln wax), bis-(methylene aryl or 35
pounds with the aid of mercuric acetate in acetic
alkaryl sul?des), etc.
acid ‘is described below in greater detail:
A sample of 50 V. 1. Mt. Poso furfural railinatc
was ?rst extracted with glacial acetic acid to re
terially below about 5%, such as California and
Venezuelan oils, different methods for recovering 40 move nitrogen bases. Glacial acetic acid satu
rated with mercuric acetate was then added to
the active sulfur compounds must be employed
the oil, with stirring, in the amounts shown in
than that described for Utanol. Since oils hav-_
the table below. The mixture was allowed to
ing a relatively low sulfur content may display
As indicated before, when starting with crudes
or fractions thereof having sulfur contents ma
a ratio of aromatics to sulfur that is higher, for
settle and the lower layer drawn off.
This ex
example, than with Utanols, it is necessary to 45 traction may be performed several times on a
sample (as shown in the table) and the remain
?rst remove from these oils some of the aromatics,
as by selective solvent extraction with a “naph
ing oil then washed with acetic acid to remove
the remaining mercury compounds. It is also
thenic" solvent of the type described earlier, and
advantageous to carryout the extraction in the
if necessary augment this treatment with others
such as sulfuric acid treatment. Likewise, crudes 50 presence of an inert, oxygen-excluding agent
relatively low in asphalt and aromatic content . such as nitrogen or natural-gas which may be
bubbled through the liquid to minimize oxida
do not show the desired concentration of the
tion. The extracts and acetic acid end-wash are
sulfur compounds by the removal of their smaller
then combined. The acetic acid may be distilled
amounts of undesirable constituents. The sul
fur components, however, can be concentrated 55 o? and the mercury then released from the oil,
for example, by heating say to 100° C. with dilute
‘by methods such as the following:
acid (e. g. 2 vols. of 15% HCl) or by saturating
Extraction with aceticacid containing a soluble
with Has, the oil then being diluted with iso
mercury salt such as mercuric acetate, mercuric
pentane or other suitable solvent, water-washed,
chloride, etc. to form ‘a mercury complex extract
which is then worked up to recover the extract 60 dried and clay-treated before removal of solvent.
The variables for several such runs are shown
oil and if necessary further re?ne the latter.
in the following table:
Extraction with a liquid mixture of SbCh and
A101: to form a complex which may be separated
Run number
and decomposed to recover the oil.
Extraction with AlCh at temperatures between
I
about 0 to 80° C. as described in U. S. Patent
2,309,337 to form a complex which may be de
composed to recover the oil.
.
All three of these extraction methods yield rela
tively dark' oils, even though the starting ramnate 70
may have been of light color. Moreover, the
.SbCla-AICI: extraction, as well as the A101: ex
traction, tend to cause accumulation in the sul
fur concentrate of whatever aromatics have been
left over from the preceding solvent extraction,
and therefore result in auliur concentrates of 76
Weight of oil used, gms .... -_
No. of dumps of reagent ..-.
Volume of acetic acid, mls...
_.~
e20
3
' i190
Volume of HgAc; plus acetic acid,‘
mls ............................. .- -
II
'
.'
111
901
738
3
216
3
150
,
.
485
060
Temperature of treatment‘, ° 0. .-..
30
18
Tot
00
136
treating time minutes ..... --
Wei ht per cent yield of extract (on,‘
Po“ “tnliii------------ "ll-lull"--er cen s
urremaining
o
.----
‘
l
60
106
‘
OLI: 0 1446;
.
.
Per cent sulfur in extract oil (average) ............................ ..
540
-
0.165.‘:
(
8.00
8.88
8. ll
2,404,871
10
Extract from Run No. II was incorporated in
white oil to the extent of 3%. This increased the
time required for 100 g. to absorb 1800 ml. of
oxygen from less than 2 to 236 hours.
Corre
sponding extracts obtained at higher (e. g. re?ux)
temperatures were considerably less effective.
used in connection with other additives in lubri
cating media, for example, detergents formed
from the oil-soluble salts of various bases with
detergent forming acids. Such bases include
metallic as well as organic bases. Metallic bases ~
include those of the alkali metals, as well as Cu,
It has been found that when this mercuric
acetate extraction of the oil is carried out at
Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni,
acetic acid) the content of desirable sulfur con
Examples of detergent forming acids are the .1
various fatty acids of, say, 10 to 30 carbon atoms, '
Co, etc. Organic bases include various nitrogen
bases as primary, secondary, tertiary and
room temperature or lower (i. e. below about
20° C. and preferably near the melting point of 10 quaternary amines.
stituents in the extract is greater than if the oil
wool fat acids, paraffin wax acids (produced by
is re?uxed or maintained at a higher tempera
oxidation of paraf?n wax), chlorinated fatty
ture while treating with the mercury salt. In
general, any mercury salt, particularly the mer 15 acids, aromatic carboxylic acids including aryl
fatty acids, aryl hydroxy fatty acids, paraffin wax
curic salts soluble in acetic acid such as the
mixtures, may be employed in like manner as
benzoic acids, various alkyl salicyclic acids,
phthalic acid mono esters, aromatic keto acids,
the mercuric acetate, since these salts will give
aromatic ether acids; diphenols as di-(alkyl
oxalate, carbonate, chloride, sulfate, etc. or their
mercuric acetate in the acetic acid solution. The 20 phenol) sul?des and disul?des, methylene bis
alkylphenols; sulfonic acids such as may be pro
solubility of the acetate is considerably greater
duced by treatment of alkyl aromatic hydro
than for the other salts, hence it is generally
carbons or high boiling petroleum oils with sul- '
more advantageous to start with the mercuric
furic acid; sulfuric acid mono esters; phosphoric
acetate. As compared with salts of other metals,
the mercury salts are de?nitely superior for this 25 acid mono and di-esters, including the corre
sponding thiophosphoric acids; phosphonic and
purpose as shown by the foregoing data.
The herein described compositions possessing
arsonic acids, etc.
Non-metallic detergents include compounds
the required amount of available or reactive sul
fur may also be incorporated advantageously in
such as the phosphatides (e. g. lecithin), certain
extreme pressure lubricants, cutting oils, roll oils, 30 fatty oils as rapeseed oils, voltolized fatty or
wire drawing lubricants, greases, hypoid gear
1 mineral oils.
I Other detergents are the alkali earth phosphate
lubricants, etc. They may also be used to impart
anti-wear and/or anti-oxidant properties to
di-esters. including the thiophosphate di-esters;
lubricants not necessarily subject to high pres—
the alkali earth diphenolates. speci?cally the cal
sure, such as turbine oil, refrigerator oil, lubri
cium and barium salts of diphenol mono and poly
cants for bearings, in particular, modern alloy
sul?des; etc.
bearings comprising cadmium-silver, cadmium
Our sulfur additives may also be used in asso
nickel, copper-lead, “high lead” alloys, as Well as
ciation with other anti-oxidants, for example
alkyl phenols such as 2.4.6-trimethylphenol,v
I Babbit metal, and the like. The lubricating media
' also need not be derived in whole or in part from
mineral oil but may consist in whole or part of
vegetable or animal lubricants such as palm oil,
cottonseed oil, ?sh oil, animal wax, phosphatides,
etc., as well as the so-called synthetic lubricants
pentamethylphenol,
2.4 - dimethyl - 6 - tertiary
butyluhenol,’ 2.4-dimethy1-G-octylphenol, 2.6-di
tertiary-butyl-li-methylphenol, 2 4,6-tri-tertiary
butylphenol, etc.; amino phenols as benzyl amino
phenols; amines such as dibutylphen'ylene
(e. g. polymers of ole?ns derived from cracked 45 diamine, diphenylamine, phenyl-alpha-naphthyl
wax). In addition, by reason of their anti
amine, phenyl-beta-naphthylamine, dinaphthyl
oxidant properties, such additives may be in
amines; etc.
corporated advantageously in organic substances
Other corrosion inhibitors may also be present
not intended for use as lubricants at all, such as
gasoline, kerosene, spray oil, medicinal oil, trans
former or electrical insulating oil, cleaning ?uid,
synthetic or natural rubber, Diesel fuel, photo
graphic developers, etc.
Particular reference may be made to the in
such as dicarboxylic acids of 16 and more car
bon atoms, alkali metal and alkali earth salts of ,
sulfonic acids and fatty acids, etc.
Likewise, other additives may be present in a.‘
lubricating oil or grease such as blooming agents,
anti-foaming agents, viscosity index improvers.
clusion of the herein described anti-oxidants as 55 etc.
additives for coating materials such as asphalt,
Instead of ?rst producing the herein described‘
resins, oils, waxes, varnish, insulating or mois
additive and then adding it to a lubricating oil,
ture-protective substances such as oiled or
a high sulfur asphaltic crude such as raw
“waxed" paper, etc. Such plastic or semi-plastic
Utanol may be added to a crude petroleum, for
vehicles may also contain, for example, anti 60 example a topped crude suitable for the manu
rusting agents and be applied to metal surfaces
facture of lubricants, and the mixture then sub-a
to provide a corrosion-resistant coating. Also
jected to one or several treatments adapted to
such oxidation inhibited adhesive coatings may
remove substantially all asphaltenes and at
least a portion of aromatic hydrocarbons such
be applied to wood, paper, cardboard, felt, stone,
laminated glass, fabric. concrete, plastic composi
as previously described. Amounts of this high
tions, Transite board, etc., by such methods as
sulfur oil which may be added to the crude lu
roller coating, dipping. brushing, spraying and the
bricating stock vary with the amount and avail
ability of the sulfur content of the former, as
like.‘
When the sulfur compounds of this invention
explained before. and may range preferably from
are intended for addiiton to lubricating oils, they 7 0 about 2% to 15%.
or the concentrates which contain them should
We claim as our invention:
have boiling temperatures above gas oil range
1. A process for obtaining a sulfur~containing
and preferably within or above lubricating oil
fraction possessing anti-oxidant and other val
range.
uable properties, which process comprises ex
These compounds may also be advantageously
tracting a substantially para?inic lubricating oil
9,404,”:
11
12
ra?lnate with a mercury salt under temperature
para?lnic lubricating oil ramnate with a mer
cury salt under temperature conditions to pro
duce a mercury salt-sulfur compound complex
and breaking the resulting mercury salt-sulfur
compound complex to regenerate and recover
conditions to produce a mercury salt-sulfur com
pound complex and breaking the resulting mer
cury salt-sulfur compound complex to regenerate
and recover the extracted sulfur compounds.
2. A process for obtaining a sulfur-containing
fraction possessing antioxidant and other valu
able pronerties, which process comprises extract
ing a substantially para?'inic lubricating oil rai
?nate with a mercury salt under conditions of
atmosphere and ‘temperature to substantially
avoid any oxidation and to produce a mercury
therefrom the extracted compounds.
-
9. An organic composition comprising a pre
dominant amount oi.’ a mixture 01' hydrocarbons,
which mixture is unstable-against oxidative de-.
terioration and which is responsive to sulfur-con
taining antioxidants. and an added antioxidant
amount of a concentrate oi! natural-occurring sul
fur containing compounds from petroleum oil pos
salt-sulfur compound complex. and breaking the
sessing antioxidant and other valuable prop
resulting complex to regenerate and recover the
15 erties prepared by the process which comprises
extracted compounds.
extracting a substantially para?lnic lubricating
3. A process for obtaining a sulfur-contain
oil ra?inate with a mercury salt under tempera
ing fraction possessing antioxidant and other
' valuable properties, which process comprises ex
tracting a substantially parai?nic lubricating oil
ture conditions to produce a mercury salt-sul
fur compound complex and breaking the result
ra?lnate with a mercury salt at a temperature 20 ing complex to regenerate and recover the ex
below about 20° C. and breaking the resulting
sulfur complex to recover the extracted sulfur
compounds.
4. A process for obtaining a sulfur-contain
tracted compound.
.
10. An oleaginous composition comprising a
predominant amount of an oleaginous material
which is unstable against oxidative deterioration
ing fraction possessing antioxidant and other 25 and which is responsive to sulfur-containing an
valuable properties. which process comprises ex
tioxidants, and an added antioxidant amount of
_ treating a substantially para?lnic lubricating oil
a concentrate of natural-occurring sulfur-con
raillnate with glacial acetic acid saturated with
taining compounds from petroleum oil possessing
mercuric acetate and breaking the resulting sul
antioxidant and other valuable properties prefur complex to recover the extracted sulfur com 80 pared by the process which comprises extracting
pounds.
~
a substantially paraii'inic lubricating oil raiiinate
5. A process for obtaining a sulfur-contain
with a mercury salt under temperature conditions
ing fraction possessing antioxidant and other
to produce a mercury salt-sulfur compound com
valuable properties, which process comprises ex
plex and breaking the resulting complex to regen
tracting a substantially paramnic lubricating oil 85 erate and recover the extracted compound.
ra?lnate with a mercury salt at a temperature not
11. A lubricant comprising a predominant
above about 50° 0.. thereby producing a mercury
amount of a re?ned mineral oil, a small added
salt-sulfur compound complex, and breaking the
amount of a normally corrosive detergent, and
resulting complex to regenerate and recover the
an added small amount su?lcient to render the
40
extracted compounds.
resultant mixture substantially non-corrosive of
6. A process for obtaining a composition pos
sessing antioxidant and other valuable proper
ties, which process comprises extracting a sub
stantially para?lnic lubricating oil ra?lnate with
a mercury salt at a temperature not above about
50° C., thereby producing a mercury salt addi
tion compound. and breaking the resulting ad
dition compound to regenerate and recover the
extracted compounds.
7. A process for obtaining a composition pos
sessing antioxidant and. other valuable proper
ties, which process comprises treating a substan
tially para?lnic lubricating oil ramnate with gla
cial acetic acid saturated with'merouric acetate,
thereby producing a mercuric acetate addition
compound, and breaking the resulting addition
compound to regenerate and recover the extract
ed compounds.
8. An organic composition comprising a pre
dominant amount of an organic substance which
is unstable against oxidative deterioration and
which is responsive to sulfur-containing anti
oxidants. and an added bene?ciating amount of
natural-occurring sulfur-containing compounds
from petroleum oil possessing antioxidant and
other valuable properties prepared by the proc
ess which comprises extracting a substantially
a concentrate of natural-occurring sulfur-con
taining compounds from petroleum oil possessing
antioxidant and other valuable properties pre
pared by the process which com-prises extracting
a substantially parai?nic lubricating oil raf?nate
with a mercury salt under temperature conditions
to produce a mercury salt-sulfur compound com
,plex and breaking the resulting complex to regen
erate and recover the extracted compound.
12. A lubricant comprising a predominant
amount of a re?ned mineral oil and character
ized by a normal tendency to corrode metal bear
ing surfaces, and an added corrosion-inhibiting
amount or a concentrate of natural-occurring
sulfur-containing compounds from petroleum oil
possessing anticorrosive and other valuable prop
erties prepared by the process which comprises
extracting a substantially para?lnic lubricating
oil ra?lnate with a mercury salt under tempera
ture conditions to produce a mercury salt-sulfur
compound complex and breaking the resulting
complex to regenerate and recover the extracted
compound.
PAUL R. VAN ESS.
FORREST J. WATSON.
GARY M. WHITNEY.
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