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2,406,041
‘UNITED STATES PATENT OFFICE
Patented Aug. 20,1946
2,408,041
CHEMICAL PROCESS
_
Helmuth G. Schneider, Roselle, and James E. J.
Kane, Elizabeth, N. J. assignors to Standard
Oil Development Company, a corporation of
Delaware
No Drawing. Application April 20, 1944,
Serial No. 531,993
9 Claims. (Cl. 252-423)
1
2
ticularly in heavy duty oils used for lubricating
high speed Diesel and gasoline engines, for the
?de. Barium tertiary octyl phenol monosul?de
may. be represented by the general formula
Ba[O(CaHn)CaI-Isla$ or, if the tertiary octyl
stock in about 25 to 50%, usually about 40%.
This invention relates to an improved process
concentration, with or without incorporation of
of preparing or improving metal derivatives of
lesser amounts of other additives such as higher
alkyl phenols or their derivatives, as well as to the
aliphatic alcohols, e. g, stearyl alcohol, or all
products thus prepared and to uses thereof. As
a speci?c instance, the invention relates to the 5 phatic nitrlles, etc. used as defoamers, plasticiz
ers, mutual solvents or as detergency promoters,
improvement of chemical compounds such as the
and ?nally this solution is neutralized with the
barium salt of diisobutyl (i. e. tertiary isooctyl)
desired basic metal compound such as barium
phenol or of the corresponding sul?de or. other
hydroxide octahydrate or monohydrate. The re
derivative thereof.
7 '
Chemical compounds of the class just referred 10 sulting product, after ?ltration, is a mineral oil
concentrate of barium tertiary octyl phenol sul
to have been used as lubricating oil additives, par
reason that these additives have excellent deter
gent properties and improve the performance of 15 group is assumed to be in a position para to the
phenolic oxygen, and the sulfur linkage in a meta
the lubricant. -They do, however, possess to some
position, by the following graphic formula:
extent the undesirable property of being water
sensitive, that is when contacted with a small
amount of water, they form a sludge which may
remain emulsi?ed in the oil or settle out as a 20
?occulent precipitate. This characteristic of the
additive, while not affecting the performance of
the oil, is nevertheless undesirable in certain re
sHn
sHn
spects such as in storage or handling where the
If
the
sulfur
linkage
is
in‘
an
ortho position the
oil is apt to become contaminated with water. 25
graphic formula would be:
The primary object of the present invention is
therefore to treat such additives during the proc
ess of manufacture in order to render them
water-insensitive so that lubricating oils, or other
products in which they may be used, will not tend 30
to emulsify or form sludge when contacted with
water.
Before discussing the particular improvements
of this invention, the general manufacture of
The exact location of the various radicals and
such products will be explained as applied, for 35 linkages in such compounds has not been deter
example, to the treatment of alkylated hydroxy
mined with certainty, but it is probable that the
aromatic compounds, such as a tertiary octyl
product resulting from the commercial operation
phenol with a sulfurizing agent, e. g, sulfur di
chloride or sulfur monochloride, to form an alkyl
of the described process is a mixture of com
pounds having the radicals and linkages in sev
hydroxy aryl sul?de which is then converted into 40 eral different positions, there being for instance
a corresponding metal derivative by neutraliza
some tertiary octyl groups in an ortho position
tion, preferably in oil solution, with a basic metal
or even in 9. meta position unless the original
neutralizing agent such as barium hydroxide, thus
tertiary octyl phenol‘used was an absolutely pure
forming a metal salt of an alkyl hydroxy aryl
para compound. Also it is more than likely that
sul?de. Throughout this speci?cation and the 45 the commercial product which may be given the
claims the word “sul?de” is used in a generic
general formula Ba[O(CaHn)CaHa]z_Sn where n
sense to include monosul?de, disul?de or polysul
has an average value of at least 1.0 and less than
?de or mixtures of these. Such a process may be
2.0, contains at least small amounts of disul?de
and polysul?de compounds as well as some poly
illustrated by the reaction of about 2 mols of ter
tiary octyl phenol with 1 mol, or a slight excess, 50 meric material. In any event corresponding
of sulfur dichloride to produce tertiary octyl
compounds may readily be made by starting with
phenol sul?de. When preparing the alkyl phenol
ortho or meta alkyl phenols and mixed alkyl
phenols may be used with alkyl groups in any two
‘sul?des on a commercial scale, using technical
or more positions. If desired, dialkyl phenols
grades of sulfur dichloride, ratios of 1.5 or so mols '
of S012 to 2 mols of alkylated phenol will often 55 may also be used such as 2,4-ditertiary butyl
phenol, 2,4-diamyl phenol, 2,6-diamyl phenol, di
be found desirable. (The tertiary octyl phenol is
tertiary octyl phenol, etc. For some purposes it
readily prepared by alkylating phenol with di
may even be desirable to use alkyl hydroxy aryl
isobutylene in the presence of suitable catalysts.)
compounds having more than two alkyl groups,
In practice the phenol sul?de is then usually dis
solved in a suitable mineral lubricating oil base 60 but the monoalkylated products are preferred,
2,408,041
4
particularly when the ?nal product is desired to
Corresponding metal derivatives of the follow
ing illustrative types of substituted phenolic
have greatest corrosion inhibiting properties.
The invention is considered to apply broadly to
compounds are among those that can be used, in
which R represents an alkyl group, preferably
substituted metal phenolates or compounds con
taining at least one grouping having the general 5 having at least 4 carbon atoms:
formula M-Y,—-Ar(X)n where M is a metal, Y
is an element in the righthand side, of group VI
of the Periodic Table (Mendeleeif), Ar is an arc
matic nucleus which contains like or unlike sub
stituents, X, n. in number, replacing nuclear hy 10
drogen, n being at least one.
M may be any metal such as barium, calcium,
aluminum, cobalt, chromium, magnesium, man
ganese, sodium, nickel, lead, tin, zinc, copper,
iron, cadmium, potassium, lithium and the like, 15
polyvalent metal being preferred.
The substitutents, X, may be organic, inorganic,
or both. For example, they may be alkyl radi
cals or groups containing one or more of the non
metallic elements belonging to groups V, VI, and 20
All these'compounds when employed in high
VII of the Periodic System (Mendeleeff): nitro
gen, phosphorus, oxygen, sulfur, and halogens,
temperature lubrication service tend to corrode
such sensitive engine parts as copper-lead and
as in amino, nitro, phosphite, phosphate, hydroxy,
—alkoxy, sul?de, thioether, mercapto, chloro
cadmium-silver bearings. This characteristic
can usually be corrected by including, in the lu
groups, and the like, or they may be organic radi 26 bricating composition, suitable anti-oxidants or
other anti-corrosion agents, e. g. benzyl para
cals containing one or more of the inorganic
groups.
amino phenol, alpha naphthol, tertiary amyl
phenol ‘sulfide, triphenyl phosphite, dibutyl
In the phenolate salts, it only one of the
amine, etc. —It may be mentioned that metallic
tuted phenolic radical, such as —O—-A1‘(X)n, the 30 soaps of carboxylic acids are considerably more
valences of a polyvalent is connected to a substi
other should be connected to other organic groups
or to inorganic constituents, For convenience,
corrosive than the phenolic salts and that their
corrosiveness is less amenable to correction by
non-phenolic radicals or groups, as well as phe
the use of antioxidants, etc.
However, this corrosion problem can also be at
nolic groups, attached to the metal are indicated
broadly by R in the following types of composi 35 least partially and in most cases completely taken
care of by chemically incorporating an element
tional formulae, which broadly represent metal
derivatives of substituted phenolic compounds
of the sulfur family (i. e. S, Se, and Te), sulfur
containing
the
characteristic
compositional
itself being very effective, ‘into the structure of
the substituted phenolate metal salts, thus mak
_
R
O-Ar(X).
o-imx).
40 ing unnecessary the addition of any separate
anti-corrosion agent. Thus the metal derivatives
M/ ,
M/
‘ M/ (x'o-w
of the following illustrative types of substituted
phenolic compounds are preferred over those list
\o-imx), \0-Ar(x')..¢
0-A1-(x')..'
ed in Group A above.
Where oxygen is shown in these formulae it may
be replaced by sulfur, selenium or tellurium, as in 45
Group B
the case‘ of thiophenolic compounds.
grouping described:
More specifically, some of the structures which
substituted divalent metal phenolates may have
are indicated in the following list of formulae
containing benzene nuclei of compositions 50
—CsH4—-, —CcHa—-, etc., with X, as before, stand
ing for nuclear substituents, e. g., —caHzn-l-l, ‘
—NOz, —Cl, -S—, —Sa——, —NI-Ia,
etc.) :
65
H0(R) Can-s-mnnm-on
Corresponding monovalent metal derivatives
would be:
s
70
Similarly trivalent or other polyvalent metal
derivatives may be used such as:
M(O—CcHa-X)a or more
M:[(O—(X)CtI-Ia—):X']:, etc. '
‘2,400,041
.5
e. g. Barium salts of 2 chloro, 4 octadecyl phenol,
2,6-dichloro, 4 diisobutyl phenol, and 8 chloro,
These preferred phenolates may also contain
sulfur. in other positions or groups .at the same
2,4-ditertiary amyl phenol
time as in the places shown in the formulae in
-
Group B. Furthermore, the formulae in Group
III. Alkyl amino phenolates
A may have sulfur incorporated therein. More
Ba} OCcHa [CHaN (CrHy) :] (01.82am) }:
broadly it maybe stated that inorganic substit
uents, particularly negative inorganic groups con
e. g. barium salts of dicyclohexyl amino methyl
taining non-metallic elements of groups V, VI.
cliisobutyl phenol
and VII of the Mendelee? Periodic System, bene
?cially in?uence the phenolates by increasinz 10 IV. Thioethers of alkyl phenolates
their potency for stabilizing the lubricatinz oils
and by making the phenolates, in themselves,
more stable, as for instance, against hydrolysis.
Especially preferred, because they are both very . e. g. barium tertiary’octyl phenol sul?de, barium
tertiary amyl cresol sul?de, and barium 2,4-di
efficient and also lend themselves to easy and eco 15
tertiary amyl phenol sul?de
nomical manufacture, are compounds containing
at least One grouping having the general for
' V. Disul?des of alkyl phenolates
mula:
Ba[O-CaHa—C»Hm+il:B:
M
20 e. g. salts of tertiary amyl phenol disul?de
t
v1. Phosphorus acid esters of alkyl ph'enol sul
-
?des
'
5
'
Where Ar is an aromatic nucleus, R is an or;
ganic group, Z is a member of the sulfur family, 26
e. g. salts of tertiary amyl phenol sul?de mono
and n is an integer of l to 5. Z is preferably sul
phosphite
fur, and nsis preferably 1 or 2. R represents an
organic group which may be either aryl, alkyl,
alkaryl, aralkyl or cycloalkyl, and which may
contain substituent groups such as halogen, par
Other examples of metal alkyl phenol sul?de
which may be treated in accordance with the pres
30 ent invention include: calcium tertiary amyl
ticularly chlorine, nitro, nitroso, amino, hydroxy,
phenol sul?de, tin salts of wax alkylated salicylic
carboxy, alkoxy, aroxy, mercapto, land the like,
acid sulfide, magnesium tertiary octyl phenol sul
but R preferably is or contains an alkyl or al
?de, and barium salts of Clo-C20 branched chain
kylenyl group, and preferably contains at least 4
alkyl phenol sul?des prepared from phenols alkyl
carbon atoms but may contian many more, such 35 ated with re?nery butene polymers, etc. An ex
ample of a trivalent metal alkyl phenol ‘sul?de is
as 8, 10, 16, 18, 24, etc.
The con?gurations of the compounds are not
aluminum tertiary amyl phenol sul?de which may
be represented in a general way by the formula ,
limited to certain positions for the substituent
groups, for these may be in ortho, para, or meta
relations to one another. Also, the substituents, 40
X, in broader formulae discussed previously in
any aromatic nucleus may be alike or different.
The aromatic nucleus may be polycyclic as in
naphthalene,
phenanthrene,
diphenyl,
etc.
Where oxygen occurs, it may be replaced by sul
fur, selenium, or tellurium, as in the case of thio
phenolic compounds.
The alkyl hydroxy aryl compound should have
45 more than three aliphatic carbon atoms and pref
erably more than 6, such as 8, 10, 12, etc., up to
24 or more as in the case of para?inlc radicals
derived from paraffin wax or olefinic polymers,
An important feature of this invention issues
such as dimers, trimers, tetramers, etc., of iso
from the observation that metal phenolates are 50 butylene. Branched, especially highly branched.
alkyl radicals are preferred.
bene?ted in solubility and effectiveness as hy
_ The aromatic nucleus of the alkyl hydroxy aryl
drocarbon lubricating oil blending agents when
compound may be mononuclear as in the case of
they contain a total of at least 8 and preferably
10 or more carbon atoms per molecule in ali
a benzene nucleus or polynuclear as in the case
phatic groupings, when sulfur is present in the 55 of a naphthalene nucleus. Instead of using pure
individual phenolic materials, one may use crude
molecule, and at least 16 carbon atoms and pref
commercial products which may be mixtures of
erably 18 or more, if no sulfur is present.
two or more alkyl hydroxy aryl compounds, such
Speci?c examples of preferred substituted
as crude petroleum phenols which have an aver-‘
phenolates falling into the classses mentioned,
having at least one alkyl radical as a substituent, 60 age chemical composition indicating the presence
of four aliphatic carbon atoms and an amount of
and using barium as example of a suitable
oxygen slightly in excess of that called for by
metal, are formulated as follows:
I. Alkyl phenolates
the formula C4HaCsH4OH. Similarly crude phe
nolic materials of coal tar origin may be used
65 such as the so-called tri-cresol which is a mix
ture of isomeric ortho, meta and paracresols,
which should, of course, be further alkylated with
e. g. barium salts of diisobutyl phenol, (p-tert.
a higher alkyl group, for best results from an oil
solubility point of view.
octyl phenol), octadecyl phenol, and 2,4,diter
In case of reaction of the alkyl hydroxy aro
tiary amyl phenol
70
matic compound with a sulfurizing agent which is
II. Alkyl chlorphenolates
preferably a sulfur halide, e. g. $012 or $2012, a
small amount of halogen may be found to com
bine with the aromatic compound in some un
75 known manner, but the proportion of such com
2,400,041
bined halogen is very small‘ and is not objection
able.
Before carrying out the neutralization of the
the reaction by treating with 00: prior to the
finishing operation. Although the exact amount
or proportion of treating agents such as carbon
alkyl hydroxy aromatic compound for convert
ing the latter into the corresponding metal de
dioxide and steam undoubtedly must be varied
to some extent according to the particular type
rivative or salt, the alkylated phenol or sul?de or
of metal salt being treated and the way in which
it was prepared, ordinarily the amount of carbon
dioxide, or other weakly acid gas used, should
be less than about 25%, and preferably less than
other derivative thereof is preferably dissolved
in alubricating oil base stock having a viscosity
within the approximate limits of 35 to 70 seconds
Saybolt at 210° F., and the oil derived from any 10 5%, by weight based on the amount of metal
salt in the oil solution being treated. If the pro
suitable petroleum crude and having any desired _
viscosity index.
The basic metal neutralizing agent is preferably
portion of carbon dioxide is calculated on the
weight of the entire oil solution being treated
then'it should be preferably about 0.5%-to 2%
a ?nely divided oxide or hydroxide of the desired
metal such as an alkaline earth metal, e. g. cal 15 by weight. Similarly the amount of H20 should
be in the same general range, i. e.. less than
cium, barium, magnesium, etc., or other polyval
ent metals such as nickel, cobalt, tin, lead, zinc,
copper, cadmium, manganese, iron, chromium.
about 20%, preferably less than 5%, based .on the
weight of metal salt being treated, and preferably
about 0.1 to 2 or 3% by weight based on the total
aluminum, etc., or even monovalent metals such
as sodium, potassium, lithium, etc. Although 20 oil solution being treated.
the invention is intended to apply particularly to
metal salts resulting directly-from a basic metal
neutralizing agent, it maybe used to some advan
tage in the case of corresponding metal salts‘
made by double decomposition from other corre
The use of controlled amounts of water or steam
provides better control of the product and more
uniform results than if the blowing with carbon
dioxide is carried out in the absence of any H2O.
The amount of water or steam used is important.
It has been found that there is a slight loss of
' sponding metal salts. For instance, one may ?rst
metal content of the metal salt during the treat
prepare a sodium salt of an alkyl hydroxy aryl
ment with CO2 and H20 if used simultaneously
sulfide such as tertiary amyl phenol sul?de and
and that this loss increases with the amount of
then treat the latter with anhydrous barium bro
-mide to form the corresponding barium salt of 30 H20 used.
After the treatment with carbon dioxide and
tertiary amyl phenol sul?de. In such a case the
COa-HaO treatment may be applied eitherto the
?rst-formed salt (1. e. the sodium salt) or to the
one formed by double decomposition (i. e. the
barium salt) or to both‘.
when using a basic metal neutralizing agent,
steam, or equivalent treating agents, the entire
mixture is ?ltered, preferably with the use of a
?lter aid such as Hy?o, Dicalite or other inert di-'
atomaceous earths or active clays such as, Super
Filtrol, attapulgus, etc. Usually about 0.05 to
0.25 lb. of ?lter aid per gallonwill give satisfactory
improvement in the ?ltration.
The improved process of this invention, namely
the reaction is preferably carried out at a tem
perature between the approximate limits of 20° C.
(or room temperature) and about 200° 0., pref
erably about 90° C. to 175° C. The mixture is 40 the treatment with carbon dioxide and steam, or
preferably stirred during this neutralization reac- .
tion, for a sufficient length of time to insure com
plete reaction, and ordinarily an excess of the
basic metal neutralizing agent is used so as to
insure incorporation of the metal atom in each
molecule of the alkyl hvdroxy aromatic compound
or sul?de thereof, to produce for example a metal
alkyl phenolate or a metal alkyl phenol sul?de,
etc.
.
Now according to the present invention the
resultant solution of metal salt in lubricating oil,
with or without minor amounts of stearyl alcohol
or other additives such as mentioned above, is
treated with a weakly acid substance, preferably
equivalent materials, may be carried out by batch
operation or continuously, depending upon equip
ment available and quantity of material being
processed. For batch operation the oil solution of
the metal salt can be placed in any suitable con
tainer such as an open or closed tank, drum or
kettle, etc. provided with heating or cooling coils
or exchanger and a pipe or other suitable means
of passing the carbon dioxide and steam (or wa
ter) into the oil-salt solution preferably near the
bottom thereof so that the gas bubbling up
through the solution will effect suitable agitation.
A mechanical agitator may, of course, be provid
ed. After the reaction has been completed the
solution should then be discharged from the bot
by blowing the solution with a weakly acid gas
tom of the container by gravity or by pressure
such as carbon dioxide, hydrogen sul?de,‘ etc.,
blowing. or conveyed by any other suitable means
preferably one whose alkali or alkalineearth salts
such as by pumping, to a ?lter. On the other
are insoluble in oil, to reduce the water-sensitivity
hand, for continuous operation several alternative
of the metal salt in the oil. Although such blow
ing with carbon dioxide, for instance, may effect 60 types of equipment may be used, one being an
open vertical drum in which the fresh oil-salt so
a substantial bene?t when used alone, it is pref
lution is fed in at one side either at the surface
erable to carry out this treatment in the presence
of, or subsequent to a treatment with, a controlled
or at the bottom or at some intermediate height,
and the carbon dioxide and steam are blown
amount of H20 either in the form of water or
steam which is believed to effect a partial hy 65 into the solution near the bottom of the tank
either through a pipe ?tted to the bottom of the
drolysis of some of the metal salts present. It
tank or else through a removable pipe which ex
is to be noted that water itself below its boiling
tends from the top of the tank down through the
point substantially hydrolyzes the metal salts, but
liquid near to the bottom, and the treated solu
during subsequent drying and ?nishing opera
tions the hydrolyzed fractions recombine to form 70 tion is then drawn oil through a suitable over
?ow outlet or by a syphon or otherwise. For
water-sensitive material. It is the function of the
larger scale continuous operation'it is probably
C0: to render the metal inactive during ?nishing
best to use a vertical tower which may be of any
operations. Accordingly if the hydrolysis is car
desired dimensions of height and diameter and
ried out with water alone at temperatures below
the boiling point _of water, it is necessary to stop
may contain packing materials such as rings, eta,
2,406,041
or may be equipped with bubble trays and the
stock or an S. A. E. 20 grade having a viscosityv
like or not, in any case the oil-salt solution be-
index oiabout 100.
‘ -
Table 1
Time of treat
15 111-.
1 111-.
134 hrs.
'
" 2 hrs.
214-1111
3 hrs.
Per cent H10 Per cent H1O Per cent H10 Per cent H10 Per cent H|O Per cent H10
Ba
Per cent water added:
0
9. 49
ass
9. 41
9. l7
sens.
Ba
412
so
8
l0
sens.
9
1
5
5
9.00
9. 49
7. 99
9. 47
10
7. 83
9. so
as
s. 44
Ba
sens.
Ba '
sens.
7
10
l
6
9. 54
9.00
9. 32
7. 34
7
11
2
3
9. 50
o. 12
9.36
7. 56
7
11
2
2
9. 50
9.011
9.25
7. 61
7
11
6
2
7
6. 16
2
6. 31
1
6. 33
l
5
a. as
1
o. as
1
5. 01
1
9. 54
ass
9.44
7. 74
7 ........ ..
11
1. so
Ba
sens.
Ba
sens.~
Blank sample (no treat): 9.66% Barium, 65 c. c. water-sensitivity.
The data in the above Table 1 indicate that
the greatest or at least the most practical reduc
tion of water-sensitivity is effected with the use
ing fed into the top of the tower and the car
bon dioxide and steam or water being fed into
the bottom of the tower so that the solution and
treating agents will ?ow countercurrently and the 25 of 1% or less of added water and a carbon diox
ide blowing treatment of about 2 to 21/2 hours.
treated solution will be discharged continuously
If much more water is used or a much longer
at the bottom of the tower by gravity and residual
treating time is used, the loss of barium from the
gases released at the top of the tower. Or the
?nished product is substantially increased, with
treatment with CO1 and water (or steam) can be
conducted either batch or continuous while main 30 out any compensating advantage by further de
crease in water-sensitivity.
taining a slight pressure of CO1 or steam on the
In another set of experiments a. similar oil
system. Such pressure will improve the solubility
solution of the same type of metal salt, namely
of the CO1 and water (or steam) in the oil, re
barium tertiary octyl phenol sul?de, was heated
sulting in better contact of the liquid and gas and .
thereby e?ecting better utilization of the treat 35 to 150° C. with constant CO2 treatment, and
ing agents.
traces of water (steam) were used. By trace is
meant less than 0.15% based on the charge.
The data in the following table show the e?‘ect
The results were as follows:
of various amounts of water in a series of tests
Table 2
95 hour
Per- Percent
00. 11,0
cent
5
5
0
Ti‘.
\
1 hour
2 hours
PerPer- Per- PerPer- Per‘
cent
Ba “5
Hl’g- cent
00, mo
cent cent
Ba g5?- cent
001 H1O
cent
9.54
9.29
8
12
10
10
______________________ _- 0.25
______________________ ._ 0.26
0
Ti‘.
9.58
9.61
Ti‘.
0.13
9.69 __-_.- 0.50
9 66
9
0.50
9
7
20
20
8 hours
Percent
Ba
-
Percent
00.
PerB10
cent
Percent
Ba
4 hours
g5?-
0
Tr.
9.56
9.64
10
10
30
80
0
Tl‘.
9.65
9.50
5
5
Tr.
0.26
9.6
9.77
10
2
0.75
0.75
Ti‘.
0.39
9.69
9.68
8
1
Percent
001
PerH1O
cent
Per
cent
Ba
-
.......................... ._
.......................... __
1.06 <.l5
9.64
10
1.06
0.54 .._.-..
2
Blank sample (no treat): 9.66% Ba, 65 c. c. H10-sensitivity.
The data in the above Table 2 indicate that
in which a solution of 40% of barium tertiary 55
when the barium salt solution was treated at 150°
octyl phenol sul?de in oil was treated with a
C., 3 hours treatment with carbon dioxide was
constant amount (10% by weight/hour based on
su?icient to produce a very substantial reduction
the total solution) of carbon dioxide at 85-90° C.
in water-sensitivity, from 65 cc. to 8 or 5 cc. when
for various periods of time ranging from 1A.; hour
to 3 hours. The barium salt used in this series 60 no water was used and from 65 cc. to 12 or 5 cc.
of tests was made by neutralizing tertiary octyl
when a trace of water (steam) was used disre
garding the amount of carbon dioxide. It is fur
phenol sul?de in oil solution with barium hy
ther noted that with small percentages of car
droxide octahydrate at about 120° C. The percent
bon dioxide from 0.5 to 1.0% (by weight on the
of barium in the treated product, and the water
sensitivity thereof are shown for each concentra 65 total solution) as the water (or steam) increases
the water-sensitivity improves from the blank of
tion of water used and each duration of carbon
dioxide blowing. The term “water-sensitivity” is
65 cc. to 1-2 cc. As to Table 2 per se it is evident
that larger amounts of steam with relatively small
the amount of sediment that settles out from 500
cc. emulsion after 24 hours standing at room
amounts of carbon dioxide are e?ective in reduc
temperature when 600 gms. of a (1.0%) solution 70 ing the water-sensitivity to a minimum.
Another series of tests was made using as the
of the metal salt in oil is contacted with 1% by
metal salt one made by neutralizing tertiary octyl
weight of water and stirred for 15 minutes with
pheno1 sul?de at 85° C. with barium hydroxide
a motor-driven egg-beater type of mixer at
octahydrate, and then treating a 40% solution
Bil-90° F.; the oil used in these tests was a sol
vent extracted Midcontinent lubricating oil base 75 thereof in oil with carbon dioxide and steam at
ll
150° C. (as in Table 2).. The results
were as
follows:
Table 5
-
Table}!
Time of treatment
Per cent
H|O sensi
B8
“WW
Time of treat.
'
35 hr.
Per
1 hr.
'
HID
Per
18
9.03
2 hrs.
H|O
Per
13
9.11)
3 hrs.
H10
Per
10
8.94
H30 10
egg‘ sens. “1;? sens. 0%? sens. 0%? sens.
Per cent wa
ter
added:
trace ______ _. 8.91
10
C’ c.
9. B8
9. 08
9. 04
8. 99
65
65
40
46
9. 24
ll
9. l4
9. 26
9
ii
It is not intended that this invention be limited
to any of the speci?c examples which have been
15 given solely for the purpose of illustration nor un
necessarily by any theory suggested as to the
The data in the above Table 3 show that here
again the carbon dioxide treatment with a trace
of steam was successful in reducing the water
sensitivity from 18 down to 10 in 2 to 3 hours.
20
. nechanism of the operation of the invention, but
only by the appended claims in which it is in
tended to claim all novelty inherent in the inven
tion as well as all modi?cations coming within the
Some plant performance data showing the
scope and spirit of the invention.
effect of steam and carbon dioxide treatment of
It is claimed:
1. The process of improving the water-sensi
barium tertiary octyl phenol sul?de are given
tivity of a metal salt containing at least one
herebelow:
Table 4
25 grouping having the general formula
Water sensitivity
Percent Ba
where M is a metal connected through oxygen to
llcfmc (‘Oi-Hi0
After treat-
Before treat-
trcatmont
ment
mcnt
After treat
mcnt v
(7:.
32
45
Ge.
5
7
9. 0i
9.68
8. 90
9. 67
46
3
8. 97
8. 91
The above Table 4 shows that in commercial
operation which was carried out by injecting the
steam-C02 mixture into the discharge line of a
system which consisted of a vertical drum
equipped with a stirrer and a centrifugal circu
lating pump taking suction at bottom of drum
discharging through a heat exchanger into the
top side of the drum, the water-sensitivity was
successfully reduced from relatively high figures
an aromatic nucleus Ar containing one or more
80 alkyl substituents R, 11. indicates the number of
such substituents, Z is a member of the sulfur
family, and 11' indicates the number of Z radicals,
which comprises blowing a solution of the said
salt in an inert solvent with a weakly acid gas in
the presence of H20.
2. Process according to claim 1 in which the
salt treated contains at least one grouping having
the general formula M—O-Ar(R)--S where M
is a polyvalent metal connected at least through
40 one oxygen linkage to an aromatic nucleus Ar
containing an alkyl substituent R.
3. The process of improving the water-sensi
tivity of a polyvalent metal salt of a higher mono
alkyl phenol sul?de which comprises blowing an
oil solution of said salt with a weakly acid gas in
the presence of H20, and ?ltering to remove un
such as 32-45 down to relatively low ?gures such
as 3-7, without effecting more than a trace loss of
desirable precipitate.
4. The process for improving the water-sensi
percent barium. The metal salt used during the
accumulation of the data reported in Table 4 was 50 tivity of a crude polyvalent metal salt of a higher
monoalkyl phenol sul?de which comprises blow
made by neutralizing tertiary octyl phenol sul?de
ing an oil solution of said salt with carbon diox
at about 120° C. with barium hydroxide octahy
ide in the presence of H20 and ?ltering to remove
drate, using about 0.7 to 0.75 lbs. of the hydrate
undesirable precipitate.
per pound of the sulfide, thus being a, 11-15% ex
5. Process according to claim 4 in which an
cess of hydrate over the theoretical amount re 55
amount ranging from a trace to about 5% is used
quired for neutralization. The subsequent CO2
of the C02 and of the H20, and the treatment is
steam treatment was carried out at a tempera
carried out at about 20-200° C. for about 1 to 10
ture of about 140-150° 0., using about 1.0% CO:
hours.
.
and about 1.0 to 2.0% steam, based on the weight
6. The process of improving the water-sensitiv
of the barium salt being treated.
60 ity of a crude barium salt of tertiary octyl phenol
An alternate method of carrying out the water
sul?de which comprises blowing a 20-60% solu
proo?ng reaction is to treat the metal salt solu
tion of said salt‘ in mineral oil with about 1% of
tion with water alone at temperatures below about
carbon dioxide and about 1% of steam (based on
100° C. to eifect partial hydrolysis of the salt, then
the weight of solution treated) at a temperature
follow this treatment with CO: prior to drying 65 of about '75 to 150° C. for about 2 to 6 hours, and
and ?nishing. This type‘ of operation is illus
?ltering to remove undesirable precipitate.
trated in the following example summarized in
7. The process of reducing the water-sensitiv
Table 5.
‘
ity of'a metal salt of an alkyl hydroxy aromatic
This experiment was conducted by reacting a
sul?de having at least 8 aliphatic carbon atoms
40% metal solution in oil with 15% by weight 70 which comprises treating a mineral oil solution of
said salt with a weakly acid gas in the presence
of water on total solution at 80-90° C. for vary- ing periods of time. In each case the wet solu
of H20.
8. The process of reducing the water-sensitivity
tion was quenched with C02 prior to heating to
of a metal salt of an alkyl hydroxy aromatic sul
140° C. and ?ltering. The water-sensitivity data
75 ?de having at least 8 aliphatic carbon atoms '
and analyses are as follows:
13
2,400,041
which comprises blowing a mineral oil solution of
14
amount or each ranging from a trace to about
said salt with carbon dioxide in the presence oi! a
5% based on the solution treated, said treatment
small amount of moisture.
being carried out at a temperature of about 20
9. The process of reducing the water-sensitivity
200° C. for about 1 to 10 hours, and-?ltering the
of barium tertiary octyl phenol sul?de which 5 treated mixture to remove undesired precipitate.
comprises blowing a mineral oil solution of the
HELMUTH G. SCHNEIDER.
same with carbon dioxide and steam, using an
JAMES E. J. KANE.
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