United States Patent (19) 11 Patent Number: 4,780,224

Jao 45 Date of Patent: Oct. 25, 1988

54 METHOD OF PREPARING OVERBASED Attorney, Agent, or Firm-Jack H. Park; Kenneth R.
CALCIUMSULFONATES Priem; Richard A. Morgan
75) Inventor: Tze-Chi Jao, Fishkill, N.Y. (57) ABSTRACT
(73) Assignee: Texaco Inc., White Plains, N.Y. In an overbased sulfonate process calcium hydroxide is
21) Appl. No.: 129,618 formed in situ by first adding 25% of the total water and
then adding the remainder of the water uniformly to the
(22 Filed: Dec. 7, 1987 calcium oxide over the entire hydration and carbon
511 Int. Cl." ........................................... C10M 135/10 ation time rather than incrementally. It has been found
52 U.S. C. ........................................ 252/25; 252/33; experimentally that by first adding at least 25% of the
252/33.4; 252/18 total water in a single aliquot that crystalline calcium
58 Field of Search .................... 252/33, 33.4, 18, 25, carbon formation is suppressed.
252/135 A300 TBN product is formed with an H2O/CaO molar
(56) References Cited ratio of 0.4 and a 3 hour hydration time. A 400 TBN
U.S. PATENT DOCUMENTS
product is formed with an H2O/CaO molar ratio of 0.8
and 3 hour hydration time.
4,427,559 1/1984 Whittle ............................... 252/33.2 Improved storage stability is achieved by eliminating
4,597,880 7/1986 Eliades ............................... 252/33.4 crystalline calcium carbonate formation. Crystalline
4,604,219 8/1986 Whittle ............................... 252/33.4 calcium carbonate has been related to engine wear.
4,698,170 10/1987 Le Coent ..................•oses or 252/33.2
Primary Examiner-Jacqueline V. Howard 8 Claims, No Drawings
 1.
4,780,224
2
is added in a single portion. Then carbon dioxide and
METHOD OF PREPARING OVERBASED the remaining water are added continuously at a uni
CALCIUMSULFONATES form rate over 1 to 4 hours. The final molar ratio of
water/calcium oxide is 0.1 to 1.2 and molar ratio of
BACKGROUND OF THE INVENTION 5 calcium dioxide/calcium oxide is 0.6 to 0.9. The mixture
This invention is an improved method of preparing is worked up and a micellar dispersion of calcium car
overbased calcium sulfonates which are used as deter bonate produced in the neutral calcium sulfonate.
gent and reserve alkalinity lubricating oil additives. DESCRIPTION OF THE PREFERRED
DESCRIPTION OF THE PRIOR ART O EMBODIMENTS
In the course of operation, internal combustion en The invention is an improvement in U.S. Pat. No.
gines convert lubricating oil to acidic degradation prod 4,604,219 issued Aug. 9, 1986, to J. R. Whittle incorpo
ucts. Those acidic degradation products attack and rated herein by reference.
corrode engine parts and catalyze the formation of In accordance with the present invention, calcium
sludge, thereby reducing lubricity and accelerating 5 sulfonates derived from natural or synthetic feedstocks
wear of moving parts in contact with the lubricating oil. or a mixture thereof can be overbased by introducing
It is desirable to add substances to the lubricating oil into a mixture comprising a neutral calcium sulfonate, a
which neutralize acids as they are formed in the engine lower alcohol, a light hydrocarbon diluent carbon diox
before they reach concentrations sufficient to cause ide and water. First, at least 25% of the water is added.
corrosion or to catalyze the sludge reaction. Adding 0 The remainder of the water is then added at a uniform
alkalinity agents to the detergent in motor oil for this rate over 1 to 4 hours, preferably 1 to 3 hours into the
purpose is known as overbasing. Colloidal carbonates of heated mixture with carbon dioxide. The total amount
alkaline earth metals have been found to be well suited of water is added in a molar ratio water/calcium oxide
of 0.1 to 1.2 preferably 0.4 to 0.8. It has been found that
for this purpose. These colloidal carbonate dispersions 25 both
are stabilized by oil soluble surface active agents such as the water rate and amount are critical. It has been
sulfonates of the alkaline earth metals in which the discovered experimentally that an amorphous calcium
sulfonic acid portion of the molecule has a molecular carbonate containing product free of crystalline cal
weight of preferably 450 to 600. The sulfonates are cium carbonated is formed by first adding a minimum of
made by sulfonation of lubricating oil fractions from 25% of the total water in a single aliquot with the re
petroleum and by sulfonation of alkylbenzenes having 30 mainder added continuously during carbonation rather
the required molecular weight. Benzene alkylates with than the entire amount charged at the beginning of the
carbonation or the entire amount introduced continu
straight chain alkyl groups are especially effective.
U.S. Pat. No. 4,427,557 discloses an overbased sulfo ously. By the present invention a highly overbased
nate process in which a mixture of calcium hydroxide 35 calcium sulfonate product with improved storage stabil
and calcium oxide are used. The solids content of the ity is formed with good lime utilization. When less than
crude product is reduced without the use of an amine or 25% of the total water is added in this manner, it was
ammonia promoter such as disclosed in U.S. Pat. No. was found experimentally that the exceptional improvement
4,086,170 and without overbasing in stages with solvent not achieved.
removal, water treatment and dehydration steps after tabulated The operating parameters of the present process are
each stage as disclosed in U.S. Pat. No. 3,878,116. The in Table I.
patent teaches that the mole ratio of calcium hydroxide TABLE I
to calcium oxide is critical to produce a bright and Variable Inventive Range Preferred Range
clear, oil soluble product. However, previous attempts 1. First Portion of Water At least 25% 25% to 30%
to prepare overbased sulfonates by in situ hydration of of Total
calcium oxide have not been totally satisfactory. (25% to 40%)
2. Reaction Temperature 100 to 170 F. 30 to 50 F.
SUMMARY OF THE INVENTION 3. Pressure, psig O to 50 0 to 20
4. Mole ratio 0.1 to 1.2 0.4 to 0.8
The invention is an improved process for producing H2O/CaO
an overbased calcium sulfonate. Calcium sulfonates 5. Mole ratio 0.6 to 0.9 0.8
derived from natural or synthetic feedstocks or a mix 50 CO2/CaO
ture thereof are overbased by diluting a neutral calcium 6. Hydrocarbon Solvent, 37 to 50 40 to 50
wt %
sulfonate with a light hydrocarbon solvent in a molar 7. Alcohol, wt % 4.7 to 7.2 4.8 to 5.8
ratio of solvent/neutral calcium sulfonate of about 15 to 8. Carbonation and 60 to 240 60 to 180
30; and with a lower alkanol in a molar ratio of al Hydration Time, min
kanol/calcium oxide of about 0.5 to 3.0. Then calcium 55
oxide is mixed in a molar ratio of a calcium oxide/neu Examples of useful and preferred reactants which
tral calcium sulfonate of about 7 to 28 and the mixture may be employed in the practice of the invention are
heated to about 100 F. to 170 F. at 0 to 50 psig. Next, listed in Table II.
at least 25% and not more than 40% of the total water
TABLE II
Reactants Example Preferred Reactants
1. Calcium Oxide One with a total slaking
time of 4.5-35 minutes
and a temperature rise of
6. C. max in the first 30 sec.
as measured by ASTM C-100-76a.
2. Calcium Sulfonate Neutralized sulfonic acid Blends of neutralized
derived from a natural sulfonic acids from natural
 4,780,224
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TABLE II-continued
Reactants Example Preferred Reactants
feedstock. Neutralized and synthetic feedstocks.
sulfonic acid derived
from a synthetic feedstock.
Blends of neutralized
sulfonic acids from natural
and synthetic feedstocks.
3. Diluent Oil 100-500 SUS (G 40 C.) pale 100 SUS pale stock hydro
stock. 00-500 SUS solvent finished
neutral oil.
4. Hydrocarbon Solvent Straight run gasoline, Crude heptane
dehexanized raffinate
gasoline, normal or mixed
hexanes, normal or mixed
heptanes, benzene or toluene.
5. Lower alcohols C1-C5 normal or branched Methanol
chain alcohols.

ment was stopped 120 minutes after the CO2 bubbling

started.
The subject alkaline earth metal carbonate-overbased 20
The filtered and solvent-stripped final product had a
alkaline earth metal sulfonates, particularly calcium TBN value of 330-360 by IR and had no trace of crys
carbonate-overbased calcium sulfonates, are blended in talline product formed. The filtration rate of the crude
any desired oil of lubricating viscosity to impart deter product was about 0.1 ml/sec through a Whatman No.
gency and alkaline reserve properties. Such oil may also 1 filter paper.
contain any of the conventional lube oil additives in an 25
amount sufficient for their intended purposes. Gener EXAMPLE 3
ally, the product of the present process will be incorpo The package storage stability of products containing
rated in such oils in an effective amount ranging from amorphous and crystalline calcium carbonate were
about 35 to about 80 weight percent of the oil for a compared. Though none of the test samples were made
concentrate and in an amount from about 0.1 to 20 30 according to the instant process, laboratory testing has
weight percent based on the amount of neat oil for a shown that the instant process produces an amorphous,
lubricating oil formulation. crystalline free calcium carbonate which is similar to
This invention is better shown by way of example. the amorphous calcium carbonate samples tested here.
EXAMPLE 1. 35
A blend containing 32 parts by weight of a normal Package Storage Stability Test Results
sulfonate, 91 parts heptane, 8 parts methanol and 18 Stability
parts calcium oxide was brought to reflux at 65 C. in a after 3
Additive Sulfonate State of months G
500 ml reaction flask. One part of water was added. The Blend Package Additive Carbonate 150° C.
mixture was refluxed for 10 minutes. CO2 was then 40
A TLA-688A TLA-674 amorphous no ppt.
introduced into the reaction mixture at a rate of 40 B TLA-688A TLA-142 amorphous - precipita
ml/min. At the same time, water was added at a rate of crystalline tion
1.65 ml/hr. The total amount of water used was 4 parts. C TA-2200 TLA-414 amorphous no ppt.
The addition of water was terminated 20 minutes before D TLA-2200 TLA-414(WA) amorphous -- precipita
crystalline tion
the completion of CO2 addition. The CO2 addition was 45
stopped at 130 minutes after the CO2 bubbling had TLA-688A is the additive package containing 300TBN overbased sulfonate for API
SF/CC grade (gasoline and diesel engine grade).
started. TLA-2200 is the additive package containing 400 TBN overbased sulfonate for API
The filtered and solvent-stripped final product had a SF grade (gasoline engine grade).
TLA-64 is a 300 TBN overbased sulfonate.
TBN value of 440-470. Its IR spectrum showed a sym TLA-421 is a 300 TBN overbased sulfonate.
metric band with a frequency of 865 cm (-1) indicating 50 TLA-44 is a 400 TBN overbased sulfonate.
TLA-44CWA) is a 400 TBN overbased sulfonate made according to U.S. Pat. No.
amorphous calcium carbonate and no trace of crystal 4,604,219.
line carbonate (875 cm (-1)) produced. The filtration TBN - Total Base Number, a measure of alkalinity.
rate of the crude product was about 0.3 ml/sec through
a Whatman No. 1 filter paper and was about the same as While particular embodiments of the invention have
the rate for samples from the regular water-addition 55 been described, it will be understood, of course, that the
process. invention is not limited thereto since many modifica
EXAMPLE 2. tions may be made, and it is, therefore, contemplated to
cover by the appended claims any such modifications as
A blend containing 48 parts of a normal sulfonate, 78 fall within the true spirit and scope of the invention.
parts heptane, 10 parts methanol and 16 parts of calcium 60 What is claimed is:
oxide was brought to reflux at 65 C. in a 500 ml reac 1. A process for preparing an overbased oil-soluble
tion flask. A 0.6 part portion of water was added. The calcium sulfonate comprising in order:
mixture was refluxed for 10 minutes. CO2 was then (a) diluting a neutral calcium sulfonate with a light
introduced into the reaction mixture at a rate of 40 hydrocarbon solvent and a lower alkanol;
ml/min. At the same time, water was added at a rate of 65 (b) mixing calcium oxide with the calcium sulfonate;
1.20 ml/hr. The total amount of water used was 2.6 (c) heating the resulting mixture to about 100 F. to
parts. The addition of water was terminated 15 minutes 170 F. at pressure of about 0 to 50 psig;
before the completion of CO2 treatment. The CO2 treat (d) adding 25% to 40% of the total liquid water;
 5
4,780,224
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(e) introducing continuously over a time of about 60 6. A process for preparing an overbased oil-soluble
to 240 minutes and at a uniform rate into the heated calcium sulfonate comprising in order:
mixture gaseous carbon dioxide and liquid water in (a) diluting a neutral calcium sulfonate with a light
hydrocarbon solvent and a lower alkanol;
a molar ratio of water/calcium oxide of 0.1 to 1.2; 5 (b) mixing calcium oxide with the calcium sulfonate;
(f) adding a diluent oil; (c) heating the resulting mixture to about 130 F. to
(g) separating solids from the liquid; and 150 F. at pressure of about 0 to 20 psig
(h) stripping the solvent from the resulting liquid (d) adding 25% to 30% of the total liquid water;
product. 1 (e) introducing continuously over a time of about 60
2. The process of claim 1 wherein the molar ratio of O to 180 minutes and at a uniform rate into the heated
water/calcium oxide is 0.4 to 0.8. mixture gaseous carbon dioxide and liquid water in
a molar ratio of water/calcium oxide of 0.4 to 0.8;
3. The process of claim 1 wherein the time is about 60 (f) adding a diluent oil;
to 180 minutes. (g) separating solids from the liquid; and
4. The process of claim 1 wherein the molar ratio of 15 (h)product.stripping the solvent from the resulting liquid
calcium oxide/neutral calcium sulfonate is about 9 and
the molar ratio water/calcium oxide is about 0.4. 7. The process of claim 6 wherein the light hydrocar
5. The process of claim 1 wherein the molar ratio of bon solvent is heptane.
8. The process of claim 6 wherein the lower alkanol is
calcium oxide/neutral calcium sulfonate is about 21.3 20 methanol.
and the molar ratio water/calcium oxide is about 0.8. s: k k k

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