United States Patent Office Aspruns

28318 :
Patented Apr. 22, 1953
2
product can be used as such, though it is preferred to
2,831,811 mill the grease to insure uniform consistency.
The quantity of water initially added in our novel
PRODUCTION OF ANEHYDROUS CALCUM process is about 0.25 to 2.0 parts by weight per part of
GREASE 5 the fatty component of the grease with about 0.5 to 1.0
Martin M. Riccormick, Chicago, and John W. Nelson, parts of water being preferred. By employing water in
Lassing, al., assignors to Sinclair Refining Conapatay, the defined quantities initiation of the reaction at low
New York, N. Y., a corporation of Maine temperatures, i. e., about 130 F., is facilitated, and the
No Drawing. Application July 8, 1954 greases produced are characterized by water stability.
Seria No. 442,198
10 Equally important in our process is control of the ratio
of starting oil to fatty component; we have found ratios
3 Claims. (Cl. 252-39) (parts by weight) of about 2 to 4:1 to be highly satis
factory and prefer a 3:1 ratio. About 3 parts (by weight)
Our invention relates to greases and more particularly to all of the remainder of the oil to be employed in the
final grease, and preferably about 5 parts, is added to the
relates to methods for the manufacture of anhydrous thickened soap-starting oil reaction mass after partial de
calcium grease. hydration, i. e., removal of free water. This oil is pref
The usual processes for preparing anhydrous calcium erably added slowly to avoid abruptly thinning the re
greases are characterized by lengthy reaction times and action mass. This oil can be added all at one time with
violent foaming and generally produce lumpy greases 20 out deleteriously affecting the quality of the grease prod
having high soap contents for a given penetration. uct; however, we have found it desirable to add the oil
Lengthy reaction times constitute inefficient use of equip incrementally to avoid any possibility of excessive foam
ment. Foaming necessitates the employment of larger ing. Upon complete dehydration of the reaction mass
equipment than would be sufficient ordinarily to contain any oil remaining is added to adjust the grease to the
the reaction mass. Lumps in a grease necessitate a special desired end properties.
milling step to obtain homogeneous greases, and fre Mineral lubricating oils, such as neutral oils, and Syn
quently even milling may not remove all lumps satis thetic oils normally used in calcium grease manufac
factorily. And, of course, high soap content constitutes turing processes can be used in our process. We prefer
poor yield when it is possible to obtain a high quality to employ a blend of solvent-refined Mid-Continent
grease of the same consistency with a lower soap content. crudes having a viscosity of about 80 SUS at 100 F.
We have now discovered in the preparation of an The lime employed can be in any of the forms usually en
hydrous calcium greases, in contrast with the prior art ployed in grease manufacture, i.e., calcium oxide, calcium
methods, that forming the soap in the presence of defined hydroxide, hydrated calcium oxide, calcium carbonate,
amounts of water and oil added at the initiation of the etc., and is present in amounts ranging from about the
soap forming step and adding further quantities of oil stoichiometric amount to about a 10% excess. The var
following partial dehydration of the soap-oil mixture in ious hydroxy stearic acids, such as 9-hydroxy stearic
conjunction with the use of low temperatures throughout acid, 9,10-dihydroxy stearic acid and the like, can be
the grease making procedure results in high yields of employed; the preferred fatty component is 12-hydroxy
smooth greases, and the process is characterized by short 40 stearic acid.
reaction time and an absence of foaming during its course. The method of our invention will be illustrated by the
By our method foaming is eliminated, high yields of following example:
Smooth greases result, processing time is about 3 to 6
hours rather than the usual 12 or more hours and greases EXAMPLE I
containing 5 to 25 weight percent soap and of all of 45 Twenty pounds of 12-hydroxy stearic acid, 10 pounds
the NLGI grades can be produced. In addition to these of water, and sixty pounds of mineral oil containing 2.9
advantages other economies are effected by our novel pounds of hydrated lime previously slurried in part of
process such as the savings attendant upon the use of this oil were mixed in a steam heated kettle at G0 F.
lower temperatures, the increased capacity of grease The mineral oil used was an 82 SUS/100 F. blend of
making equipment by virtue of the shortened reaction 80 volume percent solvent treated Mid-Continent neutral
time, the increased yields and the absence of foaming. and 20 volume percent conventionally refined naphthenic
According to the method of our invention lime, solid base Coastal stock. The temperature was raised gradually
fatty acid, water and oil are mixed at a low temperature, and at about 130 F. a pronounced thickening occurred
for example ambient temperature or about 70 to about indicating reaction. The initial formation of a smooth
110 F., and then heated. Thickening will generally 55 soap took place in the heterogeneous phase system at a
occur at temperatures of about 120 to 145 F. during temperature well below the melting point of the acid.
which time cloudy water begins to appear around the i. e., below about 160 F., as indicated by presence of a
grease kettle at the edge of the grease. The temperature few solid acid flakes on the kettle walls where temperature
is gradually raised to about 190 F. while the reaction was maximum. During formation of the smooth, homo
goes to substantial completion; completion of the reac 60 geneously thickened mass in the temperature range 130
tion is indicated by the change in color of the free water to 190° F. free water was rejected, appearing at the
from cloudy to clear. Upon completion of the reaction, surface and edge of the reaction mass in the kettle. The
the mass is partially dehydrated at a temperature of about separated free water changed from cloudy to clear, show
190 to 225 F., that is, the free water is evaporated. ing essentially complete reaction of the lime and acid.
After evaporation of the free water, additional oil is 65 The temperature was raised from 190° F. to 225 F. to
added while continuing the heating. After addition of evaporate visible non-emulsified water in order to preclude
the oil the reaction mass is dehydrated substantially com later foaming. An additional five parts of the oil blend
pletely at a temperature below about 260 F. and pref (based on weight of fatty acid employed) was incor
erably in the range of about 240 to 255 F. When de porated while raising the temperature from 225 to 240 F.
hydration is complete heating is stopped and any addi Dehydration in the temperature range of 225 to 240 F.
tional oil needed or desired is blended into the mixture was accompanied by gradual, smooth gel formation. The
until the product shows the desired penetration. The temperature was then raised to about 250 to 255 F. and
 2,831,811
3 4.
held one hour to insure complete dehydration after which positions wherein a mineral lubricating oil is thickened
the grease was cooled to 170 F. while incorporating the to grease consistency with calcium 12-hydroxy stearate,
remainder of the oil (90 pounds) and about 1.35 pounds the steps of adding, at a temperature from about room
of diphenyl amine oxidation inhibitor. The grease was temperature to 110 F., the 12-hydroxy stearic acid to
then milled at 170 F., 0.005 inch clearance and a flow a slurry containing about a stoichiometric quantity of
rate of 1.5 pounds per minute in a conventional colloid lime to saponify the 12-hydroxy stearic acid, about 0.5
mill. part by weight of water and about 3 parts by weight of
The process of Example I was characterized by a com a mineral lubricating oil each based on the 12-hydroxy
plete absence of foaming. The anhydrous grease pro stearic acid, elevating the temperature whereby thicken
duced was analyzed and tested for penetration according ing begins occurring at about 130 F. and free water
to the standard tests specified by the American Society begins to form, raising the temperature to about 190 F.
for Testing Materials with the following results. while the saponification goes to substantial completion,
Table I
evaporating the free water at a temperature above about
190 F. while elevating the temperature to about 225 F.,
Calcium soap, weight percent----------------- 740 5 incorporating additional mineral lubricating oil until about
Moisture, weight percent---------------------- 0.00 5 parts by weight based on the 12-hydroxy stearic acid
Free alkali as CaO, weight percent.-------------- 0.10 have been added, dehydrating the reaction mass at a
Oxidation inhibitor, weight percent------------- 0.50 temperature between about 240 and 255 F., and then
Mineral oil, weight percent------------------- 92.00 adding the remainder of the oil of the final composition
Penetration at 77 F., 150 g. cone: 20 while permitting the grease to cool.
Unworked ----------------------------- 308 3. In the preparation of anhydrous calcium grease
60 strokes------------------------------ 305 compositions wherein a lubricating oil is thickened to
From the foregoing it is apparent that we have dis grease consistency with a calcium hydroxy stearate, the
steps of forming a heterogeneous mixture, at a tempera
covered a process which produces high quality grease in ture from about room temperature to 110 F., of hydroxy
an economical and efficient manner. stearic acid, lime to saponify the fatty component and
We claim:
1. In the preparation of anhydrous calcium grease com form a soap, about 0.2 to 2.0 parts by weight of water
positions wherein a mineral lubricating oil is thickened weightonof the
based fatty component and about 2 to 4 parts by
to grease consistency with a calcium hydroxy stearate, 30 heating the mixture to oilprovide
a lubricating based on the fatty component,
a thickening of the oil
the steps of forming a heterogeneous mixture, at a tem at about 120 F. to 145 F. and an initial formation of
perature from about room temperature to 110 F., of soap below the melting point of the acid, raising the
hydroxy stearic acid, lime to saponify the fatty component temperature to about 190° F. while the saponification
and form a soap, about 0.2 to 2.0 parts by weight of goes to substantial completion, evaporating free water
water based on the fatty component and about 2 to 4 35 from the mass, adding
parts by weight of a mineral lubricating oil based on the amount of the remainderfrom of
about 3 parts to the total
the oil of the final composi
fatty component, heating the mixture to provide a thicken tion and then dehydrating the grease at a maximum tem
ing of the oil at about 120 F. to 145 F. and an initial
formation of soap below the melting point of the acid, perature of below about 260 F.
raising the temperature to about 190 F. while the saponi 40 References Cited in the file of this patent
fication goes to substantial completion, evaporating free UNITED STATES PATENTS
water from the mass, adding from about 3 parts to the
total amount of the remainder of the oil of the final 2,607,734 Sproule et al. ----------- Aug. 19, 1952
composition and then dehydrating the grease at a maxi 2,607,735 Sproule et al. ---------- Aug. 19, 1952
mum temperature of below about 260 F. 45 2,613,182 Sproule et al. ----------- Oct. 7, 1952
2. In the preparation of anhydrous calcium grease com 2,618,599 King et al. ------------ Nov. 18, 1952