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Patented Nov. 5, 1946
' 2,410,578
UNITED STATES, ' PATENT OFFICE‘,
MINERAL OIL COMPOSITION
John J. Giammaria, Woodbury, N. ., assignor to
Socony-Vacuum Qil Company, Incorporated, a
corporation of New York
,
No Drawing. Application September 28, 1944,
Serial No. 556,287
10 Claims. (Cl. 252-56)
i
2
This invention relates to mineral oil composi
tions and more particularly relates to viscous
mineral oil fractions containing small amounts
of an added material which imparts improved
Representative of the aliphatic acids which
form one component of the esters contemplated
>...\
herein are palmitic, stearic, arachic, behenic, lig
noceric, cerotlc, melissic, etc. Preferred of such
pour or ?ow characteristics thereto.
acids, however, are palmitic and stearic.
With respect to the second component of the
As is well known in the art, mineral oil frac
tions, such as those derived'from paraffin base
aforesaid esters, namely, lignin, it is recognized
crudes which have been re?ned for use as lubri
‘that the structure thereof is still in the con
troversial stage. Yet, many aspects of its nature
cants, normally contain an amount of wax- such
that,they congeal or become non-flowing at tem 10 are known and are such as to de?nitely establish
peratures only slightly below normal tempera
‘its identity in the art. It is known that it occurs
tures. Obviously, oil fractions so characterized
in plant life, such as shrubs, straw, trees, such
are impractical for general use. Although it is
as hardwoods, typi?ed by oak, and softwoods typi
possible to remove an appreciable amount of this
?ed by pine, etc.; and may be extracted there
wax by additional re?ning operations and there 15 from by various means. For example, lignin
by materially reduce the “pour point" of the oil,
may be extracted from plant life with cold con
such re?ning operations are expensive and, in
addition, seriously reduce the lubricant qualities
centrated acid, with hot caustic solutions, etc. It
is also known that lignin differs from carbohy
of the oil. Apparently, the wax present in the oil
drates in its carbon and hydrogen content, an
solidi?es in the form of a lattice-like structure 20 alyses for lignin generally ranging from about 60
and encloses the oil, thereby undesirably con
per cent to 65 per cent carbon and 5 per cent to 6
gealing the oil, yet contributing desirable lubri
per cent ,carbon, with the remainder oxygen. It
cating qualities thereto. Accordingly, rather than
has also been. established that the methoxyl
resort to expensive re?ning operations to remove
(-—OCH3) content varies from about 14 per cent
the wax and sacri?ce some of the lubricating 25 to about 21 per cent indicating the presence of 5
quality of the oil, it has become the practice to
or 6 methoxyl groups per unit molecule. Analyses
allow the wax to remain in the oil and to counter
have also indicated that lignin is-characterized
act its undesirable e?ect upon the pour charac
with 4 or 5 hydroxyl (-OH) groups. It has
teristics of the oil by incorporating therein a - rbeen suggested, for example, that lignin obtained
small amount of an agent capable of improv 30 from hardwoods has 6 methoxyl groups and 5 by
ing the said pour characteristics. Improving
droxyl groups; whereas lignin obtained from soft
agents of this type are generally described as
woods, usually has 5 methoxyl and 5‘ hydroxyl
“pour depressants” in view of their ability to
groups. The molecular weight of lignin obtained
modify or retard wax crystallization so that im-v
from various plants has varied considerably,
pairment'of ?ow does not take place except at 35 workers in this ?eld reporting molecular weights
temperatures well below those normally encoun
from about 780 to about 1800. Strong acids
tered in the use of the oil. The present inven
have little or no effect upon lignin, as have most
tion has to do with an improving agent of this
organic solvents. Lignin is illustrated herein
type which is greatly effective in very small quan
after in the examples.
"I:
tities.
'
40
The preferred method of preparing the esters
The present invention is predicated upon the
discovery that a mineral oil fraction containing
contemplated herein is that wherein lignin is dis
solved ~ln pyridine and is heated at an elevated
a small amount of an ester of lignin and of an
temperature with an acid halide, followed by
aliphatic acid having at least about 16 carbon
precipitation of the‘ ester so formed upon the
atoms is characterized by an appreciably lower 45 addition of water. The ester so. precipitated is
pour point than is the mineral oil fraction alone.
then puri?ed; it is washed with water and there
While all esters of the aforesaid class possess pour
.after dissolved in hot benzol. The benzol solupoint depressant properties, those of certain sub
tion so obtained is ?ltered, and the ?ltraterdise
classes are particularly effective in this regard.
tilled to remove benzol therefrom. At this stage,
Lignin esters wherein at least 3 hydroxyl groups 50 the ester is relatively pure and may be used here
of the lignin are esteri?ed with a saturated mono
in; however, it may be further puri?ed whensdis
carboxylic aliphatic acid of the aforesaid type
solved in ether, then waished'withsodiumear
are outstanding and particularly so are those
bonate solution, dried‘ with a drying agentsuch
esters wherein the lignin is obtained from hard
wood.
'
.
as calcium chloride and heated to evaporates'ether
55 therefrom.
_- 5
at
'
To facilitate handling, the esters may be pre
pared in an oil blend. For example, after lignin
has been reacted with an acid halide, three parts
by weight of mineral oil may be added to the re
action mixture and the puri?cation procedure, de
Table
on
Cone.
weight PM: gm"
per cent
scribed ,above, may then be followed. _ In this
way, the ?nal product is obtained as a 25 per
cent blend in mineral oil, which is more con
venient to work with than a more concentrated,
or pure, product.
Illustrative of the lignin esters and of their
........ --
+20
+15
. 10
-m
.20
~20
........ ._
examples provided below. The lignin used in the
preparation of the esters described below is ob
'
0. 05
. a)
methods of Preparation are those described in the .
tained from hardwood such as spruce chips ac
Lignin ester
-s
+5
.05
-5
. 10
~15
.20
--15
From the foregoing data, it will be apparent
that lignin esters of the class contemplated here
liquor obtained by cooking spruce chips, that is
in depress the pour points of oils to which they
hardwood chips, in an autoclave, under pressure,
are added to a substantial degree, although used
therein in but minute quantities.
for several hours with a 5 per cent sodium hy
droxide solution was evaporated until the speci?c 20
Not only are the aforesaid lignin esters of value
gravity was about 1 and the total solids about 20
as pour point depressants, but they are of value
cording to the following procedure. A soda black
15
per cent. Carbon dioxide was passed into the so
lution until the pH thereof was lowered to about
as wax modi?ers for other purposes such as de
waxing aids in oil re?ning and the like. In gen
8.5, whereby a portion of the lignin separated out.
_ eral, they may be used in all cases wherein it is
The lignin so separated was coagulated by heat 25 desired to modify the crystal structure of paraf
ing the same to about 100° C. and thereafter cool
ing it to about 50° C. It was then ?ltered, washed
with water, and then washed with dilute min
eral acid. It was ?nally washed with water and
dried. The lignin so obtained had a molecular 30
weight of about 850.
'
Examru: ONE
Preparation of lignin 'stearate
Forty grams of lignin, described above, was dis
?n wax. They may be used in mineral oil frac
tions in concentrations of from about 0.05 per
cent to about 10 per cent depending upon the
character of the oil fractions and their conditions
of use. Satisfactory results, however, are gen
erally obtained with concentrations of the order
of 005-02 per cent.
It is to be understood that while certain pre
ferred ‘procedures for synthesizing the improving
35 agents contemplated herein and certain illustra
solved in 30 grams of pyridine and 100 grams of
dioxane, and warmed to about 50° C. Eighty
grams of stearyl chloride was then added slowly,
tive reactants which may be employed have been
.13‘. .The results of pour tests upon oil blends of
these oils and typical ligm‘n esters are provided
mono-carboxylic aliphatic acid having at least
about 16 carbon atoms, at least 3 hydroxyl groups
of the lignin being esteri?ed with the said acid.
recited herein, the invention is not to be con
strued as limited thereto. Rather, the invention
is to be broadly construed in the light of the lan
during a. thirty minute period, to the lignin dis
solved in pyridine and dioxane. After all of the 40 guage of the appended claims.
I claim:
stearyl chloride had been added, the resulting
1. A mineral oil composition comprising a vis
mixture was heated to 100° C. and was main
cous mineral oil fraction having in admixture
tained at the latter temperature for about 2
therewith a minor proportion, suf?cient to de- hours. Thereafter, the mixture was cooled and
press the pour point of said oil fraction, of a
diluted with water whereupon the crude product,
lignin ester of an aliphatic acid having at least
lignin stearate, precipitated out of the mixture.
about 16 carbon atoms.
The crude product was washed with water and
2. A mineral oil composition comprising a vis
then dissolved in benzol. The benzol solution
cous mineral oil fraction having in admixture
thus formed was ?ltered and the benzol was dis
therewith a minor proportion, from about 0.05
tilled from the ?ltrate to obtain substantially
percent to about 10 percent, of a lignin ester of
pure lignin stearate. The product is a hard,
an aliphatic acid having at least about 16 carbon
‘brown. wax-like solid.
atoms.
3. A mineral oil composition comprising a vis
ExAMPLn 'Iwo
55 cous mineral oil fraction having in admixture
Preparation of lignin. palmz‘tate
therewith a minor proportion, su?icient to de-‘
press the pour point of said oil fraction, of a. lignin
‘Thirty-one grams of lignin, described above,
ester of a saturated mono-carboxylic aliphatic
were dissolved in 25 grams of pyridine and 100
acid having at least about 16 carbon atoms.
grams of dioxane, and reacted with 50 grams of
4. A mineral oil composition comprising a
palmityl chloride as described in Example One 60
viscous mineral oil fraction having in admixture
above. The product, lignin palmitate, is also a
therewith a minor proportion, su?icient to de
hard, brown, wax-like solid.
press the pour point of said oil fraction, of an
The following data illustratethe pour point
ester of lignin and of a saturated mono-carboxylic
depressing action of the lignin esters contem
plated herein upon mineral oils of the motor lu 65 aliphatic acid having at least about 16 carbon
atoms, at least 3 hydroxyl groups of the lignin
bricant type. The oils used in these tests were:
being esteri?ed with said acid.
oil A, a Mid-Continent, solvent-re?ned, S. A. E.
5. A mineral oil composition comprising a vis
30 grade. oil having a Saybolt Universal viscosity
of 65seconds at 210° F., and a pour point of +20" - cous mineral oil fraction having in admixture
F.; oil B, a chlorex-re?ned Pennsylvania S. A. E. 70 therewith a minor proportion, sui?cient to de
10>gradeoil having a Saybolt Universal viscosity
press the pour point of said oil fraction, of an
,of 45 seconds at 210° F. and a pour point of +5°
ester of a hardwood lignin and of a saturated
in the table below.
.
2,410,578
6. A mineral oil composition comprising a vis
cous mineral oil fraction having in admixture
therewith a minor proportion, su?icient to de
press the pour point of said 011 fraction, of an
ester of a hardwood lignin having a molecular
weight of about 850' and of a saturated mono
.
6
i
press the pour point of said oil fraction, of a lig
nin stearate, said lignin having a molecular
Weight of about 850 and having at least 3 hy
droxyl groups esteri?ed with said acid.
9. A mineral oil composition comprising a vis- _
cous mineral oil fraction having in admixture
carboxylic aliphatic acid having at least about 16
therewith a minor proportion, sufficient to de
carbon atoms, at least 3 hydroxyl groups of the
press the pour point of said oil fraction, of an
lignin being esteri?ed with said acid.
ester of a hardwood lignin and of palmitic acid,
'7. A mineral oil composition comprising a vis-_ 10 at least 3 hydroiwl groups of the lignin being es
cous mineral» oil fraction having in admixture
teri?ed with said acid.
therewith a minor proportion, su?icient to de
10. A mineral oil composition comprising a vis
press the pour point of said oil fraction, of an
cous mineral oil fraction having in admixture
ester of a hardwood lignin and of stearic acid, at
therewith a minor proportion, su?icient to de
least 3 hydroxyl groups of the lignin being esteri 15 press the pour point of said oil fraction, of a
?ed with said acid.
lignin palmitate, said lignin having a molecular
8. A mineral oil composition comprising a vis
weight of about‘850 and having at least 3 hy
cous mineral oil fraction having in admixture
droxyl groups esteri?ed with said acid.
therewith a minor proportion, suiiicient to de
.
JOHN J‘. GIAMMARIA.
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