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Патент USA US3065272

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United States Patent
Fice
3,065,262
Patented Nov. 20, 1952
1
3,065,262
ALKYL ARYL SULFONATES
Roy C. Sias, Ponca City, Okla, assignor to Continental
Oil Company, Ponca City, Okla., a corporation of Del
aware
No Drawing. Fiied Sept. 22, 1958, Ser. No. 762,260
4 Claims. (Cl. 260-505)
The present invention relates to the production of oil
soluble alkyl aryl sulfonates and relates more particularly
to the production of oil-soluble alkyl aryl sulfonates which
are of a light color.
Sulfonation of alkyl aryl hydrocarbons has generally
2
invention is operable regardless of the speci?c sulfonation
process employing sulfur trioxide as the sulfonating agent.
The reaction vessel used was a modi?ed version of a
Votator, which is commercially available and is generally
described in United States Patents Nos. 2,063,065 and
2,063,066, issued December 8, 1936. Brie?y, the proce
dure is as follows: the sulfur trioxide used is ?rst diluted
with air in a ratio of air to sulfur trioxide which varies
from 30:1 to 1:1. The sulfonatable material is intro
duced into one end of the Votator and in passing there
through forms a ?lm on the refrigerated surface of the
Votator. When ?rst contacted with sulfur trioxide, this
?lm is only partially sulfonated and is removed in that
‘followed the procedure wherein about 1.3 to 2 parts by
weight of 100 to 105 percent sulfuric acid is used per part 15 conditon by the progressively moving scrapers. The par
tially ‘sulfonated material is then reapplied to the refrig
by weight of ‘the alkyl aryl hydrocarbon. Other sulfonat
erated surface further along in the Votator as a ?lm and
ing agents have been used including oleum and sulfur tri
contacted with an additional quantity of sulfur trioxide.
oxide; but whatever agent used, the resulting mixture
‘The steps of removing the ?lm, reapplying to the surface,
upon completion of the sulfonation reaction followed by
neutralization has many times produced an off-colored 20 and contacting \with additional sulfur trioxide are re
peated until the completely sulfonatable materials are re
sulfonate. ‘Obviously, as a general rule, the lighter the
moved from the other end of the Votator. The total
color of the ?nal product, the more acceptable the prod
residence time of the sulfonatable material in the Votator
uct is commercially. Methods as used heretofore for
may vary from a fraction of a second to two minutes,
bleaching have involved such procedures as separating the
while the temperature employed may vary from 50 to
desired sulfonated hydrocarbon from the undesirable ma 25 about
200° F.
terials which consists of sulfuric acid, unreacted hydro
carbons, carbonaceous materials, and other miscellaneous
materials. Typical methods used to effect this separation
include the addition of water or a hydrocarbon solvent
A more detailed account of this sulfonation procedure
may be found in United States Patent No. 2,768,199,
issued to Horace E. Luntz and Daniel 0. Popovac.
followed by settling to stratify the materials, after which 30 Suitable oil-soluble alkyl aryl hydrocarbons which may
be used are those obtained by the reaction of excess ben
the desired product is drawn off. It is obvious that such
zene, toluene, xylene, naphthalene, or simlar hydrocar
procedures are costly and time consuming; furthermore,
bons with an alkylating agent in the presence of a Fn'edel
they are generally ine?icient, as the color improvement
Crafts type catalyst such as boron ?uoride, hydrogen
resulting from such a process is low.
When sulfuric acid or oleum is used as the sulfonating 35 ?uoride, sulfuric acid, etc. The alkylation may be made
under the in?uence of a catalyst with alkylating agents
agent, the sulfonic acid mixture will contain varying
having a carbon atom content which provides that the
amounts of sulfuric acid. Recently, sulfur trioxide has
resulting alkyl aryl hydrocarbon is oil-soluble. Other
‘been used as the sulfonating agent. The use‘ of sulfur tri
-0xide aslthe sulfonating agent has a number of advantages
preferred sulfonic acids are those obtained by the sul
as a‘continuous process; and, ‘in addition, contamination
with sulfuric acid of the ?nal product is eliminated. One
serious disadvantage in the use of sulfur trioxide, how
genated petroleum wax having from about 18 to more
than 30 carbon atoms. A preferred sulfonic acid for use
in the process of my invention is the sulfonic acid pro
as compared to sulfuric acid or oleum. One of these is 40 fonation of a hydrocarbon prepared by the alkylation of
benzene or toluene with one or more equivalents of halo
that a process employing sulfur trioxide can be operated
' ever, is that the sulfonic acid and ?nal sulfonate produced 45 duced by sulfonating the product known as postdodecyl
benzene. For the sake of simplicity, this material is often
"is generally of a darker color than the sulfonic acid and
referred to as PDB and will be so used in this disclosure.
final sulfonate produced employing sulfuric acid or
Postdodecylbenzene consists of monoalkylbenzenes and
oleum as the speci?c sulfonating agent.
dialkylbenzenes
in the approximate mole ratio of 2 to 3.
It is, therefore, a principal object of this invention to
provide an improved process, which process obviates the 50 Its typical physical properties are as follows:
disadvantages of the prior art methods. It is another ob
Speci?c gravity at 38° C___________________ __ 0.8649
ject of my invention to provide an improved method of
Average
molecular weight _________________ __
385
treating neutralized alkyl aryl sulfonic acids whereby a
Percent sulfonatableum _________ _‘.___' ____ __
88
light-colored sulfonate may be obtained. Further objects
A.S.T.M., D-158 Engler:
. ,
and advantages of the invention will become apparent as 55
the description proceeds.
I.B.P. _________________________ __° -F_-_
‘647
5 _____________________________ __° F-..
682
The foregoing objects and advantages are obtained by
50 ____________________________ __° -F__
715
a process wherein the neutralized sulfonate is heated to a
90 ____________________________ __ ° ‘F__
760
temperature within the range of 75 to 160° C. for a period
95 __ ___________________________ __° F__
775
of time which may vary from about 1 to 168 hours. Gen 60
F.B.P ____________________ __'______° F__
779
erally, I prefer to heat the neutralized sulfonate to a tem- ..
\Re‘frac'tiv‘e'index at 23° C__________________ __ 1.4900
perature range from about 85 to 150° C. for a period of
Viscosity at:
time varying from about 4 to lOOhours.
.7
,
Before describing the invention in more detail, it may
be well to give a description of the preferred sulfonation 65
procedure used and the test method used for determining
color. It should be understood, however, that this descrip
tion is given by way of illustration only; and the present
—-10° C. __'________ __'.._.___i__c'entipoises__
2800
20° C. ____________________ __do____.
280
40° C. _______ __‘_._.._“_'_; _'_:. ____ -.-dO..___
78
80° C. _______________________ __do____
18
Aniline point
Pour point
a i
:
° C__
69
C__
25
8,065,262
3
tion of sulfonic acid was neutralized with aqueous sodium
hydroxide. The solvents were removed by distillation,
and the activity of the product was adjusted to 62 percent
solution is then poured into a cuvette (19 x 105 mm.
round) and the optical density determined at 530 milli
microns wave length in a Coleman spectrophotometer,
using distilled water as the standard. Optical densities
below 0.600 are read to the nearest 0.005 and above
0.600 are read to the nearest 0.01.
4
acid-oil with methanol, after which the methanolic solu
The colors of the sulfonates were determined by the
Lovibond test method. In this method a 7 percent (by
weight) solution of the sulfonate (on a 100 weight per
cent active basis) is prepared in white oil. The sulfonate
Lovibond colors are
by the addition of 170 Pale Oil. The product had a Lovi
bond color of 4.7.
A sample of this sulfonate was placed in a constant
temperature oven maintained at 82il° C. for 48 hours.
The Lovibond color on this heat-treated product was 3.5
10 ‘and is shown in Table I also.
then calculated by multiplying the optical density by 11.3
EXAMPLE ‘IV
and rounding off the results to the nearest tenth.
In order to disclose the nature of the present invention
The sample of Example I which had been heated at
85:10 for 48 hours (product B, Table I) was mixed
be given. It is to be understood that the invention is 15 with 10 percent (by weight) of water and dehydrated
not to be limited to the speci?c conditions or details set
by heating to 140° C. The Lovibond color was again
forth in these examples except in so far as such limitations
found to be 7.1 and is shown in Table I also.
are speci?ed in the appended claims.
EXAMPLE V
20
EXAMPLE I
still more clearly, the following illustrative examples will
A sodium PDB sulfonate was prepared from a sulfur
trioxide sulfonated PDB, prepared in the manner pre
viously described. The conditions of sulfonation were
PDB was sulfonated as described above wherein the
sulfonation conditions employed were as follows:
Temperature,
° F __________________________ __
Back pressure, lbs/sq. in ____________________ __
150 25 as follows:
14
Temperature, ° F __________________________ __
S03, percent of theoretical ___________________ __
130
S03, percent of theoretical ___________________ __
The crude sulfonic acid was 'diluted with 3 volumes 30
of naphtha for acid sludge removal, contacted with 2
percent (by weight) of Attapulgus clay, blown with nitro
acid was then neutralized with aqueous sodium hydroxide.
The solvents were removed by distillation, and the activ
150
The crude sulfonic acid was diluted with white oil and
allowed to settle for two hours.
The acid-oil was de
canted ‘from the sludge and treated with 1 percent (by
gen for one hour at ambient temperature to remove S02,
and then ?ltered through Hy?o. The puri?ed sulfonic
110
Back pressure, lbs/sq. in ____________________ __
11
Air-S03 volume ratio _______________________ __ 10:1
Air-S03 volume ratio _______________________ __ 19:1
weight) of Attapulgus clay with simultaneous degassing
35 by nitrogen blowing for one hour at ambient temperature.
The puri?ed acid-oil was ?ltered through Hy?o and then
ity of the product was adjusted to 62 percent by the ad
dition of 170 Pale Oil (which is a para?inic mineral oil
having an SSU viscosity at 100° F. of 170). The prod 40
uct had a Lovibond color of 9.7.
Samples of this sulfonate were placed in a constant
temperature oven maintained at 85:1“ C. for 418 hours
and 120 hours, respectively. Lovibond colors on these
heat-treated products is shown in Table I.
extracted with methanol. The methanolic solution of
PDB sulfonic acid was then neutralized with aqueous
sodium hydroxide. The solvents were removed by heat
ing to a pot temperature of 140° C., whereupon the
activity of the product was adjusted to 63.4 percent by
the addition of white oil. This product had a Lovibond
color of 3.9.
Two procedures were used for heat-treating samples of
this example. In most cases, about 100 grams of sample
was placed in a test tube which was immersed in a con
EXAMPLE II
stant temperature bath. Duplicate samples were used,
with stirring being applied to one of the samples. At
timed intervals, portions of the samples were removed
a different sample of PDB was used and methanolic 50 and the Lovibond color determined. The following tem
peratures were used: 83° 0., 120° C., 134° C., and
sodium hydroxide was used. The product had a Lovi
A sodium sulfonate was prepared using the procedure
described in Example I, with the ‘following exceptions:
150° C.
bond color of 5.7.
A sample of this sulfonate was placed in a constant
temperature oven maintained at 82i1° C. for 48 hours.
The other procedure consisted of placing 100 ‘grams of
sample in a test tube, which was then placed in a con
stant temperature oven. This procedure was employed
‘only at 85° C.
The data for the samples of this example are shown
The Lovibond color on this heat-treated product was
3.6 and is shown in Table I also.
in Table II.
EXAMPLE III
I
Table I
A sodium PDB sulfonate was prepared from a sulfur 60
trioxide sulfonated PDB, prepared in the manner pre
viously described. The conditions of sulfonation were
HEAT BLEAOHING OF SODIUM PDB SULFONATES
SUMMARY OF DATA ON SAMPLES 0F EXAMPLES I-IV
as follows:
Temperature, ° F
_
Back pressure, lbs/sq. in ____________________ __
14
Tempera-
B. Example I ______________________ ..
0. Example I ______________________ __
130
70
The cnlde sulfonic acid was diluted with white oil for
Hours
Lovibond
ture, ° 0.
A. Example 1.-
Air-S03 volume ratio _______________________ __ 19:1
S03, percent of theoretical ___________________ __
Sample
150 65
85:};1
85*1
D. Example II ................................. __
E. Example II _____________________ _825:1
color
0
9.7
48
120
7.1
5.6
0
48
5. 7
3. 6
acid sludge removal, contacted with 1 percent (by weight)
F. Example III ................................ -.
0
4.7
of Attapulgus clay, blown with nitrogen for one hour at
ambient temperature to remove S02, and then ?ltered
through Hy?o. The sulfonic acid was extracted from the 75
G. Example III ____________________ ..
82:1:1
48
3. 5
H. Example IV ____________________ .-
82;};1
48
7.1
Jan-
8,065,262
6
Table II
HEAT BLEACHING OF SODIUM PDB SULFONA’I‘ES SUM
MARY OF DATA ON SAMPLES OF EXAMPLE V
Sample
Stirring
Tempera
Hours
ture, ° 0.
The data presented in Tables I and ‘II clearly indicate
that heating the sulfonate product un der selected condi
tions of temperature and time improves the color of the
product. The data further indicate that temperatures in
Lovibond
5 the range of 130-155° C. are more effective but that the
time interval is more critical at these temperatures. Ex
3.9
not a?ected by heating with water. It is also shown that
Color
ample IV shows that the color improvement obtained is
Untreated product
4039280462
_
-.
Yes_______
Yes
YesIIIIIII
Yes____.__
.
5—A___________-___
5—B.__
--___.
2451629.7%4K9m 0
N0_-______
No________
1 These samples were heated in a constant temperature oven.
ZLIQA.7530962
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,832,801
Bernstein ___..___________ Apr. 29, 1958
40 2,847,459
Mitchel1_____________-_Aug.12,1958
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