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Procedure i J f I
The snlfonat~on was carried out b y charging the SULFONIO AGTD VISCOSITY
vs
dodecylbcnzene to the kettle and agitating with cool- % so 3 AODITION
o . . . . . . . -!
this reason a small amount of air is always intro- b- iooc ! l
duced through the SOs line in the kettle during the
~5 c
charging of dodeeylbenzene. This is continued until
the SOs flow is started, thus preventing dodecylben- i f°
o~ 60c - - - - - -
zene from backing into the SOs delivery line. z
I t was found necessary to use a near m a x i m u m
charge of dodecylbenzene in the kettle in order to get
the greatest degree of sulfonation with a m i n i m u m 20C
Experimental
Sulfonation temperatures f r o m 45 ° to 80°C. were orimeter, employing a No. 42 blue filter. An 8.7%
studied. Viscosities of the sulfonic acid were meas- solution based on active material was used.
ured over a range of temperatures and at various F i g u r e 4 shows t h a t the high viscosity encountered
times during the reaction. Colors of the finished so- occurs only after 75% of the required SOs has been
dium sulfonates were also obtained at the various added.
sulfonation temperatures. Analyses were r u n to de- The quantity of SO3 required to reduce the unsu!-
termine the degree of sulfonation. The final quan- fonated oil to less than 1.9% was slightly different,
tity of SOs added for all runs in this, phase of the depending upon whether d r y ice or external heat
s t u d y was 110% of theory. F i g u r e 3 shows the rela- exchangers were used for cooling. W i t h external
cooling only 5 to 6% excess SOs over theory was re-
quired. W i t h d r y ice cooling 10% excess was re-
quired. One h u n d r e d per cent of theory is equiva-
lent to 0.34 pound of SOs p e r p o u n d of alkylate.
400 Volume ratios of air to SO3 were also studied, and
it was f o u n d t h a t high volumes of air to SOs (at
i300 least 9:1) gave the best results in regard to sulfo-
hate color and degree of sulfonation. Reduction of
~- ~00
the air to SOs ratio resulted in significantly poorer
I00 "--
colors and a decline in degree of s~dfonation. I t is
believed t h a t this poorer degree of sulfonation m a y
>. 16 have been the result of reducing the dispersion of the
o m
a i r - S Q input. Since all the work was done with the
o
cnm 1200 same size holes in the a i r - S Q delivery tube, a n y re-
50 duction of air velocity would result in a reduction in
<z
dispersion. I t is possible t h a t the o p t i m u m volume
ratio m a y be different f o r other equipment.
I n the equipment described about two hours were
required to complete the SOs addition. I t is desir-
4o 5O 6O 70 80 90 able to c a r r y out the reaction in a m i n i m u m of time
TEMPERATURE °G
followed b y immediate neutralization of the su]fonic
Fro. 3 acid. W h e n the time of contact with SOs was appre-
ciably extended, the color of the finished sulfonate
was dark.
tionship of sulfonic acid viscosity and sulfonate color I n an effort to improve color further, a n u m b e r
to sulfonation temperature. I t can be seen that the of runs were made in which 97% sulfuric acid was
viscosity r a p i d l y decreases with increases in sulfona- added prior to the SOs. This was added in an amount
tion temperature. F r o m a processing Standpoint it equivalent to 9% of the dodecylbenzene charge. The
would be desirable to r u n at as high a t e m p e r a t u r e purpose of this " a c i d h e e l " was to reduce viscosity
as possible. Color of the finished sulfonates b e g a n to d u r i n g sulfonation and thus obtain lighter colored
darken r a p i d l y however as sulfonation t e m p e r a t u r e s sulfonates. This technique resulted in sulfonates of
exceeded 55°C.; therefore, in order to achieve maxi- better color. No reduction of S03 requirement was
m u m quality at the lowest viscosity, a sulfonation realized. Analysis of this product showed the com-
t e m p e r a t u r e of 55°C. was considered optimum. Tem- position to be comparable to that of typical sulfonate
p e r a t u r e had no noticeable effect on degree of sul- prepared, using sulfuric acid for sulfonation.
fonation in the range studied. Sulfonate colors were F i g u r e 5 shows the relationship of the degree of
obtained with a Klett-Summerson photoelectric col- the sulfonation and of sulfonate color to the SO s in-
202 THE JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VOL. 31
I I I r about 175 B.t.u. per pound (1, 2)]. The high viscos-
SO s SULFONATION
ity of the sulfonation mass resulted in low heat trans-
MAXIMUM TEMF~ 55°C fer to the cooling medium in the kettle jacket. There
DRY ICE COOLING
is also present a smaller volume of reaction mixture
Oc125
0
~o AGID HEEL (95% AGTIV£t
OlD HEEL ( 87 % AGTWEI / per weight of alkylate when using SOs. The combi-
8100 // nation of these factors results in a requirement for
tu I more efficient heat removal. The use of a Votator
75~-=
heat exchanger as an external heat exchanger on pilot
50
scale batch sulfonation was very successful.
t
o
__.r.-- I
Long time of contact with SOs during sulfonation
25 and low neutralization temperatures result in neu-
tralized slurries which increase in acidity upon stand-
ing. F o r example, a slurry which has been neutral-
J~ ized to the basic side may develop a p H of less than
m4
o 7. The free oil content of such a slurry immediately
2
after neutralization is also higher than that of the
I -------- - - L h -t same slurry after standing. These phenomena are
0 I00 105 I10
believed to be due to the slow breakdown of anhy-
SO3 -- % OF THEORY drides of t h e sulfonic acids present in the neutralized
Fro. 5 mass.
2. The SO~ type of s u l f o n a t i o n requires no a g i n g or diges- This m a y be at least partially offset by reduction in
tion period and no drowning steps to remove spent acid. equipment required f o r spent acid removal.
This simplification results in a significant reduction in 2. The high sulfonic acid Viscosity ~ecessita£es more effi-
the time required to complete the operation. Depending cient heat t r a n s f e r equipment.
upon the p a r t i c u l a r process and equipment used, this 3. The p H d r i f t of the neutralized product f r o m salfona-
reduction can be as great as 60%. tion without an acid heel m i g h t result in the requirement
3. The increased activity and lower salt content resulting of a reneutralization step.
f r o m s t r a i g h t SO~ sulfonation offer an obvious a d v a n t a g e
to the m a n u f a c t u r e r or potential m a n u f a c t u r e r of liquid
formulations. I t has also been reported by some observ-
Acknowledgment
ers t h a t the sulfonate odors are improved as a result of We thankfully acknowledge the cooperation of the
SO~ sulfonation. Color of s u l f o n a t e is equal to t h a t f r o m General Chemical Division of Allied Chemical and
oleum sulfonation.
Dye Corporation for their supporting laboratory data
4. Smaller volume equipment is required f o r a given quan-
tity of alkylate.
on this study.
REFERENCES
5. The use of a h i g h e r s u l f o n a t i o n t e m p e r a t u r e t h a n with
oleum facilitates heat removal. 1. Booklet, "Neolene 400, Intermediate for Synthetic Detergents,"
Continental Oil Company, 1953.
Disadvantages 2. Gilbert, E. E., Veldhuis, B., Carlson, E. J., and Giolito, S. L.,
Ind. Eng. Chem., 45, 2065 (1953) .
1. The equipment required for the vaporization and h a n d l i n g
of SOs is more extensive t h a n t h a t f o r h a n d l i n g oleum. [Received October 28, 1953]
N ].919 Rojahn (1, 2) prepared tables for deter- when the water content varies between 0 and 2.5%
I mining trimethylene glycol in high gravity and
C.P. glycerines based upon the specific gravity
so that the limited range for moisture will not in-
clude C.P. glycerines which contain approximately
and the water content. These tables are useful al- 5% Water. Therefore a procedure was sought which
though it has long been recognized that they are would not require a table and could be applied to
slightly in error (3) due to the lack of sufficiently most of the conditions that are encountered in C.P.
pure material and the shortcomings of the available and high gravity glyeerines.
methods. For this reason and because more exact The procedure which was investigated involved
data were available on the specific gravity of glyc- measuring the specific gravity at 25°/25°C. (8) and
erol (4) and the more accurate Fischer volumetric the water content by the Fischer volumetric method
method for water (5), it seemed appropriate to bring (5). Trimethylene glycol, including similar constit-
this phase of glycerine analysis up to date. uents, is calculated from these measurements and
Analyses of sweet water concentrates have shown the change in specific gravity (0.0023) caused by a
the presence of from 5 to 10% propylene glycol and change of 1% in trimethylene glycol content. The
50 to 60% trimethylene glycol (6). These two com- factor (0.0023) was calculated from data in Lawrie's
pounds have very similar boiling points so that some book (7) and was checked experimentally. The tri-
propylene glycol will no doubt be present in high methylene glycol is calculated as follows:
gravity and C.P. glycerine whenever trimethylene
glycol is present. Refined glycerine usually does A ~ % water by A.O.C.S. Fischer volumetric
not contain a determinable amount of trimethylene method (5)
glycol. Chemical methods like those of Pohle and B ~ s p e c i f i e gravity at 25°/25°C. by A.O.C.S.
Mehlenbacher (6) are satisfactory and generally Method (8)
applicable to samples containing more than 3% pro- C ~ % glycerol from water content ~ 100-A
pylene and trimethylene glycols but cannot be con-
sidered suitable for smaller amounts. In the lower D ~ specific gravity at 25e/25°C. of a glycerol-
range the specific gravity and water methods must water solution with a glycerol content of C.
be employed. Trimethylene glycol, % ~ (D-B)/0.0023~-E
The glycerol content of C.P. and high gravity
glycerines can be determined most accurately by the Glycerol, %~-100-- (A~-E)
specific gravity method (2) and somewhat less accu-
rately from the water content determined by the TABLE I
Fischer volumetric method (5). When the sample con- Properties and Oompositlon of Compounds Used in Preparing
tains only water and glycerol, 100 -- % water equals Known Mixtures
the glycerol, and these results agree with the glycerol Trimeth- Pro-
found by the specific gravity method. When the sam- Compound
Sp. gr. Water, ylene pylene Glyc-
25°/25° % g l y c o l , glycol, erol,
ple also contains trimethylene glycol, the percentage c. % % %
of glycerol found by the two methods does not agree, 3. P. glycerin a.................... ! 1.2492 4.9 0.0 0.0 95.0
and the exact glycerol content is uncertain. Lawrie High gravity glycerine
(3) gives a table for determining trimethylene glycol (containing trimethyl-
ene glycol) b...................... 1.2583 0.5 1.1 98.4
in high gravity glycerine from the specific gravity Primothyleme glycol (6) ...... 1.0533
Prc)pylene glycol (6) ............ 1.0377,
0.0
0.0
100.0
0.0
013
100.2
0.0
0.0
and water content of the sample. However it covers a GIycerol from specific gravity measurements.
only the range of 0 to 3.0% trimethylene glycol bTrime$hylene glycol and glycerol from method described above.