Oct. 31, 1967 R. J.

BROOKS ETAL 3,350,428

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62 SULFONIC INVENTORS
RICHARD J. BROOKS
BURON BROOKS

BY 4%22zz a 4-2-
ATTORNEYS
 United States Patent Office 3,350,428
Patented Oct. 31, 1967
2
3,350,428 the batch system, wherein a heel of sulfuric acid is added
CONTINUOUS SULFONATION PROCESS to lower the viscosity of the organic reactant, after which
Richard J. Brooks and Burton Brooks, Seattle, Wash., the Sulfur trioxide, mixed with air in a concentration of
assignorsa corporation
Wash., to The Chenithon Corporation, Seattle, about
of Washington 5%, is introduced. The difficulty with this system
Filed Oct. 31, 1963, Ser. No. 320,301 is that the heel of sulfuric acid, to a great extent, over
16 Claims. (CI. 260-400) comes the advantage of the sulfur trioxide process, name
ly, obtaining a substantially salt-free product.
This application is a continuation-in-part of applica batch Other disadvantages encountered when employing a
tion Ser. No. 244,096, filed Dec. 12, 1962, and now U.S. System for producing organic sulfonates are the
Patent No. 3,259,645. 10 inherent difficulties in agitation and/or temperature con
This invention relates to a process for the sulfonation the trol. Many attempts have heretofore been made to modify
of Organic reactants, and relates more particularly to an Thus,batch system to overcome the deficiencies thereof.
for example, one method formerly employed was
improved process for the rapid and continuous sulfona to
tion of alkyl aryl hydrocarbons, fatty alcohols, eth 5 cause a tank containing a sulfonation reaction mix
Oxylated alkyl phenols and other sulfonatable organic ture to overflow into a series of tanks in order to provide
compounds. a semi-continuous sulfonation process. The results, how
The term "Sulfonating,' as employed hereinafter in the yield ever, were not entirely Satisfactory in that the quality and
Specification and in the claims, is used sometimes in its of the product varied, and/or a product of good
generic Sense as applying both to true sulfonating and 20 color characteristics was not obtained.
to Sulfating, and sometimes in its specific sense, that is, notThus, prior to the instant invention, it generally has
been considered commercially practicable to develop
to true Sulfonating. Where the context in which the term
'Sulfonating' is used does not require the specific sense, degree a fully continuous sulfonation process wherein a high
it is to be construed generically. tained. of purity as well as optimum yields could be ob
Organic Sulfonic acids and organic sulfonates are be 25 It is therefore the principal object of this invention to
coming increasingly important due to their use in the
preparation of liquid detergents, particularly in the prep provide a continuous process for the Sulfonation of or
aration of relatively salt-free detergents having good ganicprior
reactants which is free from the disadvantages of
solubility characteristics. Normally, the sulfonated de theAnother processes.
object of the present invention is to provide
tergents are prepared by sulfonation processes employing 30 an extensively
concentrated Sulfuric acid or oleum. In such processes, Sulfonation of rapid and fully continuous process for the
alkyl aryl hydrocarbons, fatty alcohols
the reaction mixture contains a residue of sulfuric acid
and water as a byproduct. Unless special techniques are andA other sulfonatable organic materials.
further object of the present invention is to provide
followed, the separation of the desired reaction product
from the final reaction mixture is extremely difficult. 35 ganic a fully continuous sulfonation process in which the or
Moreover, due to the presence of the residual sulfuric reactants may be continuously fed and the resultant
acid in the final reaction mixture, when neutralizing the temperaturesreaction products continuously withdrawn at controlled
and pressures.
So-formed sulfonated product with, for example, Sodium Still another object of the present invention is to pro
hydroxide, the residual acid is neutralized along with the
sulfonated product, the residual acid forming sodium 40 vide isployed.
a fully continuous sulfonation process in which there
very little hold-up time in the processing equipment en
sulfate. While the use of sodium sulfate is desirable for
some purposes, its use is definitely undesirable for other A still further object of the present invention is to
purposes, particularly in processes for the preparation of
salt-free detergents having good solubility characteristics. provide a fully continuous sulfonation process which is
adapted to be carried out in processing equipment that
In
moved.the latter processes, the sodium sulfate must be re is simple to control and requires relatively small plant
Space.
There has developed a great interest in the production An additional object of the present invention is to pro
of salt-free detergents by the use of sulfur trioxide due
to the facts, on the one hand, that the oleum is in short vide a fully continuous sulfonation process wherein a
Supply, and, on the other hand, of the necessity for dis 50 Sulfonated product is prepared which easily can be sep
charging spent acid, both major problems in many of arated from the product mixture obtained.
Yet another object of the present invention is to pro
the countries of the world. Sulfur trioxide in stabilized
form is highly satisfactory as a sulfonating agent, and vide a fully continuous sulfonation process wherein a
it is possible for even the small consumer to buy the substantially salt-free sulfonated product is obtained in
same in small drum quantities for use in the preparation 55 relatively high yield.
of salt-free detergents. A stabilized liquid sulfur trioxide Still an additional object of the present invention is to
having a more than 99 percent available sulfur trioxide provide a fully continuous sulfonation process wherein
content, sold commercially under the trade name "Sulfan,” a Sulfonated product of excellent and uniform quality
is useful in the instant invention. is obtained in commercially attractive yields.
Prior efforts to develop a sulfur trioxide/air sulfona 60 A particular object of the present invention is to pro
tion process, however, were unsatisfactory in that a yel vide a fully continuous sulfonation process wherein a re
low or brown colored detergent was generally obtained. actant mixture cooling technique is employed which re
This discolored product required bleaching in order to Sults in a Sulfonated product being obtained which re
compete with the products obtained by oleum sulfona quires no bleaching and is of good color, odor and purity.
tion, which bleaching step added considerably to the cost 65 The above-mentioned and other objects and advan
of production. Moreover, the resultant bleached product tages of the present invention will become apparent as
was still substantially inferior in both color and quality the invention is more thoroughly discussed hereinafter.
to the Sulfonates produced
employing oleum. -
by the prior art processes Broadly described, the present invention provides a
continuous process for Sulfonating a sulfonatable organic
Gilbert, in U.S. Patent No. 2,723,990, describes one 70 reactant, preferably an organic reactant selected from the
of the prior methods for sulfur trioxide sulfonation by group consisting of compounds having an olefinic linkage,
compounds having an aromatic nucleus, and compounds
 3,350,428 4.
3 stantaneous and not suitably controlled, with the result
having an alcoholic hydroxyl group, wherein said or that the heat of the reaction causes the temperature of
ganic reactant is reacted with sulfur trioxide to provide the reaction products to rise very rapidly, causing deterio
a corresponding sulfonic acid, which comprises intro ration and degradation of the final product as well as
ducing into an externally cooled reaction zone (1) a poor product color. This problem has now been com
stream of said organic reactant and (2) a stream of a pletely overcome in the instant invention.
mixture of sulfur trioxide and an inert diluent, thorough The present invention contemplates the utilization of
ly mixing said organic reactant and said sulfur trioxide any organic reactant which is reactive with sulfur tri
containing mixture in said reaction zone for a time oxide to provide a sulfonated product. The method of
period of at most about 10 seconds to provide a reaction the present invention is particularly applicable to the
mixture in the form of a film having a thickness of at 10 sulfonation of organic compounds which contain an
most about 0.04 inch, preferably in the range of from aromatic nucleus, organic compounds which contain an
about 0.001 to about 0.04 inch, removing said reaction olefinic linkage, and organic compounds which contain
mixture from said reaction zone at the end of said time an alcoholic hydroxyl group, which organic compounds
period, and immediately introducing said reaction mix yield, upon the sulfonation thereof, surface active mate
ture withdrawn from said reaction zone into a cooling rials. Such sulfonatable organic compounds utilized in
Zone to effect a rapid cooling of said reaction mixture the invention include, without limitation, olefins contain
and provide a sulfonic acid-rich mixture. ing from about 8 to about 20 carbon atoms, such as
The invention also contemplates embodiments of the octene, decene, dodecene, tetradecene, hexadecene, octa
above-described process wherein, subsequent to said rapid decene, eicosene, tetradecadiene, and octadecadiene, ole
cooling of said reaction mixture, said sulfonic acid-rich 20 finically unsaturated acids such as oleic acid and linoleic
mixture is withdrawn from said cooling zone, said inert acid; fatty alcohols containing from 8 to about 20 carbon
diluent and unreacted sulfur trioxide is separated there atoms, such as octyl alcohol, decyl alcohol, lauryl al
from, and the resulting mixture is passed to a digestion cohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol,
Zone and maintained therein for an additional time period 25 tallow alcohol, octadecyl alcohol, and eicosyl alcohol;
while being agitated without substantial back-mixing, to ethoxylated derivatives of the above fatty alcohols, such
substantially complete the reaction. as polyoxyethylene ethers of lauryl alcohol and tridecyl
In contrast to the prior art sulfur trioxide/air proc alcohol; ethoxylated derivatives of alkyl phenols wherein
esses which resulted in a yellow or brown colored de the alkyl group contains from about 8 to about 16 carbon
tergent that had to be bleached to compete with the 30 atoms, such as nonylphenyl polyoxyethylene ethers; eth
products produced by oleum sulfonation, it has been un oxylated derivatives of partial esters of polyhydric alco
expectedly found, in accordance with the present inven hols such as polyoxyethylene ethers of lauric acid partial
tion, that a commercially satisfactory, fully continuous esters of sorbitol; and monocyclic and polycyclic aromatic
Sulfonation process can be successfully carried out if hydrocarbons and alkyl substituted derivatives thereof
there is careful control of certain of the process variables 35 wherein the alkyl group contains up to about 20 carbon
during sulfonation. The sulfonation process of this inven atoms, such as benzene, biphenyl, naphthalene, toluene,
tion produces an excellent yield of products which are Xylene, ethylbenzene, propyl benzene, butylbenzene, di
substantially white, thereby requiring no bleaching. butyl benzene, hexyl benzene, octyl benzene, nonyl ben
The conditions which are utilized and controlled in Zene, decyl benzene, dodecyl benzene, tridecyl benzene,
the instant method are the following:
(a) the temperatures of the entering sulfur trioxide/ 40 tetradecyl benzene, hexadecyl benzene, octadecyl benzene,
nonyl toluene, decyl toluene, dodecyl toluene, tetradecyl
inert diluent mixture and the organic reactant; toluene, dodecyl xylene, dodecyl ethyl benzene, dodecyl
(b) the temperature of reaction in the reaction zone; isopropyl benzene, methyl biphenyl, ethyl biphenyl, pro
(c) the removal of mist from the entering sulfur tri pyl biphenyl, butyl biphenyl, dipropyl biphenyl, dibutyl
oxide-containing gas; biphenyl, hexyl biphenyl, octyl biphenyl, decyl biphenyl,
(d) the concentration of the sulfur trioxide/inert dil 45 tetradecyl biphenyl, octadecyl biphenyl, dodecyl methyl
luent(e)mixture; biphenyl, isopropyl tetradecyl biphenyl, methyl naphthal
the thorough agitation and mixing of the reactant ene, ethylnaphthalene, isopropylnaphthalene, butyl naph
streams in the reaction zone; thalene,
(f). the thickness of the film of the reaction mixture hexyl naphthalene, diisopropyl naphthalene, dibutyl naphthalene,
octyl naphthalene, decyl naphthalene,
50 tetradecyl naphthalene, octadecyl naphthalene, dodecyl
in (g)
the the
reaction zone;
maintenance and reaction time in the reaction methyl naphthalene, ethyl tetradecyl naphthalene, and
Zone;
(h) the velocity of the sulfur trioxide/inert diluent theAslike. the organic reactant, the invention also contem
mixture in the reaction zone;
(i) the immediate and rapid cooling of the reaction which the
55 plates utilization of sulfonatable organic compounds
mixture leaving the reaction zone in the cooling zone; themselves or precursors thereof have been sub
(j) the separation of unreacted sulfur trioxide from jected to a preliminary sulfonation treatment whereby
the reaction mixture after cooling same and preliminary double or polysulfonated products are produced.
The alkyl benzenes which are preferred for utilization
to the digestion thereof; and
(k) the digestion of the reaction mixture after leaving 60 inin thethe
practice of the present invention are well known
art and can be conveniently represented by the
the cooling zone and separation of unreacted sulfur tri
oxide therefrom, the digestion being carried out while formula
employing thorough agitation and substantially without
allowing back mixing.
It has unexpectedly been found that with the use of the 65
{D-R
present method wherein thorough and vigorous mixing wherein chain,
R is an alkyl radical, either straight or branched
containing at least 8 carbon atoms, and preferably
of the reactant streams is effected under controlled tem from 8 to 20 carbon atoms. Such alkyl benzenes and
perature conditions and the resultant reaction mixture their preparation are disclosed in a large number of U.S.
immediately thereafter is subjected to the described rapid patents, illustrative of which are U.S. Patents Nos. 1,992,-
cooling, the problem of controlling both the viscosity of 70 160; 2,161,173; 2,210,902; 2,218,472; 2,223,364; 2,220
sulfonic acids as well as the extremely reactive nature of 099; and 2,597,834.
sulfur trioxide which has plagued prior art sulfonation Sulfur trioxide used in the present invention suitably
processes is alleviated. In prior art processes, when sulfur may be made in various ways, such as, for example, by
trioxide is injected into a once-through reaction stage, 5 carefully metering and burning sulfur and catalytically
the exothermic reaction with the organic reactant is in
 5 3,350,428
oxidizing the resultant sulfur dioxide to sulfur trioxide, 6
and thereafter feeding the resultant sulfur trioxide/air actor. This mist can be formed by small traces of moisture
mixture directly to the organic reactant to sulfonate the present in the inert diluent which react with the sulfur
later. Furthermore, a side stream of converter gas from trioxide upon the mixing thereof to form sulfuric acid
a sulfuric acid manufacturing plant may be metered and driplets if the mixture is allowed to cool to too low a
utilized as the sulfonating agent for the organic reactant. temperature. In the instant process, any mist present pref
Also, SO3 can be prepared by stripping the SO3 gas from erably is removed from the sulfur trioxide/inert diluent
concentrated oleum. In accordance with the instant inven stream prior to its introduction into the reactor.
tion, the sulfur trioxide for use in the process of this in Another feature of this invention which has been
vention is preferably first diluted with inert gas such as 10 found to give a more completely pure sulfonated product
air, nitrogen, carbon dioxide, etc. is the introduction of the reactants into the process at as
In accordance with the instant invention, the sulfur low a temperature as possible consistent with obtaining
trioxide enters the system under pressure in a controlled adequate mixing, since the lower the temperature of the
stream of inert diluent which gives it added velocity, and reaction the better the quality of the final product. In
at the same time the concentration of the entering sulfur order to maintain optimum conditions throughout each
trioxide is also controlled, preferably from about 2% stage of the process, the reaction between the sulfur tri
to about 8% by volume. The pressure at which the re oxide and the reactants should take place at as low a
actants enter the system is also of importance because temperature as possible until the viscosity of the reactants
as the back pressure of the entering reactants increases, starts to rise to a high value. When this increased vis
the reactivity of the sulfur trioxide gas also increases. 20 the cosity occurs, the temperature is permitted to rise, keeping
However, in the present invention a relatively low pres viscosity at a fairly constant value.
sure is required for passage of the sulfur trioxide/inert With regard to the actual feed temperatures of the
diluent mixture through the system. The sulfur trioxide/ organic reactants used in the process of the instant inven
inert diluent stream generally enters the system under a tion, it is preferred to first mix the organic reactant with
pressure ranging up to about 75 p.s.i.g., preferably from 25 air and thereafter pass the resulting mixture through a
10 to about 15 p.s.i.g. It has been found that pressures heat exchanger wherein it is cooled or heated to the lowest
above 75 p.s.i.g. are increasingly harmful to the final practical temperature consistent with its being in liquid
product quality. Also, the velocity of the sulfur trioxide/ form. Accordingly, when an alkyl benzene is employed
inert
second. diluent stream should be at least about 75 feet per as the reactant, i.e., the material to be sulfonated, the
30 temperature of the material added to the reaction zone
The amount of sulfur trioxide employed is also an im may be as low as 0 F. Other aromatics and aromatic
portant factor in the present invention, particularly with containing compounds, such as benzene, toluene, xylene,
regard to the specific classes of materials which can be and the like, may be precooled to temperatures similar
sulfonated. For example, when substituted aromatics are to that employed for alkyl benzene, if desired. When
employed, e.g., dodecyl benzene, as the material to be using a fatty alcohol as the organic ractant, such as, for
sulfonated, generally an excess, preferably 8 to 10 mole example, lauryl alcohol, which is solid at room temper
percent excess, of sulfur trioxide is employed. However, ature, it must be heated to a temperature of about 85 F.
when utilizing tridecyl benzene, which does not sulfonate whereby the reactant will be melted. Tallow alcohol,
as completely or as readily as dodecyl benzene, a Some when employed, may have to be heated somewhat higher,
what greater mole excess preferably is used, e.g., a 10 to 40 for example, up to a temperature of about 125 F. Fur
15 mole percent excess. A fatty alcohol, when used as thermore, when a non-ionic, which is liquid at room
the organic reactant, degrades quite easily when side re temperature but very viscous, is employed, it has to be
actions take place; accordingly, it is preferred to utilize warmed somewhat, for example, up to a temperature of
from about a 15% mole deficiency to about a 6 mole 90 F., and maintained at a constant temperature so that
percent excess of sulfur trioxide. When it is metered to the reaction zone through a rotam
Xylene and toluene present a different problem, for 45 eter, the metering is always accurate. In the process of
these materials form sulfones and the larger the excess this invention, it was found useful to use a temperature
of sulfur trioxide used, the more sulfone formation takes controlled storage tank for each of the organic reactants
place. In order to avoid sulfone formation, it is essential so that they will always be fed to the reaction zone at
that the sulfonation take place with a deficiency of sulfur 50 a constant temperature.
trioxide, e.g., about 60% sulfur trioxide based on the One of the major problems present in the prior art
moles of hydrocarbon feed. The unreacted xylene and sulfonation processes has been the inability to control
toluene may be extracted and recycled back through the
proceSS.
the viscosity of the products at various stages of reaction,
with the result that poor product color and low purity
Non-ionics such as nonyl phenol present another prob were always evidenced in the final product due to the
lem when they are being sulfonated. Thus, it is possible 55 inability to adequately mix the sulfur trioxide with the
to sulfate or sulfonate a non-ionic on the ring, but ring product. However, this problem has been obviated in the
sulfonates are not desirable as detergents. Therefore, in instant process by employing adequately high temper
accordance with the instant invention, ring Sulfonation is atures to control viscosity during the introduction of the
to be avoided. Accordingly, with non-ionics the mole 60 reaction mixture into the reaction zone, coupled with
sexcess of sulfur trioxide employed should be between 0 thorough and vigorous agitation therein and thereafter
and
OC.
about 6 percent, depending upon the particular non instantly cooling the reaction mixture. The viscosity of
the product-reactant mixtures in the process of this in
In accordance with the method of the present inven vention is reduced at the higher temperatures, and mixing
tion, the sulfur trioxide/inert diluent mixture is intro 65 is more efficient when the reactants come in contact with
duced into the reaction zone at a temperature which the sulfur trioxide. Thus, the problem of controlling the
generally is somewhat lower than the average temperature viscosity of the reactants is directly related to the tem
of the reaction mixture in the reaction Zone. In the pre perature at each stage of reaction, which temperature, in
ferred embodiments of the invention, the temperature of turn, is based upon the quantity of fresh reactants used
the sulfur trioxide/inert diluent mixture is in the range 70 in the reaction and the temperature at which the re
of from about 90 to about 120 F. actants enter the reaction Zone. Generally speaking, it is
Another factor that has caused poor product color in desirable to sulfonate at as low a temperature as possible,
previous sulfonation processes has been the presence of consistent with keeping the viscosity low enough to get
sulfuric acid and/or sulfur trioxide mist in the gaseous extremely good mixing. Different materials have different
sulfur trioxide sulfonating agent when it enters the re 75 viscosities as the reaction progresses, and require different
operating temperatures. Fatty alcohols, for example,
 3,350,428 8
7 containing an alcoholic hydroxyl group such as a fatty
lauryl and tallow, when sulfated have little viscosity in alcohol containing from about 8 to about 20 carbon
crease as the reaction progresses, and the initial reaction atoms, e.g., lauryl alcohol and tallow alcohol, it has been
temperature is about the same as the final temperature. found that the temperature in the reaction zone must be
Alkyl benzene, on the other hand, can be introduced at maintained within the range of from about 85 F. to
much lower temperatures due to its low melting point, about 145 F., with the temperature being at most about
but its viscosity rises excessively as the reaction pro 135 F. after the reaction of the sulfonatable material
gresses, and thus the temperature must be allowed to rise is about 60% complete for optimum results to be ob
in the final stages of reaction. tained. For the sulfonation of an ethoxylated alkyl phenol,
It has been well known that in the prior art sulfonation 10
optimum results are obtained when the temperature in
processes complete reaction of the reactants has been the reaction zone is in the range of from about 90 to
practically impossible. The reason for this is that as the about 180° F., and above about 120 F. after the reac
reaction progresses the viscosity of many reactants in tion is about 60% complete. In the case of other aroma
creases which, in turn, causes poor mixing unless other tic organic reactants and organic reactants having an
conditions in the process are changed. Accordingly, prior olefinic linkage which yield surface active agents upon
to the instant invention, no method of successfully con 15 the sulfonation thereof, the optimum conditions involve
trolling the viscosity of reactants in a single mixing stage the utilization of reaction zone temperatures in the range
by controlling the temperature of same during sulfonation of from about 80° F. to about 200 F., with the tem
was known. The instant process, by the use of controlled perature being at least about 120 F. after 60% of the
addition of organic reactant and sulfur trioxide, thorough 20 reaction has been completed.
and vigorous agitation of the resulting reaction mixture In accordance with the present method any suitable
in the form of a thin film, and immediate cooling after means may be satisfactorily employed to effect the
the mixing thereof, has successfully given the answer to thorough and vigorous mixing of the streams of organic
viscosity control of the reactants in order to produce reactant and sulfur trioxide/inert diluent mixture and
sulfonated products of superior quality. form the film of the resultant thoroughly mixed reac
While the aforementioned features of the present in 25 tion mixture in the reaction zone. It has been found
vention are extremely essential, the most important aspect that it is important that the reaction zone be externally
of this invention is to have the temperature of the reac cooled and that the reaction mixture film be contacting
tants sufficienly high for a very short period of time the cooled walls of the reaction zone to dissipate the heat
prior to the rapid cooling step so that excellent mixing 30 of reaction and preclude the temperature of the reaction
can take place due to the lowered viscosity of the reac products thereby formed from rising too rapidly and
tants. As a result of careful study, it has been found uncontrollably which would result in a final product of
that the viscosity characteristics of the material to be inferior quality and color. It is preferred that the reac
sulfonated are extremely important, and a determination tion Zone be externally cooled in such a manner that a
of each material's optimum temperature is essential to 35 temperature gradient exists over the length of the reac
obtain superior mixing conditions. It has been found tion Zone. Specific examples of such suitable means con
generally that higher temperatures usually result in poor templated to be utilized in the present invention as the
sulfonation products; therefore, it is most desirable to mixer-reactor include the rotating blade-type mixers
effect the sulfonation at as low a temperature as possible. exemplified by that disclosed in applicants' co-pending
For example, in the prior art a maximum temperature 40 application Ser. No. 244,096, and the turboannular flow
of around 120 F. to 130 F. is normally specified for type mixers exemplified by that disclosed in U.S. Patent
the sulfonation of alkyl benzene having from 8 to 20 No. 2,923,728. With certain of the mixer-reactors utilized
carbon atoms in the side chain. When operating at this in embodiments of the present method, such as the turbo
temperature, the sulfonate formed is extremely viscous annular flow-type reactors, an inert gas of the type which
and the known methods of agitation are entirely in 45 is present in the sulfur trioxide feed stream also may be
adequate to obtain high product quality with this high used as a driving and carrying expedient for the or
viscosity material. In contradistincion to the known meth ganic material feed stream. As stated above, the thick
ods employed in the prior art, the instant process, when ness of the film of the reaction mixture in the reaction
using alkyl benzenes as reactants, requires that the react Zone contemplated for utilization in the present method
ants be introduced into the reaction zone at a temperature is at most about 0.04 inch, and preferably from about
which is relatively low but sufficiently high to provide 50 0.001 to about 0.01 inch.
inorganic reactant having a viscosity which allows it to The residence time of the reaction mixture in the reac
be mixed, that the temperature be allowed to rise to a tor Suitably may be in the range of from about 0.1 sec
maximum of as high as 200 F., preferably between Ond to about 10 seconds, and preferably from about 0.4
140 and 170 F., during the few seconds that the ma Second to about 2 seconds. Extensive tests have disclosed
terial is in the reactor, and that the reaction mixture that if the reaction mixture is in the reactor for a longer
thereby formed then immediately be cooled. For ex period of time or for the same period of time without
ample, such an alkyl benzene can be introduced at am being cooled immediately at the end of this time period,
bient temperatures and the temperature will rise to product degradation takes place. The residence time of
around 150 to 170 F. during the few seconds that the 60 the main gas stream in the reactor is much less than that
reactant is in the reaction zone prior to cooling. By al of the liquid reaction mixture. The actual Superficial gas
lowing the temperature to increase in this manner and Velocity of the sulfur trioxide/inert diluent mixture em
then immediately cooling the reaction mixture, it sur ployed may vary depending primarily upon the type of
prisingly has been found that when an alkyl benzene is mixer-reactor being utilized. For example, when mixer
employed as the sulfonatable material there is a very 65 reactors of the rotating blade-type are employed, the
rapid decrease in viscosity when the temperature reaches reactant feed gas velocity preferably is at least about 75
130 to 140 F. and higher. Then, after vigorous mixing feet per second, and more preferably in the range of from
for a second or two at this high temperature, i.e., above about 75 to about 300 feet per second. This gives the main
140 F., the material is immediately cooled to a tem feed gas stream a residence time of only about 0.01 to
perature of about 120 F. It has been found that for
optimum results to be achieved the temperature of the 70about 0.05 second in the reactor. In embodiments wherein
a turboannular flow-type reactor is employed the Super
reaction must be controlled to be above about 120° F. ficial gas velocity of the reactant gas stream preferably
after the reaction of such a sulfonatable material is about is within this same range. -
60% complete. Little degradation is found in the re Another outstanding feature of the instant invention is
Sulting
Withproduct.
respect to the sulfonation of an organic reactant 75 the (discovery that the reactant, i.e., sulfonatable material,
 9 3,350,428
should enter the system with a relatively high velocity in 10
a stream of gas diluent so that none of the sulfur trioxide is characterized by a sufficiently large cooling surface to
will diffuse into the entering stream of reactant, where it effect the requisite cooling of the reaction mixture. When
would be apt to react in a zone where there is not a water-cooled heat exchangers are employed for this pur
high degree of mixing. Thus, the sulfonatable reactant water pose, itnotisbepreferred that the temperature of the cooling
less than about 35 F.
preferably is passed into the reaction zone with an inert
gas stream. The inert gas employed for such a purpose The residence time of the reaction mixture in the cool
suitably may be the same or different from the inert ing Zone in accordance with the present invention usually,
diluent used in the sulfur trioxide/inert diluent feed and preferably, is only on the order of magnitude of
stream. Specific examples of such gases are air, nitrogen, O Several Seconds. In preferred embodiments of the present
carbon dioxide, and the like. invention, the reaction mixture then is immediately with
The invention contemplates embodiments wherein the drawn from the cooling zone and passed to a separation
Sulfur trioxide/inert diluent mixture flows into the reac Zone
reactedto sulfur
effect trioxide.
the removal of the inert diluent and un
tion zone through a single or a plurality of inlet points
leading directly to the reactor. The sulfur trioxide inlet The separation of the inert diluent and unreacted sulfur
points are adapted to control the amount of sulfonating 5 trioxide present from the mixture recovered from the
agent added to the mixture. Uniform concentration is cooling Zone suitably may be carried out by any expedient
necessary to reduce localized overheating at the point of means known to the art for rapidly separating gases from
injection, and ease the problem of mixing the reactants. liquids, such as those involving centrifuging and the like
techniques.
In accordance with the method of the present inven 20
tion, at the end of the above-described mixing period of In embodiments of the invention wherein the organic
said reaction mixture in said reaction zone, all of the reactant is free of alcoholic hydroxyl groups a liquid
resultant materials are removed from the reaction zone stream rich in Sulfonic acid then is removed from the gas
and the materials recovered from the reaction zone im separation Zone and at least a portion thereof is passed
mediately are rapidly cooled, i.e., within a matter of sec 25 directly to a digestion Zone wherein it advantageously is
onds, in a cooling zone to prevent degradation of sulfona maintained while being mixed for a time period so that
tion products present. The rapid cooling may be carried additional reaction of ingredients in the resultant sulfur
out by any suitable manner, such as by immediately trioxide-free mixture may take place. As described below,
passing the materials into and drowning same with mix while all of the liquid stream removed from the gas
ing in a relatively cool mass of sulfonic acid correspond 30 separation Zone suitably may be passed to the digestion
ing to that present in the reaction mixture, whereby the Zone, the invention contemplates embodiments wherein a
reaction mixture is contacted and quench cooled thereby, quench cooling technique is employed in the above de
or by immediately passing the reaction mixture rapidly Scribed cooling step wherein a portion thereof is suitably
through a heat exchanger wherein it contacts a large cooled and then recycled as at least a portion of the sui.
cooling surface which effects a rapid reduction in the 35 fonic acid coolant liquid mass introduced into the quench
temperature of the mixture. Preferably, the rapid cooling cooling
ture Zone to thereinto.
introduced contact and cool additional reaction mix
is carried out by means of a quench cooling technique.
The actual temperature to which the reaction mixture The sulfonic acid-containing liquid obtained from the
from the reaction zone must be cooled in the cooling gas separation Zone is maintained with cooling in the
zone in a particular case is that requisite to prevent 40 digester at a temperature sufficiently low to preclude de
product degradation from occurring and, hence, varies gradation of the acid product. The maximum tempera
depending upon, inter alia, the particular organic reactant ture usually employed is about 135 F. The preferred
employed, the amount of sulfonating agent employed, the digestion temperature is between about 100° and 125 F.
reaction zone exit temperature of the reaction mixture, The effect of digestion is to lower the inorganic salt con
and the residence time of the reaction mixture in the tent of the neutralized product as well as to reduce the
reaction zone. Usually the reaction mixture is cooled to free oil content. The reactions which take place during
a temperature of below about 130 F. and preferably in the digestion of the sulfonic acid-containing mixture are
the range of from about 100 to about 125 F. relatively complex, but, briefly, there is involved the re
In preferred embodiments of the method, wherein the action of Sulfonic anyhdrides which are formed during sul
cooling step is carried out utilizing a quenching bath in fonation with some of the unreacted hydrocarbon. if left
the cooling zone, the temperature and relative amount 50 undigested, Subsequent water addition to the anhydride
of sulfonic acid coolant employed in the quench cooling containing material breaks down the anhydride to form
zone is such that a sufficient mass thereof is present an organic Sulfonic acid and sulfuric acid, the latter of
whereby the reaction mixture is drowned when contacted which forms undesirable sodium sulfate upon neutraliza
therewith to effect substantially instantaneously, i.e., 55 tion of the product mixture. About 92 to 96% of the
within a matter of seconds, the requisite cooling of the reaction takes place in the mixer-reactor and about 1 to
reaction mixture. In accordance with the more preferred 4% takes place in the product cooler before the sulfur
embodiments of the present invention the sulfonic acid trioxide gas is separated. The final 0.5 to 1.5% of the
cooling mass has a temperature of from about 2 to reaction takes place in the digester. The majority of the
about 15 F. lower than that to which the reaction mix 60 anhydride breaks down immediately in the cooling tank,
ture is desired to be cooled thereby. The relative amount and the rest at a reduced rate in the digester. If a diges
of sulfonic acid employed to effect the desired cooling at tion temperature of about 135 F. is employed there will
such temperatures usually is such as to provide a weight be a somewhat lower sulfate and free oil content in the
ratio of said cooling mass to said reaction mixture in the final product, but the product color will also be inferior.
range of from about 4:1 to about 50:1. The optimum degree of digestion, or the length of time
Any suitable expedient means can be utilized to effect 65 necessary for complete digestion, is determined on the
the quench cooling of the reaction mixture in the cooling basis of the characteristics of each material to be sul
zone. For example, either or both of the reaction mixture fonated. In preferred embodiments of the invention, par
and the sulfonic acid cooling mass may be introduced into ticularly when an alkyl benzene is employed as the or
the cooling zone as a spray to effect the requisite mixing 70 ganic reactant, the digestion time is below about 30 min
of the two streams. The reaction mass also suitably may utes, usually from about 1 to about 30 minutes.
be introduced as a jetted stream into a swirling mass or
film of the sulfonic acid. The reaction in the digester is effected much more rap
In embodiments of the invention wherein the cooling idly if vigorous mixing is employed. The reason for this is
step is carried out in a heat exchanger, the heat exchanger 75 that diffusion of the viscous sulfonic acid solution is ex
tremely slow and thereby controls the rate of reaction.
 3,350,428 2
11 In certain embodiments of the present invention where
When the fusion is aided by agitation the rate at which in a fatty alcohol is employed as the organic reactant, it
the reaction takes place increases considerably. also is advantageous to recycle a portion of the sulfated
It is also important that during digestion the portion product obtained in the process from the gas separation
of digested material leaving the digester is not mixed Zone and/or the digestion Zone if digestion is employed,
back with the undigested material entering same, which to the reaction Zone wherein it is introduced with addi
back-mixing undesirably would reduce significantly the tional organic alcohol reactant.
reaction rate attained in the digester. The Sulfonated product obtained in the digestion step
The addition of amounts, usually ranging up to or, in some embodiments wherein the organic reactant
amounts which are approximately equivalent to the an contains an alcoholic hydroxy group, the product ob
hydride content of the reaction mixture, e.g., from about 10 tained from the gas separation zone then may be passed
1 to about 2% by weight based on the originally entering to a neutralization zone wherein it is reacted with a
organic reactant, of a sulfonatable reactant including, requisite amount of an alkali such as an aqueous solution
without limitation, alcohols such as fatty alcohols, as well of sodium hydroxide in accordance with conventional
as benzene, toluene or xylene, in the last stage of the neutralization techniques to provide the corresponding
digestion step will further cut down the inorganic salt 5 Sulfonate salt in the form of a substantially completely
content of the final product by their reaction with the
anhydrides to form corresponding organic sulfates and/or sulfonated While theproduct.
above discussion generally has been limited
sulfonates. Moreover, in order to completely break down to a description of a process wherein only a single mixer
all of the remaining anhydrides, a final water addition 20 reactor is employed as the reaction zone it will be under
may be employed. stood that the invention contemplates embodiments
In embodiments of the present invention wherein the wherein a plurality of mixer-reactors are connected in
organic reactant contains an alcoholic hydroxyl group, a parallel and are adapted to discharge the reaction mix
liquid stream containing an organic sulfuric acid is re tures formed therein into a common cooling zone and/or
covered from the gas separation Zone, the digestion step digestion zone.
usually preferably is bypassed, and the liquid stream im A more detailed description of an embodiment of the
mediately is neutralized. However, if it is entered into the process of the present invention will be given with refer
digester, the period of time it remains therein generally ence to the accompanying drawing which diagrammati
should be relatively short. cally represents a flow sheet of the instant method.
An instance wherein it is desirable to digest sulfuric 30 With reference to the drawing, a continuous stream of
acid products obtained in accordance with the present in inert diluent (e.g., air, nitrogen, etc.) entering the system
vention is when a fatty alcohol is employed, preferably through pipe 10 flows through a compressor 11 wherein
one having from about 8 to about 20 carbon atoms, as the inert diluent is compressed to the desired pressure.
the organic reactant, and the digestion of the resultant Thereafter, the compressed inert diluent flows to a cooler
sulfate-containing mixture is carried out by combining 35 12. The compressed, cooled inert diluent then flows into
and mixing same in the digestion zone with a sulfonated a moisture trap 13 wherein excess water is removed, there
alkyl benzene prepared in accordance with the invention after to an oil filter 14 to remove other impurities, espe
in a reaction zone connected parallel to the reaction Zone cially free oil and dust, next to a dryer 15 whereby the
in which the alcohol sulfation is conducted. As stated compressed inert diluent is dried prior to passage into
above, fatty alcohols tend to rapidly degrade in color 40 the sulfonation zone. The inert diluent leaving dryer 15
when an excess of the sulfur trioxide is utilized to effect is split into two streams, one of which goes through a
complete sulfation thereof. By completing the sulfation rotameter 16 and then to a sulfur trioxide vaporizer 17.
of the fatty alcohol in said embodiments of the inven The other of said streams goes through a rotameter 8
tion in the presence of the sulfonated alkyl benzene which and thereafter is mixed with the incoming organic re
contains sulfonic acid anhydrides, a final product having actant material entering through pipe 25. The major por
both good color and a low level of unreacted oil is 45 tion of the inert diluent entering through pipe 10 goes
obtained. through a rotameter 19 and to the vaporized sulfur triox
To accomplish such results in such embodiments of the ide/inert diluent stream 20 in order to further dilute the
invention, the sulfation of the fatty alcohol is carried out Sulfur trioxide to the proper value, prior to its entry into
using a mole ratio of sulfur trioxide to alcohol of about 50 apipe reactor 24. Sulfur trioxide entering the system through
21 is introduced into a proportioning pump 22 and
0.85:1 to about 1:1, and the sulfonation of the alkyl
benzene is conducted utilizing an excess of Sulfur trioxide, passes to a vaporizer 17 wherein inert diluent is intro
preferably in an amount corresponding to a mole ratio duced as heretofore described, thereafter is fed under
pressure into the stream 20 for further dilution, and then
of sulfur trioxide to alkyl benzene of from about 1.05:1
to about 1.15:1. The two reaction streams are each sep 55 through a mist eliminator 23 before entering reactor 24.
arately and rapidly cooled, then either separately or in The organic reactant is introduced into a proportioning
combination separated from excess sulfur trioxide and pump 26 wherein it is mixed with inert diluent entering
thereafter digested with agitation in combination in the through pipe 27. The organic reactant/inert diluent mix
digestion zone in a manner which prevents back-mixing. ture passes through a cooler 28, under pressure, to reactor
The digestion of the mixed streams generally varies from 60 24. For the purpose of effecting further cooling, i.e., to
about 1 to about 30 minutes. The actual digestion time remove a portion of the heat of reaction, reactor 24 is
employed depends upon, inter alia, the amount of sul provided with a Water jacket 29. The sulfur trioxide/inert
fur trioxide used in each reaction, the digestion tempera diluent mixture enters reactor 24 through multiple inlets
ture, and the nature of the particular organic reactants. 30 and 31, and the two mixtures are subjected to thorough
When lower relative amounts of sulfur trioxide are em 65 and vigorous mixing to provide a thin film of resultant re
ployed, longer digestion times are utilized; when higher action mixture in contact with the walls of reactor 24. The
amounts of sulfur trioxide are used, the reverse is true reaction mixture is allowed to remain in reactor 24 for no
in order to attain completion of the sulfation. The diges longer than about 10 seconds and the entire reaction
tion temperature suitably may vary from about 110 to mixture in mixer 24 then immediately is passed to a
135 F., depending upon the alcohol employed, and the 70 quench cooler 36 and is instantaneously drowned in a
mixing ratio of alcohol to alkyl benzene. In the digest large mass of sulfonic acid present therein which is cooled
tion step, unreacted fatty alcohol reacts with anhydride by coils 37. Additional cooling is effected, if desired, by
formed in the alkyl benzene sulfonation. Usually, the recycling sulfonic acid coolant through a cooler 39.
fatty alcohol and alkyl benzene reaction mixtures are Thereafter, the recycled sulfonic acid is passed by pump
mixed for digestion in approximately equal mole propor 40 back into cooler 36. The time during which the reac
tions but any mixing ratio Suitably may be employed. 75
 13
3,350,428
tion mixture is in cooler 36 is extremely short, that is, on 14
the order of a few seconds. The mixture of cooled Sul little excess SO3, obtained from the reactor has a tempera
fonic acid and air is recovered from cooler 36 and is ture of about 160 F. and is immediately cooled in a
introduced into a centrifugal separator 41 whereby waste quench cooling tank containing cool sulfonic acid corre
air containing a small portion of sulfur trioxide is re sponding to that in the reaction mixture in an amount
moved through outlet 42. The sulfonic acid exits from the corresponding to provide a weight ratio of said sulfonic
bottom of separator 43 through pipe 43', and at least a acid to said reaction mixture of about 10:1. The initial
portion thereof enters a digester 44 wherein it passes temperature in the tank of the Sulfonic acid coolant is
through a series of compartments, to minimize backmix 120 F. and the entering reaction mixture is immediately
ing, at temperatures below 135 F. for a period of up to 10 mixed into this large mass of acid coolant and is diluted
30 minutes. and cooled to 120 F. almost instantaneously. A mixture
If desired, the sulfonic acid stream coming from sepa of air (with some SOs remaining in it) and sulfonic acid
rator 41 may be split into two or three streams. A stream is removed from this tank and passed to an air separator,
may be split off and recycled through pipe 62 back to where the air/sulfur trioxide mixture is removed and
reactor 24, another stream may be split off and recycled passed to waste, and the sulfur trioxide-free sulfonic acid
through pipes 62 and 100 and cooler 39 to quench cooler dropped out to the bottom. The separated sulfonic acid is
36, and one stream is passed to digester 44 by means of then digested in a violently agitated mixer with multiple
pipe 60. Digester 44 is cooled during the mixing stages compartments for 12 minutes, after which 1% toluene,
by means of cooling coils 48, and cold water is con based on the originally entering alkyl benzene, is added
tinuously added by way of inlet 45 and removed through 20 and the resultant mixture is digested for an additional 12
outlet 46. During this stage of the reaction approximately minutes. Following this final digestion, a small amount,
0.5 to 1.0% of the original organic reactant reacts with approximately 2% based on the originally entering alkyl
the sulfonic anhydride formed in the process. The sul benzene, of water is added to break the anhydrides still
fonic acid mixture in digester 44 is transferred to a second remaining, and the resulting mixture is then neutralized
digester 49 wherein 1 to 2% by weight of sulfonatable 25 with lows: caustic soda. The analysis of the product is as fol
reactant, such as benzene, toluene, Xylene, or fatty alco
hol, is simultaneously introduced and added to the Sul Free oil-1.3% on the basis of active ingredient.
fonic acid mixture and further digestion is effected. Color-70 Klett for a 5% solution and a 40 mm. light
Digester 49 is cooled by coils 51 and cold water is path, using No. 42 blue filter.
continuously added through inlet 52 and removed through Ratio of active ingredient to sodium sulfate-98.5:1.5.
outlet 53. Most of the remaining acid is removed in the 30 Example 2
second digester and the resulting product is passed to a
mixer 54 where it is mixed with water which enters In this example, commercial xylene containing some of
through inlet 55, to decompose any remaining anhydrides. each of the isomers is sulfonated using the reactor de
Mixer 54 is equipped with internal cooling coils 56 to Scribed in Example 1 with SO3 prepared by vaporizing
maintain a controlled temperature. The resulting product stabilized liquid sulfur trioxide. The SOs concentration in
is removed from the mixer 54 and passed to neutralizer the air is 4% by volume and no excess SOa is employed.
56 through pipe 57, to which neutralizer caustic soda is Xylene enters the reactor with a stream of air at 40° F.
added through inlet 58 to obtain the desired pH. There The residence time of the reaction mixture in the reactor
after, the sulfonated product is discharged as neutralized 40 is about 2 seconds. The reaction mixture is recovered
slurry through outlet 59. from the reactor at a temperature of about 130° F. and,
When employing an alcoholic hydroxyl-containing after leaving the reactor, the reaction mixture immedi
material as the organic reactant, the digester preferably ately is cooled to below 120° F. by mixing it in a quench
is bypassed, as at 61, and the reaction mixture sent di ing tank with cool sulfonic acid, as in Example 1. After
rectly to neutralizer 56, except when an alcohol is being 45 cooling, the Xylene sulfonate is separated from the air
co-sulfonated as previously mentioned. stream in a separator. The xylene sulfonate mixture is
In order to further disclose the present invention, the digested for 2 minutes in a digester, as set forth in Ex
following examples are illustrative of the practice of the ample 1. The exiting air/sulfur trioxide stream is passed
invention. It will be understood, of course, that numerous through an adsorber to remove free Xylene. The other
other examples will readily occur to those skilled in the 50 details of the processing are the same as set forth in Ex
art in the light of the guiding principles and teachings set ample 1, and the xylene sulfonic acid is neutralized with
forth herein. The examples, therefore, are not to be con Sodium hydroxide or ammonium hydroxide. The analysis
strued as restricting in any manner the proper scope of of the neutralized product shows no free Xylene and an
the invention. ether extractable content of about 6%.
Example 1 55 Example 3
A mixture of alkyl benzenes having from 8 to 18 car Lauryl alcohol containing about 95% C atoms is
bon atoms in the side chains and a nominal value of Sulfated with Sulfur trioxide gas prepared by vaporizing
about 13 carbon atoms in the side chains is sulfonated SO. from Stabilized liquid sulfur trioxide. The SO, enters
with sulfur trioxide derived from stabilized SO3. An air/ 60 in an air stream containing 4% sulfur trioxide by volume.
Sulfur trioxide mixture enters a reactor at 98 F. under About 2% excess sulfur trioxide over theoretical is em
a pressure of about 20 pounds per square inch gauge. ployed, and the mixer of Example 1 is used. The alcohol
The SO concentration in the air is 5% by volume. Twelve enters at 85 F. because of its melting point. A reaction
percent excess SO3 over theoretical is employed for the time of about 2 seconds is employed. The sulfuric acid
sulfonation. Before the air/sulfur trioxide mixture enters 65 mixture is recovered from the reactor at a temperature of
the reactor, it is passed through a mist eliminator which about 120 F. and is immediately cooled to below 100°F.
removes any sulfuric acid fog from the stream. In this in the quench Surge pot, as in the other examples. After
example, a mixer-reactor of the type described in ap cooling the Sulfuric acid material is separated from air
plicants' co-pending application Ser. No 244,096 is em and Sulfur trioxide in a gas separator. A portion of the
ployed, having six inlets for the air/sulfur trioxide feed cooled reaction mixture in an amount of about 10 times
streams. The alkyl benzene enters at ambient temperature 70 the rate of feed is recycled to the organic reactant inlet
in a stream of cooled air. The residence time in the re of the reactor to aid in cooling the reaction and decrease
actor is about 2 seconds. The reactor has a maximum the residence time of the reactants in the reactor. In this
clearance of .01 inch, and the SO3/air velocity is 175 feet example no digestion is employed and no other ingredi
per second. The mixture of sulfonic acid and air, with a 5 ents are added. Following the removal thereof from the
gas separator, the non-recycled acid is passed directly to
 3,350,428 16
15 organic sulfuric acid corresponding to that in said re
the neutralizer where it is neutralized with sodium hy action mixture.
droxide. The product, after neutralization, has a color of 6. The process according to claim 1 wherein at least
50 Klett, based on a 5% solution, and an unreacted alco a part of the sulfonic-acid rich mixture withdrawn from
hol content of about 1.2% on the active basis. the cooling zone and introduced into the separation Zone
Example 4 is recycled back to the cooling zone wherein said recycled
mixture aids in cooling the fresh reaction mixture being
Dodecyl benzene is sulfonated with SO3 at a mole ratio introduced into the cooling zone.
of SO to dodecyl benzene of about 1.1:1 in a single stage 7. A continuous process for substantially completely
film reactor at a maximum temperature of 170 F. Simul sulfating a fatty alcohol having from about 8 to about 20
taneously, tallow alcohol of an equal mole percentage as O carbon atoms wherein said fatty alcohol is reacted with
the alkyl benzene is sulfated with SO3 at a mole ratio of sulfur trioxide to form a corresponding Sulfuric acid
SOs to alcohol of about 0.91:1 in a second single stage compound which comprises introducing into an externally
film reactor at a maximum temperature of 140 F. Each cooled reaction zone (1) a stream of said fatty alcohol
of the film reactors provides a reactant film thickness of 15 in liquid form and (2) a stream of a mixture of sulfur
less than 0.04 inch. The residence time of each of the trioxide and air from which any mist present previously
reactants in the separate reactors is about one second. has been removed, the stream of sulfur trioxide and air
Each stream obtained from the two reactors separately entering said reaction zone at a temperature of about 90
is cooled to about 125 F., the cooled streams then are F. to about 120 F., the concentration of sulfur trioxide
mixed together, and subsequently the resultant combined 20 in said sulfur trioxide/air mixture being in the range of
streams are passed through a cyclone separator wherein from 2 to about 8% by volume, at a pressure of at most
excess SO3 is removed. The stream obtained from the gas about 75 pounds per square inch thoroughly mixing said
separator is then passed to a digester and maintained fatty alcohol and said sulfur trioxide/air mixture in said
therein for 12 minutes at a temperature of 125 F. An reaction zone for a period of at most about 10 seconds
analysis of the product obtained shows it to have an un to provide a reaction mixture in the form of a film having
reacted oil content on the active basis of about 2.5% and 25 a thickness of at most about 0.04 inch, said mixture of
a Klett color for a 5% solution and a 40 mm. light path sulfur trioxide and air being introduced into said reaction
of about 80. Zone at a velocity of at least 75 feet per second said re
It is to be understood that the foregoing detailed de action mixture being maintained in said reaction zone at
scription is given merely by way of illustration and that 30 a temperature in the range of from about 85 F. to about
many variations may be made therein without departing 145 F. and a temperature of at most about 135 F.
from the spirit of this invention. after the reaction is about 60% complete, removing said
What is claimed is: reaction mixture from said reaction zone at the end of
1. A continuous process for sulfating an organic re Said time period, immediately introducing said reaction
actant having an alcoholic hydroxyl group wherein said 35 mixture withdrawn from said reaction zone into a cooling
organic reactant is reacted with sulfur trioxide to provide zone wherein said reaction mixture is contacted and mixed
a corresponding organic sulfuric acid compound which with a cool mass of sulfuric acid corresponding to that in
comprises simultaneously and continuously introducing said reaction mixture to effect a rapid cooling of said re
into an externally cooled reaction zone (1) a stream of action mixture to a temperature in the range of from
said organic reactant and (2) a stream of a gaseous mix 40 about 100 F. to about 125 F. and to provide a substan
ture of sulfur trioxide and an inert diluent, from which tially non-degraded sulfuric acid-rich product, withdraw
any mist present previously has been removed, without ing said sulfuric acid-rich product from said cooling zone,
premixing said streams, at a temperature which reduces Separating said air containing any unreacted sulfur tri
the viscosity of said organic reactant sufficiently to effect oxide therefrom, and thereafter neutralizing at least a
optimum mixing, thoroughly mixing said organic reactant part of the resultant sulfur trioxide-free, sulfuric acid-rich
containing and said Sulfur trioxide-containing streams in 45 product.
said reaction Zone for a time period of at most about 10 8. A continuous process for sulfonating a sulfonatable
Seconds to provide a reaction mixture in the form of a organic reactant selected from the group consisting of
thin film, removing said reaction mixture from said re olefins, aromatic hydrocarbons and unsaturated fatty acids,
action Zone at the end of said time period, immediately 50 wherein
introducing said reaction mixture withdrawn from said oxide tosaid organic reactant is reacted with sulfur tri
provide a corresponding sulfonic acid, which
reaction Zone into a quench cooling zone to effect a rapid comprises introducing into an externally cooled reaction
cooling of said reaction mixture to a temperature below
about 130 F. and provide a substantially non-degraded Zone (1) a stream of said organic reactant and (2) a
organic sulfuric acid-rich product, withdrawing said sul 55 stream of a mixture of sulfur trioxide and a gaseous inert
furic acid-rich product from said quench cooling zone, removed,from
diluent, which any mist present previously has been
Separating said gaseous inert diluent containing any un taining andthoroughly
said sulfur
mixing said organic reactant-con
trioxide-containing streams in said
reacted sulfur trioxide therefrom, and thereafter neutraliz reaction Zone for a time period of at most about 10 sec
ing at least part of the resultant sulfur trioxide-free, onds to provide a reaction mixture in the form of a thin
Sulfuric
2. Theacid-rich
processproduct.
according to claim 1 wherein the or 60
film, removing said reaction mixture from said reaction
ganic reactant is a fatty alcohol having from about 8 to Zone at the end of said time period, and immediately
about 20 carbon atoms and the temperature in the re introducing said reaction mixture withdrawn from said
action zone is maintained within the range of about 85
reaction Zone into a quench cooling zone to effect a rapid
cooling of said reaction mixture to a temperature below
F. to about 145 F.
3. The process according to claim 1 wherein the or
about 130 F. and provide a substantially non-degraded
65 Sulfonic-acid rich mixture, withdrawing said sulfonic-acid
ganic reactant is an ethoxylated alkyl phenol and the rich mixture from said quench cooling zone, passing the
temperature in the reaction zone is maintained within the same through a separation Zone and separating said gas
range of about 90 F. to about 180° F. eous inert diluent containing any un-reacted sulfur tri
4. The process according to claim 1 wherein said reac Oxide therefrom, and digesting at least a part of the result
tion mixture is cooled to a temperature in the range of ing
70 mixture in an agitated digestion zone without substan
from about 100 F. to about 125 F. in said cooling zone. tial back-mixing to provide a product richer in sulfonic
5. The process according to claim 1 wherein said cool acid than that introduced into the digestion zone.
ing of said reaction mixture withdrawn from said reaction 9. The process, according to claim 8, wherein at least
Zone is carried out by contracting and mixing said re 75 a part of the Sulfonic-acid rich mixture withdrawn from
action mixture in said cooling zone with a cool mass of
 17
3,350,428
the cooling zone and introduced into the separation zone 3.
is re-cycled back to the cooling Zone wherein said re to Said Sulfonic acid-rich mixture in said digestion zone
cycled Imixture aids in cooling the fresh reaction mixture and at the end of said digestion time period the resultant
being introduced into the cooling zone. Sulfonic acid product is neutralized.
if). The process according to claim 8 wherein the reac 35. A continuous process for the co-sulfonation of an
5 alkyl aryl hydrocarbon having from 8 to 30 carbon atoms
tion mixture in the form of a thin film has a thickness
of at most about 0.04 inch and wherein the digestion of in the alkyl group and fatty alcohol sulfate with sulfur
the sulfonic acid-rich mixture is at a temperature of from trioxide to produce the corresponding sulfonic acid
about 100 to about 135 F. for a time period in the which comprises introducing into one externally
range of from about 1 to about 30 minutes to provide cColled reaction Zone (1) a stream of said alkyl
a Sulfonic acid-rich product. 0. aryl hydrocarbon in liquid form and (2) a stream of
11. The process according to claim 8 wherein said Sulfur trioxide and air and separately introducing into
cooling of said reaction mixture withdrawn from said a Second externally cooled reaction zone, (3) a stream
reaction zone is carried out by contacting and mixing of fatty alcohol and (4) a stream of a mixture of sulfur
said reaction mixture in said cooling zone with a cool trioxide and an inert diluent thoroughly mixing streams
mass of sulfonic acid corresponding to that in said reac (1) and (2) in said reaction zone to provide a reaction
tion mixture. mixture in the form of a thin film, thereafter removing
12. The process according to claim 8 wherein during said reaction mixture from said reaction zone and in
said digestion step a sulfonatable organic reactant is mediately cooling said reaction mixture and to provide
added to said Sulfonic acid-rich mixture in said digestion a Substantially non-degraded sulfonic acid-rich mixture,
Zone, and at the end of said digestion time period the withdrawing said mixture from said cooling zone, sepa
resultant sulfonic acid product is neutralized. rating air containing any unreacted sulfur trioxide there
i3. A continuous process for substantially completely from and thereafter digesting at least a portion of such
Sulfonating an alkyl aryl hydrocarbon having from 8 imixture in an agitated digestion zone in the presence of
to 20 carbon atoms in the alkyl group wherein said aiky the reaction product produced in said second reaction
aryl hydrocarbon is reacted with sulfur trioxide to form Zone from the interaction of streams (3) and (4), said
a corresponding sulfonic acid, which comprises intro reaction product being Sulfatable and having been pro
ducing into an externally cooled reaction zone (1) a duced in the form of a thin film which has been rapidly
stream of said alkyl aryl hydrocarbon in liquid form and cooled prior to the addition of said sulfonic acid-rich
(2) a stream of sulfur trioxide and air wherein said mixture in the digestion zone, said sulfatable reaction
trioxide and air enters said reaction zone at a temperature product being sulfated during said digestion.
of about 90° F. to about 120° F., thoroughly mixing i6. A process as defined in claim 5 wherein the
said alkyl aryl hydrocarbon-containing and said sulfur mole ratio of SO3 to alkyl aryl hydrocarbon in streams
trioxide-containing streams for a time period of at most (1) and (2) being in the range of about 1.05:1 to 1.15:1
about 10 seconds to provide a reaction Imixture in the and the mole ratio of SOs to fatty alcohol in streams (3)
form of a thin film, said reaction mixture being main and (4) being in the range of about 0.85:1 to 1:1.
tained in Said reaction zone at a temperature in the References Cited
range of 80° F. to about 200 F. and a temperature
of at least about 120 F. after the reaction is about 60% UNITED STATES PATENTS
complete, removing said reaction mixture from said reac 40 2,088,027 7/1937 Law et al. ---------- 260-459
tion zone at the end of said time period, immeditaely 2,448,184 8/1948 Lemmon -------- 260-686 X
introducing said reaction mixture withdrawn from said 2,613,218 10/1952 Stoneman -------- 260-457 X
reaction zone into a cooling zone wherein it is contacted 2,691,040 10/1954 Bloch et al. -- 260-459 X
and mixed with a cool mass of sulfonic acid corresponding 2,768, 199 10/1956 Luntz et al. ------- 260-686 X
to that in said reaction mixture to effect a rapid cooling 45 2,828,331 3/1958 Marisic et al. ----- 260-400 X
of said reaction mixture to a temperature in the range 2,923,728 2/1960 Falk et al. --------- 260-459
of from about 100 F. to about 125 F. and to provide 3,024,258 3/1962 Brooks et al. ------ 260-459 X
a substantially nondegraded sulfonic acid-rich mixture, 3,058,920 10/1962 Brooks et al. ------ 260-686 X
withdrawing said sulfonic acid-rich mixture from said 3,169,142 2/1965 Knaggs et al. ----- 260-686 X
cooling zone, separating air containing any unreacted sul 50
fur trioxide therefrom, and digesting at least a portion FOREIGN PATENTS
of the resultant sulfur trioxide-free, sulfonic acid-rich 230,108 8/1960 Australia.
mixture in an agitated digestion zone without substantial 553,598 5/1943 Great Britain.
back-mixing at a temperature in the range of from about 799,038 7/1958 Great Britain.
100° F. to about 135 F. for a time period in the range 55 799,199 8/1958 Great Britain.
of from about 1 to about 30 minutes to provide a sul
fonic acid product. CHARLES B. PARKER, Primary Examiner.
14. The process according to claim 13 wherein during F. D. HIGEL, Assistant Examiner.
the digestion step a sulfonatable organic reactant is added