United States Patent Office 2,952,639

Patented Sept. 13, 1960

2
said U.S. Patent No. 2,607,740, and need not be elabo
rated upon at this point in this disclosure. The main
2,952,639 point here involved is that a commercially suitable com
PURFICATION OF DETERGENT COMPOSITIONS 5 position must necessarily have suitable properties in con
nection with the critical considerations such as viscosity,
Vincent A. Sullivan, Jr., Lyon, and Zdzislaw Joseph selective solvent, cloud point, foaming, grease emulsifica
Ptasinski, Chicago, Ill., assignors, by mesne assign tion, soil removal, adequate concentration and lack of
ments, to The Stepan Chemical Company, Chicago, irritants in the composition. In general, the liquid deter
Ill., a corporation of Delaware gent compositions heretofore known have left something
No Drawing. Filed June 30, 1954, Ser. No. 440,544 0 to be desired in connection with one or more of the fore
going critical consideration, because of the presence
14 Claims. (C. 252-161) therein of the salt impurities just mentioned.
The purification problem here involved may best be
analyzed by a careful study of the procedure employed
Our invention relates to novel and unique synthetic 5 for preparing such detergents. In general, the first step
detergent compositions and an improved method for their involves sulfonation of a suitable compound such as do
preparation, and more particularly, to improved composi decylbenzene to yield a crude mixture of dodecyl benzene
tions of the type characterized by the presence therein of sulfonic acid and the sulfonating agent. Any suitable sul
water-soluble anionic sulfonated detergents in the liquid fonating agent may be used, and those most commonly
state, and the method of preparing the same. 20 employed are concentrated sulfuric acid (H2SO4), chloro
As is well known, the ever increasing need for im sulfonic acid (ClSOH) and sulfur trioxide (SO). The
proved liquid detergent compositions has resulted in the equations involved may be represented as follows:
expenditure of a substantial amount of research time and 1 mol 1.1 no
attention. The particularly complicated physical and
chemical phenomena here involved have, however, added 25 (1) C12H2
a great deal of confusion to the art and have given rise to --2SO -->
a great plurality of conflicting theories and concepts.
The complexity of the overall problem is readily appre
ciated when one considers the fact that the phenomena (2)
C12H25- Cia
here involved include suspension, interfacial tension, 30
--CSO3H -->
micellar structure, dispersion, emulsion, foam stability
and the like.
As is pointed out in United States Patent No. 2,607,740, (3)
issued August 19, 1952, to Peter T. Vitale and Ralph C12H2 C1E SOE
Spencer Leonard, and assigned to Colgate-Palmolive-Peet 35 --SO3 ->
Company, recently synthetic detergents of a type known
as organic sulfonates have been developed, and the deter
gents of this characteristic type have been found to have The product shown in each case is a true sulfonic acid
certain properties which render them much more suitable having a C-SO3H group and this is the predominant
than ordinary soaps for certain uses. Since these deter 40 productobtained using vigorous anhydrous reaction condi
gents have many properties substantially different from tions. Actually, at least some sulfate (i.e. C-O-SOH)
the properties of soaps, and particularly, since they be is usually formed also. The conditions involve minimum
have in a substantially different manner in aqueous solu reaction temperatures (i.e. not above 100-110 F. if pos
tion, for example, by the non-formation of insoluble pre sible) to avoid discoloration and a substantial excess of
cipitates in hard water, the improvement or alteration of 45 the sulfonating agent to insure substantially complete
the general behavior characteristics of these detergents sulfonation of the hydrocarbon (which is by comparison
has opened up an entirely new field of research. One of relatively expensive).
such fields of research involves certain attempts to pre The next step involves washing of the crude sulfonated
pare these detergents substantially free from impurities, product with water to remove the excess sulfonating
and particularly inorganic salt impurities. The presence agent (which is effectively converted into H2SO4 by the
of such salts often adversely affects such properties as the 50 Washing process) so as to remove the bulk of the excess in
cloud point (in liquid compositions) and also has an ad the form of a concentrated (80%) solution of HSO4.
verse effect upon the overall cleansing properties. It is In order to avoid excessive loss of the sulfonated hydro
highly desirable to have detergent compositions of this carbon (and to obtain a concentrated HSO solution)
particular type which possess excellent clarity in combina only a relatively small amount of water is used. The
tion with excellent detersive efficiency; and this partic 55 dodecyl benzene sulfonic acid, however, has a selective
ular combination of properties is of very appreciable im retention or absorption with respect to the sulfuric acid
portance in connection with consumer appeal for home and it is impossible to remove all of the sulfuric acid
use, as well as for industrial use. from the sulfonic acid by this washing. The resulting
Although detergents of this type can be, and are cur 60 washed crude sulfonic acid product has a composition of
rently being, packaged and sold in dry particular form, about 88% dodecyl benzene sulfonic acid, 7% sulfuric
the presence of such salt impurities therein tends to create acid, 4% water and 1% dodecyl benzene. Prior to our
additional precipitate deposits during use. Also, certain work in this field, no practical method had been devised
features of this type of packaging leave something to be for removing a greater proportion of the sulfuric acid.
desired; and there has developed a very great demand on 65 The next step involves neutralization of the washed
the part of home users as well as industrial users for suit crude sulfonic acid; and this may be done by the use of
able synthetic detergent compositions in liquid form. inorganic bases such as alkali metal or ammonium hy
Those skilled in the art, however, recognize fully that a droxide or by the use of organic bases such as the
rather substantial number of critical considerations are ethanolamides. Here again, low temperature of not
involved in the formulation of a suitable liquid detergent 70 more than about 100-110 F. is used to avoid discolora
composition, and certain of the more important of these tion. If, for example, sodium hydroxide is used, the
particular considerations are set forth at some length in resulting neutralized sodium dodecyl benzene sulfonate
 2,952,639
3 4.
contains about 12% Na2SO4 (As used herein the terms
“%” and "parts' means percent and parts by weight,
unless otherwise designated). Other inorganic bases
cause the formation of the corresponding amounts of their
sulfate salts. It will thus be seen that the presence of
such inorganic sulfate salts in the final neutralized Sul
fonated product is inherent and unavoidable.
As those skilled in the art will readily appreciate, the
rather substantial amount of the inorganic salt impurity
in such compositions greatly impairs their use as chemi
cal intermediates for other reactions and also as in
gredients suitable for admixture with other ingredients to
form detergent compositions, for example. Moreover,
the inorganic sulfate impurity has solubility character
istics that are substantially different from those of the
organic sulfonate and the use of selective solvents in
liquid detergent compositions containing these sulfonated
detergents is further complicated. It will also be ap
preciated that the sulfonated detergent per se is generally
looked upon as the sulfonic acid, or the sulfonic acid
anion properly speaking, but it is necessary as a prac
tical matter to neutralize the sulfonic acid to form the
salt thereof for use in detergent compositions. As has
been pointed out, however, there was heretofore no known
practical method of separating the sulfate anion (neutral
ized or unneutralized) from the sulfonate; and the in
herent presence of these substantial amounts of sulfate
anion is not at all desirable.
If an organic base, such as triethanolamine, is used
to neutralize the crude washed sulfonated detergent then
triethanolamine sulfate impurities are formed. Such or
ganic sulfate impurities are not as radically different from
the solubility characteristics of the sulfonate as are the
inorganic sulfates. For this reason, the inorganic base
neutralized sulfonated detergents have been replaced by
those neutralized by organic bases in many uses. The
organic base neutralized sulfonated detergents also leave
much to be desired, however, since their use may involve
the use of a sulfate having better solubility but never
theless a sulfate which introduces undesirable sulfate 40
anions into the system. Also, the organic bases such as
the alkylolamines are relatively expensive and the alkylol
amine employed in neutralizing the sulfuric acid is for
all intents and purposes lost or wasted as far as detersive
efficiency is concerned. 45
It is, therefore, an important object of our invention
to provide an improved method of producing low-sulfate
content anionic sulfonated detergents, and the improved
detergents resulting therefrom.
It is a further object of our invention to provide an 50
improved method of treating a composition comprising
essentially 100 parts of water-soluble salt of anionic
sulfonated detergent having a long aliphatic chain of 8
to 22 carbon atoms that has been neutralized only to a
pH of 6-6.5 and contains 1 to 20 parts of inorganic sul 5
fate salt whereby the amount of inorganic sulfate salt
therein may be reduced to a predetermined amount x,
within the range of 0.4 to 0.8 part, which comprises
intimately admixing the composition with 4 to 5 times
its weight of a one phase solvent system of water ad 60
mixed with low molecular weight solvents of the class
consisting of alcohols, ketones, esters and others in an
amount sufficient to reduce the total solubility of the
system for the inorganic sulfate salt to x, then main
taining the admixture at 130-140 F. for a time suffi
cient to completely dissolve the sulfonated detergent and
to effectively crystallize the undissolved inorganic sulfate
salt particles therein, and then filtering the admixture to
remove the crystallized salt particles therein.
It is another object of our invention to provide an
improved filter aid for use in the above indicated process
for producing a substantially (inorganic) salt-free de
tergent. - diethanolamine, triethanolamine salts and mixtures there
Other objects, features and advantages will become
apparent to those skilled in the art from the following
detailed disclosure of preferred embodiments of our in
vention.
A basic aspect of our invention consists in a method
of treating a composition comprising essentially water
soluble alkaryi anionic sulfonated detergent having a long
aliphatic chain of 8 to 22 carbon atoms having residual
sulfonating agents therein that comprises first neutraliz
ing only to a pH of 6-6.5 and then intimately admixing
the composition with substantially an equal weight of
O ethanol and water in volume ratio of 50:50 to 60:40,
heating the admixture to from 115 F. to boiling tem
perature for a time sufficient to completely dissolve the
sulfonated detergent and to effectively crystallize the undis
solved inorganic sulfate salt particles therein, and then fil
5 tering the admixture to remove the crystallized salt par
ticles therein.
The anionic sulfonated detergents which we may em
ploy in the practice of our invention are a well known
class of compounds, as is pointed out in said Patent No.
20 2,607,740. These detergents are all made by procedures
comparable to that hereinbefore described. The sulfona
tion may take place using a variety of suitable source
materials each having an aliphatic chain of about 8 to
about 22. - The sulfonation may take place with higher
25 fatty alcohols, so as to obtain, for example, lauryl sul
fonate and preferably Co-Cs alkyl sulfonates. Most
preferably, however, alkylaryl compounds are used. The
aromatic or alkylaryl sulfonate detergents are well known
in the art. They may be mononuclear or polynuclear in
30 structure. More particularly the aromatic nucleus may
be derived from benzene, toluene, xylene, phenol, cresols,
naphthalene, etc. The alkyl substituent on the aromatic
nucleus may vary widely, as long as the desired detergent
power of the active ingredient is preserved. While the
number of sulfonic acid groups present on the nucleus
may vary it is usual to have one such group present in
order to preserve as much as possible a balance be
tween the hydrophilic and hydrophobic portions of the
molecule.
More specific examples of suitable alkyl aromatic sul
fonate detergents are the higher alkyl aromatic sulfo
nates. The higher alkyl substituent on the aromatic
nucleus may be branched or straight-chain instructure;
it comprises moreover such groups as decyl, dodecyl,
keryl, pentadecyl, hexadecyl, mixed long-chain alkyls de
rived from long-chain fatty materials, cracked paraffin
wax olefins, polymers of lower monoolefins, etc. Pre
ferred examples of this class are the higher alkyl mono
nuclear aryl sulfonates wherein the alkyl group is about
8 to about 22, and preferably about 12 to 18 carbon
atoms. More particularly, it is preferred to use the
higher alkyl benzene sulfonates wherein the higher alkyl
group is about 12 to 16 carbon atoms. For example,
propylene may be polymerized to the tetramer and con
densed with benzene in the presence of a Friedel-Crafts
catalyst to yield essentially the dodecyl benzene deriva
tive which is suitable for sulfonation to the desired sul
fonate compounds.
The above mentioned anionic detergents are used or
ultimately obtained in the instant invention in the form
of their water-soluble salts, which salts include the am
monium, alkali metal and alkaline earth metal salts, ob
tained by neutralization with an inorganic base, and the
alkylol amine salts normally obtained by neutralization
with the corresponding organic base. Such salts include
the lower three alkali metals (lithium, sodium and potas
sium, which are the only commercially significant alkali
metal salts), the lowest alkaline earth metal-magnesium
(which is the most significant of this class) the ammoni
70 um salts, and the triethanol amine salts. Although in
certain instances, the alkylol amine salts have been found
to be particularly preferable (e.g., the monoethanolamine,
of have been found to be particularly useful); however,
75 we have also found that the alkali metal salts, particu
 2,952,639
S 6
larly the alkali metal alkyl benzene sulfonates are ad
vantageous in many respects including economic aspects
and are preferred for use in the instant invention. The
problem here solved is that of obtaining these sulfonate
salts in a substantially sulfate-free condition.
As also explained, the procedure for the preparation of
the sulfonated detergent inherently results in the incor
poration therein of the sulfate (anion); and subsequent
Theutralization merely results in the formation of the cor
responding sulfate salt as an impurity. No practical
method was heretofore known for avoiding the presence
of the neutralized or unneutralized sulfate in such sul
fonated detergent compositions. V (system) is capable of fully dissolving the sulfonate de
The details of the sulfonation process per se are old
and well known to those skilled in the art, and need not
be discussed at length herein. The formation of a sul
fonated anionic detergent is, likewise, a well known pro
cedure. A suitable sulfonatable detergent source mate
rial (having a long aliphatic chain of about C-C2a)
which may be a hydrocarbon (e.g. dodecyl benzene), an
alcohol (e.g. lauroyl diglyceride), etc., is reacted with
one of the sulfonating agents hereinbefore described.
Most preferably the source material is a C1-C1s alkyl
benzene, and the claims herein are addressed primarily
to the purification of the alkaryl detergent.
The result of the sulfonating reaction is a member of
the well known class of detergents called "anionic sul
fonated detergents'; and such sulfonated compounds by
virtue of their retentive powers for the sulfonating agent
inherently contain substantial quantities of the same, even
after Washing or any other known refining treatment.
After washing, these sulfonated detergents inherently con
tain from about 3% to about 10% of the sulfonating
agent, depending to some extent upon the particular
agent. (Using sulfur trioxide it is possible to obtain a
lower percent retained than by using sulfuric acid.)
Neutralization of the washed sulfonated product results
in a neutralized product which may contain from about
5% to about 20% of the neutralized sulfonating agent
as the sulfate salt of the neutralizing base. Again, the
neutralized sulfate-containing product is well known in
the art.
Our invention contemplates departing from the well
known “complete' neutralization step to the extent that
neutralization is carried only to a pH of 6-6.5 to obtain
the neutralized product as a starting material, when such
is neutralized with an inorganic base; and this material
is here defined as a composition comprising essentially
“water-soluble alkaryl anionic sulfonated detergent salt
having a long aliphatic chain of 8 to 22 carbon atoms
having a pH of 6-6.5 and containing 5 to 20 weight per
cent thereof of inorganic sulfate salt.” The invention
also contemplates the use of certain specific filter aid
compositions which have been found to be usually superior
in performance.
The nature of our invention may probably best be
demonstrated by carrying out a specific process embody
ing the invention, as follows:
A starting material is provided which has the following
approximate formulation:
88% dodecyl benzene sulfonic acid,
7% sulfuric acid,
4% water, and
1% dodecyl benzene.
This material is obtained by sulfonating a suitable alkyl
aromatic compound (viz. dodecyl benzene) with any of
the aforementioned sulfonating agents (specifically, chlo
rosulfonic acid) in slight excess, followed by washing
with about an equal volume of water to remove the bulk 70
of excess sulfonating agent. Next, the material is neu
tralized by an inorganic base (i.e. sodium hydroxide)
using an amount sufficient to raise the pH only to about
6-6.5. This results in the presence of only a slight trace
of free acid in the composition.
The composition thus comprises essentially water
soluble alkaryl anionic sulfonated detergent salt having
a long aliphatic chain of 8 to 22 carbon atoms, having
a pH of 6-6.5 and containing 1 to 20 weight percent
thereof of an inorganic sulfate salt, and more specifically,
sodium dodecyl benzene sulfonate containing 12% sodi
um Sulfate (whose preparation was described in detail
hereinbefore). The composition was admixed with an
equal weight (and, preferably, 2-1/2 times the compo
0. sition weight) of 55 volumes of ethanol and 45 volumes
of water, which effectively reduces the sulfate concentra
tion to 6% in the admixture. This ethanol-water solvent
tergent, but it is capable of actually dissolving only about
15 0.3% sulfate maximum, which means that 5.7% sulfate
is excluded from the solvent phase and a two-phase sys
ten involving a second dispersed sulfate phase is formed.
Ethanol: water volume ratios of 60:40 to 50:50 may be
used to obtain admixtures which dissolve about 0.2-0.4%
20 sulfate.
As will be appreciated, the neutralization to pH 6-6.5
with sodium hydroxide was carried out at temperatures
not in excess of 100-110 F. and the subsequent solvent
addition has served to cool the admixture substantially
25 below the neutralization temperatures. Under such con
ditions the second dispersed sulfate phase is barely ap
parent, if at all, since we have found that the dispersed
sulfate particles are extremely minute in character. In
fact, it might be expected that the presence of the sul
30 fonate in solution would create a selective solvent system
for all of the sulfate; instead, we believe that the sulfonate
contributes materially to the almost infinitely fine disper
sion here obtained but does not actually retain the sulfate
in solution (in excess of the 0.3%).
35 There is no known way of separating this fine sulfate
dispersed phase from the solvent phase so as to obtain a
one-phase (solvent-phase) system. As such, the dispersed
sulfate cannot be filtered out or removed by any other
known practical means. We use the term "dispersed
40 sulfate' to describe the undissolved sulfate advisedly be
cause we have found that the sulfate is, in fact, not solu
ble in this system and must, therefore, be undissolved and
dispersed therein. Others may not have appreciated this
fact, and considered the sulfate to be dissolved, but with
45 or without the knowledge that the sulfate cannot be dis
solved in true solution there is still no apparent method
of removing the (undissolved) sulfate.
A key to the sulfate removal, we have found, is, first,
carrying neutralization only to pH 6-6.5 and, secondly,
50 heating instead of additional cooling (normally permitted
to take place). For example, the above described ad
mixture was heated to 135 F. and maintained thereat for
one-half hour, and it was found that noticeable precipita
tion and/or dispersion crystallization had taken place in
55 connection with the sulfate particles. The removal of
these crystallized particles by filtration, at the heated
temperature, using a standard grade filter cloth or screen,
plus standard filter aids in a filter press is then accom
plished and the filtered product has a sodium sulfate
60 content of 0.3% (in the one-phase solvent system).
As mentioned, one important feature here involved is
the neutralization only to pH 6-6.5. Neutralization to
a lesser extent could be used (only to 5 or 5.5 pH, for
example) but no improvement in results will be obtained
65 and the amount of free acid remaining is appreciably
greater so as to create a corrosion problem and to result
in the formation of an appreciable amount of inorganic
salt during a subsequent neutralization completely to pH
7. With neutralization to pH 6-6.5 the free acid remains
only in trace amounts; and subsequent neutralization to
pH 7 does not result in the formation of an appreciable
amount of inorganic salt. Neutralization beyond about
pH 6.5 appears not to be helpful because the reduction
in the trace amounts of free acid is inconsequential; and
5 filtration is made more difficult,
 2,952,639
7 8
Although it is not desired to limit the invention to any
particular theory, we believe that the unusual result here
obtained may be explained as follows:
The addition of the ethanol-water solvent to the sul
fonate having "dissolved” therein the sulfate creates a
System wherein only a smail part of the sulfate is soluble
and the remainder of the sulfate proceeds to precipitate
or separate from the solvent phase. The initially pre
cipitated or separated particles are almost colloidal in
size but under ordinary conditions would build up into
crystals of appreciable size. The sulfonate in this sys
tem, however, prevents this build-up perhaps by forming
a protective film on the surface of these particles as soon
as they take form. The result is what appears to be a
true solution but which has a relatively high cloud point.
In our invention, however, we heat this system for the
purpose of increasing the solubilizing activity of the sol
vent phase presumably so that this protective film may
be removed or otherwise rendered ineffective and coagul
lation of the minute particles may take place to form a
filterable precipitate. It is also understood that sol-gel
systems are responsive to the pH, there being a tendency,
for example, for silica "sol' solutions to remain stable at
pH 7 but to gel at a pH above or below. Here the lower
pH (which might even be caused by addition of another 25 Mg,
acid after complete neutralization) may well contribute solution
to the coagulation or gelling of the colloidal-size parti of, for example,
cles, or it may merely interfere with the dispersing func
tion of the detergent and/or assist the aqueous alcohol
in removing the protective detergent film. In any event, 30 mixture with the sulfonate so that the resulting one-phase
the operating temperatures and times are both reduced
materially by the use of the lower pH. (e.g. pH 6-6.5).
- In the solvent system here employed, the proportions
of the solvents used are determined by two considera
tions, the amount of sulfate to be retained in solution
and the ultimate solvent proportions desired in the filtered
one-phase system which, in turn, is governed by the sub
sequent use contemplated. For example, if a dry pow
dered detergent were to be made, then any reasonably
volatile solvent might be used. If a concentrated liquid
detergent were to be made, then those solvents to be used
as the selective solvent (in the proportions desired) should
be used, if possible.
Certain considerations are quite important, however;
first of all, the solvent must contain at least some and
preferably about 20 volume percent water. If all etha
nol is used, it is found that effective crystallization (upon
heating) cannot be obtained. Again, the reason for this
is not fully understood, but apparently the solvent sys
tem requires some water to act upon the sulfonate which
is believed to prevent effective crystallization. In addi
tion, the presence of water in the solvent system pre
vents the undesirable colloidal precipitation of the inor
ganic salt. Most preferably an ethanol-water mixture is
used, since ethanol is the ideal organic solvent for liquid
detergents, having no characteristic odor or other fea
tures which might limit its use in such compositions.
Also, the most effective coagulation results are obtained
using the ethanol-water system. In general, the ethanol:
water volume ratio should be 50:50 to 60:40, and most
preferably it is 55:45 which effectively results in a reduc
tion of the sulfate to about 0.3% as described. Ac
tually, the ethanol: water volume ratio may be adjusted
through the range of, for example 3:5 to 4:1 to suit
particular circumstances. At a 4:1 ratio a minimum
amount of sulfate (i.e. about 0.1%) is retained in solu
tion; and at 3:5 ratio proportions of sulfate in the range
1%-5% may be obtained so as to bring the sulfate con
centration at least below that ordinarily possible during
careful washing and neutralization. At ethanol: water
ratios of less than 1:1 (or 50:50), however, the coagul
lation rate is slower. In general, the 60:40 to 50:50
ethanol: water range is preferred and this results in (after
admixture with an equal weight of crude sulfonated deter
gent) about a 0.2 to 0.8% sulfate content.
Lower concentrations of sulfate in a given one-phase
system may be obtained, for example, by the use of 4:1
ethanol: water with an equal weight of crude sulfonate,
so as to obtain a 50% sulfonate solution containing about
5 0.1% sulfate and then diluting the solution with equal
its weight of other detersive or the like agents and/or
solvents so as to obtain as little as 0.05% of the sulfate.
A sulfate:sulfonate weight ratio of about 1:500 is about
the minimum, however; and sulfate concentrations in the
0 range 0.05-0.2% must usually be obtained by also di
luting the sulfonate concentration to as low as 25%. The
result is a one-phase system of lower sulfonate concen
tration that is capable of dissolving only 0.05-0.2%
sulfate.
15 Although we have emphasized the use of ethanol in
our process, as the preferred organic solvent, it should be
understood that our invention also contemplates the use
of other organic solvents. Such solvents include partic
ularly the water-miscible alcohols (e.g. methanol and
propanol), ketones (e.g. acetone), esters (e.g. methyl
20
formate), and ethers (e.g. dimethyl ether). As will be
appreciated, the water-miscible organic solvents are ca
pable of forming a one-phase solvent system with water,
and each of the inorganic sulfates (e.g. Li, Na, K, NH4,
etc. sulfates) is substantially insoluble in these or
ganic solvents. Accordingly, if it is desired to obtain a
containing x amount of sulfate (within the range
0.4–0.8 part per 100 parts of Sulfonate),
one selects a predetermined water-solvent system for ad
(sulfonate-containing system) will have a total sulfate
solubility of 0.4–0.8 part. In so selecting the System to
be used, the amount to be used may also be considered
since the crude sulfonate may be admixed with from about
35 4 to about 5 times its weight of solvent if desired (al
though about equal the weight is preferred in making con
centrated liquid detergents). -
It will also be understood that the instant invention
does not preclude the use of water-immiscible solvents,
40 but these solvents must be used in a system in which they
are miscible, if a one-phase system is to be obtained.
Thus, if it is desired to use butanol which is only about
9% soluble in water, it would be necessary to use a water:
propanol: butanol system of perhaps 70:15:15 volume
ratio in order to obtain a one-phase system.
It will thus be seen that the selection of the solvent
system to be used may be made from a variety of com
pounds and proportions, in the light of the present teach
ings, so as to obtain a number of different predetermined
50 results. -
After the sulfonated detergent has been neutralized to
a pH 6-6.5 by an inorganic base (which might be a car
bonate or other basic compound instead of the hydroxide)
and the inorganic salt of the sulfonated detergent contain
ing the residual inorganic sulfate has been admixed with
55
the selected solvent system, at the neutralization tem
perature or below, it will be noted that no appreciable
coagulation can be observed. The next step, however, in
volves the effective crystallization of the undissolved (un
dissolvable) sulfate; and this step involves just the opposite
60
to what would normally be done at this time. Up to this
point in the procedure the avoidance of heating the com
position is very important; and, as a general rule, it was
assumed that heating above the minimum temperature
maintainable during neutralization should never be car
65
ried out.
We have found, however, that just the opposite is true.
After the neutralization is completed, so that no harm
ful effects (possibly because of sulfuric acid present) can
be obtained by heating, then we add the solvent system
70
and heat the admixture for a time sufficient to completely
dissolve the sulfonated detergent and also to effectively
crystallize the undissolved inorganic sulfate salt particles
thereon. Actually, the first step, dissolving the sulfonated
75 detergent, takes place rather rapidly (even in the absence
 - - 2,952,639
9 O
of heat); but the second step of crystallizing the sulfate
particles is substantially slower. In its initial aspects
cloudiness appears (and this would ordinarily be a signal
to anyone to avoid heating); but particles of suitable size
to be filtered develop upon still further heating. The de
velopment of particles of filterable size will, of course,
be ascertainable to an operator from testing samples of
the batch. In general, at least about one-half hour of heat
ing is required for heating at the preferred temperatures
of 120-150 F. (the most preferred being 130-140 0.
F.). In general, also the mixture must be heated to at
least about 115 F. to get an effective crystallization rate
and heating above about the boiling temperature at least
So as to produce conditions more vigorous than moderate
reflux is usually not desirable. Atmospheric pressure is 5
suitable, of course. As mentioned, the effective comple
tion of the crystallization step is readily ascertainable by
routine examination and testing.
Next, the mixture is filtered. Any type of filtration gen
erally suitable for removing solids from a solvent system 20
of this type may be used (although a distinctly superior
filter aid has been found and will be described). Filter
systems of the type used to purify lacquer solutions, liquid
food products or the like materials having usually only
Small sized particles therein may be used. Actually, 25
the crystallization step changes the sulfate from a finely
divided unfilterable stage (conceivably of the nature of
the sol-gel water glass systems), to a stage capable of
filtration in standard filter equipment. Most preferably,
a filter cloth employing a precoat.
An important aspect of the filtration step is the main
tenance of heat in the admixture. In other words, the
mixture is filtered hot, preferably at the temperature of
crystallization and at least prior to any appreciable cool
ling thereof. Complete cooling of the mixture to down 35
below the neutralization temperature, for example, tends
to impair appreciably the effectiveness of the filtration
process. Most preferably the mixture is filtered at at
least the minimum effective crystallization temperature
(i.e. about 115 F.). This has an additional advantage 40
that maximum crystallization is, in fact, maintained dur
- ing filtration so as to have maximum sulfate particle re
moval.
Actual tests of the final product indicate that this prod
uct is, in fact, a one-phase system having dissolved there
in the sulfonate and a very minor amount of residual
Sulfate. The solvent system above is capable of dissolving
as much sulfate as is finally retained in the system; and
accordingly, the only sulfate in the system is in solution.
As hereinbefore explained, the organic solvents here
used are capable of dissolving substantially no inorganic
sulfate salt, so the amount of organic solvent used in the
solvent system is selected as the principal factor governing
final sulfate-concentration. At least some water is used,
presumably to cooperate with the organic solvent and the
sulfonate to effect coagulation, and this amount of water
is ordinarily sufficient to make possible the presence of
at least dissolved sulfate, in minor or trace amounts.
An important additional aspect of the invention resides
in the discovery of a uniquely Superior filter aid. A vast
number of filter aids are known and used commercially.
Most of these include essentially inorganic non-fibrous
materials such as filter clays; but the general particle
sizes, characteristics, etc. of all of these materials effec
tively classify the same under the genus "filter aids' on
the basis of their known function of collecting (before or
during) filtration on the filter screen or cloth and thereby
affording a filter bed impervious to the material being
filtered out but readily penetrated by the filtrate. We
have found that ordinary filter aids assist in the removal
of the sulfates if the conditions hereinbefore described 70
are used; or if (neutralization is not stopped at 6-6.5 pH
and) the instant composition in the presence of the sol
vent solution is heated at least to 135 F. (preferably to
175-195 F. and most preferably to 185° F.) until 75 kylaryl sulfonates are the triethanolamine salts, which
crystallization takes place. If neither procedure is fol
lowed, however, ordinary filter aids are not sufficiently
effective. We have found a filter aid composition which
is, however, effective if heating is carried out only to
about 115 F. or more; and this composition is even
more effective (than any other filter aid) if either of the
above procedures is also carried out.
The filter aid which we have found to be unusually ef
fective is one comprising at least 5% vegetable fiber
filter aid and particularly, cellulose fiber filter aid. The
remainder can be any commercial grade filter aid-vege
table or mineral-fibrous or non-fibrous. Cellulose fiber
filter aids actually have very short fiber sizes, in the na
ture of ball milled cellulose fibers used as synthetic resin
fillers. The surface area of cellulose fibers is, however,
immense. The fibers are understood to comprise elon
gated interwoven fibrils about 1.4 microns thick; the
fibrils are bundles of ultrafibrils which are 0.1-0.3 micron
thick; the ultrafibrils are, in turn, composed of micells
also assumed to be interwoven long slender threads; and
the micells may be pictured as ropes comprising 100-150
cellulose molecular chains arranged as a crystal lattice.
The micells are understood to have a diameter of about
60-70 Angstrom units and a length of at least 600 Ang
strom units. The space between the cellulose molecular
chains is very small, sometimes as small as 10-15 Ang
strom units. Apparently, the dispersed sulfate particle
size remains small enough to pass through this fine lat
tice of molecular chains when neutralization is first car
30 ried out and it is not until heating at at least about 115
F. for a little while that these particles coagulate to the
extent necessary to be trapped in this fiber lattice dur
ing filtration. If the heating is carried out at at least
about 135 F. or if neutralization is carried only to pH
6-6.5 (with heating to at least 115 F.), then the filtra
tion process is greatly facilitated and the cellulose fiber
filter aid is clearly helpful (although absolutely essential
to satisfactory commercial operation).
Most satisfactory filtration is obtained using not more
than about 25% cellulose fiber filter aid, about 10% be
ing most preferred. The remaining filter aid preferably
contains an equal amount of fibrous inorganic material,
Such as asbestos or chrysolite, amphibole fibers, etc.
Typical formulations are as follows:
Formulation I
For each 80 parts of material to be filtered:
1 part of 50% asbestos fiber-50% cellulose fiber
(“Chrysolite #5')
50 5 parts of diatomaceous earth ("Dicalite 4200'), and
1 part of filtering clay.
Formulation II
For each 80 parts of material to be filtered:
55
1 part of powdered cellulose fibers,
5 parts of diatomaceous earth, and
1 part of clay filter aid.
The cellulose fibers are thus about 5-25% and the re
60 mainder is preferably inorganic filter aids, with about
5-25% fibrous inorganic filter aids.
Still another aspect of the instant invention resides in
an improved method for producing certain organic base
neutralized sulfonated detergents. As will be appreciated,
65 the organic base sulfate salts are soluble in the organic
Solvents (such as ethanol) here employed and such sul
fate may not be eliminated as the inorganic sulfates may.
The organic bases are usually the amine bases and the
most common of these are the alkylolamines (i.e. C-C
alkanol amines having not more than one OH group on a
C atom), including monoalkylol, dialkylol, trialkylol, etc.
amines, specific examples of which include monoethanol,
diethanol, triethanol, monopropanol, etc. amines. At
present, the most satisfactory commercially available al
 2,952,639
11
are considered superior to various other organic as well within
sas, inorganic base neutralized sulfonates of this class. prises
One of the reasons for this alleged superiority is based waters
-upon the superior, solubility of triethanolamine Sulfate, as the classadmixed
compared to the inorganic sulfates. However, the pres in an amount
ence of the triethanolamine sulfate is still not desirable;
it is merely less undesirable.
In our invention, we use...as a neutralizing agent for termined
the sulfonated detergent an ammonium base. Such as .am 0. sulfonated
. . monia or ammonium hydroxide so, as to obtain a com
position consisting essentially of ammonium Salt of the dissolved inorganic sulfate, salt particles therein, and
. . sulfonated detergent, as for example, by substitutingam
monia for the sodium hydroxide. used in the demonstra
tion hereinbefore described so; as to obtain: a composi
tion of ammonium dodecyl benzene Sulfonate containing
about 10% ammonium sulfate. (The ammonium cation
has less molecular weight... than the sodium cation). We
may then use an equal-weight of anhydrous ethyl alcohol
and carry out the mixing, heating and filtering as de
: scribed so. as to obtain a one-phase system containing
, about 0.3% ammonium sulfate dissolved therein. To
precipitate the ammonium salt substantially, anhydrous
... alcohol (alkanol) must be used, and preferably, anhy
drous ethanol.
Next, we add to this system a small amount of tri 25
ethanolamine (so as to insure maintenance of an alkaline
pH during the subsequent reaction) and we react the
ammonium dodecyl benzene sulfonate therein with a suit
able. C-C alkylene oxide. such as ethylene, or propylene
soxide. The ethylene oxide combiness at a ratio of 3 30
mols to one of the sulfonate so as to form triethanolamine
dodecyl benzene sulfonate. The reaction of ethylene ox
ide with an ammonium salt is well known - and need
not be detailed herein. The ingredients are preferably
enclosed in a vessel and the ethylene oxide is added
thereto, with agitation under a slight pressure of 10
pounds per square inch (gauge) and at temperatures of
100-200 F. Other known amine addition reactions may
be employed to obtain other. amine salts of the detergent.
- Comparable results to those obtained using a sodium
. . base, neutralization. may also be obtained using other
metal bases, such as the lithium, magnesium or potas
sium bases. Likewise, comparable results may be ob
tained using other sulfonated detergents such as the
Co-C16 alkyl aryl hydrocarbons such as decyl benzene,
lauryl benzene, keryl benzene, tetradecyl benzene, myristyl
benzene and hexadecyl benzene -sulfonates.
Alterations and modifications may be made in the for
rmulations herein without departing from the scope of
the present invention.
We claim as our invention:
1. A method of producing a substantially inorganic
salt-free detergent from a composition consisting essen
tially of a water-soluble alkaryl anionic sulfonated de
tergent salt having a long aliphatic chain of 8 to 22 car
bon atoms containing 1 to 20; weight: percent... thereof of
an alkali metal sulfate. salts and having a pH of just
less than 7, which method comprises intimately admixing
the composition, with substantially an equal-weight of
ethanol and water in volume ratio of 50:50 to 60:40,
maintaining the admixture.at 120-150°F. for a time suffi
cient to completely dissolve the sulfonated detergent and
to effectively crystallize the undissolved sulfate, salt par
...ticles therein, and then separating the crystallized salt
particles from the dissolved. detergent. and neutralizing
the-detergent to at least pH 7.
2. A method of producing a substantially inorganic
salt-free detergent from a composition consisting essen
tially of 100 parts of a water-soluble alkaryl- anionic
sulfonated detergent. salt having a long...aliphatic chain
of 8 to 22 carbon atoms, having a pH of 6-6.5 and con
taining 1 to 20 parts of an inorganic sulfate salt of the
class consisting of alkali metal and alkaline earth metal
a sulfates, whereby, the amount. of inorganic-sulfate salt
therein may be reduced to a predetermined amount,
12
the range of 0.4 to 0.8 part, which method com
intimately admixing the composition with /2 to
5 times its weight. of a one-phase solvent System of
with low molecular weight. Solvents of
consisting of alcohols, ketones, esters and ethers
sufficient to reduce the total solubility of
the system for the inorganic sulfate salt to said prede
amount, then maintaining the admixture at 120
150° F. for a time sufficient to completely, dissolve the
detergent and to effectively crystallize the un
then filtering the admixture to remove the crystallized
salt particles therein.
3. The method of claim 2 wherein the solvent system
5 consists essentially of water and an alkanol having 2 to
3 carbon atoms.
4. The method of claim 2 wherein the detergent is a
salt of higher alkyl mononuclear arylsulfonate detergent,
said higher alkyl group having. 8 to 22 carbon atoms.
20 5. The method of claim 3-wherein the alkanol is
ethanol.
6. The method of claim 4 wherein the detergent and
the inorganic salt are both salts of an alkali metal.
7. The method of claim. 5- wherein the detergent is
sodium dodecylbenzene sulfonate and the inorganic Sul
fate salt is sodium. Sulfate.
8. A method of reducing the sodium sulfate content
to 0.2-0.4 weight percent of a composition having. a pH
of 6-6.5. and consisting-essentially of sodium dodecyl
benzene sulfonate detergent, and 5 to 15 weight percent
thereof of sodium sulfate, which method comprises ad
mixing the composition with substantially equal its weight
of ethanol and water in volume ratio of 55:45, holding
the admixture at 135 F. for at least about/2 hour. to
35 completely dissolve the detergent and to effectively cry
tallize the undissolved sodium sulfate and then filtering
the admixture to remove the undissolved sodium sulfate.
9. A method of reducing the sodium sulfate content
to 0.2-0.4 weight percent of a composition having a pH
40 of 6-6.5 and consisting essentially of sodium dodecyl
benzene sulfonate detergent and 5 to 15 weight percent
thereof of sodium sulfate, which method comprises ad
mixing the composition with substantially /2 to 1% times
its weight of ethanol and water in volume ratio of 55:45,
45. holding the admixture: at 115. F. to the boiling point
for at least. about 4 hour to completely dissolve the
detergents and to effectively crystallize the undissolved
sodium sulfate and then filtering the admixture through
a filter aid of 95-75% minerals and 5-25%. vegetable
50 fibers to remove the undissolved... sodium sulfate.
10. A method of preparing a substantially -inorganic
salt-free detergent, that comprises -sulfonating dodecyl
benzene by reaction therewith of a suitable excess of a
sulfonating agent of the class consisting-of-concentrated
55 sulfuric acid, chlorosulfonic acid and sulphur trioxide,
under substantially anhydrous-conditions, then-washing
the reaction product to obtain a composition consisting
essentially of dodecylbenzene sulfonic acid and residual
sulfonating agent, neutralizing the composition to a pH
60 of just less than pH 7 with-a-sodium base to-obtain a
composition consisting essentially--of sodium dodecyl
benzene sulfonate - and sodium-sulfate salt, in-residual
amounts and admixing the neutralized composition with
substantially an equal weight of ethanol and water in
65 volume ratio of 50:50 to 60:40, maintaining the ad
mixture at 120-150° F. for a time sufficient to completely
dissolve the sulfonated detergent and to effectively crys
tallize the undissolved sodium sulfate salt particles there
in, then separating the crystallized salt particles from
70 the mixture and finally neutralizing to at least pH 7.
11. A method of preparing a substantially inorganic
salt-free detergent, that comprises sulfonating dodecyl
benzene by reaction therewith of a suitable excess-of a
sulfonating agent and then washing the reaction product
75 to obtain a composition consisting: essentially of dodecyl
 2,952,689
13 14
benzene sulfonic acid and residual sulfonating agent, admixing the neutralized composition with substantially
neutralizing the composition to a pH of 6-6.5 with an an equal weight of anhydrous ethanol, maintaining the
ammonium base to obtain a composition consisting es admixture at 115 F. to boiling temperature for a time
sentially of a dodecylbenzene sulfonate salt of the base sufficient to completely dissolve the sulfonate and to
containing residual amounts of a sulfate salt of the base, 5 effectively crystallize the undissolved sulfate, filtering to
then intimately admixing the composition with substan remove such crystallized undissolved sulfate, and then
tially an equal weight of anhydrous ethanol, maintaining treating the filtered composition with ethylene oxide to
the admixture at 120-150 F. for a time sufficient to convert the ammonium sulfonate to triethanolamine sul
completely dissolve the Sulfonated detergent and to effec fonate.
tively crystallize the undissolved inorganic sulfate salt O 14. A method of preparing a substantially inorganic
particles therein, and then filtering the admixture to salt-free detergent, that comprises sulfonating an alkyl
remove the crystallized salt particles therein, benzene having 10 to 14 carbon atoms in the alkyl group
12. A method of preparing a substantially inorganic by reaction therewith of a suitable excess of a sulfonating
Salt-free detergent, that comprises sulfonating alkyl agent of the class consisting of concentrated sulfuric acid,
benzene having 10 to 14 carbon atoms in the alkyl group 5 chlorosulfonic acid and sulphur trioxide, under substan
by reaction therewith of a suitable excess of a sulfonating tially anhydrous conditions, and then washing the reac
agent of the class consisting of concentrated sulfuric acid, tion product to obtain a composition consisting essen
chlorosulfonic acid and sulphur trioxide, under substan tially of the alkylbenzene sulfonic acid and residual sul
tially anhydrous conditions, and then washing the reac fonating agent, neutralizing the composition to a pH of
tion product to obtain a composition consisting essen 20 6-6.5 with an alkali metal base to obtain a composition
tially of the alkylbenzene sulfonic acid and residual sul consisting essentially of the alkylbenzene sulfonate salt
fonating agent, neutralizing the composition to a pH of of the base containing residual amounts of a sulfate salt
6-6.5 with an alkali metal base to obtain a composition of the base, then intimately admixing the composition
consisting essentially of the alkylbenzene sulfonate salt with substantially an equal weight of ethanol and water
of the base containing residual amounts of a sulfate salt 25 in volume ratio of 50:50 to 60:40, heating the admixture
of the base, then intimately admixing the composition to from 115 F. to boiling temperature for a time sufi
with substantially an equal weight of ethanol and water cient to completely dissolve the sulfonated detergent and
in volume ratio of 50:50 to 60:40, heating the admixture to effectively crystallize the undissolved inorganic sul
to from 115 F. to boiling temperature for a time suffi fate salt particles therein, and then filtering the admixture
cient to completely dissolve the sulfonated detergent and 30 to remove the crystallized salt particles therein.
to effectively crystallize the undissolved inorganic sul
fate salt particles therein, and then filtering the admix References Cited in the file of this patent
ture through a filter aid comprising at least 5% vegetable UNITED STATES PATENTS
fiber filter aid and the remainder mineral filter aid to re
move the crystallized salt particles therein. 2,283,199
35 Flett ------------------ May 19, 1942
13. A method of preparing a substantially sulfate-free 2,316,719 Russell ---------------- Apr. 13, 1943
triethanolamine dodecyl benzene sulfonate, that com 2,463,497 Smith ----------------- Mar. 1, 1949
prises sulfonating dodecyl benzene by reaction therewith 2,467,130 Hunt ------------------ Apr. 12, 1949
of a suitable excess of a sulfonating agent and then wash 2,567,854 Nixon ---------------- Sept. 11, 1951
ing the product to obtain a composition consisting es 40 2,678,906 Kohn ----------------- May 18, 1954
sentially of dodecylbenzene sulfonic acid and residual sui 2,687,420 Brady ---------------- Aug. 24, 1954
fonating agent, neutralizing the composition to a pH of OTHER REFERENCES
6-6.5 with an ammonium base to obtain a composition
consisting essentially of ammonium dodecylbenzene sul Seidell: Solubilities of Organic and Inorganic Com
fonate and ammonium sulfate in residual amounts, then 45 pounds, vol. 1, 1919, page 671.