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Патент USA US2129896

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Sept. 13, 1938.
2,129,896
D. s. WHITEMAN
APPARATUS AND METHOD FOR SULÉHONATING FATTY COMPOUNDS
2 Sheets-Sheet 1
Filed Jan. 50, 1935
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Sept. 13, 1938.
2,129,896
D. s. WHITEMAN
APPARATUS AND METHOD FOR SULPHONATING FATTY COMPOUNDS
Filed Jari. so, 1935
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2,129,896
Patented Sept. 13, 1938
UNITED STATES
PATENT OFFICE
2,129,896
APPARATUS AND METHOD FOR SULPHO
NATING FATTY COMPOUNDS
Daniel S. Whiteman, Philadelphia, Pa., assignor
to Reilly-Whiteman-Walton Company, Conshohockcn, Pa., a corporation of Pennsylvania
Application January 30, 1935, Serial No. 4,055
' 20 Claims.
(Cl. 87-12)
Further purposes appear inthe specification
My invention relates to methods and apparatus
for sulphonating fatty compounds, such for ex
ample- as glyceryl esters of fatty acids or fatty
acids.
`
A purpose of my invention is to treat any quan
agent as a continuous process accompanied by
mechanical mixing, without burning or discolor
E ing the fatty compound and without extensive
hydrolysis in the case of a fatty oil.
A further purpose is to produce sulphonated
fatty oils of comparatively low free 'fatty acid
content.
A further purpose is to subject the -sulphonat
ing temperature of fatty oils to more accurate
control and at the same time to make the temper
ature of fatty oil sulphonation less critical.
'A further purpose is to permit the operation
'upon fatty compounds at higher sulphonating
temperatures without harmfully alfecting the re
.
A further purpose is to maintain continuous
control at all times of the proportions of fatty
compound and sulphonating agent fed to a sul
phonation mixing vessel.
_
A further purpose is to continuously mechan
ically mix a fatty compound and sulphuric acid
or another sulphonating agent quickly and inti
0
The present application relates both to the
methods involved and to the apparatus used.
'
tity of fatty compound, large or small, with sul
phuric acid or another suitable> sulphonating
sulting product.
and in the claims.
mately, to cool the reacting ingredients rapidly by
-removing them from the‘zone of initial mixing
and holding them at reduced temperature for a
suñicient time to complete the reaction, to mix
In the drawings I have shown one main em~
bodiment of the invention, with a modification,
choosing the main embodiment and modification
from the standpoints of convenience in illustra
tion of the principles involved, satisfactory oper
ation and simplicity.
,
10A
All of the drawings are schematic, and are in
tended to avoid _details which any person skilled
in the art can readily supply.
Figure 1 is a diagrammatic view of a typical
apparatus constructed in accordance with my in
vention.
Figure 1u is a fragmentary diagrammatic viev
of a modification of Figure 1.
Fi'gure 2 is an enlarged central vertical section
of one of the mixing mills shown in Figures 1 or 20
`la.
«
»
. Figure 3 is an enlarged section of Figure 2 on
theline 3-3 thereof.
_
Figure‘l: is an enlarged central vertical section
of sulphonation completion vessel shown in Fig
ures 1 and 1a.
25
l.
In the drawings like numerals refer to like
parts.
My invention relates to the sulphonation of
fatty compounds. The sulphonating agent may 30
be, for example, concentrated sulphuric acid,
oleum, fuming sulphuric acid, sulphur trioxide
vapor. Various fatty compounds may be treated.
For example, fatty acids such as oleic acid may
be sulphonated in accordance with my invention. 35
Fatty oils, such as castor, oilve, rapeseed, teaseed
rate the sulphonated fatty compound from the__ and- neatsfoot, may also be treated in accordance
neutralization and washing products.
with my invention. These fatty oils are glyceryl
A further purpose is to pass-a fatty compound esters of unsaturated fatty acids, but 1 am not
and sulphuric acid or another sulphonating agent restricted to glyceryl esters, but may sulphonate 40
through a mixing mill containing a relatively thin esters of fatty acids with mono-, di- or poly
envelope of liquid, sol that a thin lfilm of'fatty hydric alcohols, for example glycol esters._
compound and sulphuric acid are mixed and cool
sulphonation of fatty compounds, such as ani
ing of the mixture is facilitated by the thinness of mal or ‘vegetable oils, is commonly resorted to
the envelope and the nearness of metallic cooling to change the properties of the oils, as to change
surfaces'to all parts of the mixture.
.
A further purpose is _to subject a mixture of a the viscosity or surface tension, or to render the
fatty compound and a sulphonating agent to a. oils soluble in water. For example, castor oil is
slow mixing action in a sulphonation completion sulphonated to form turkey red oil, primarily to
the reaction products quickly and intimately with
a neutralizing and washing agent, to complete the
neutralizing reaction and to centrifugally sepa
5
vessel after initially relatively violently intermix
ing the fatty compound and sulphonating agent.
A further purpose is-automatically to propor
tion the neutralizing or washing agent to the ex
render the oil soluble.
i
When a fatty oil, for example glyceryl trioleate
50
` or olein, istreated with concentrated sulphuric
acid, a. series of complicated reactions takes place,
cess sulphonating agent in continuous apparatus
depending upon the temperature, concentrations,
for sulphonating fatty compounds.
etc. At low temperatures the primary reaction 55
2
2,129,896
appears to be the addition of Sulphuric acid at
neutralized, the lower the free 'fatty acid content.
points of unsaturation.
Hydrolysis of the reaction products to form free
fatty acid continues as long as the reaction mix
ture is in the acid condition. One of the impor
tant advantages of this invention is to shorten the
-
n.
total time required for sulphonating glyceride oils,
Olein
from the initial mixture of the oil and sulphonat
-
H
S 04H
ing agent to the final yseparation and ñnishing,
and particularly from the neutralization or wash
ing to the ñnal separation and finishing.
Sulphuric acid also tends to dehydrate and oxi
dize the glycerides and the albuminous matter
10
ciaooo(camcncmcnmom '
H s 04H
Sulphonated olein or acid sulphate
15
There is authority (Hyddleton and Barry, Fats:
Natural and Synthetic, pages 56-60) for the opin
ion that a true sulphonic aci‘d, for example
20
H0
B OaH
CHzOOC(CH2)7CH¿}H(CH:)1CH:
'
Ho
s om
of Sulphuric acid, which is thus present at a given
point in excessive concentrations, and by unduly
high localized temperatures. Mere thorough
mixing of the fatty oil and Sulphuric acid, without
more,J does not solve the problem, because, while it
,
H000 (CHMIEHbmCHmCH:
4H
This is known in the trade as
both favored by the presence of unmixed masses
cmoocwnijfcncmonmom
25
present in the oil.
“charring" or “burning," and is accompanied by
the development of an undesirable dark color and
by the odor of sulphur dioxide which is produced
when Sulphuric acid is reduced by the material
oxidized by the acid. Temperature is undoubt
edly a factor in charring of the oil.
Hydrolysis and charring of the fatty oil are
SOaH
results at higher temperatures, for example above
breaks up the masses of Sulphuric acid and homo
genizes the mixture, it does not take care of the
100° C.
heat developed when the fatty oil and sulphuric
This reaction takes place to some extent
30 at lower temperatures, or sulphated olein gradu
acid react.
ally changes to the sulphonic acid.
Simultaneously with the sulphonation, some of
the fatty oil is hydrolyzed or partially hydrolyzed.
For example, if one> molecule of olein -were hy
35 drolyzed by one molecule of water, the result
would be
conductivities, and, while the heat conductivity of
Sulphuric acid is higher than that of the fatty oils,
The fatty oils have quite low heat CD
it is still relatively low.
The heat conductivity of
the reaction mixture is of the same order of mag
nitude as those of the reacting components.
This explains the reason for the'diñiculty en
CHaOH
cmooC(CH,)1CH=CH(CH,)1CH»
Oleic acid
Glyeeryl dioleate
The presence of sulphonic acids catalyzes the
hydrolysis (i. e., Twitchell reagents) and the result
is that, unless precautions are taken, the content
countered when fatty compounds are sulphonated
of free fatty acid may build up to an undesirable
mass of oil containedwithin a vat or kettle.
extent during sulphonation.
though the stirring may be vigorous enough and
'
The matter is complicated by the fact that the
products of the hydrolysis may react with sul
50 phuric acid. Thus glyceryl dioleate mayform a
mixed ester
in a conventional apparatus in which Sulphuric
acid is dropped slowly into a stirred and cooled
Even
the introduction ofthe sulphonating agent slow '
enough to prevent large masses of unreacted sul
phuric acid from becoming localized, the develop
.ment of localized temperature rises, with conse
quent hydrolysis and charring, is diflicult to pre- '
vent. And of course, slow application of acid
'
increases the cost.
55
Even when continuous streams of the fatty
which may in turn be sulphonated at one of the
double bonds. And the oleic acid may react with
Sulphuric acid at the double bond in one of the
manners referred to above, to form either sul
phated oleic acid or oleic sulphonic acid. Sul
phated oleic acid may be hydrolyzed to replace the
(SOiH) group by an (OH) group. The sulphonic
acid already contains an (OH) group. Either
hydrolyzed sulphated oleic acid or the sulphonic
65 acid may condense, with molecular rearrange
ment, with the (COOH) or acid group to form a
lactone.
, Thus it is'seen that the consequences of hy
_
compound and Sulphuric acid fiow together in
the presence of a blast of air, as in Dutch Patent
No. 27,274, issued July 15, 1932, and the mixture
is ledthrough a cooling coil, the danger of hy
drolysis and charring because of incomplete mix
ing and localized temperature elevations is notcompletely eliminated. And of course the air
blast favors oxidation and renders heat conduc
tion less efficient by reason of the frothing of
the reaction mixture.
,
A
I have discovered that sulphonation of a fatty
compound may be greatly improved by spreading
the fatty compound as a ñlm over a cooling sur
drolysis are disastrous from the standpoint of face, suitably 'of' some; highly heat conducting
obtaining a pure sulphonated glyceride.
. material such as metal, `by mixing the sulpho
„ From the standpoint of obtaining finished sul
nating agent with the film on the cooling surface,
phonated glyceride oils of low free fatty acid con
and causing continuous motion of Ithe film t0
' tent, the time consumed in the processes is a vital 4 homogenize the mixture. The film is preferably
factor, and, in general, the more quickly the sul
moved by a'rotor. l Du'e to the thinness> ofthe
'phoriation is completed and the Sulphonated oil is film, the distance of heat travel through the re
en,
3
2,129,896
action mixture to the cooling surface is very
small, and serious localized> elevations in tem
perature are not possible.
'I'he motion of the rotor tends to cause the fatty
compound and sulphuric acid to unite into a
homogeneous film. The high velocities attained
4favor homogenization.
After the initial mixing, the reaction mixture
is carried by me to a reaction completion vessel,
where the sulphonation is completed while the
mixture is being slowly stirred and cooled. 'I‘he
complete sulphonation requires some time, and
instantaneous contact between the fatty com
pound andthe sulphuric acid is not` enough.
15 After the eflicient mixing which takes place in
the sulphonation mixing milll and the end of the
primary reaction, the dangers due to high tem
perature are Vno longer serious.Y
solution, from 10% in the evening to 18% the
next morning. My centrifuge separation avoids
this difiiculty by virtue of the rapidity of its
action.,
Where I refer throughout the specification and
claims to neutraliaztion, I mean to include partial
„ neutralization. In fact, in the art neutralization
is normally not completed until separation of the
sulphonated fatty compound from the neutral
izíng and washing liquid, and the‘completion of 10
the neutralization is commonly known as “finish-_
ing”. Washing, for example with an aqueous
salt solution, is similar >in its effect to neutraliza
tion,v as it lowers the acidity of the reaction mix
ture, and I intend to include it when I refer to
the neutralizing step.
>Onen of the factors which, according to my ex- ’
.periments, assists in obtaining sulphonated fatty
I next spread the mixture of the fatty com
20 pound and excess sulphonating agent in a film
upon a cooling surface and introduce an aqueous
developed in the neutralization or washing is
readily‘carried to the cooling surface.
I preferably further mix the reaction products
compounds of low free fatty acid content is the
shortness of the elapsed time from the neutrali 20
zation (or washing) of the sulphonation reaction
mixture to the separation of the sulphonated fatty
compound from the neutralizing (or washing)
liquid. It will be‘noted that, in the conventional
practice and in the processes according to my 25
invention, the neutralized (or washed) reaction
mixture is still slightly acid and is considerably
diluted-and therefore much more susceptible to
and neutralizing or washing solution to insure
lhydrolysis than the more concentrated acidic re
neutralizing or washing solution into contact
with the film of fatty compound and excess sul
, phonating agent. The ñlm is turbulently mixed
25 and, due to the thinness of the film, the heat
30 removal of the excess sulphuric acid, and then
centrifugally separate the sulphonated fatty com
pound and the neutralization products or wash
action mixture.
30
«
I have observed that. where the neutralized
reaction mixture is allowed to stand for. an ex
ing solution.
Careful tests with my novel method of sulpho
nation of fatty compounds have shown that I can
produce continuously a lighter colored or less
charred product than that of the prior art, and
can safely allow- the sulphonating temperature
to rise to higher values than those at which prior
40 Aart sulphonators have been successfully operated.
In normal sulphonating operations upon ‘fatty
oils, the oil is charred if the temperature rises
tended ‘length of time before separation from the
neutralizing (or washing) liquid, or where a sepa
rating process such as settling is used which en 35
tails extended delay, considerable increase in the
free fatty acid content results and the free fatty
acid content may even double in an ordinary case.
To avoid this diiilculty I find that very rapid
separation of the neutralizing (or washing) liquid 40
from the sulphonated fatty compound is» desirable
and that the neutralizedfor washed) reaction
above about 35° C., but I have obtained extremely
mixture should pass to the separating mechanism
- light colored sulphonated fatty oils when the
almost immediately after neutralization. Where
„temperature rose to as high‘as about 66° C. This
is, of course, an exceptionally high temperature
and the sulphonation will desirably be carried
out at lower temperature. One explanation of
the fact thatcharring does not occur at tempera
tures as high as 66° C_. is that localized‘tempera
ture elevations present in prior art sulphonators,
but never accurately measured in them, are
avoided in my sulphonator. Another explana
tion is that cooling is very rapid in my sulpho
55 nator, so that the fatty oil is subject to the high
temperature for a very short time.
^
Thus by my process the fatty oil is' never
subjected simultaneously to any appreciable
localized excess of free sulphonating agent'and
60 high temperature.
I also ñnd that I‘ can produce sulphonated fatty
oils of lower free fatty acid content than the
. commercial methods of the prior art.
This I
attribute partly to the decreased hydrolysis dur
ing sulphonation, and partly to the continuous
and relatively rapid separation of the sulpho
nated oil from the neutralization products or
washing solution. I have observed that, if a
vmixture of sulphonated oil, excess sulphuric acid
and salt solution be allowed to stand indefinitely,
for example over night for settling purposes,- the»
content of free fatty acid increases markedly.
For example. I have found that the free fatty
acid of the ñnishedoil, increased in one ‘instance
75 after standing over >nlghi: in contact with salt
’
the elapsed time from neutralization (or wash
ing) to separation is less than 15 minutes, the
increase in free fatty acid is very slight, and good
results are obtained even when the elapsed time
is as great as 30 minutes. vLonger times produce
marked increase in free fatty acid content.
I may by my method sulphonate any quantity
of fatty compound, from a few gallons up. The
proportions of fatty compound and sulphonating
agent are under full control at all times.
The sulphonator of my invention is'not to be
confused with devices intended to refine pe
troleum by treating it with sulphuric acid to re
move unsaturated compounds, sulphur com
pounds and other impurities as a sludge. The
reaction here is instantaneous, and merely in 60
volves direct addition to the unsaturated com
pounds at the double bond.
As the bulk of the -
petroleum `consists of saturated compounds which
are inert to sulphuric acid even at rather high
temperatures, the need for accurate temperature 65
control does not exist in the case of petroleum.
Hydrolysis and charring are not to be feared
where petroleum is concerned.
‘.The reaction mixture of fatty oils and sulphuric
acid is a single phase. Petroleum and sulphuric
acid form distinct immiscible phases. Separation
is a much less difiicult problem in the case of
petroleum than with fatty compounds; it can
even be «accomplished without neutralizing or y
washing.
.
2,129,896
In the drawings I illustrate a typical fatty com
Ul
cold Water. The fatty compound leaves the tank
20 through`a pipe 2t to a fatty compound feed
pump 25 which may be a centrifugal pump.
As later explained, all of the pumps used in
tion from the fatty compound.
The rotor 53 is preferably of uniform cylin
`:my apparatus may desirably have a common
tion to have the clearance space 5l so small that
drive, so that the rate of production of sulpho
nated fatty compounds may readily be controlled.
I illustrate an electric motor 26 driving a cone
pulley 2l, which in turn drives a cooperating cone
pulley 2B through a belt 29, suitably guided by
means not shown.
The cone pulley 25 is on a
common drive shaft 3il,‘which rotates in suitable
' bearings, not shown.
By varying the position
of the belt 29 on the cooperating cone pulleys 2l
and 2t, any suitable speed of rotation of the
common drive shaft 3@ may be obtained.
The common drive shaft 50 carries suitable
25 sprockets 3 l, 32 and 33, the latter of which drives
the sprocket till on the fatty compound feed pump
25 by a chain 35.
From the fatty compound feed pump 25, the
fatty compound passes by the pipe 35 to the sul
30 phonation mixing mill 35. A suitable sulpho
nating agent, for example concentrated sulphuric
acid, is held in a corrosion resistant tanlr. 5l. It
will be understood that all parts of my apparatus
which come in contact with corrosive chemicals
35 are made of suitable corrosion resisting material,
such as stainless steel or lVIonel metal. From the
tank 3l, the sulphonating agent is withdrawn
though a pipe 35 by a sulphonating agent feed
pump 39 which passes measured quantities of sul
40
the clearance space 5l between the cooling sur
pound sulphonator constructed in accordance face t8 and the rotor 53-at the bottom through
with my invention. The fatty oil, fatty acid, etc.„ the pipe 35, and courses upwardly. The sul
phonating agent enters through the pipe ¿l0
which is to undergo treatment in contained with
in a tank 20 cooled by a cooling coil 2l having slightly above the fatty compound inlet, thus
suitable inlet and outlet connections 22 and 23 protecting the bearing 56 somewhat from the sul
to a source of cooling medium such as brine or phonating agent, and insuring it perfect lubrica
phonating agent to the sulphonation mixing mill
through a pipe élu.
The sulphonating agent feed pump 35 is driven
by a chain All from the common drive shaft
sprocket 32 to a sprocket t2 of a variable speed
transmission t3, which in turn drives the sul
phonating agent feed pump 39 by a sprocket Mi,
drical cross section for a substantial part of its
axial length.
It is of importance in my inven
the fatty compound and sulphonating agent
spread out in a thin ñlm against the cooling sur
face. Experiment indicates that the distance
from the surface of the rotor 53 to the cooling
surface ¿3_8 should be less than one-quarter of an
inch and that best results are obtained with a
distance of less than one-eighth of an inch. I
have found a clearance of about one-tenth of 20
an inch to be very desirable.
During the axial travel of the fatty compound
and sulphonating agent in the mill, the ñlms of
fatty compound and sulphonating agent are tur
bulently mixed and the heat developed during 25
the reaction is extracted by the cooling surface.
To obtain rapid and intimate mixing the rotor
is preferably operated at high peripheral speed,
desirably in excess of 500 feet per minute. The
peripheral speed is of course .a function of the
speed of rotation and of the rotor diameter.
While I am not prepared to explain in full detail
the reasons for the' very efficient turbulent mixing
obtained in the sulphonation mixing mill, I believe
that one of the powerful factors in procuring this .
turbulent mixing is the hydraulic shear between
ñlms respectively adhering to the stationary cool-‘
ing surface and to the rotor. One effect of the
turbulent mixing is to cause the reactants to dis
perse in a molecularsense and another effect is 40
constantly to re-orient the reactant molecules
with respect to each other and thus greatly in
crease the probability of molecule to molecule
contact while the molecules are oriented in that
Position most favorable for chemical interaction.
When the mixture of partially sulphonated
through a chain :i5 to a sprocket ¿i6 on the pump.
fatty compound and excess sulphonating agent
The speed of the sulphonating agent feed pump
39 with respect to the c_ommon drive shaft Si@
reaches the top of the sulphonation mixing mill,
50 may be varied infinitely within any chosen range
by the speed change lever @l in well known
manner.
`
It will be evident that the fatty compound and
the sulphonating agent are supplied to the sul
phonation mixing mill under pressure from' the
respective pumps.
The sulphonation mixingmill 35 is shown more
in detail in Figures 2 and 3. In the form shown
its axis is vertical, to avoid the necessity of
60 having a tight packing between the mill and the
motor at the top, but, subject to the need of
proper packings, the axis of the mill may be in
any direction. The mill comprises a preferably
stationary cooling surface which in this case is
65 outside and a moving surface, in close proximity,
which in this case is inside. The cooling surface
it is received in the space 58, thrown centrifugal
1y to the outside, and discharged through a pipe 50
59 to a reaction completion vessel, as shown in
Figure 1, or, by modification of the apparatus,
discharged through a pipe lill to another sul
phonation mixing mill as shown in Figure 1a.
The shaft 53 is reduced in diameter at the top at
Sil, and the reduced shaft is surrounded by a cap
Gi, which prevents any travel of the reaction
mixture up the shaft and into the motor 56.
The reaction completion vessel 62 is shown in
detail .in Figure 4. In the case of sulphonating 60
fatty` compounds, the reaction is not instan
taneous, Yalthough it is by no means so slow as
prior art .intermittent methods would indicate.
lI do not intend to indicate that the size of the
reaction completion vessel with respect to the 65
other parts of the apparatus will necessarily be
as indicated in the drawing, since the reaction
completion vessel will be of a suitable size for
the particular sulphonation, so that the reaction
-will be substantially complete when the reac 70.
¿i8 is a tubular metallic casing which is main
tained at a low temperature by a cooling jacket
59, through whose hollow interior 50 a cooling
medium, suitably brine or cold water, flows from
an inlet 5l to an outlet 52.
f tion mixture leaves the reaction completion ves
Within the annular cooling surface a rotor 53, sel. After the mixing of the fatty compound and
sulphonating agent has taken place in one or
rotatably supported on a bottom bearing 5t se
cured to the base 55 of the mill, is driven at high more sulphonation mixing mills, the reaction mix
75 speed by a motor 5t. The fatty compound enters
ture enters the hopper 63 of the reaction comple
75
2,129,896
tion vessel through the pipe 59, and, while in the
reaction completion vessel, is stirred at rela
tively low speed by the stirrer 64 on the shaft
65, journalled at the base 66 in a bearing 61. 'I‘he
shaft 65 is driven by the motor 68 through speed
reduction gearing 69, of well known character.
The wall 10 of the reaction completion vessel is
surrounded by a cooling jacket 1|, having inlet
'and outlet at 12 and 13 for a cooling medium,
such asbrine or cold water.
'I‘he rate of withdrawal of reaction mixture
from the reaction completion 'vessel 62 through
the pipe 14 is controlled by the reaction mixture
pump 15, which discharges a volume roughly
equal to the total volume of fatty compound and
liquid sulphonatlng agent added te the sul
phonation mixing mill. The reaction mixture
5
the neutralizing agent, and also allows time for
some slight localization of globules of the respec
tive phases in the emulsion.
From the mixing trough |0| the emulsion ñows
by gravity through 'a pipe |04 to a centrifugal
separator |05, preferably entering the bottom of
the separator. 'I‘he heavy sodium sulphate solu
tion is separated from the lighter sulphonated
fatty compound in the centrifugal separator, the
washing liquid passing by the pipe |06 from the
centrifugal separator to the sump |01, and the
sulphonated fatty compound flowing by the pipe
|08 to the tank |09, in which suitable ñnishing
may be carried out, preferably at once.
While I prefer to use a liquid sulphonatlng 15
agent, a gaseous sulphonatlng agent may be sup
pump 15 is driven from common shaft sprocket
3| by ~a chain 16 to a sprocket 11 of the variable
plied if desired. Figure 1a is similar to Figure l
except in certain features., mentioned below.
Fatty compound supplied as explained in con
speed transmission 18, equipped with the speed
change lever 19 which permits infinite speed
nection with Figure 1 passes through a plurality ot 20
variation within the chosen range. The variable
speed transmission 18 drives two sprockets 80 and
8| at the same speed and preferablyÍ on the same
sulphonation mixing mills 36' and 362 connected
by a pipe | l0. Gaseous sulphur trioxide' from a
suitable source conventionally illustrated at |||
is fed to the respective sulphonation mixing mills
shaft, and the latter sprocket drives the reaction
mixture pump 15 by a chain 82 to the pump
through pipes 00' and 402 having valves H2 and 25
sprocket 08.
phonation mixing mill.
The through-put of the sulphonator may be
'
t
From the reaction mixture pump 15, the mix
ture of sulphonated fatty compound and excess
sulphonating agent passes to a neutralizing mill
84 through a pipe 8_5 which isdesirably surrounded
for part of its length by a cooling jacket 86 which
H3 to control the proportional feed to each sul
controlled by'the speed of common drive shaft
30. In experimental work I have found a through 30
put of one gallon of fatty compound per minute'
to be entirely satisfactory for continuous opera
tion, with a clearance of about 0.1 inch and a rotor
receives a cooling medium through an inlet 81
and discharges it through an outlet 88. If de i diameter of about 1.5 inches.`
'I'he proportion of sulphonatlng agent to fatty „.1.
sired, the cooling jacket 86 may be omitted, as
shown in Figure 1a. The neutralizing mill 84 re
compound may be varied by shifting the speed
ceives a neutralizing agent, for example sodium change lever'41 of the variable speed transmission
hydroxide solution, from a tank 89 through a pipe 43 in Figure l. The extent of neutralization may
90, a neutralizing agent pump 9| and a pipe 92. be controlled in Figure 1 by shifting the change
The neutralizing agent pump 9| is driven from speed lever 98 of the variable speed transmission
sprocket 80 of .variable speed transmission 18 95. This is conveniently done by taking samples
through chain 98 to sprocket 94 of variable Speed at the sample tap ||4, and adjusting the >neu
transmission 95, which in turn drives pump ~ tralization until the samples 'show neutrality to
sprocket 96 by chain 91 from sprocket 98. Speed congo red paper, or a pH of about 4.
change lever 99 permits inñnite change in the . . If desired, the neutralization or washing may be
speed of neutralizing agent pump 9| with re
automatically controlled by any suitable auto
spect to common drive shaft 30 within the chosen matic hydrogen ion control mechanism, the detail
^ range. The speed of neutralizing agent pump 9|
i's9 of course also affected by speed change lever
'I'he neutralizing mill 84 may be desirably ex
actly like the sulphonation mixing mill 30 already
described. The same' advantages of thorough
mixing and eiilcient heat removal already de
scribed in the case of the sulphonation mixing
mill are also true of the neutralizing mill. The
ñlm of sulphonated fatty compound and excess
sulphonatlng agent is mixed with the neutralizing
agent, and the heat of the reaction is extracted,
in the neutralizing mill.
`
of which is no part of my invention. For ex
ample, I may use an antimony electrode cell hy
drogen ion controller of the type now generally 50
'available on~ the market. In Figure la I show an
antimony cell ||5 continuously measuring the
hydrogen ion concentration in the mixing trough
|0| and continuously regulating the feed of neu
tralizing or washing agent bythe controller ||6,
connected electrically at -||1 with the antimony
cell and changing the speed of the variable speed
transmission 95 to vary the feed of neutralizing
or washing agent.
55
-
While I generally prefer to introduce the 60
If desired, the neutralizing mill 84 may be used A smaller volume of liquid into a moving ñlm of the
purely as a washing mill, in which case the tank larger volume of liquid, that is, to introduce the
89 will desirably contain sodium chloride or other sulphonatlng agent into a moving film of the
salt solution. The use of the mill 84 for neutraliz»` fatty compound or the neutralizing (or washing)
liquid into a moving ñlm of the reaction mixture,
ing is the preferable use, however, so that else
where I refer generally to the neutralizing use, the procedure may to somewhat less advantage be
although where I refer to neutralizing I mean to reversed, introducing the fatty compound into a
moving ñlm of the sulphonatlng agent or intro
include, the introduction of aqueous solutions gen
erally, for example for washing. As already ducing the reaction mixture into a moving ñlm
noted, neutralization is not really- complete until
~ ñnishing. if then.
The effluent from the neutralizing mill 84 passes
*of neutralizing (or washing) solution.
It will be evident that other forms of control
may be supplied by persons skilled in the art.
by a pipe |00 to a mixing trough |0|, where a
In view of my invention and disclosure varia
stlrrer |02 driven by a motor |03 equalizes any tions and modifications to meet individual whim
slight momentary inequalities in distribution of ` 91' particular need will doubtless become evident
70
- ß
'
2,129,896
to others skilled in the art, to obtain all or part
of the benefits of my invention without copying
the structure shown, and I, therefore, claim all
such in so far as they fall within the reasonable
spirit and scope of the following claims.
Having thus described my invention, what I
claim as new and desire to secure by Letters Pat
ent is:
1. rIi'he method of sulphonating a fatty com
pound, which comprises continuously progressing
10
the fatty compound as a film between relatively
moving adjacent surfaces and introducing a sul
phonating agent into the continuously moving
film of fatty'compound.
15
agentl to complete the reaction, continuously
progressing proportioned quantities of the reac
tion mixture'and a neutralizing agent as a mixed
film between relatively moving adjacent surfaces,
one of which is a second cooling surface, with
drawing heat formed through the second cooling
surface, homogenizing the mixture and centrif
ugally separating the sulphonated fatty com
pound from the remainder of the mixture.
9. The method of sulphonating a fatty com
pound, which comprises continuously mixing a
fatty compound and a proportioned quantity of
2. The method of sulphonating a fatty com
a sulphonating agent as a film between relatively
pound, which comprises continuously progressing
moving adjacent surfaces, the thickness of the
mixed film not exceeding one-_quarter of an inch,
the fatty compound as a film of less than one
quarter of an inch thickness between relatively
moving adjacent surfaces and introducing ‘a
20 sulphonating agent into the continuously moving
ñlm of fatty compound.
3. The method of sulphonating a fatty com
pound, which comprises continuously progressing `
the fatty compound as a ñlm between adja
25 cent surfaces, relatively moving the surfaces,
cooling one of the surfaces and adding a sul
phonating agent to the continuously moving film
v of fatty compound.
4. The method of of sulphonating a fatty com
30
formed through the first cooling surface, slowly
mixing thel fatty compound and sulphonating
pound, which comprises continuously progressing
the fatty compound as a film‘of less than one
quarter of an inch thickness, between relatively
moving adjacent metallic surfaces, adding a sul»
phonating agent to the continuously moving film
35 of fatty compound and withdrawing the heat
developed through one of the metallic surfaces,
whereby the thinness of the film facilitates with
drawal of the heat and assists in avoiding char
rîng of the fatty compound.
40
5. The method of sulphonating a fatty com
pound, which comprises continuously progressing
the fatty compound as a iilrn, adding a sul
phonating agent to the continuously moving film
of fatty compound, shearing the film between re
45 latively moving walls separated not more than
one-quarter of an inch and concurrently with-v
drawing the heat formed, whereby the thickness
of the film facilitates withdrawal of the heat and
assists in avoiding charring of’ the fatty com
50
adjacent surfaces, the thickness of the mixed
film not exceeding one-quarter of an inch, and
concurrently withdrawing heat formed.
25
l0. The method of sulphonating a fatty com
pound, which comprises continuously mixing a
fatty compou'nd and a proportioned quantity of
a sulphonating agent as a film between relatively
moving adjacent surfaces, the thickness of the 30
mixed film not exceeding one-quarter of an inch,
concurrently withdrawing heat formed, con
tinuously stirring the mixture for reaction
completion, continuously mixing the stirred re
action mixture and a proportioned quantity of a ‘ 35
neutralizing agent as a film between relatively
moving adjacent surfaces, the thickness of the
mixed film not exceeding one-quarter of an inch,
concurrently withdrawing heat formed, and con
tinuously centrifugally separating the sulphon- n
ated fatty compound from the remainder of the
mixture.
11. In a sulphonator for fatty compounds, rela
tively rotatable cooperating members having a
clearance space of. film thinness between them
through which the fatty compound and sulpho
nating agent may ñow means for rotating one of
the members, means for cooling one of the mem
bers, means for pumping a fatty compound,
conduit means communicating from said means
which comprises continuously progressing the
ance space, meansl for pumping a sulphonating
agent proportionally to the means for pump
ing the fatty compound and conduit means com
municating from said means for pumping the
sulphonating agent to the clearance space.
6. The method of sulphonating a fatty oil,
acid to the whirling film of fatty oil,u shearing
55 the- film between relatively rotating metallic sur
faces and withdrawing heat through one of the
metallic surfaces, whereby a sulphonated oil of
reduced free fatty acid content is produced.
7. The method of neutralizing the excess sul
60 phonating agent in. a reaction mixture resulting
from the sulphonation of a fatty compound,
which comprises continuously progressing the
reaction mixture as a film between relatively
moving adjacent surfaces, introducing a neutral
izing agent into the film, shearing, the neutraliz
ing agent and reaction mixture between the sur
faces and concurrently withdrawing the heat
formed from the mixed film through one of the
surfaces.'
8. The method of sulphonating a fatty com
pound, which comprises continuously progressing
proportioned quantities -of the fatty compound
and a sulphonating agent as a mixed film be
tween relatively moving adjacent surfaces, one of
75 which is a ñrst cooling surface, withdrawing heat
20
ture and a proportioned quantity of a neutraliz
ing agent as a film between relatively moving
pound.
fatty oil as a whirling nlm, adding sulphuric
70.
œncurrently withdrawing heat formed, continu
ously stirring the mixture for reaction completion,
continuously mixing the stirred reaction mix
for pumping the fatty compound to the clear
' l2. In a sulphonator for fatty compounds, a
casing having an annular interior, means for
cooling the casing, a rotor within and cooperat
ing with the casing having a slight clearance
from’the casing for a substantial axial length, a
plurality of inlet conduits adjacent one endv of
the rotor and communicating with the clear
ance space, an outlet conduit adjacent the oppo
site end of the rotor and means for driving the
rotor.
13. A tubular mixing mill for the sulphona
tion of fatty compounds comprising a tubular
casing, means for cooling the casing, a rotor of
substantially uniform cross section for a sub 70
stantial axialdistance within and cooperating
with the casing, having a clearance from the
casing of less than one-quarter inch, means for
turning the rotor, an inlet to the clearance space
adjacent one end of the rotor and an outlet 75
7
2,129,896
from the clearance space adjacent the other
end.
14. A mixing mili for use in the sulphonation
of fatty compounds comprising cooperating rela
tively rotatable circular members having a clear
`ance of less than one-quarter of an inch for
a substantial axial distance, means for rotating
one of the members, means for cooling one of the
members, means for introducing the reaction in
10 gredients adjacent one end and passing them
through the mill and means for withdrawing
the reaction mixture adjacent the other end of
the mill.
`
15. A mixing mill for use in the sulphonation
15 of fatty compounds comprising a tubular ver
tical casing, cooling means for the casing, a cylin
drical vertical rotor within and cooperating with
the casing, leaving a clearance'space between the
casing and the rotor of less than one-quarter of
20 an inch, inlet and outlet conduits to and from
ing one wall with respect to the opposing nearly
adjacent other wall and means for concurrently
progressing streams of the fatty compound and
of the sulphonating agent into the conduit at
parts of the conduit toward one end thereof and
for delivering the resulting stream of sulphonat
ing compound out of the conduit from a part of
the conduit toward the other end thereof,
19. In a device for sulphonating a fatty com
pound by a sulphonating agent, a mixing mill 10
having an annular conduit of ñlm thinness pro
vided With angularly relatively movable nearly
adjacent inner and outer walls, means for an
gularly rotating one wall .with respect to the
opposing nearly adjacent other wall, means for 15
cooling one of the walls, and means for con~
currently progressing streams of the fatty com
-poundi'and of the sulphonating agent into the
conduit at parts of the conduit toward one end
thereof and for delivering the resultant stream 20
of sulphonated compound out of the conduit from
the clearance space adjacent the ends thereof,
and means at the top of the rotor for driving ' a part of the conduit toward the other end
the rotor at a peripheral speed in excess of 500 thereof, the sulphonating agent being progressed
into the conduit at a point longitudinal of the
feet per minute.
conduit between the part at which the fatty 25
16. A sulphonation mixing mill for fatty com
25
pounds comprising a tubular vertical casing, compound is introduced and the part at which
cooling means for the casing, a cylindrical ver
tical rotor within and cooperating
ing, having a clearance from the
30 than one-quarter of an inch for
axial lengtn, a bearing for the
with the cas
casing of less
a substantial
rotor at the
bottom, means for introducing -a fatty com
the sulphonated stream is delivered, whereby the
stream‘of sulphonating agent is delivered into a
stream of fatty compound, as distinguished from
delivering the stream of fatty compound into a 30
stream of sulphonating agent.
`
20. In a device for sulphonating a fatty com
pound under pressure adjacent the bearing,
pound by a sulphonating agent, a mixing mill
means for introducing a sulphonating agent un
having an annular conduit of film thinness pro
35 der pressure above the point of introduction of
the fatty compound, means for withdrawing the
reaction mixture adjacent the top of the rotor
and means for1 driving the rotor at the top,
whereby the fatty compound under treatment
40 serves to lubricate the bearing.
17. In a sulphonator for fatty compounds, a
sulphonation mixing millhaving a cooling sur
face and having a rotor providing a clearance
space of not more than one-quarter inch between
45 the surface and the rotor, in which space tur
bulent mixing takes place, means for continu
ously introducing a fatty compound to the space
and means for continuously introducing sulphur
trioxidey to the space.
`
18. In a device for sulphonating a fatty com
pound by a sulphonating agent, a mixing mill
having an annular conduit of film thinness pro
, vided with angularly relatively movable nearly
adjacent inner and outer walls, means for cool
55 ing one of the walls, means for angularly rotat
vided with angularly relatively movable nearly 35
adjacent inner and outer walls, means for angu
larly rotating the inner Wall about its longi
tudinal axis, means for cooling one of the walls,
a bearing for the inner wall near one end of
the conduit and means for concurrently pro
gressing streams of the fatty compound and of
the sulphonating agent into the conduit at parts
o1" the conduit toward the end having the bear
ing and for delivering the resulting stream of
sulphonated compound out of the conduit from
a part of the conduit toward the other end
thereof, the fatty compound being progressed
into the conduit at a part of the conduit located
longitudinally of the conduit between the bear
ing and the said part into which the sulphonat 50
ing agent is progressed, whereby the stream of
fatty compound protects the bearing from the
stream of sulphonating agent.
DANIEL S. WHITEMAN.
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