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Патент USA US3069253

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Dec. 18, 1962
3,069,243
R. J. BROOKS EI'AL
REACTION APPARATUS
Filed Nov. 18, 1958
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Dec. 18, 1962'
R. J. BROOKS ETAL
3,069,243
REACTION APPARATUS
Filed NOV. 18. 1958
2 Sheets-Sheet 2
COOLED
RE -
CIRCULATION
MIXTURE
United States Patent O?fice
3,069,243
Patented Dec. 18, 1962
2
1
3,069,243
REACTION APPARATUS
Richard J. Brooks and Burton Brooks, Seattle, Wash., as
signors to The Chemithon Corporation, Seattle, Wash,
a corporation of Washington
Filed Nov. 18, 1958, Ser. No. 774,740
5 Claims. (Cl. 23-260)
This invention relates to a sulfonation process, a sulfa
of sixty (60%) percent sulfuric acid dilution is up to
approximately one hundred times that of eighty (80%)
percent sulfuric acid dilution.
Turning now to a speci?c separation of the sulfonic
acid from the ‘excess sulfonating agent for the batch
process employing a 2,300 gallon batch of the alkyl ben
zene and the sulfuric acid, the sulfuric acid is diluted to
a concentration of approximately eighty (80%) percent
strength and the temperature range is maintained in the
tion process and apparatus for carrying out these proc 10 range of approximately one hundred and thirty to one
hundred and thirty-?ve (130-135“ F.) degrees. For this
esses, and more particularly, to said processes where the
reactant and the active sulfonating and/or sulfating agent
are substantially completely simultaneously contacted,
mixed and reacted, and then subjected to conditions to
2,300 gallon mixture a four-hour setting time is required
to yield a product comprising approximately eighty-?ve
remove the extraneous gas added or generated therein.
extraneous material. In all, for the batch process of
sulfonation and separation of the excess sulfonating agent
from the sulfonic acid product there is required a total
time of approximately seven to eight hours.
The sulfonic acid product has a typical analysis as fol
A number of processes have been employed for re
acting organic materials such as an alkyl aromatic, i.e.,
alkyl benzene, having l0—l8 carbon atoms in the side chain
with a sulfonating agent to produce an alkyl benzene sul
(85%) percent sulfonic acid and ?fteen (15%) percent
fonic acid, and an organic material like an ester with a 20 lows: sulfonic acid, 87.7%; sulfuric acid, 8.5%; and,
water, 3.8%. This product, even when neutralized may
sulfating agent. A typical batch reaction process may
be carried out in a 2,500 gallon glass lined vessel equipped
with a mixer. Additional mixing is also provided by an
external circulation system which discharges into the top
of the sulfonator through a distributor head. A heat ex
changer of about 1,000 square feet is employed in the
circulating system to remove the heat of sulfonation.
still contain considerable quantities of extraneous salt.
A product that is nearly salt free can be made by using
either sulfur trioxide or chlorosulfonic acid as the sulfonat
25 ing or sulfating agent.
In a continuous process for the sulfonation of an alkyl
aryl the alkyl aryl and sulfonating agent such as twenty
two (22%) percent fuming sulfuric acid, oleum, and in
Stainless steel (type 316) is satisfactory for the circulating
timately mixed to form a reaction solution or mixture.
system and may be used for the reactor if desired. The
sulfonation cycle starts with the charging of 1,400 gallons 30 This mixture is allowedto digest at a temperature of
approximately 120° F. for a period of from eight to
of an alkyl benzene to the vessel. Circulation of alkyl
?fteen minutes. Then the mixture is mixed with water
benzene is started through the exchanger and oleum is
so as to form an emulsion comprising as the continuous
slowly added to the alkyl benzene at the suction side of
phase excess sulfonating agent, i.e., with water and excess
the circulating pump. The acid addition rate is controlled
so that the reaction temperature does not exceed 85° F., 35 sulfonating agent as sulfuric acid, and as the discontin
uous phase the sulfonic acid product. The viscosity of
and usually about one and one-half to two hours, are
this emulsion is relatively low and by allowing the same
required for the acid addition. After 740 gallons of twen
to ?ow into a separation vessel the emulsion separates
ty-two (22%) percent oleum have been added the mixture
into the lighter sulfonic acid product and the heavier
98-99% of the alkyl benzene is converted to alkyl ben 40 excess sulfonating agent. The time for the separation
step is approximately ten minutes. The total time to sul
zene sulfonic acid. A typical analysis of the stock at this
fonate the alkyl benzene and then to separate the excess
stage shows: sulfonic acid, 60-61%; sulfuric acid, 38
sulfonating agent from the sulfonic acid product is ap
39%; water, 0.5%; and, residual oil, 0.5%.
proximately, 18-25 minutes. As contrasted with the batch
Turning now to a batch process for separating the
process the continuous process is considerably shorter in
alkyl benzene sulfonic acid from excess sulfonating agent,
the time requirement, i.e., 18—25 minutes as contrasted
it has been found that the excess sulfonating agent must
is digested at 85° F. for one hour. With these conditions ,
be diluted with water to lower the concentration to a
with seven to eight hours.
value of approximately eighty (80%) percent sulfuric
In this invention we have developed continuous sul
fonation and sulfation processes and an apparatus for
:
acid so as to ‘obtain a substantially complete separation
from the sulfuric acid from the sulfonation mix. This 50 carrying out the same wherein a reactant may be reacted
with the sulfonating agent and/or a sulfating agent to
is a result of the mutual insolubility of the sulfonic and
produce a product. The gas employed in or generated
sulfuric acids. This dilution step requires a thorough
in the reaction may be removed. More particularly, the
mixing of the diluted sulfonated mix in order to remove
reactant and the agent are substantially simultaneously
the localized gel structure formed between sulfonic acid
and the water. The temperature during dilution is con 55 completely contacted, mixed and reacted to form the
trolled to a value in the range of 135-145 ° F. maximum -
' product.
There is no long digestion time for digesting
the reactant and the agent to form the product. Actually,
the agent and the reactant are so intimately mixed that
zene sulfonic acid. As is well known, if the temperature
upon mixing the same the. reaction takes place. This
increases to above approximately 145° F., even with the
60 mixing time may take two or three seconds. Then, the
decrease in the concentration of the sulfuric acid, there
mixture of the reactant to the agent is diluted with a
is further reaction between the alkyl benzene sulfonic
large excess of a previously prepared product so as to
acid and the sulfuric acid to degrade the color of the sul
substantially stop the reaction. This resulting mixture
fonic acid. If the acid is diluted below approximately
is then subjected to a pressure condition wherein the
eighty (80%) percent sulfuric acid, the product does not
extraneous gas is removed therefrom. Then, the degassed
have any higher active content of sulfonic acid but the
resulting mixture comprises the product. There is no
setting time required to separate the sulphonic acid and the
need to separate the product from excess sulfonating
sulfuric acid is reduced. However, the chief disadvantages
agent in the degassed resulting mixture because the
of greater dilution are that corrosion of stainless steel
amount of excess sulfonating agent is so small that it is
equipment (sulfonator heat exchanger) is greately in 70 not practical to separate the same. Furthermore, the
creased and the color quality of the product is poor. For
contamination by this small amount of excess sulfonating
example, laboratory tests indicate that the corrosive rate
agent is less than in previous process and systems wherein
so as to minimize the color degradation of the alkyl ben
3,069,243
3
the excess sulfonating agent has been separated from the
reactant. Therefore, if a neutralized product is desired
it is possible to mix the acid product with an alkaline
or caustic material to form the salt of the acid product.
As is seen, the total reaction time to carry out this
sulfonation and/ or sulfation process is very short, approxi
mately four minutes or less. Also, the apparatus re
quired to carry out this sulfonation and/or sulfation
process is less than in the previous batch processes or the
tained at a minimum. Furthermore, degradation is also
largely eliminated because there is mixed in with these
fresh reactants a large excess of the previously prepared
and cooled product. This large excess on a volume basis
is approximately at a minimum of ?fteen parts of the
product to one part of the combined volume of the
reactant and the agent (15:1). The temperature of the
recycled product is approximately 118° F. Therefore,
due to its large excess, functions as a dilution factor
previous continuous processes.
10 and prevents the reaction mixture from staying at a rela
Accordingly, it is an object of this invention to provide
tively high temperature. In other words, due to the
a sulfonating process, a sulfating process, and apparatus
large excess of the previously prepared product the tem
therefor which requires less time for the sulfonation
perature of the new reaction mixture is brought down to
and/ or sulfation of a reactant.
one in the range of approximately 120° F.
The new
A further object is the provision of apparatus for 15 reaction mixture or diluted mixture is then degassed or
sulfonation and/or sulfation wherein intimate contact is
the extraneous gas is removed. This is possible by spray
achieved between the sulfonating agent and/ or the sulfat
ing agent and the reactant.
A further object is the provision of a sulfation process
ing the diluted mixture into a tank whereby the pressure
inside of the tank is such that the extraneous gas escapes
and is removed. Some of the resulting degassed mixture
and a sulfonation process and apparatus therefor wherein 20 is recycled through a heat exchanger and back into the
mixing means so as to function as the coolant as previ
a high quality product is realized as there is less degrada
tion of the product by the sulfonating agent and/or the
sulfating agent.
ously explained.
Some of the degassed mixture is then
mixed with an alkaline material to form a neutralized
Another object is the provision of a sulfating process,
product.
a sulfonating process, and apparatus therefor, and which 25
Restricting this at the present time to the reaction of
allows for the continuous removal of extraneous gas
chlorosulfonic acid with an alcohol and a non-ionic deter
introduced to the reaction or generated in the reaction,
gent, it is seen that the chlorosulfonic acid, a liquid, is
and also to provide for the contacting of the reactants
mixed with the reactant to be sulfated. This mixmg is
under various absolute pressures.
carried out in a mixing pump whereby the acid and the
An additional object is the provision of a sulfonating
reactant are substantially simultaneously mixed and re
process and a sulfating process and apparatus therefor
acted within a very short period of time, i.e., less than
wherein there is less sulfonating agent and/0r sulfating
about ?ve seconds. There is employed a slight excess
agent in the ?nal product as contaminants.
of the acid. More particularly, there is employed an
A still further object is the provision of a sulfating
approximately 2-5 mol percent excess of the acid with
process and a sulfonation process wherein less costly and 35 respect to the reactant so as to insure su?icient acid
less complicated apparatus is required ‘than in previous
present to react with all the reactant. The temperature
processes.
A still further important object of this invention is the
of the reactants are about room temperature. Upon the
reactants being mixed the temperature rapidly rises to
provision of a sulfonation process and a sulfation process
one in the range of 132—138° F.
requiring lower cost equipment than previous processes.
These and other important objects and advantages of
is in this temperature range for only a short period of
time as it is diluted with a large excess of previously
prepared product at a temperature of about 118° F.
The reaction mixture
the invention will be more fully brought forth and pre
sented in the following speci?cation and claims.
Also, degradation of the product is partially avoided
Referring to the drawing, it is seen:
because there is a very small excess of the acid. Upon
FIGURE 1 is a schematic outline of the apparatus
the mixing of the reaction mixture with the previously
required to carry out the sulfonation and sulfation proc
prepared product there is formed a dilution mixture.
asses of this invention and also illustrates in schematic
When using chlorosulfonic acid to sulfate, large volumes
form the process.
of hydrogen chloride gas are liberated. Therefore it is
FIGURE 2 is a fragmentary schematic outline of
necessary to remove this gas in order to produce a satis
another variation in the process for reacting a sulfating 50 factory product. This dilution mixture is sprayed into
agent and a reactant; and
a column or tank or tower at a pressure of approximately
FIGURE 3 is a fragmentary schematic outline of a
?fteen to twenty-?ve inches Hg, absolute pressure, or
variation in the process for reacting the product with a
conversely, at a vacuum of about ?ve to ?fteen inches
small amount of water prior to neutralizing the product.
Hg. At this pressure the hydrogen chloride gas or any
This invention is for the processes of sulfonation and 55 extraneous gas in the dilution mixture is allowed to
sulfation and includes the apparatus for carrying out
escape. The resulting degassed mixture is split into two
these processes. Generally, in these processes a reactant
parts. The ?rst part is recirculated through a heat ex
capable of reacting with a sulfonating or sulfating agent
changer and introduced into the mixing means so as to
is contacted with the agent in a mixing means. This
act as a diluent, as previously explained, for the reaction
mixing means is capable of substantially simultaneously 60 mixture. Upon leaving the heat exchanger the tempera
completely contacting and mixing the reactant and the
ture of this ?rst part is approximately 117-118° F. The
agent. The contacting and mixing is so complete that
second part of the degassed mixture is introduced into
the reaction takes place in a very short period of time,
i.e., almost upon the contacting and mixing of the re
actant and the agent. However, degradation of the
product is avoided because of the small excess of the
agent with respect to the reactant and because of the
low concentration of the agent in the mixture. Upon the
basis of 100 mols of reactant there is normally employed
a mixing means along with sodium hydroxide, or other
neutralizer, to form a neutralized sulphate or product.
Referring now to the reaction between a reactant and
sulfur trioxide it is seen that the sulfur trioxide may be
employed as a sulfonating agent and as a sulfating agent.
It is used to sulphate alcohols and unsaturated oils. As
a sulphonating agent it is used on alkyl benzene and un
103 to 105 mols of the agent so as to provide an excess 70 saturates. The process for reacting the reactant with sul
of approximately 3 to 5 mols of the agent. With this
fur trioxide varies from that for reacting a reactant with
small excess of the agent, with the dilution of the sulfo
chlorosulfonic acid. More particularly, sulfur trioxide, as
nating or sulfating agent with an excess of gas admitted
is well known, is a gas at temperatures above 115° F. The
to the reaction or generated in the reaction, or with a
gaseous sulfur trioxide is mixed with an inert gas such
.low partial pressure of the agent degradation is main 75 as air, carbon dioxide ornitrogen to make a gaseous mix
3,069,243
5
6
a centrifugal pump 17 are two concentric pipes 18 and
ture. This gaseous mixture is then led into the mixing
means along with the reactant. The ratio of the inert gas
to the sulfur trioxide in this gaseous mixture is approxi
mately 4 to 11 volumes of inert gas to one volume of
the sulfur trioxide. In the mixing means the gaseous
mixture and the reactant are substantially simultaneously
20. These concentric pipes terminate approximately one
eighth to one-fourth inch from the impeller blade in the
pump. "By terminating such a short distance from the
impeller blade the gaseous mixture and the reactant are
substantially simultaneously contacted and mixed. The
gaseous mixture may be, for example, introduced through
pipe 18 and the reactant may be fed by pipe 20 into the
mixing pump 17. Following this pump, as previously
completely contacted, mixed and reacted in a relatively
short time. The temperature of the reactants‘ are at
approximately room temperature and rises to about 132°
stated, the gaseous mixture and the reactant are substan
F. with the addition of nearly seventy (70%) percent of
tially simultaneously contacted and mixed into a reaction
the sulfur trioxide. Thereafter the temperature of the
mixture. There is also introduced into the centrifugal
reaction mixture is maintained in the range of 132~138°
pump, near the periphery of same, a cooled recirculation
F. until completion of the addition of the sulfur trioxide.
mixture 21. The volume of this cooled recirculation
In this process there is employed from 2—5% excess sul
fur trioxide over the theoretical requirement. The higher 15 mixture is at least ?fteen volumes to one volume of
reaction mixture. The mixing of the cooled recirculation
temperatures in the later stages of this mixing process is
mixture and the reaction mixture in the mixing means
necessaryto keep the viscosity su?iciently lo»! to permit
17 causes the formation of a diluted mixture 22. The
the necessary violent agitation. While Within the same
temperature of the cooled recirculation mixture 21 is
mixing means or of another mixing means the reaction
mixture is diluted with a large excess of the previously 20 approximately 117-118" F., and the temperature of the
diluted mixture is about 122—123° F. The diluted mix
prepared product at a temperature of about 117—118° F.
ture 22 is sprayed into a degassing column 23 by spray
This dilution with a large excess of the previously pre
means 26. This degassing column 23 has a cylindrical
pared product at a lower temperature to form a dilution
Wall and a cone cap 25 therein. The cone cap, at its
mixture decreases the temperature‘ of the reaction mix
ture to a value of approximately 120~1Z2° F. The dilu 25 periphery, does not completely contact or is not in com
plete contact with the Wall 24. When the mixture 22 is
tion mixture is then sprayed into a tower, so as to allow
sprayed into the column 23 extraneous gas escapes there
extraneous gas to escape therefrom. The pressure in this
from. The mixture ?ows down the walls of the column
tower or column may vary from approximately eleven
and collects in the bottom of the same to form a degassed
inches of mercury absolute to about twenty-eight and
one-half inches mercury absolute.‘ In the reaction be 30 reaction mixture 27. There is an exhaust means 28 and
an aspirator or pressure unit 30 for adjusting the pressure
tween the reactant and the sulfur trioxide there is em
in the column 23.
.
ployed approximately 2—5 mol percent excess of the
In combination with the degassing column 23 is a level
sulfur trioxide. The sulfur trioxide is apparently 'dis~
control 31 comprising a control unit 33 and a ?oat 32
solved Within the product so that in the degassing step
the sulfur trioxide is not removed or does lnot escape. 35 inside of the column. This ?oat varies with the level of
the degassed reaction mixture in the column, and the
Therefore, in this degassing step the inert gas such as air,
control 33 connects with a control valve 34 whereby the
nitrogen or carbon dioxide escapes or is removed while
flow of the product 37 is regulated. This will be more
the sulfur trioxide remains dissolved in the product. The
particularly described hereinafter. Connecting with the
product is then split into fractions. The ?rst fraction
is pumped through a heat exchanger whereby the tem 40 degassing column 23 is a pumping means 35 such as a
perature is lowered to a value of approximately 117
118° F.‘ andv then introduced into the mixing pump to
act as a diluent for the reaction mixture. The amount
of ?rst fraction recycled is at least ?fteen volumes to
one volume of the combined volume of the reactant. The 45
centrifu gal pump or .a gear pump. The degassed reaction
mixture flows to purnp35 and from there is split into two
fractions, a recirculation mixture 36 and a product 37.
There is a valve 38 in the recirculation mixture line which
can be used for throttling the ?ow of the recirculation
mixture. It is desirable to maintain the pressure on the
tank does not exceed three minutes maximum. The sec
ond fraction is then pumped to a mixing means wherein
it is mixed with a neutralizing agent such as aqueous
degassed reaction mixture entering the recirculating pump
35. One Way of accomplishing this is to position’ the
residence time in the recycle loop including the ‘degassing
pump 35 a number of feet below the degassing column
50 23. For example, the pump 35 may be approximately
three or more feet below the outlet of this column. The
ever, before mixing with the neutralizing agent the second
sodium hydroxide to form a neutralized product. How
fraction may be mixed with a small amount of water,
approximately two (2%) percent by weight so‘ as to
rleact with any anhydrides present and thereby break
t em.
In the schematic diagram illustrating the apparatus
proper and the combination of the apparatus, the separate
units for carrying out sulfonation and sulfation are
a.a.
recirculating mixture 36 ?ows to a heat exchanger 40.
As previously stated the temperature of this cooled re
circulation mixture is approximately 117-118“ F. The
55 temperature of the recirculation mixture 36 entering the
heat exchanger is approximately 122—123° F. The total
residence time in the recirculating loop should not exceed
three minutes, and preferably much less.
The product 37 ?ows through valve 34 to centrifugal
presented in FIGURES 1, 2 and 3. Referring to FIG
URE 1, this ?gure illustrates .sulfonation and sulfation 60 pump 41. Leading into this pump are two concentric
pipes 42 and 43. These two pipes terminate about one
with sulfur trioxide. It is seen that there is a source of
eighth to one-fourth inch from the impeller blade. The
sulfur trioxide 10. Generally, the sulfur trioxide‘is sup
product 37, for example, can be fed into the pump, 4.1
plied in a liquid state and has been through a proportion~
through pipe 42 and a neutralizing agent, such as aque
ing pump 11. It is introduced into a ?ash evaporator 12
whereby it is changed from a liquid state to a vapor 65 ous sodium hydroxide 44, may be fed into the pump
through pipe 43. By so introducing the product and the
state. As sulfur trioxide by itself ‘is not employed for
neutralizing agent into the pump they are substantially
sulfonating because of its degrading qualities with .a reac
simultaneously contacted, mixed and reacted to form a
tant, there is mixed with the sulfur trioxide an inert gas
such as air or nitrogen or carbon dioxide. ' Air 13 is fed
into a proportioning pump 14. ‘ The gaseous sulfur'tri
neutralized product 45.
oxide from the ?ash evaporator 12 and the air are fed
into a mixer 15 whereby there is formed a gaseous mix
ture for reacting with the reactant 16. The gaseous mix;
ture of inert gas ‘and sulfur trioxide and the reactant are
31 so as to regulate the flow of the product 37.
As previously stated the valve 34 is controlled by unit
By
regulating the ?ow of the product 37 it is possible to
‘maintain. the level of the degassed reaction mixture in
the column 23 at a constant low level. For example, if
fed into a mixingmeans 17. Leading into the intake of 75 the level’ of the degassed mixture 37»becomes too high
8,069,243
8
7
Example 11
then the valve 34 is opened so that more product can
?ow. Conversely, if the level of the mixture 37 becomes
too low then the valve 34 is closed so as to decrease the
quantity of the product 37 ?owing therethrough. The
same result can be accomplished with a sight glass and
An alkyl benzene having from ten to ?fteen carbon
atoms in the side chain was sulfonated with sulfur triox
ide.
The liquid sulfur trioxide was vaporized and the
a manual control valve.
vapors mixed with air to make a mixture containing by
through pipe 20. A cooled recirculation mixture 21 is
they were substantially simultaneously contacted and
neutralized product. As previously stated the contacting
average residence time was about one minute.
volume, about eig'it (8%) percent sulfur trioxide. Five
In FIGURE 2 there is illustrated a fragmentary por
pounds per minute of the alkyl benzene were mixed with
tion of the apparatus for reacting the reactant 46 with
one and sixty-?ve hundredths pounds per minute of sul
chlorosulfonic acid 47. The reactant 46 may be intro
duced into centrifugal pump 17 through pipe 18 and the 10 fur trioxide. The reactants were kept separated until
they were introduced into a centrifugal pump wherein
chlorosulfonic acid may be introduced into the pump
mixed into a reaction mixture. In turn the reaction mix
also introduced intot he pump 17 near its periphery and
ture was mixed with a recycled cooled reaction mixture,
there is expelled therefrom a diluted mixture 22. The
rest of the system is the same as presented in FIGURE 1. 15 ?ow rate of twenty-?ve gallons per minute, or in the ra
tio of about one part reaction mixture to about twenty
In FIGURE 3 there is presented a modi?cation of the
?ve parts recycled mixture (1:25), to form a dilution
sulfonation apparatus of FIGURE 1. In this modi?ca
mixture. This dilution mixture ?owed directly to a de
tion there is inserted between the valve 34 and the mix
gassing chamber about twelve (12") inches in diameter
ing means 41 a centrifugal pump or mixing means 48.
Leading into this pump 48 through a pipe 51 is an aque 20 and about eighteen (18") inches in height, and main
tained at an absolute pressure of about ten (10") inches
ous medium such as water 52. Also, leading into this
of mercury. From the bottom of the degassing chamber
mixing means is pipe 50. The product 37 ?ows through
the acid was pumped by means of a positive displacement
valve 34 and through pipe 50 into the means 48. Water
pump and through a heat exchanger where the tempera
52 ?ows through pipe 51 into this means 48. There
results an aqueous product which ?ows through pipe 43 25 ture was adjusted to about 125° F. The cooled reaction
mixture then was recycled, to the mixing pump and a
into mixing means 41. Aqueous sodium hydroxide solu
quantity of sulfonic acid equal to the rate of feed over
tion 44 flows through pipe 42 into the mixing means 41
?owed. The volume of the system was such that the
where it is mixed with the aqueous product to form a
Before
of the product 37 with an aqueous medium, approxi 30 ‘being neutralized the acid was mixed with two (2%)
percent by weight of water, and then mixed with an eight
mately two (2%) percent water by weight, breaks any
een (18%) percent by weight sodium hydroxide solution
anhydrides present in this product.
to form a neutralized product having the following
The size of the degassing column 23 depends upon‘the
analysis.
plant capacity, but a column sufficient to handle two
pounds of alkyl benzene per minute may be approxi 35 Component:
Percent by weight
mately four inches in diameter, about twelve inches in
Active sulfonic acid __________________ .._
39.6
height from the level of the degassed reaction mixture
Free alkyl benzene oil ________________ __
0.4
which is maintained approximately four inches in depth.
Having presented a speci?c teaching of the sulfonation
process, the sulfating process and the apparatus used for
carrying out these processes, we will now present ex
amples illustrating the same. It is to be understood that
these examples are by way of illustration only and are
1.9
Having presented our invention it is to be realized that
it may be employed with many different types of organic
compounds such as the esters of organic acids, unsatu
rated and saturated esters, aliphatic aromatic compounds,
alcohols both saturated and unsaturated, and the like.
not to be taken as limitations on the invention.
Example I
We claim:
A saturated fatty alcohol having the following com
position is sulfated with chlorosulfonic acid:
Component:
Sodium sulfate ______________________ __
Water _____________________________ _.. Balance
Percent by weight
1. An apparatus for continuously reacting reactants,
comprising, in combination, a centrifugal purrp having
an impeller blade, two concentric pipes leading into the
50 centrifugal pump and terminating near the edge of the
C‘—12
________________________________ __ 65.7
impeller blade, one of said concentric pipes being used to
C-14
_________________________________ __ 20.2
convey a ?rst ?uid reactant into the pump, the other one
of said concentric pipes being used to convey a second
?uid reactant into the pump, said impeller blade simul
This alcohol is fed at a rate of nine pounds per min
taneously contacting and mixing said ?uids to form a re
ute through concentric pipes to the mixing pump 17 55 action mixture in the pump, a degassing chamber, means
where it is mixed with 6.3 pounds per minute of chloro
to vary the absolute pressure in the degassing chamber
C-16
_______ _~_ ____________________ __
Balance
sulfonic acid. The reactants are also mixed with a large
to a pressure less than atmospheric to permit extraneous
gas to escape from the reaction mixture, a ba?ie plate in
said degassing chamber, a means to spray the reaction
of approximately 123° F., is sprayed into the degassing 60 mixture over said ba?le plate so as to have a large sur
column 23 at an absolute pressure of approximately ?f
face area per unit volume of the reaction mixture, con
teen inches Hg. The recirculation rate of'the cooled re
veying means interconnecting the pump and the degass
excess of recirculated acid from the degassing chamber.
The resulting diluted reaction mixture, at a temperature
action mixture, at a temperature of approximately 117°
ing chamber to convey the reaction mixture from the
F., is at least twice the feed rate of the fresh reactants.
pump to the means to spray the reaction mixture over
65
The product 37 is neutralized with caustic soda to form
said ba?le plate, said degassing chamber removing ex
a neutralized product. The resulting sulfate has the fol
traneous gas from said reaction mixture to form a lower
lowing analysis:
degassed reaction mixture layer and an upper gaseous
layer, means in said degassing chamber responsive to the
Component:
Percent by weight
Active ingredient ____________________ __
26.4 70 level of the degassed reaction mixture for controlling the
level of the same, a recirculating pump, a heat exchanger,
Unreacted alcohol ____________________ __
1.5
Sodium chloride _____________________ __
Sodium sulfate ______________________ __
Water
Color
(Tristumulus) ____ _...._____ __,____..,__
means interconnecting the degassing chamber, the recir
culating pump, the heat exchanger and the centrifugal
Balance
pump for conveying the degassed reaction mixture from
4 75 the degassing chamber through the recirculating pump,
0.26
1.5
3,069,243‘
to?
through the heat exchanger and to the centrifugal pump,
a mixing means having a product outlet, means intercon
necting the recirculating pump and the mixing means to
convey the degassed reaction mixture from the forrrer to
the latter, and a means connecting with the mixing means
to introduce an aqueous alkaline material into the said
mixing means.
i
2. An apparatus comprising, in combination, a cen
trifugal pump for continuously and simultaneously con
tracting and mixing two reactants to form a reaction
mixture, said centrifugal pump having three inlets and
an outlet, one of said inlets being adapted to convey
a gaseous reactant into said centrifugal pump, a second
of said inlets being vadapted to convey a ?uid reactant
pump to dilute the reaction mixture therein, a mixing
pump having two inlets and an outlet, means connecting
said second recirculating pump outlet with one of said
mixing pumpinlets to permit said degassed reaction
mixture to ?ow from said recirculating pump and into
said mixing pump, said second mixing pump inlet be
ing adapted to convey an aqueous reactant into said
mixing pump, said mixing pump outlet being adapteed
to discharge said reaction mixture product.
4 An apparatus comprising, in combination, a cen
trifugal pump for continuously and simultaneously con
tacting and mixing reactants to form a reaction mixture,
said centrifugal pump having three inlets and an outlet,
tWo of said inlets being adapted to carry reactable ?uids '
into said centrifugal pump, a degassing chamber hav 15 into said centrifugal pump, a degassing chamber having
ing an inlet and an upper gas outlet and a lower ?uid
said reaction mixture into an upper gaseous layer and a
an inlet and upper gas and lower ?uid outlets, means to
vary the absolute pressure in the degassing chamber, a
ba?le plate in said degassing chamber, a means to spray
the reaction mixture over said baf?e plate, conveying
means interconnecting said centrifugal pump outlet and
the degassing chamber inlet to convey said reaction mix
lower substantially degassed reaction mixture layer, a
ture from the centrifugal pump to the means to spray
recirculating pump having an inlet and two outlets, a
heat exchanger having an inlet and an outlet, means con
the reaction mixture over said battle plate, said degassing
chamber removing extraneous gas from said reaction mix
outlet, means connecting said centrifugal pump outlet
and said degassing chamber inlet to flow said reaction
mixture from said centrifugal pump into said degassing
chamber, means in said degassing chamber to separate
necting said lower degassing chamber outlet with said 25 ture to form an upper gaseous layer and a lower degassed
recirculating pump inlet to ?ow said degassed reaction
reaction mixture layer, an interface control in said de
gassing chamber responsive to the level of the degassed
mixture from the former and into the latter, means con
necting one of said recirculating pump outlets with said
reaction mixture for controlling the level of the same,
a recirculating pump, a heat exchanger, means inter
heat exchanger inlet to ?ow said degassed reaction mix
ture from the former to the latter to cool the degassed 30 connecting said lower ?uid outlet of the degassing cham
ber, the recirculating pump, the heat exchanger and said
reaction mixture, means connecting said heat exchanger
third centrifugal pump inlet for conveying the degassed
outlet with said third inlet of said centrifugal pump to
reaction mixture from the degassing chamber through the
?ow said degassed reaction mixture from the former to
recirculating pump, through the heat exchanger and into
the latter, said recirculating pump thereby pumping the
said third centrifugal pump inlet, the total residence time
degassed reaction mixture into said centrifugal pump
from said centrifugal pump outlet to said third centrifugal
to dilute and cool the reaction mixture in the latter, a
pump inlet being less than about three minutes, a con
mixing means having two inlets and a product outlet,
trol valve and a mixing means having two inlets and
means interconnecting said second recirculating pump
a product outlet, means interconnecting the recirculat
outlet and one of said mixing means inlets to convey
the degassed reaction mixture from the former to the 40 ing pump, the control valve and oneof said mixing means
inlets to convey the degassed reaction mixture from the
latter, and a means connecting with said secondmix-v
recirculating pump through the control valve and to the
ing means inlet to introduce an aqueous material into said
'mixing means.
mixing means, means connecting with said second mix
ing means inlet to introduce an alkaline material into said
3. A reaction apparatus comprising, in combination,
a centrifugal pump for continuously and simultaneously 45 mixing means, and means connecting said interface con
trol and said control valve to regulate the ?ow of said
contacting and mixing reactants to form a reaction mix
degassed reaction mixture.
.
ture, said centrifugal pump having three inlets and an
5. An apparatus for continuously reacting reactants,
outlet, two of said inlets being adapted to convey ?uid
comprising, ‘in combination, a centrifugal pump having
reactants to said centrifugal pump, a degassing chamber
having an inlet and an upper gas venting outlet and a low
er reaction mixture outlet, means connecting the outlet
of said centrifugal pump with the inlet of said degassing
chamber to ?ow said reaction mixture from the former
to the latter, said degassing chamber inlet being adapted
an impeller blade, two concentric pipes leading into
the centrifugal pump and terminating near the edge of
the impeller blade, one of said concentric pipes being
used to convey a ?rst ?uid into the pump, the other
one of said concentric pipes being used to convey a
to spray said reaction mixture over a ba?le to form 55 second ?uid into the pump, said impeller blade simul
taneously contracting and mixing said ?uids to form a
a lower ?uid level and an upper gaseous, level in said
reaction mixture in the pump, a degassing chamber,
degassing chamber, said lower fluid level consisting of
means to vary the absolute pressure in the degassing
a substantially degassed reaction mixture, means in saidv
chamber to a pressure as low as ?fteen inches of mercury
degassing chamber responsive to the level of said de
gassed reaction mixture for controlling the level of' the 60 absolute pressure, a ba?le plate in said degassing chamber,
same, a recirculating pump having an inlet and two
outlets, means connecting the lower degassing chamber
outlet and the recirculating pump inlet, a throttling valve
to throttle the recirculating degassed reaction mixture,
a means to spray the reaction mixture over said baffle
plate so as to have a large surface area per unit volume
of the reaction mixture, conveying means interconnect~
ing the pump and the degassing chamber to convey the
a heat exchanger having an inlet and an outlet, means 65 reaction mixture from the pump to the means to spray
connecting one of said recirculating pump outlets with
the reaction mixture over said baffle plate, said degassing
said throttling valve, means connecting said throttling
chamber removing extraneous 'gas from said reaction
valve with the heat exchanger inlet to permit said de
mixture to form an upper gaseous layer and a lower de
gassed reaction mixture to be recirculated from said 70 gassed reaction mixture layer, means in said degassing
chamber responsive to the level of the lower degassed
degassing chamber through said recirculating pump,
reaction mixture layer for controlling the level of the
through said throttling valve, and through said heat
same, a recirculating pump, a heat exchanger, means
exchanger, means connecting the heat exchanger outlet
interconnecting the degassing chamber, the recirculating
and the third inlet of said centrifugal pump to permit
said degassed reaction mixture to return to said centrifugal
pump and the heat exchanger for conveying the de
3,0 69,243
12
11
gassed reaction mixture from the degassing chamber
through the recirculating pump and to the heat exchanger,
means interconnecting the heat exchanger and the cen
trifugal pump to ‘convey the degassed reaction mixture
from the former to the latter to act as a coolant and
diluent in the latter, said recirculating pump having the
capacity to pump at least ?fteen volumes of the de
gassed reaction mixture per one volume of the com
bined volumes of the ?rst and the second ?uids enter 10
ing the centrifugal pump, a mixing means having a prod
uct outlet, means interconnecting the recirculating pump
and the mixing means to convey the degassed reaction
mixture from the former to the latter, and a means con
necting with the mixing means to introduce an alkaline 15
material into said mixing means.
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,929,659
2,187,244
2,192,094
2,210,175
2,332,527
2,350,095
2,673,211
2,676,185
2,723,990
2,761,768
2,843,625
1933
1940
1940'
Muncie ______________ __ Aug. 6, 1940
Pyzel ________________ __ Oct. 26, 1943
Carlson et al __________ __ May 30, 1944
Blinoff ______________ __ Mar. 23, 1.954
Melstrom ____________ __ Apr. 20, 1954
Gilbert et a1 __________ __ Nov. 15, 1955
Diels et a1. ____________ __ Sept. 4, 1956
Gebelein _____________ __ July 15, 1958
Trumble et a1 __________ __ Oct. 10,
Mills ________________ __ Jan. 16,
Moore ______________ __ Feb. 27,
FOREIGN PATENTS
553,598
Great Britain ________ __ May 27,
1943
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