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Патент USA US2412916

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Patented Dec, 17, 1946
Jere C. Showalter, Goose Creek, Tex., assignorto
Standard Oil Development Company, a corpo-g
ration of Delaware
‘Application August 21, 1944, Serial sq. 550.395
(on. was”).
recoveryoi the solvent employed and that ‘the
extract indicated asebeing removed from the unit
‘ The present invention is directed to a process
for. preparing water-soluble alkali metal sul‘fo
vi'aiine ll 'willbe substantially free mm‘ selective
notes. More particularly, it is directed to the
preparation of petroleum suli‘onates which may be
the petroleum fraction to be sulfonated, by con
trolling the conditions of sulfonation and by em
ploying a particular sequence oi steps in cleans
ing the sulfonic acids.
By‘ the careful control of
'the'steps of the process. I am able to obtain a
the extract and sulfuric acid initially at atmos
treating mineral or petroleum oils with sulfuric
acid of sulionating strength and subsequently neu
tr‘alizing the sulfonic acids with an alkali to ob
taln sulionates suitable for use as detergents and 15
ionates having novel characteristics by selecting
suli'onatlng' step ls‘preferably carried out with
It is well known to produce sulfonic acids and
salts, of sulfonic acids of varying properties by
In accordance with the present invention, I
300 to 400 pounds of acid per barrel of extract.
In the acid treating step approximately 50% of
the extract is converted ‘to sulfonated oil. The
as a. shampoo.
propose to prepare water soluble salts of sul
‘In Y-‘acld treating unit IS‘ the extract is admixed
with "98%~ sulfuric acid in amountsranging irom
useciin‘soit or hard water or in sea water. These
sulfona-tes do not leave a deposit of gummy resi
"dues or foreign bodies on the object being
cleansed, and are particularly suitable for use
cleansing agents.
" "
pheric temperatures, and Lie maximum temper
ature of the reactants increasing to a temperature
in the range of 120" to 170° F. as the sulfonation
reaction proceedsv
From unit l5 the mixture of reactants is with
drawn by line I] to ‘settler i8, where the react
ants separate into a lower sludge layer, which is
removed via line l9,’ and an upper layer or su1~
20 fonated oil, which is removed through line 20.
To the sulfonated oil flowing through line 20 is
added water via inlet 21 in ‘an amount ranging
from 3% to 5% ,0: thesulfonated ollkand the
two‘comppneints are;the_n passed through ‘mixing
metal salt of sulfonic acid readily soluble in water 25 deyice 9 to ‘cause the thorough admixture oi ,wa
ter with the 'suli’onated oil and the mixture is
and appearing as a clear, light colored, aqueous
then passed through line ill to a second settling
solution. free from contaminating solid bodies and
vessel 22. The addition of the water to the mix
capable of being used as a detergent without leav
turecausesa separation to take place in‘settler
lngan undesirable residue on the object being
30 22 witl'isulfi'onidacids andwater, in addition to
entrained oil, settling as a bottom layer and un
The present invention will now be described in
converted oil separating as a top layer; The un
conJunction with the drawing, in which the sole
converted oil is withdrawn from the upper por
?gure is in the ‘form oi a flow sheet diagrammat
tion oi‘ settler 22 via line 23 and discarded from
ically illustrating the process of the present in
the system'. The suifonic acids, water and oil
entrained therein settling in the lower portion of
A distillate fraction having a viscosity in the
vessel 22 are withdrawn via line 24.
range of 75 to 85 seconds Saybolt at 100° F. and
To the mixture flowing in line 24 is added an
obtained by fractionation of a naphthenic crude
alkali metal hydroxide via inlet 25 in an amount
oil is passed via inlet Ii into a solvent extraction
unit l2, where it is contacted with phenol as the 40 sui?cleht to neutralize the sulionlc acids. It is
preferred to employ either sodium or potassium
selective solvent under conditions to form 8. ref
hydroxide and to add an amount Just su?icient
?nate fraction and an extract fraction. The step
to neutralize the suli'onic acids and convert them
of solvent extraction with selective solvents is well
to suli’onic soaps‘ It will usually be found desir
known to the art. and for this reason the oper
ating conditions in this unit will not be described 45 able to pass the mixture of sulionic acids and al
kali metal hydroxide through mixer 26 in order
in detail. It will be suiiicient to say that usually
to insure a thorough admixture of the compo
the extract will have approximately 35% of the
nents. While a series ofbafiies have been indi
volume of the original distillate and the rai’?nate
cated in the schematic mixer shown in the draw
will comprise the remaining 65% of the distillate.
ing, it will be understood that a "essel provided
The ra?inate may be discarded from the solvent
with a mechanical stirrer may be employed and
extraction unit via outlet l3 and the extract may
the mixture maintained in the vessel until the
be withdrawn through line 14 to acid treating
sulfonic acids have been neutralized with the hy
unit I5. It will be understood that the unit des
ignated by numeral [2 as the solvent extraction
The solution of sulionic soaps is withdrawn
unit will include suitable distillation columns for
from mixer 28 and is treated for the removal of
impurities thereirom. These impurities will
usually include unreaeted oil and water-insoluble
sulionates, as well as foreign bodies which may
have been present in the feed or may have been
such use it is desirable to employ a mixture com
prising 15% of the alkali metal sulionates and
85% water. The water content of the solution
may, of course, be readily controlled, but for pur
poses of illustration the addition of water thereto
picked up in the apparatus. The material from
mixer it passes through line 21 and isopropyl al
cohol is added thereto via line 2!. It is desirable
for controlling the concentration of the solution
is indicated by inlet line IS.
The aqueous solution oi water-soluble alkali
to use isopropyl alcohol commonly known as 50%
metal suifonates has a pH 01' 'l and is free from
alcohol, that is, 50% of the alcohol diluted with 10 contaminating materials and solids which would
50% of water, and in an amount of one volume 0!
be undesirable in a detergent material. The al
the alcohol solution to one volume of the sulionic' .
kall metal salts oir thesuiionates are readily soluble
soap solution. The constituents in line 21, are
in water, audit is, therefore, unecessary to em
then passed into mixer 29, where they are thQre
ploy a vehicle or solvent, such as alcohol, in the
oughly admixed. The mixture is removed by line 15 solution in order to maintain the sulionate salt
30, where light hydrocarbon material is added by
in solution.
inlet II and then passed through a mixer 32' and
It is to be emphasized that the washing steps
line I3 into settling vessel 34. A number of light
and settling steps in the described process are
hydrocarbon fractions are suitable in the use of
necessary in order to obtain a detergen-t'material
this extraction step. For example, lique?ed pro 20 having the characteristics given above. The omis
pane, butane or pentane fractions may be used
sion of any of these steps results in a product
as well as higher boiling fractions, such as hexane
which is not free from solids and gummy con
or light naphtha or liquid mixtures including
these constituents. It will usually be desirable to
stituents and is unsuitable for use as a deter
gent in shampoos and like compositions.
employ a light naphtha as the light hydrocarbon 25 stated above, the dual ?ltering step illustrated
and to employ one volume of the light hydrocar
is optional and may be omitted in case satis
bon to two volumes of the alcohol-sulionic soap
factory settling is obtained in the preceding
solution. The addition of the isopropyl alcohol
and light hydrocarbon to the aqueous sulfonic
Having fully described the present invention,
soap solution causes the segregation of the oil and
what I desire to claim is:
light hydrocarbon as one fraction and the alcohol
l. A method for producing a detergent suitable
and aqueous soap solution as another fraction,
for use as a shampoo comprising the steps of
and these two fractions are separated by settling
extracting a naphthenlc distillate having a vis
in unit M. The oil and light hydrocarbon sepa
cosity in the range of 75 to 85 seconds Saylbolt
rates as an upper layer and is removed from unit 35 at 100° F. with a selective solvent under condi
34 via outlet 35, and may be discarded. The
tions to form a raillnate and an extract, contact
lower layer, comprising alcohol and sulionic soap
ing the extract with concentrated sulfuric acid
solution, is withdrawn through outlet 36 to a dis
in the range oi’ 300 to 400 pounds of acid per bar~
tillation column 31, where the alcohol is vapor
reel 01’ extract under conditions to lorm a sludge
ized and removed as overhead via outlet ll.
40 layer and a suli’onated oil layer, separating the
The alcohol-tree sulionlc soap solution is with
sludge layer, adding from 3% to 5% ct water to
drawn from the lower portion of the distillation
the sulionated oil layer and settling .to produce an
tower 31 through line 38 and sent to a settling
oil layer and a sulionlc acid layer, withdrawing
vessel 40, where it is allowed to settle for a sub
the sulionic acid layer and contacting it with a
stantial interval of time to separate a minor wa
solution of an alkali metal hydroxide to form
ter-lnsoiuble soap fraction from the remaining
a soap, mixing the soap with isopropyl alcohol,
portion oi the solution. It will be iound desirable
extracting the mixture with a light hydrocarbon,
to allow the solution to remain in settler 40 in
distilling the extracted soap to remove alcohol
a quiescent state for an interval of time of the
order of 24 hours, After the mixture in unit 40
has settled to form an insoluble soap traction and
a soluble soap fraction, the soluble soaps may be
withdrawn as indicated through outlet Ii and the
insoluble soaps may be withdrawn from the bot
tom of the vessel through outlet 42. Under some
conditions the settling step in unit 40 may not re
move all of the solids from the soluble soaps, and
under such conditions it may be desirable to pass
the water-soluble soaps via line ‘I through ?lter
43 in order to obtain a puri?ed water~soluble sul
fonate solution, However. the settling step may
separate substantially all of the solid materials
from the water-soluble soaps, and if such be the
case the ?lter may be bypassed by line H. Valve
I3’ is indicated for controlling the flow through
filter '3 and valve 44' for controlling the ?ow
through bypass line H. The puri?ed aqueous so
lution of alkali metal salts of sulfonates may be
passed either through ?lter 43 or bypass line 44
into outlet line 45. from which they may be with
drawn to suitable storage facilities, not shown.
The aqueous solution is line ‘5 is free from
harsh alkalies and solid materials and is suitable
for use as a detergent.
The aqueous solution has
and light hydrocarbon therefrom and settling to
form a layer of water-insoluble soap and a layer
of water-soluble soap and removing the water
soluble soap as product.
2. A method for producing a detergent suitable
for use as a shampoo comprising the steps of
extracting a. naphthenic distillate having a vis
cosity in the range of '75 to 85 seconds Saybolt at
100° F. with a selective solvent maintained under
conditions to form a ra?lnate and an extract,
separating the extract from the rafilnate and con
tacting it with 98% sulfuric acid in the amount
of lrom 300 to 400 pounds of acid per barrel oi
oil and at a temperature in the range of atmos
pheric to 170° F. to form a sludge layer and a
suiionated oil layer, removing the sludge layer,
adding from 3% to 5% or water to the sulionated
oil layer and settling to obtain an oil layer and
a sulfonlc acid layer, withdrawing the sulionlc
acid layer and contacting it with a solution or an
alkali metal hydroxide to form a soap, adding iso
propyl alcohol to the soap to form an admixture,
extracting the admixture with a light hydrocar
bon, distilling the extracted mixture to remove
alcohol and light hydrocarbons therefrom, and
subsequently settling to form a layer of water
been found suitable for use as a shampoo, and for 76 insoluble soap and a layer of water-soluble soap
and removing the water-soluble soap as product.
3. A method for producing a detergent suitable
for use as a shampoo comprising the steps of ex
tracting a naphthenic distillate fraction having a
viscosity in the range of '15 to 85 seconds Saybolt
at 100“ F. with a selective solvent maintained un
der conditions _to form an extract having approxi
mately 35% of the volume of the original distil
late and a ra?inate, separating the extract from
the rafi‘lnate and admixing therewith 98%~sul
(uric acid in amounts ranging from 300 to 400
pounds of acid per barrel oi.’ extract and at a
temperature inthe range of atmospheric to 170°
F’. to form a sulfonated oil portion comprising ap
proximately 50% oi.’ the extract and a sludge por
tion, settling to form a sludge layer and a sul
tonated oil layer, removing the sulfonated oil
layer, adding from 3% to 5% water thereto and
settling to iorm an oil layer and a sulionic acid
layer, withdrawing the sulfonic acid layer and
contacting it with a solution of alkali metal hy
droxide in an amount sufficient to neutralize the
sulfonic acid layer and form a soap. mixing the
resulting soap with an equal volume of isopropyl
alcohol, adding to the mixture of soap and iso
propyl alcohol a light hydrocarbon in the amounts
of 2 volumes of soap alcohol mixture to 1 volume
oi’ a light hydrocarbon and subsequently settling
to obtain a light hydrocarbon layer, an alcohol
aqueous and soap solution layer, removing the al
cohol and aqueous soap solution layer and dis
tilling to remove alcohol therefrom, removingal
cohol-free suli'onic soap solution from the dis
tillation step and settling to form a layer 01
water-insoluble soap and a. layer of water-soluble
soap and removing the layer of water-soluble soap
as product.
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