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Патент USA US2406763

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Patented Sept. 3, 1946
2,406,763
UNITED STATES PATENT OFFICE
PURIFICATION OF OIL-SOLUBLE
SULPHONATES
William K; Griesinger, Drexel Hill, Pa., assignor
to The Atlantic Re?ning Company, Philadel
' phia, Pa., a corporation of Pennsylvania
No Drawing. Application September 29, 1944, ‘
Serial No. 556,473
11 Claims.
.
(Cl. 260-504)
l
,
The present invention relates to improvements
in the puri?cation of oil-soluble'sulphonates, and
-
2
’
hydrocarbon may be exempli?ed by lique?ed nor
mally gaseous hydrocarbons such as liquid pro
pane or the liquid butanes, or mixtures thereof;
particularly petroleum mahogany sulphonates.
The conventional re?ning treatment of lubri
catingoil. distillates derived from petroleum in
cludes the application of fuming sulphuric acid.
This reacts with the oil, producing a sludge con
‘
5
pentane, hexane, heptane, or octane; benzene,
toluene, xylene; and petroleum naphthas, par
ticularly those boiling within the range of 190°‘
F‘. to 275° F.
taining tarry material, spent sulphuric acid, and
certain types of sulphonic acids. Though the
The low viscosity hydrocarbon or ‘
concentration of S03 in thefuming acid may vary
hydrocarbon mixture employed must be capable
of dissolving the sulphonates, but not the salts
or water, and must be capable of ready removal
considerably, a’20% ‘fuming acid is employed in
from the puri?ed sulphonates, for example, by
most cases." Asia result of the high degree of sul
phonation obtained in the acid treatment, a con
distillation at temperatures below the decom
position temperature of the sulphonates. The
lower aliphatic alcohols which are utilized in ac
siderable amount of sulphonic acids is produced.
These are principally of tWo types, namely, the
water-soluble type predominantly contained in
the sludge, and the oil-soluble type predominant
ly. found‘in the treated oil. The application of
cordance with this invention include methyl alco
hol, ethyl alcohol, propyl alcohol, iscpropyl alco- '
hol, and the butyl alcohols, or mixtures of two
or more of. these alcohols.
the acid is regulated in a manner well known in
In' practicing my invention, the crude oil solu
the art to produce the desired sulphonation, and 20 ble sulphonates containing inorganic salts and
in general, temperatures not exceeding 140° F.
water are thoroughly mixed With from 2 to 5
are preferred. The sulphonic acids contained in
volumes of low viscosity hydrocarbon solvent
the sludge, while limitedly soluble, if at all, in
and with 0.02 to 0.1 volume of lower aliphatic al
hydrocarbon oils, are highly water-soluble, im
cohol, based upon the crude sulphonatesv to be
parting to their aqueous solution a dark-green * puri?ed. The mixture is thoroughly agitated and
then permitted to settle and stratify into two
color, and being for-this reason referred to as
“green sulphonic acids.” The acids remaining in
layers’, one layergcomprising puri?ed sulphonates,
solution in the oil impart a reddish color to the
hydrocarbon solvent, and alcohol, the sulphonates
oil, and for this reason are generally referred to
containinglittle or no inorganic salts or water,‘
as “mahogany sulphonic acids.” After the sepa v.1: "- and a second layer comprising inorganic salts,_
ration of the oil from the acid sludge, the ma
Water, and alcohol. The layers are separated
hogany sulphonic acids are removedfrom the oil
from one another and the sulphonate-containing
:
by the ordinary re?ning method comprising con
version of the acids into salts or soaps by direct
neutralization of the acid treated oil followed
by extraction with a suitable solvent, for exam
ple, an aqueous solution of isopropyl alcohol.
The mahogany sulphonates constitute a valuable
lay-product of petroleum re?ning, and are used
for a variety of purposes including the produc
tion of oil detergents, emulsi?ers, and fat split
ting agents.
-
The crude mahogany sulphonates, as they are
derived from an acid treated oil, contain Varying
layer is subjected to treatment for the removal
and recovery of the hydrocarbon solvent and al
cohol. Such treatment may comp-rise distilla
tion at atmospheric or sub-atmospheric pres
sure, the recovered solvent and alcohol being
recirculated for the treatment of additional quan
titles of crude sulphonates. In the event that
it is desired to accelerate the separation of the
puri?ed sulphonate solution from the water, in
organic salts, and alcohol, the original mixture
of impure sulphonates, hydrocarbon solvent and
alcohol may be centrifuged after vigorous agi
amounts of inorganic salts, notably sulphates and
tation, whereby the puri?ed sulphonate solution
sulphites, as Well as considerable amounts of-oil
and water, and it is in many cases not only de
sirable but even necessary to substantially re
is separated from the impurities.
In another and preferred mode of operation,
the crude sulphonates are thoroughly mixed with
move the inorganic salts and water.
‘from 2 to 6 volumes of low viscosity hydrocarbon
‘
I have found that these impurities comprising '“
inorganic salts and water may be removed by
treatment of the crude sulphonates with a com
bination of solvents, one of which comprises a low
solvent, and the mixture is then permitted to
settle and stratify into two layers, the upper layer
comprising sulphonates, hydrocarbon solvent and
a minor amount of inorganic salts and water, and
viscosity hydrocarbon and the second compris
the lower layer comprising the bulk of the inor
ing ‘a lower aliphatic alcohol. The low viscosity 55 ganic salts and water. The layers are separated,
2,406,763
3
4
thus rendering the soap substantially neutral,
and the upper layer is thoroughly mixed with
0.02 to 0.1 volume of a lower aliphatic alcohol
and with 0.1 to 0.2 volume of water, based upon
the original volume of crude sulphonates to be
puri?ed. The resulting mixture is then per
mitted to settle and stratify into two layers, the
upper layer comprising substantially salt-free
di?iculties were avoided in the settling and sepa
ration of the layers. In the event that the crude
soap is initially approximately neutral, the addi
tion of mineral acid is of course unnecessary.
After thorough agitation of the neutralized, par
tially puri?ed naphtha solution of sulph'onate
soap with the added isopropyl alcohol and water,
sulphonates, hydrocarbon solvent, and alcohol,
the mixture was permitted to settle for at least
and the lower layer comprising water, alcohol,
36 hours to permit strati?cation into two layers,
the upper layer amounting to 3.5 volumes and
comprising a clear naphtha solution of puri?ed
soap containing a portion of the isopropyl alco
hol and traces of water, and the lower layer
amounting to 0.225 volume and comprising water,
residual salts, and the remainder of the isopropyl
alcohol. The layers were separated from one
another, and the upper layer was distilled to re
move the naphtha, alcohol, and traces of water,
while the lower layer was recycled for admixture
with an additional quantity of crude sulphonates
to be puri?ed. Upon removal of the naphtha,
alcohol, and traces of water from the upper layer
and traces of inorganic salts. The layers are
separated, the lower layer preferably being re
cycled for admixture with additional quantities
of crude sulphonateawhile the upper layer is
subjected to distillation for the removal and re
covery of the hydrocarbon solvent and alcohol.
The distillation residue constitutes the puri?ed
product, i. e., sulphonates substantially free of in
organic salts and water, and containing substan
tially all of the oil initially associated with the
crude sulphonates. If it is desired to reduce or
remove the oil from the puri?ed sulphonates, the
oil-sulphonate mixture may be subjected to fur
ther treatment with solvents to extract the oil
from the sulphonates, or the sulphonates from
the oil. Such treatment is conventional and is
not considered as constituting part of the present
invention. Generally, the separation of oil from
by distillation, there was obtained as a residue a
puri?ed sulphonate soap amounting to 0.5 vol
ume having the following composition.
Per cent
oil-soluble sulphonates is performed by diluting
Oil-soluble sodium sulpho-nate _________ __ 50.0
the oil-sulphonate mixture with naphtha and
Oil __________________________________ __ 50.0
washing the sulphonates from the diluted mix 30 Water ___________ _'_ __________________ M 0.0
ture with dilute alcohol, using relatively large
Inorganic salts ____ __' __________________ __
0.05
quantities of dilute alcohol.
This
puri?ed
soap
had
a
neutralization
number
My invention may be further illustrated by the
of 0.2 mg. KOH/g. alkaline.
following example, which, however, is not to be
While I have described my invention primarily
construed as limiting the scope thereof.
35
in connection with’ the puri?cation of white oil
A viscous hydrocarbon oil, after acid treatment
soaps or mahogany sulphonates, my process is
with fuming sulphuric acid and separation of
also applicable to ‘the puri?cation of other oil-sol
sludge, was neutralized with aqueous sodium hy
uble sulphonates such as the alkali or alkaline
earth metal soaps of sulphonic acids derived
from the re?ning or sulphonation of petroleum
droxide, and the resulting oil-soluble sulphonates
were separated from the neutralized oil by ex
traction with aqueous isopropyl alcohol. After
removal of the alcohol by distillation, there was
obtained a crude sulphonate soap having the fol
lowing approximate composition:
Oil-soluble sodium sulphonate __________ __ 25.0
___________________________________ __
Water
cating oil stocks, and the like.
‘
Per cent‘
Oil
distillate oils of lubricating oil viscosity, selective
solvent extract or naphthenic fractions of lubri
24.5
__________________________ __. ____ __
48.0
Inorganic salts ________________________ __
2.0
45
I claim:
1. The method of purifying oil-soluble petro
leum sulphonates containing inorganic salts and
water, which comprises contacting said sulpho
nates ‘with from 2 to 6 volumes of low viscosity
50 hydrocarbon solvent which dissolves the sulpho
Free sodium hydroxide _________________ __ 0.5
nates but not the salts and with 0.02 to 0.1 vol
ume of a lower aliphatic alcohol, and separating
One volume of the crude soap was thoroughly
the resulting solution of puri?ed sulphonates from
the inorganic salts and water.
2. The method of purifying oil-soluble petro
mixture was allowed to settle for 24 hours at 55
leum sulphonates containing inorganic salts and
about 75° F. Upon settling, stratification oc
water, which comprises contacting said sulpho
curred with the formation of two layers, the up
mixed with 3 volumes of petroleum naphtha hav
ing a boiling range of 190° F. to 275° F., and the
nates with from 2 to 5 volumes of low viscosity
per layer amounting to 3.53 volumes and com
hydrocarbon solvent which dissolves the sulpho
prising naphtha and sulphonates from which the
bulk of the water and inorganic salts had sepa 60 nates but not the salts and with 0.02 to 0.1 vol
ume of a lower aliphatic alcohol, settling and
rated. The lower layer amounting to 0.47 vol
stratifying the resulting mixture into two layers,
ume and comprising water containing the inor
and separating a layer comprising inorganic salts,»
ganic salts was separated from the upper layer
water, and alcohol from a second layer compris
and was discarded. The upper layer was then
ing puri?ed sulphonates, hydrocarbon solvent,
thoroughly mixed with 0.0392 volume of 91%
and alcohol.
isopropyl alcohol and 0.157 volume of water,
3. The method of purifying oil~so1ub1e petro
based upon the crude soap initially charged.
leum sulphonates containing inorganic salts and
Since the crude soap contained an undesirable
water, which comprises contacting said sulpho
excess of free sodium hydroxide, i. e., 0.5%, only
a portion of which was removed in the salt water 70 nates with from 2 to 6 volumes of low viscosity
hydrocarbon solvent which dissolves the sulpho
from the first settling operation, suf?cient min
nates but not the salts and with 0.02 to 0.1 volume
eral acid, preferably sulphuric acid, was added
of a lower aliphatic alcohol, settling and strati
to the alcohol-water diluted naphtha solution of
fying the resulting mixture into two layers, sep
the partially purified sulphonate soap to approxi
mately neutralize the residual free alkali. By 75 arating a layer comprising inorganic salts, Wa
2,406,768
5
6
ter, and alcohol from a second layer comprising
puri?ed sulphonates, hydrocarbon, solvent, and
water based upon the original sulphonates, set
tling and stratifying the resulting mixture into
alcohol, and removing the solvent and alcohol
from the puri?ed sulphonates.
4. The method of purifying oil-soluble petro
ter, and alcohol and a second layer comprising
leum sulphonates containing inorganic salts and ,_
two layers, one comprising inorganic salts, wa- '
puri?ed sulphonates, hydrocarbon solvent and
alcohol, separatingthe layers from one another,
water, which comprises contacting said sulpho
and removing the solvent and alcohol from the
nates with from 2 to _6 volumes‘ of petroleum
puri?ed sulphonates.
,
naphtha which dissolves the sulphonates but not
9. The method of purifying oil-soluble petro
the salts and with 0.02 to 0.1 volume of isopropyl
leum sulphonates containing inorganic salts and
alcohol, and separating the resulting solution of
water, which comprises contacting said sulpho-v
puri?ed sulphonates from the inorganic salts and
nates with from 2 to 6 volumes of petroleum
water.
naphtha which dissolves the sulphonates but not
5. The method of purifying oil-soluble petro
the salts, settling and stratifying the resulting
leum sulphonates containing inorganic salts and 15' mixture into twolayers, one comprising sulpho
water, which comprises contacting said sulpho
nates, petroleum naphtha and a minor amount of
nates with from 2 to 6 volumes of petroleum
salts and water, and a second layer comprising
naphtha which dissolves the sulphonates but not
salts and water, separating the layers, contacting
the salts and with 0.02 to 0.1 volume of isopropyl
the layer comprising sulphonates, petroleum
alcohol, settling and stratifying the resulting mix 20 naphtha and a minor amount of salts and water
ture into. two layers, and separating a layer com
with 0.02 to 0.1 volume of isopropyl alcohol and
prising inorganic salts, water, and isopropyl alco
0.1 to 0.2 volume of water based upon the orig
hol from a second layer comprising puri?ed sul
inal sulphonates, settling and stratifying the re
phonates, petroleum naphtha, and isopropyl al
sulting mixture into two layers, one comprising
cohol.
,
6. The method of purifying oil-soluble petro
leum sulphonates containinginorganic salts and
water, which comprises contacting said sulpho
, inorganic salts, water, and isopropyl alcohol and
a second layer comprising puri?ed sulphonates,
petroleum naphtha and isopropyl alcohol, and
nates with from 2 to 6 volumes of petroleum
separating the layers from one another.
10. The method of purifying oil-soluble petro
naphtha which dissolves the sulphonates but not
the salts and with 0.02 to 0.1 volume of isopropyl
leum sulphonates containing inorganic salts and
water, which comprises contacting said sulpho
' alcohol, settling and stratifying the resulting mix
ture into two layers, separating a layer compris
ing inorganic salts, water, and isopropyl alcohol
from a second layer comprising puri?ed sulpho
nates, petroleum naphtha, and isopropyl alcohol,
nates with from 2 to 6 ‘volumes of petroleum
naphtha which dissolves the sulphonates but not
the salts, settling and stratifying the resulting
mixture into two layers, one comprising sulpho
nates, petroleum naphtha and a minor amount of
salts and water, and a second layer comprising
and removing the petroleum naphtha and isopro
pyl alcohol from the puri?ed sulphonates.
salts and water, separating the layers, contacting
7. The method of purifying oil-soluble petro
the layer comprising sulphonates, petroleum
leum sulphonates containing inorganic salts and 40 naphtha and a minor amount of salts and water
water, which comprises contacting said sulpho
with 0.02 to 0.1 volume of isopropyl alcohol and
nates with from 2 to 6 volumes of low hydrocar
0.1 to 0.2 volume of water based upon the orig
bon solvent which dissolves the sulphonates but
inal-sulphonates, settling and stratifying the re
not the salts, settling and stratifying the result
sulting mixture into two layers, one comprising '
ing mixture into two layers, one comprising sul 45 inorganic salts, water, and isopropyl alcohol and
phonates, hydrocarbon solvent and a minor
a second layer comprising puri?ed sulphonates,
amount of salts and water, and a second layer
petroleum naphtha and isopropyl alcohol, sepa
comprising salts and water, separating the layers,
rating the layers from one another, and remov
contacting the layer comprising sulphonates, hy
ing the petroleum naphtha and isopropyl alcohol
drocarbon solvent and a minor amount of salts 50
from the puri?ed sulphonates.
and water with 0.02 to 0.1 volume of a lower ali
phatic alcohol and 0.1 to 0.2 volume of water
based upon the original sulphonates, settling and
stratifying the resulting mixture into two layers,
one comprising inorganic salts, water, and ‘alco
hol and a second layer comprising puri?ed sul
phonates, hydrocarbon solvent and alcohol, and
11. The method of purifying oil-soluble petro
leum sulphonates containing inorganic salts in
water, which comprises contacting said sulpho
nates with 3 volumes of petroleum naphtha which
dissolves the sulphonates but not the salts, set
tling and stratifying the resulting mixture into
two layers, one comprising sulphonates, petrole
separating the layers from one another.
um naphtha, and a minor amount of salts and
8. The method of purifying oil-soluble petro
leum sulphonates containing inorganic salts and 60 water, and a second layer comprising salts and
water, separating the layers, contacting the layer
water, which comprises contacting said sulpho
comprising sulphonates, petroleum naphtha and
nates with from 2 to 6 volumes of low viscosity
hydrocarbon solvent which dissolves the sulpho
nates but not the salts, settling and stratifying
a minor amount of salts and water with 0.06
layers, contacting the layer comprising sulpho
comprising puri?ed sulphonates, petroleum naph
volume of isopropyl alcohol and 0.16 volume of
the resulting mixture into two layers, one com 65 water based upon the original sulphonates, set
tling and stratifying the resulting mixture into
prising sulphonates, hydrocarbon solvent and a
two layers, one comprising inorganic salts, wa
minor amount of salts and water, and a second
ter, and isopropyl alcohol and a second. layer
layer comprising salts and water, separating the
nates, hydrocarbon solvent and a minor amount 70 tha and isopropyl alcohol, and separating the
layers from one another.
of salts and water with 0.02 to 0.1 volume of a
'
WILLIAM K. GRIE'SINGER.
lower aliphatic alcohol and 0.1 to 0.2 volume of
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