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Патент USA US2118771

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tented ay '24, i938
UNITED STATES PAEN
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:.2,il18,77l
"j'QFP-l'
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SOLVENT TREATMENT or‘ NAPn'rnAs
THE LIKE
- -,
, Ernest Tel-res, New York, and Erich -Saegebarth,
_
-
Long Island City, N. Y., and Joseph Moos, "Ber-
'
, ' ‘ lin-Mariendo'rf, Germany, assignors, by mesn'e =
assignments, to Edeleanu Gesellscliaft, m. b. 11.,
* Berlin, Germany, a corporation of Germany
No Drawing. Application May 15,, 11935,
' Serial No. 21,680
2 Claims.
(oi.
l96-37)
,
_
_
This ihvention relates to,'impi'bvements in ‘stantially below 'zero degrees Fahrenheit, and
the Edele'anu process for producing motor that, _if'the extraction temperature is chosen
fuels, especially gasolines, of ‘a high anti-knock
su?iciently low, the liquid sulphur dioxide splits
- value, described in United States Patents .‘No.' the gasoline fraction into a ra?inate being ‘prac
5 1,585,473,1dated May 18, 1926,.and No. 1,661,566, tically free of unsaturated hydrocarbons and an 5. -
dated March 6, 1928, and also tothe production’ extract containing practically only unsaturated
of improved lacquer solvents.
_
~
and aromatic hydrocarbons. v This split will be
These patents describe processes of re?ning
gasolines and kerosenes by splitting the crude
0 distillate into a lower boiling and a higher boiling
sharper and the more complete the lower the tem
perature of \extraction, and there is no technical
but only an economical limit to reducing the 10
fraction, treating the latter with liquid sulphur extraction temperatura,,
‘
dioxide and reblending the extract obtained by
Two factors are of chief importance for ?xing
such treatment with the non-treated lighter‘ the ‘temperature of treatment with liquid sul
fraction. This extract has a considerably higher phur dioxide, the one being the boiling range of
content of aromatic andnnsaturated hydrocar
bons than the original stock and, since the pres
ence of these constituents in the motor fuel-is
chie?y responsible for its anti-knock quality,’ it
is apparent that by adding the extract obtained
0 from the higher'iboiling fraction to the lower
boiling one the anti-knock value of the latter is
increased.
'
The anti-knock quality of a motor fuel is ex
pressed by its “octane number”, the antié-knock
5 value being higher the higher the octane num
ber. By eniploying the processes described in
the above cited patents it has been possible to
the gasoline out to be re?ried and the other its _15
original content of" aromatic and unsaturated
hydrocarbons. The lower the boiling range of
the gasoline fraction is and the‘ higher its con
tent of aromatic and unsaturated components
the more advisablevwill it be to employ a'very 20'
low temperature in extracting. Temperatures
as low'as -60 to -'70° F. are ‘still allowable for
technical reasons as well as'from an ‘economical
viewpoint.
.
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_
'
,
v
I
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'
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According to our invention the following. dlf-. 35
ferent steps may be employedfor producing an
extract of the speci?cation given above:
_
'
produce gasolines havingoctanenumbers of. 70 - (w) The naphtha fraction is treated with liquid
to '75. Sulphur dioxide treatment of the higher ' sulphur dioxide? at the conventional temperature
0 boiling fraction oi’ a gasoline. as described in of +14 to +20“ F. in an extractiontower of con- '30
said patents, has been customarily done at tem
ventional. type. The extract layer obtained
peratures between +14° F. and +20° F., the ex
thereby by settling is further cooled down to
tract obtained in this manner having an average ' _ about —60° to' -70° F., whereby this extract layer
concentration of aromatic and unsaturated con
5 stituents of 351to 40 percent.
a
New developments in the'design of internal
combustion engines, especially for aeroplanes.
make it desirable to re?ne the gasoline to such
an extent that the octane number is raised above
c the limit of 75 mentioned above. '
_
'
We have found that such ?rst grade gasolines
is again split in two phasespan upper ra?lnate
layer that has practically the samecharacter- 35
istics as the ra?inate obtained in the ?rst ex
traction step, and a new extract layer. which we
may call second extract .and which contains in '
some inst tnces more than twice as much aromatic
_ and unsaturated components as the extract ob- 40
tained in the ?rst step of extraction.
(b) Re?ning of the naphtha fraction is done
cut of the gasoline crude to ‘such a degree that‘ ‘in one single step, whereby the naphtha is cooled
the extracts from this re?ning step have a very down to -60 to -—70° F. and continuously intro‘
5 high content of aromatic and unsaturated hy
drocarbons and are largely free of saturated hy-' duced into the base of a conventional extraction 45
drocarbons. By blending such extracts with the tower while liquid sulphur dioxide of substan
untreated gasoline fraction of lower boiling tially higher temperature, for instance it to 20°
range, a gasoline is obtained, the octane number F., is charged vto the upper part of the tower.
3 of whichmay be as high as 85 and above. With In continuous operation a temperature gradient 50
the methods employed for re?ning motor fuel so will result from this method, the temperature of
the liquid gradually decreasing from'the top to
far, it has not been possible tocommercially pro
‘duce such a gasoline.
4
.
the‘base of the extraction tower. The extract
For producing extracts of the speci?cation given withdrawn from the base of the tower'will be su
5‘ above it is necessary to employ a solvent of ex
perior to that obtained in the ?rst step ‘oi’ the as
may be produced by re?ning the higher boiling
cellent-selectivity. Unfortunately any solvent is
only slightly selective on low boiling petroleum
fractions such as gasoline.
However, we have
found that liquid sulphur dioxide exerts a very
1 high selective solvent action at temperatures sub
method desbribed under (a),
(c) Re?ning of the naphtha fraction is done
in a single step as described under (b), but’ both
stock and .liquid sulphur dioxide are charged to
the extraction tower with ‘a temperature of -60 to
2
2,118,771
to -70° F. The extract obtained in this way will
results may be seen in detail from the following
have a concentration of unsaturated and aro
table:
.
matic hydrocarbons equal to or ‘even surpassing
that of the extract produced by method- (a), but
requires somewhat more refrigeration.
In each of the three methods described above
a series of mixers and settlers combined to make a
unit that is conventionally called multi-stage
mixing-settling equipment may be used in 'lieu
10 of the vertical single extraction tower. It is fur
ther understood that the process described herein
is not restricted to operation upon gasoline fuel
nor to the temperatures speci?ed above.
Both straight run and cracked naphtha can be
15 treated in accordance with our invention to pro
duce superior motor fuels; therefrom. '
As illustrations of the improvement, which may
be obtained in treating light oils at temperatures
substantially below zero degrees Fahrenheit, we
20 mention the following examples:
Original
cracked
nap h‘ th a
~
Extract
at —22°
Radi
nate at
Extract
F.
—60° F.
F.
Yield percent by
~
vol ............. __
100
19
81
°A.P.I-.' ________ __
46.4
59.0
43.1
'
"
40
60
58.3
Percent aromatic
and unsaturated
hydrocarbons . -_.
50
6
61
0
80
Sayholt color _____ __
+23
+25
Dark.
+25
Dark.
The two fractions of the original naphtha from
which the higher boiling one had been extracted
with the result mentioned above had the follow
ing speci?cations:
-
Lower boiling fraction
Boiling range ____________________ __ 100-180" F.
0
Amount______..___.__ 93 vol. % of original stock '
Higher boiling fraction
Example 1
Boiling range ____________________ __ PTO-250° F.
A naphtha cut with 57.9° A. P. I. gravity and
25 a. boiling range from 152 to 252° F. was treated
in the countercurrent manner with 65% liquid—
S02 at +14° F. in one case and with 60% liquid
$02 at —22° F. in another case. The yields of
ra?inate and extracts and their speci?cations are
3.0 shown in comparison with the original naphtha
in the following table:
I
Amount ______ __‘______ 7 vol. % of original stock
IS G1
The octane number of the untreated lower boil
ing fraction was '78.
'
The yield of extract from the higher boiling
fraction was 60%, and this extract contained
80% aromatic and unsaturatedcompounds. The a: 0
extract was reblended with the whole untreated
lower boiling fraction with the result that the
octane number was raised to 84.
Extract
The extraction of naphtha fractions at such
naphtha +14“ F. +14‘7 F. —22° F. —22° F.
low temperatures as mentioned above can be
- .
Raili-
Ongmal mite at
35
Extract
at
Ra?i-
nate at
at
40
vol _____________ __
100
62
38
80
20
° A. P. I ......... .1
Percent aromatic
57. 9
63. 0
49. 4
63. 0
-'
40. 1
16
+17
2. l
+23
38. 4
+10
2.0
+23
65.0
+4
and unsaturated
hydrocarbons. _..
Saybolt color _____ -_
avoided when using an auxiliary solvent, which
increases the selectivity of liquid sulphur dioxide.
Yield percent by
In this case extraction temperatures as low as 14°
F. are sui?cient to obtain extracts with higher
'contents of aromatic and unsaturated com
pounds.
I
Example 3
The naphtha fraction used in this example had
the following boiling range:
45 The content of aromatic and unsaturated hydro
I. B. P.
10
20
30
40
50
60
"I0
80
90
carbons was determined by means of sulphuric
acid of 100% strength.
A comparison of the ?gures shows that the
ra?inate yield is increased from 62% to 80% by
50 carrying out the extraction at —22° F. instead of
at +14° F., and that the concentration of the arc
matic and unsaturated components in the ex
tract was raised from 38.4% to 65%.
55
End pt. 304
Example 2
' A cracked naphtha with a 46.4“ A. P. I., boiling
range from 195 to 286° F. and containing as
much as 50% aromatic and unsaturated hydro
'60 carbons could not be extracted at all with liquid
S02 at +14° F. because of entire miscibility at
this temperature. However, by reducing the tem
perature to —22° F. a separation into ra?inate
and extract phase took place and the treatment
65
could be carried out in the normal way. For
The A. P. I. gravity of this untreated fraction was
49.0.
This naphtha fraction was extracted with sul
phur dioxide and several mixtures of the latter
with an auxiliary solvent, such as ethylene glycol,
diethylene glycol and‘ trimethylene glycol.‘ All
extractions were carried out at 14° F. and the ex
tracts showed the following specifications:
Extraction Extraction Extraction
with sul
with sul~
with sul
Extrac
diox phur diox phur diox
tion with phur
ide plus
ide plus
ide plus
sulphur ethylene
diethylene trimethyl
dioxide
one glycol
glycol
glycol
20:80
20:80
20:80
comparison the cracked naphtha was treated
with 100% S02 followed by two treatments with
50% S0: at —22° F. and in another case the same
stock was similarly treatedat —60° F. The lat
ter treatment resulted in a greatly improved
ra?lnate yield and in a higher concentration of
aromatic and unsaturated components in the ex
tract, indicating the advantage of extremely low
75 treating temperatures in some instances.
220
229
232
236
240
244
249
255
263
276
The
“A. P. I __________ __
39. 1
38. 4
38. 7
Percent aromatic
unsaturated hy
drocarbons _____ -.
48
68.7
10. 7
60. 3
Saybolt color .... __
+9
0
'10
Dark
75
aria-771.
‘Other extractions were carried out with a simi
~ mal extractions inasmuch as .they have alhigher
lar vfavorable effect with mixtures of sulphur di
solubility for lacquer because of the higher per
oxide and the following auxiliary solvents: ben-' centage of aromatic and unsaturated components '
zy'lalcohol and diacetone alcohol. The separation present. One of the great advantages of naphtha
‘ of these auxiliary solvents from the railinates and
extracts over other lacquer solvents consists in _
extracts was effected with the ?rst one by means
that their boiling range increases gradually and '
of distillation and with the second one by means
of washing out the solvent with water.
evenly without showing breaks in the distilla=
tion curve. Consequently the formation of
streaks, after applying the lacquer solution, is
eliminated. The extraction may be carried out 10
} As auxiliary solvents suitable for use in ac
10 cordance with this invention, there can be used
any solvent miscible with liquid sulphur dioxide
andselective against saturated low boiling h-y
drocarbons, which has a suitable boiling point
in the same manners as speci?ed above in refer
ence to motor fuels under (a), (b) and (c). _
A substantial improvement in results and sav
in comparison with the naphtha. fraction or ing may be obtained by following the steps of
115 which can be washed out of the ra?inates and Methods ((1) and.(b), above described, as com i5.
the extracts by means of other solvents easy to' pared with treating the entire volume of naphtha
separate from the naphtha hydrocarbons.
Naphtha extracts produced by means of liquid
at low temperatures. Thefollowing examples are
illustrative.
~
sulphur dioxide at the normally employed ex
20 traction temperatures of +14 to +20 degrees
_ Fahrenheit have also been usedlas lacquer sol
vents.
The kauri gum number is an indication
of the amount of naphthenic constituents present
in a lacquer solvent, and a good solvent should
25 have a kauri gum number of not less than 70.
Example 5
(a) A naphtha sample was treated at 0° F. 20
with 70% by volume S02. The extract solution,
instead of charging it directly to the solvent re
covery still, was ?rst cooled to -60° F. which
resulted in the separation of an intermediate oil.
The three products, ra?‘inate, ‘intermediate oil 25
and extract, were freed from S02 and analyzed,
the results being as shown in the table below.
Example 4
A naphtha from Gulf Coast crude was treated
30 with sulphur dioxide at temperatures between
-40° F. and +14“ F.
I
Four treatments with
'
(b) The same naphtha was extracted counter
currently at a temperature decreasing from 0° F.
to —-60° F. ,with 70% by volume S02, the condi— 30
3?.5% of S02 by volume were given at each tefn~
tions being such that the S02.was admitted at
perature, and the kauri gum number of the ex
the top of the extraction tower at a temperature
. tract determined.
35
Treatment with so,
I.
2
3 .
4
Original ‘
in batch volume,
(untreated)
percent
’
4X37.5
4X37.5
Temperature, °F_.__
Extract yield, vol
.ume percent ____ __
Kauri gum Now..
It can-be seen from the table that a satisfac
of 0° F. and the naphtha stock at the bottom at
a temperature of .,—60° F. By, suitable cooling
arrangements the temperature at the top of the 35
extraction tower was held at 0° F., in the middle
of the tower at _v—v30° F. and at the'bottom at
—60° F. The results are shown in the table below.
(0) For purposes of comparison, the same stock
was treated under the same conditions as-infv M
(b) excepting that a temperature of --60° F. was
‘maintained in the whole tower. The results of
table:
these treatments are shown
' in the folio
Treatment
v01)
(0)
(0)
509'
Or!
(5%“
a!
70 vol. percent 8011 at
'
0° F. extract cooled to 70 Vol‘ m'ggg
—B0° I‘. to reject inter-
40o n;
,mediato oil
5%
Ref.
Yield _____________________ -_
.
to
?nes
>
Kauri gum No ___________ __
Octane No. Q. r. n ....... __
100
46.8
'
-
1316'
Extr.
53.5 13.6
- 53.1v sec
sac
34.0
29.8
2.0
9.5
sec
46.1
51.9
32.7
Below 41
38.3
46.2
81.9
01.1
Ref.
Extr.
66.0
54.0
'
.
.
34.0
33.6
ml.
in.
sec
53.0
0.5
84.0
- 0m
32.4
Below 41
82.4
90.6
82.5
Below 41
M0
m1
-
cat
cm
01.1
.tory lacquer solvent cannot be obtained from a
It is evident from these data that the tem
naphtha distillate with a naphthenic base by
treatment at 14° F. (the usual treating tempera
ture of solvent re?ning by the Edeleanu method).
perature gradient extraction, Example 5 (b)
- nor even at 0° F., but that it is possible to pro
duce superior lacquer solvents by treating at
'
10 —14° F. and lower temperatures.
Naphtha extracts which are manufactured in
accordance with this invention by treating the
stocks with sulphur‘ dioxide at substantially be
low +14 degrew Fahrenheit, that is down to
~ —70 degrees Fahrenheit, are superior to the nor
55
gives the same yields and qualities of rates - '
and extracts as the normal treatment (Example
5 (0)). The extract obtained by rejection of
the intermediate extract in Example 5 (a) has
almost the same quality as the extracts obtained 70
in Examples 5 (b) and 5 (c), but the yield is
somewhat lower, the reason for this lower yield
being that the intermediate oil which was ob
tained by cooling the original extract solution
from zero to —B0° ‘F. still contains
1 we
4
2,118,771
amounts of aromatics and ole?nes. The inter
mediate oil may, of course, be recycled into the
extraction tower, thereby raising the extract
yield.
The invention is not restricted to vmotor fuels
and lacquer solvents, but relates to the process of
producing improved extracts and blends thereof
suitable for these and other purposes; and where
chilling the extract layer to a low temperature
of the order of minus 60 to minus 70‘? F. to
produce a second extract layer and separating
out the latter, removing the SO: therefrom and
blending the resulting extract with said low boil
ing fraction.
.
2. A process for securing a high octane num
ber motor fuel from a naphtha, comprising sepa
motor fuels and lacquer solvents are referred to . rating the naphtha into a low boiling fraction
in the claims, it is to be understood that we in
tend thereby to include any use to which the
product is adapted.
What we claim is as follows:
1. A process for securing a high ‘octane num
tu ber motor fuel from a naphtha, comprising sepa
rating the naphtha into a low boiling fraction and
a high boiling fraction, treating the high boiling
fraction with liquid-S02 at about 14-20° F. to
produce a ra?inate layer and an extract layer,
and a high boiling fraction, chilling the high 10
vboiling fraction to a low temperature of the order
of minus 60 to minus 70° F. and extracting in
the countercurrent manner with liquid-SO: in
troduced at about 14-20° F., and blending the
so-obtained extract with the low boiling fraction. 15
ERNEST TERRES.
ERICH SAEGEBARTH.
,JOSEPH MOOS.
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