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Патент USA US2411959

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2,411,959
Patented Dec. 3, 1946
UNITED STATES‘. PATENT 1 OFFICE
2,411,959
METHOD OF PURIFYING PETROLEUM
PRODUCTS
'
Melvin A. Dietrich, Claymont, Dei., and chimes J.
Pedersen, Penna Grove, N. J .,‘ assignors to E. I.
du Pont de Nemours & Company, Wilmington,
DeL, a corporation of Delaware
No ‘Drawing. Original application November 25,
1943, Serial No. 511,736. Divided and this ap
plication January 18, 1946, Serial No. 642,134v _
6 Claims. 101. 196-30)
1
2
,
This invention relates to methods for purifying
organic substances and particularly to purifying
water-immiscible organic substances which are
contaminated with catalytically active metal
compounds.
'
.
-
>
This is a division of our copending applica
.
stance being treated. Still other objects will ap
pear hereinafter.
'
-
" The above and other objects may be accom
plished in accordance with our invention which
comprises washing the contaminated water-im
miscible organic substances in the liquid state
with a dilute aqueous solution of a compound of
tion Serial No. 511,736 ?led November 25, 1943.
the class of organic thiols containing from 1 to 10
Many organic products tend to deteriorate on
carbon atoms and at least 1 water-solubilizing
aging, especially when exposed to free contact
with the atmosphere. This deterioration gener 10 group and water-soluble salts of such thiols. We
have found that, by this procedure, we are able
ally involves autooxidation due to thereaction
to very e?ectively remove from the organic sub
of the organic substances with molecular oxygen.
stances, dissolved catalytically active compounds
It has been proposed to overcome this di?‘lculty by
of heavy metals of the group of copper, iron, co
incorporating in the organic substances various
compounds which inhibit or retard the deteriora 15 balt, manganese and vanadium. This was par
ticularly unexpected since the thiols and their
tion and which are generally known as anti-v
water-soluble
salts are generally more soluble in
oxidants. Frequently, such organic substances
water than in the organic substances being
become contaminated with catalytically active
treated. It was especially surprising to ?nd that
compounds of heavy metals, such as copper, iron,
cobalt, manganese and vanadium, which speed the 20 such thiols and their water-soluble salts are far
superior to sodium sul?de when employed in the
aging of the organic substances and the oxida
> same manner and remove the catalytically active
tion of the antioxidants themselves, thereby ren
metal compounds from the organic substances
dering the stabilization with antioxidants more
much more completely.
di?lcult. - An example of this is in the copper
sweetening of gasoline wherein traces of copper 25 The-organic substances, which may be treated
in accordance with our invention, are those or
frequently remain in the gasoline and greatly
shorten its useful life. It has been proposed to
overcome. the effect of such metals by adding,
to the organic substances contaminated there
with, a metal deactivator which reacts with the 30
' metal and renders it ‘catalytically inactive.
. Methods have also been proposed for removing
ganic substances which are immiscible with water
and which are liquid at ordinary temperatures or
which may become liquid-at higher temperatures
up to about 100° C. Our invention is particularly ,
applicable to the treatment of petroleum products,
such. as gasoline, fuel oil, lubricating oils and the
like. Our invention is especially directed to the
puri?cation of copper sweetened cracked gasoline.
nated organic substances. A common and well
Our process may be employed for removing dis
known example of this is the washing of copper 35
solved catalytically active compounds of heavy
sweetened gasoline with an aqueous solution of
metals, such as copper, iron, cobalt, manganese
sodium sul?de for removing copper remaining in
and vanadium. It is particularly e?ective for re
the gasoline.
_ moving dissolved catalytically active compounds
It is an object of the present invention to pro
vide a new and, improved'method of purifying 40 of copper from organic substances and particu
larly. from petroleum products, such as copper
water-immiscible organic substances contami
sweetened cracked gasoline,
'
nated with dissolved‘ catalytically active com
We have found that organic thiols, containing
pounds of the group of copper, iron, cobalt, man
from 1 to 10 carbon atoms and at least 1 solubil
ganese and vanadium. A more particular object
is to provide a new and improved process for re 45 izing group and the water-soluble salts of such
thiols, when employed inan aqueous solution, are
moving soluble copper compounds from'cracked
very e?ective for removing catalyticaliy active
gasoline and especially from copper sweetened
compounds of heavy metals from water-immisci
gasoline. Another object is to provide such a
ble organic substances contaminated therewith.
method wherein the organic substance is washed
with an aqueous solution of a compound which 50 These compounds may be represented by the for
is unusually effective for the purpose and is much
more e?ective than sodium sul?de. A still fur
ther object is to provide such a method, employ
wherein M represents. hydrogen, ammonium or
ing aqueous solutions of compounds which are
alkali metal and R represents a pclyvalent or
more soluble in water than in the organic sub
catalytically active metals from such contami
mula
-
.
3
2,411,950
~
ganic radical containing from 1 to 10 carbon
4
liter separatory tunnel. The gasoline was sepa
rated, dried, and ?ltered by gravity through
atoms and 1 or more water-solubilizing groups.
Representative water-solubilizing groups are
paper. The induction periods or untreated and
treated samples 0! gasoline and their response to
a, commercial antioxidant (p-(n-butylamino) -
phenol, abbreviated BuPAP) were determined by
the accelerated method described in J. ‘LE. C. 25
(397 (1933)). This method consists in heatlns
wherein M represents hydrogen, ammonium or
alkali metal. irrererably, the mums and their
salts are more soluble in water than in the or
100 cc. of gasoline at 100° C. in a l-llter Pyrex
ganic substahce- to be purmed. water-soluble 10 ?ask containing pure oxygen. The internal pres
organic tniols and water-soluble salts tnereor' are
sure is observed every 10 minutes by meansoi a
manometer attached to the system. The elapsed
time. from the start of the test until thegasoline
those which are soluble in water to the extent of
at least 0.1% at the temperature at which the
treatment is to take place. The term “organic
thiols" will be understood to include compounds,
such as thlourea, thiosemicarbaziue and .N-gua
begins to absorb oxygen at the rate of 10 cc. per
10 minutes or higher, as shown by the fall in in
ternal pressure, is taken as the induction period.
It has been found that the induction period, ob
nylthiourea, which. as origmahy written, do not
appear to have a mercapto group in the structur
tained by this method, although greatly short
a1 iormulae, but which exist in tautomeric forms.
ened, is a fairly accurate measure of the relative
stability of gasoline under normal storage condi
one of which contains a mercapto group. For ex
ample, thiourea exists in the Iohowing 2 forms:
tions.
.
The results of these tests are shown in Tables I
and II.
"
a.
Table I
When the thiols are su?iciently basic to react 25
with acids, they may be employed as their water
Induction period in
soluble salts of acids, such as hydrochloric acid.
J _
minutes
carbonic acid and the like. When the tniols are
N 0.
Treatment
suiiicientiy acidic to react with strong bases, they
No
0.00257
BuPAP
BuPAlg
may be employed as their water-soluble salts of 30
bases, such as ammonia, sodium, potassium and
l. _ ___ None (no coéiper added) _____________ __
130
380
the like.
2.____ IP. P. M. u ...................... __ About20
65
Ordinarily, the aqueous solutions will be dilute,
Plus 1 P. P. M. Cu and shaken with
'
thelollowing aqueous solutions:
containing the thiol or its water-soluble salt in
3. _ _ -_
1% N-guanylthiourea carbonate. _ _
115
330
NHr-C-NH: 2 NH=C—_NH|
a concentration or‘ from 0.1 to 10%. It will gen 35 4. _ ___
1% thiosemicarbazlde ___________ __
105
325
5. . . ._
1% beta-hydroxyethyl mercaptam.
90
340
erally be preferred to employ them in a concen
6. _ _ _ _
1% cysteine hydrochloride. _
100
300
tration of about 1%. Higher concentrations than
7. _ _ _ _
1% decanedithiol-l,l0 _____ - _
95
290
8_____
10917 sodium sul?de.-__
60
250
10% may be employed where the thiol or its
9.-.“
1% lauryl meroaptan ____________ __
30
80
water-soluble salt is su?iciently soluble in water.
The upper concentration which may be used will
It will be observed that 1% solutions of the
be ?xed by the solubility of the thiol or its salt.
organic reagents belonging to this class are more
Where the organic substance to be puri?ed is
effective that even 10% sodium sul?de, a com
a liquid at atmospheric temperatures, it will ‘gen
pound widely used by the petroleum industry for
erally be found most convenient to carry out the
the removal of copper from copper sweetened
washing at atmospheric temperatures. Where
gasoline. It will also be noted that a mercaptan,
the organic substance is quite volatile, lower tem
not possessing water-solubilizing groups in addi
peratures down to just above the freezing point
tion to the —SH (lauryl mercaptan), is practi
of the aqueous solution may be employed. In
cally ineffective.
'
other cases, where the organic substance melts at
a temperature between atmospheric temperatures 50
Table II
and 100° C. and where the organic substance is
quite viscous at atmospheric temperatures, it will‘
Induction period in
generally be desired to employ temperatures
minutes
above atmospheric up to about 100° C. In some
cases, it will be possible to operate at tempera .55
tures above 100° C. by employing pressures su?i
cient to avoid vaporization of the aqueo'us me
Y
dium. Any method of intimately contacting the
No.
-
1.- ___
2___._
None (no Cu added) ________________ __
No
BuPAP
180-195
PluslP. P. M. 0m... ............. ._
0.0025%
BuPAP
465-475
65
Plus 1 P. P. M. Cu and shaken with
organic substance with the aqueous washing so
lution, such as mechanical agitation in a tank or 60
other vessel vor counter?ow contact through a
packed vertical tower, may be employed.
Treatment
the following aqueous solutions:
3. ___.
4. . _ _ _
1% thiourea _____________________ -.
'
'
5- _ ___
6._.__
1% sodium sul?de _______________ ._
>
180
485
150
445
155
355
40
90
In order to more. clearly illustrate our inven
tion, the preferred modes of carrying the same
It will be seen that the organic reagents are
into effect and the advantageous results to be 65 much superior to sodium sul?de of equal solu
obtained thereby, speci?c experiments are given
tion strength.
as follows:
In order to show that the catalytically active
A quantity of cracked gasoline, completely re
metal is actually removed from the organic sub
?ned but otherwise untreated with chemical ad
stance by our method, rather than merely de
ditives such as dyes and anti-knocks, was con
70 activated, a benzene solution was prepared con
taminated with 1 part per million of copper as -
taining 0.05 g. of copper (as copper naphthenate)
cupric oleate. Four hundred cc. of the copper
containing gasoline were vigorously shaken 300
times at room temperature with 40 cc. of aqueous
per 100 cc. of solution. This solution was shaken
with an equal volume of a 1% aqueous solution
of thiosorbit'ol.‘ The green color disappeared
solutions of the copper removing compounds in a 76 from the benzene layer which became colorless. -
2,411,959
5
compounds oi heavy metals selected from the
group consisting of copper, iron, cobalt, manga
nese, and vanadium which comprises washing
the petroleum product in the liquid state with
The benzene layer was then separated from the
aqueous solution and was evaporated on a steam
bath, leaving a trace oi’ a brownish oil which was
not water-soluble. Similar experiments were
conducted with gasoline, fuel oil and an SAE 30 .
a dilute aqueous solution of a member of the
lubricating oil with like results. The washing
with the aqueous solution removed the copper
from the organic substances.
group consisting of thiourea, thiosemicarbazide,
N-guanylthiourea, beta-amino ethyl mercaptan
‘ ___It will be understood that the above experiments are given for ‘illustrative purposes only
and that many variations and modi?cations can
contaminated with dissolved catalytically active
compounds of heavy metals selected vfrom the
and dithiourea.
2. The method of purifying petroleum products '
group consisting of copper, iron, cobalt, manga
nese and vanadium‘ which comprises washing the
be made therein without departing from the
spirit or scope of our invention. For example,
petroleum product in the liquid state with a
the concentrations of the thiols and their salts
in the aqueous solutions may bev varied; the
amount of the solution employed and the ex
tent or treatment of the organic substance there
with will vary; other solvents, such as methanol
dilute aqueous solution of thiourea‘.
3. The method of puriiying petroleum products
contaminated with dissolved catalytically active
compounds 01’ copper which comprises washing
the petroleum product in the liquid state with a
and acetone, may be added to the aqueous so
- lutions and other thiols and their salts, within 20 dilute aqueous solution of a member oi’ the group
consisting of thiourea, thiosemicarbazide, N
the scope of our invention, may be substituted
guanylthiourea, beta-amino ethyl mercaptan
for those employed in the experiments. Other
representative thiols and their salts, which are
e?ective and which come within the scope of
our invention, are-
‘
Beta-amino ethyl mercaptan
Beta-mercapto ethyl sulionic acid
Beta-mercapto ethyl phosphonic acid
Dithiourea (tautomeric)
Beta-phenylaminoethane thiol
and dithiourea.
4. The method 01' purifying petroleum products ‘
25 contaminated with dissolved catalytically active
compounds 01 copper which comprises washing
the petroleum product in the liquid state with a
dilute aqueous solution of thiourea.
5. The method of ‘purifying copper sweetened
30
Beitla1i-1(o-hydroxycyclohexylamino) ethane
o
Hydroxybenzal thiosemicarbazide
cracked gasoline contaminated with dissolved
catalytically active compounds of heavy metals
selected from the group consisting oi’ copper, iron, .
cobalt, manganese and vanadium which com
prises washing the gasoline in the liquid state
It will thus be seen that, by our invention, we 35 with a dilute aqueous solution of a member of the
have provided a very eiiective method for remov
group consisting of thiourea, thiosemicarbazide,
ing catalytically active compounds of heavy met-v
N-guanylthiourea, beta-amino ethyl mercaptan
sis from organic substances andv particularly
and dithiourea.
'
'
from petroleum products, such as copper sweet
6. The method of purifying copper sweetened
ened cracked gasoline. Our agents are more eiiec 40 cracked gasoline contaminated with dissolved ‘
tive than the well known sodium sul?de method,
even when the sodium sul?de is employed in a con
centration-ot 10 times that of our compounds.
Accordingly, we believe that our invention con
45
stitutes a substantial advance in the art.
We claim:
1. The method of purifying petroleum products
contaminated with dissolved cstalytically active
catalytically active compounds oi’ heavy metals
selected from the group consisting of copper,
iron, cobalt, manganese and vanadium which
comprises washing the gasoline in the liquid state
with a' dilute aqueous solution 01' thiourea. ’
unr-vm s. nm'mrcH,
CHARLES J. PEDERSEN.
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