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Патент USA US2131519

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Patented Sept. 27, 1938
* vi'QFFIcE *
Masakichi Mizuta, >Marunouchi, Kojimachi-ku,
Tokyo, and Teiji Yoshimura, Okubo, K'ashi
wazaki-machi, Kariha-gun, Niigata-ken, Japan,
assignors to :NipponSekiyu Kabushiki Kaisha,
Tokyo, Japan, a corporation of Japan
No Drawing. Original application August 11,
1934, Serial No. 739,500.
Divided and this ap- -
plication Aprilv 13, 1937, SerialNo. ‘136,687
1 Claim. (01. 196—’30)
The present invention is a division of our co
pending application which has matured into Pat
ent 2,080,087 May 11, 1937, and relates to aymethod
of re?ning cracked oil, characterized in that by
:31 adding to cracked oil at the ordinary temperature
or below it one or more of copper, lead, zinc and
iron salts of naphthenic acid in solid state or as
dissolved in one or mixture of two or more of
gasoline, petroleum, benzol, toluol, xylols, or tur
pentine, all the compounds of oiiensive odor and
other impurities contained in cracked oil may not
only be combined with metal or metals in dis
solved state and be precipitated as insoluble salts
together with the compounds of offensive odor,
15 but also even disagreeable smell compounds very
di?icult to react may be adsorbed and precipitated
at the same time.
The object thereof is to bring all of principal
sources of offensive odor such as thioalcohols con
tained in cracked oil into intimate contact at a
comparatively low temperature with metallic salts
of organic acids soluble in cracked oil, to make
them react upon each other directly by double
decomposition and precipitate as insoluble salts,
and at the same time to make compounds, which
are very vdifficult to react with ordinary re?ning
agents, such as disulphides deposited by the as
tringent and adsorptive actions of these insol
uble salts at the moment of their formation, thus
30 removing these sources of disagreeable odor com
pletely from cracked oil without any operation
detrimental to volatile oil, such as agitation, stir
ring, etc.
This invention relates to a method of re?ning
the cracked oil produced by the cracking process
of petroleum oils, the tars manufactured from
coal and shale, and other organic matters and is
adapted mainly for removing completely the bad
smell compounds contained in cracked oil and at
40 the same time for increasing the stability of the
The bad smell sources in cracked oil are chie?y
thioalcohols, di-sulphides and unsaturated or
ganic compounds, above all, low boiling thioalco
45 hols.
These substances even in the slightest
quantity can give offensive smell to volatile oil.
For instance, ethyl thiolacohol can still give dis
agreeable smell to gasoline even with the con
centration M0000 or tioo 000 by weight.
Thioalcohol gives out offensive smell lesser
with the increase of its molecular weight, but
even crystallizable higher member of thioalcohol
has bad smell, and thioalcohol is liable to reduce
its reactive power gradually with the increase of
55 its molecular weight.
In cracked oil, the quantity of disulphide orig
inally present in it is only very small, the ma
jority being produced by the oxidation from thio
alcohol and consequently its quantity increases
gradually with the lapse of time after the manu
facture of cracked oil. This compound is also
the cause for giving a kind of burning smell to
cracked oil. It is extremely difficult to react'wlth
ordinary re?ning agents for cracked oil and con
sequently is dif?cult to remove.
. -_
organic compounds in
If isolated, they ’
cracked oil are very unstable.
will mostly polymerize at once, but if diluted with
gasoline, they will become comparatively more’
stable. They give a kind of disagreeable odor to 15
crack-ed oil by their oxidation products. However,
they may be removed easily by treatment. with
Now, according to the present method which
is the result of the study of the constitutions and 20
properties of many such bad smell compounds,
these bad smell sources may be removed com
The known methods all employ re?ning agents
insoluble in the object to be puri?ed, so that
even by any violent agitation the intimate con
tact of a re?ning agent with the object to be
puri?ed is difficult, more so when their difference
in the speci?c gravity is greater. Therefore, only
a portion, but not the whole, of these bad smell 30
compounds are removed and consequently the
complete removing of the bad smell source can
not be expected. In the re?ning operation, the
oxidation of thioalcohols is accelerated more and
more with the violency of agitation in the atmos 35
phere and therefore this agitation operation does
not only make thioalcohols stay as disulphides, but
also causes the loss of gasoline due to volatiliza
tion and consequently the decrease of the yield
of the product.
The inventors have isolated various kinds of
thioalcohols from cracked oil and manufactured
various kinds of disulphides therefrom, and then
studied their reactions with various kinds of met
als and metallic salts of organic and inorganic 45
acids and their various properties including solu
bilities, stabilities etc. Also they have studied
the easiness and speed of the formation of me
tallic salts from the solutions of thioalcohols and
disulphides in petroleum hydrocarbons, and'the 50
behavior of these salts in petroleum hydrocarbons.
Thus, by applying the results of these studies to
cracked oil and studying the best condition with
regard to the re?ning of cracked oil, they have
succeeded in discovering the following matters:— 55
1. One or mixture of copper, lead, zinc and
iron salts of naphthenic acid are easily soluble in
which is prepared by settling and ?ltering a solu
tion of 200 kilograms of copper naphthenate in
gasoline, petroleum oil, benzol, toluol, xylols, tur
500 litres of gasoline, to the above cracked oll
pentine, etc., and, when kept as concentrated puri?ed- by alkali solution and leave the mixture
solutions, they do not change their ‘qualities.
for 8 to 12 hours to settle down insoluble salts
2. If a solution of metallic salts of these or- ~ produced, after which the supernatant oil is
ganic acids is added to gasoline or petroleum oils ?ltered through fuller’s earth ?ltering bed. Next,
containing thioalcohols, it disperses throughout subject the ?ltrated oil to steam distillation in a
the latter spontaneously, mixes with it and reacts steam still and distill o? the gasoline fraction.
10 with thioalcohols by double decomposition even
Put the gasoline fraction in a continuous treat 10
at the ordinary temperature or below it, deposit
ing apparatus and wash it with sulphuric acid,
ing metallic salts of thioalcohols. Thus, by this alkali and water by turns. The ?nished gasoline
way it is possible to remove thioalcohols complete
thus produced has an excellent quality free from
ly from the oil.
disagreeable odor.
3. Disulphide produced here is mostly adsorbed
Thus, it may be possible to obtain gasoline of
into metallic salt of thioalcohol the instant it superior quality which is not only free from dis 15
is produced and is deposited with salt if the agreeable smell, but also has very great stability.
product is allowed to be settled spontaneously
This invention as stated above has the follow
without stirring and presents the appearance as ing advantages:—
20 if this re?ning reaction had occurred according
1. As a re?ning agent is brought into very inti 20
to only the Equation 1. .
4. It is necessary that the reaction between
metallic salt of organic acid and thioalcohol
should proceed slowly. . Thus, after the comple
25 tion of the reaction and the deposition of metallic
salt of thioalcohol and disulphide, the super
natant oil is ?ltered gently through fuller’s earth
?ltering bed and thus these bad smell sources may
be separated from the oil to be puri?ed com
5. The re?ned cracked oil may be subjected to
steam distillation directly. After the part of gas
oline fraction is distilled, the residual oil is stirred
with alkali solution and thus naphthenic acid
35 may be recovered as alkali soap from the oil.
When the result of the above study was applied
to the re?ning of cracked oil, it was possible to
produce cracked gasoline entirely free from thio
alcohols and the bad smell of disulphides.
The following are a few examples of re?ning
of cracked oil for the preparation of cracked
gasoline:Add 0.5% (by volume) of 20% caustic soda
solution to 100 kilolitres of the cracked oil pro
45 duced from Dubb’s cracking plant and agitate
it to remove sulphuretted hydrogen, organic acids
and other reactive substances from the cracked
oil. This pre-treatment economizes metallic salt
of organic acid to be required. Next, after wash
ing it with water enough to remove alkali-residue
completely, dehydrate it. Then, add clear ex
tract solution of copper naphthenate in gasoline,
mate contact with the object to be re?ned easily,
it can react with the whole of bad smell sources
of cracked oil,
2. It is possible not only to remove disulphides
produced during the reaction of this re?ning, but
also to remove disulphides originally contained
in the object to be re?ned by astringent and ad- _
sorptive actions.
3. For the above reason, bad smell sources can
be removed completely from cracked oil.
4. As the object to be puri?ed is not stirred
or agitated, it is possible to prevent the oxida
tion of thioalcohols and also minimize the vapori
zation loss of the volatile portion of the object
to be re?ned.
5. The recovery of re?ning agent is easy.
We claim:
The method of re?ning cracked oil, which con
sists in dissolving oil-soluble heavy metallic soap
of naphthenic acid in a volatile organic solvent 40
which will disperse homogeneously in cracked
oil; pouring the solution thus obtained slowly into
cracked oil while in a cold state to cause same
to disperse naturally and homogeneously without
heating or stirring in the cracked oil whereby 45
same will react with the intermingling mercap
tans and precipitate same by double decomposi
tion as insoluble metallic salts; separating the
precipitate; and distilling the remaining liquor
to separate it from the organic solvent.
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