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Патент USA US2133452

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2,133,452 '
Patented Get. 18, 1938
. 2,133,452
Amiot P. Hewlett, Cranford, N.
J., assignor to
Company, a cor
Standard Oil Development
poration of Delaware
No Drawing. Application December 30, 1933,
. Serial No. 704,765
1 Claim.
(Cl. 196-44)
washed, neutralized with alkali, and redistilled or
This invention relates to the treatment of hy
drocarbon oils belonging to the kerosene, gas oil
and lubricating oil ranges with boron ?uoride or
?nished in any manner well known to the art.
Boron fluoride and other halides of similar
chemical characteristics are also very effective in
other halides of similar chemical properties. The
5 oil tobe treated may be a kerosene distillate or a
heavier distillate from petroleum. It may be a
shale oil boiling within the kerosene range or
re?ning cycle gas oils from petroleum cracking 5
operations for the production of high quality
domestic and industrial heating oils. Unre?ned
higher. Other oils of similar boiling range pro
duced by low temperature carbonization of coal,
in or by hydrogenation of coal, may be treated ac
cording to the present invention, although the
best results are obtained when the invention is
applied to the treatment of petroleum distillates
of the boiling ranges speci?ed. The treating
cycle gas oils are in many ways unsatisfactory
for heating purposes inasmuch as they contain
certain undesirable constituents which may be- 10
come highly corrosive during storage, attack
metal parts of the burner installation and result
in clogged screens and. strainers. Certain unde
sirable constituents of unre?ned cycle gas oils
15 agent is boron ?uoride or any of the other halides
of boron, such as~boron chloride, bromide, iodide,
halides of titanium, such as titanium tetrachlo
also result in the formation of carbonaceous resi- 15 -
dues on burning. These objectionable character
istics are eliminated by re?ning the cycle gas
oil according to the present invention.
ride, and halides of silicon such as silicon ?u
One object of the present invention is to re
move undesirable constituents from the distillates
The amount of treating agent used varies with
the nature of the treating agent and also with the 20
oil to be re?ned. Usually very small quantities
such as 0.1-0.4 pound of boron ?uoride per barrel
submitted to treatment.
Another object is the production of nitrogen
bases from the sludge removed by the treating
25 agent from certain distillates, especially those
boiling within the kerosene range.
I have found the halides mentioned above to be
very good selective re?ning agents by removing
undesirable constituents from the treated hydro
of oil give satisfactory treating results, while
much higher quantities such as 1-5 lbs. of titani
um tetrachloride have to be used for the same 25
degree of re?nement. The amount of treating
agent used may vary within broader limits than
those just given for illustration.
Certain petroleum and shale oil distillates,
especially those boiling within the kerosene 30
30 carbon oil. When burning oils, such as kerosene,
range, contain nitrogen bases which are valuable
are treated their burning characteristics are im
in the manufacture of drugs, special chemicals,
proved. The improvement in lubricating oils
dyes and the like.
manifests itself in an increase of gravity and
also in an improved (increased) viscosity index.
35 The viscosity index is a method of evaluating lu
bricating oils described in an article by E. W.
Dean and G. H. B. Davis, in vol. 367, No. 10,
October, 1929, of Chem. and Met. Engineering.
A viscosity index of ‘100 designates a good grade
40 Pennsylvania lubricating oil. Kerosenes, lubri
cating oils or other oils have also a greatly im
proved color after the treatment.
The treating consists in agitating the hydro
carbon distillate with the treating agent, settling
45 and separating the sludge. The treating agent
may be added directly to the distillate to be treat
ed, as, for example, by introducing boron ?uoride
gas into kerosene, or it may be ?rst dissolved in
strong,.say substantially 100% sulfuric acid, and
50 the distillate treated with the sulfuric acid solu
tion of the halide, this last method being espe
cially advantageous when lubricating oils are
treated. After the settling of the sludge, the hy
drocarbon distillate may be ?ltered in order to
55 eliminate the last traces of sludge and. then
These bases can be e?iciently
separated by the use of small quantities of boron
?uoride or similar compounds. The distillate is 35
treated as usual with the boron ?uoride or the
other agent, and the sludge separated and hy
drolyzed in order to liberate the nitrogen bases.
Hydrolysis of the sludge may be effected by inti
mately mixing the sludge with water (hot water 40
preferred) followed by neutralization with caus
tic. If preferred a caustic solution may be used
instead of water for hydrolysis. The oil con
taining the liberated nitrogen bases may be fur
ther treated by dissolving the bases with. an 45
aqueous mineral. acid, separating the acid solu
tion from the remaining insoluble oil and then
adding sodium hydroxide or other alkali until an
alkali reaction results whereby the nitrogen bases
are precipitated and can easily be separated from 50
the aqueous solution.
The following example will illustrate the pres
ent invention: A sample of heating oil consisting
of a cycle stock obtained in cracking gas oil and
having gravity of 29° A. P. 1., ?nal boiling point 65
600° F. and color 8 Robinson is treated with two
What I claim is:
ounces per barrel of boron ?uoride. The color
is improved to 12 Robinson and the total copper
ple given for illustration, but only by the follow-
ing claim in which it is my intention to claim all
10 novelty inherent in the invention.
An improved process for re?ning hydrocarbon
distillate oils having initial boiling points at least
boron ?uoride and separating the resulting sludge
from the oil.
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