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Патент USA US2109446

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Feb. 22, 1938.
M. T. KENDALL v
2,109,446
REFINING OF MINERAL OILS
l'Filed Jan. 13, 1934
‘
@Nl
«
'INVENTOR
2,109,446
Patented Feb.` 22, 1938
UNITED STATES PATENT OFFICE
2,109,446
REFINING OF MINERAL OILS
Marcus T. Kendall, Long Beach, Calif., assignor
to The Texas Company, New York, N. Y., a
corporation of Delaware
Application January 13, 1934, Serial No. 706,482
2 Claims.
This invention relates to the manufacture of a
kerosene or burning oil, and particularly to the
refining thereof by distillation and chemical
treatment.
In the manufacture of burning oil, also termed
proposed. So far as I am aware, it has not been
heretofore recognized that beneficial results and
very substantial economy in the use of refining.
agent are obtained by split stream treatment of
hydrocarbons of the kerosene range.
I have discovered that the amount of refining
lamp oil or kerosene, it is customary to distil of! ' agent, .such as fuming sulphuric acid, can be re
a
kerosene
from a crude or other petroleum oil
duced as much as 30% to 40% by weight, by
_fraction of the wide boiling range desired in the sub-dividing the kerosene hydrocarbons into
ultimate product. This kerosene distillate is then controlled lighter and heavier fractions, and sep
10 subjected to a refining treatment with chemicals,
arately treating each fraction with a strong re
such as fuming sulphuric acid, to remove aro
fining
agent of the same or similar character.
matic and sulphur hydrocarbons, and produce a It is well known Ythat kerosene fractions contain
refined oil of satisfactory burn test, or one which substantial percentages of aromatic and sulphur
will give comparatively long service in a lamp hydrocarbons, and that a rigorous refining treat 15
i. . Ol without objectionable action on the wick or
ment is necessary to remove these objectionable
blackening of the chimney. It is recognized that
constituents and produce a kerosene having a
a thorough refining is beneficial in the case of good burn test. The percentages of aromatic
such burning oils, and comparatively large quan
and sulphur hydrocarbons increase with rise in
tities of refining agents are used.
boiling points of the kerosene hydrocarbons. 20
One of the objects of the present invention Consequently, a fraction boiling between 350°
is to provide a method of producing a marketable 435° F. does not contain as large a quantity of‘
burning oil of this character while effecting a aromatic and sulphur hydrocarbons as a fraction
very substantial economy in the use of refining boiling between 435°-550° F. However, both frac
agents.
tions contain these objectionable constituents 25
Other objects and advantages of the invention and require the use of the same type of vigorous
description
will be apparent from the following
refining agent in their removal. I have found
when taken 1n conjunction with the accompany
that it is of distinct advantage to treat the lighter
ing drawing and appended claims.
kerosene fraction with a relatively small quantity
the
refin
According to the present invention,
of the effective refining agent, and the heavier
ing of the kerosene hydrocarbons is carried out kerosene fraction with a substantially larger
30
by a so-called “split stream” treatment, in which quantity of the refining agent in a concentratedKV
the hydrocarbons of the kerosene range are di
manner. In such event, the combined amounts
vided into a lighter fraction and a he avier frac
of the refining agent employed in treating the
tion, and the different kerosene fractions sepa
separated fractions are less than the amount of _3
rately refined with an effective refining agent, the same refining agent required to treat a mix
heretofore
such as fuming sulphuric acid. It has
ture of the two kerosene distillates to an equiva
been suggested to refine cracked gasoline by a lent burn test. Following the separate refining
split stream method, but the purpose and opera
of the kerosene fractions, they are then blended
tion are essentially different. In the case of to produce a burning oil of the boiling range 40
40 the cracked gasoline, the lighter fraction con
desired.
tains a substantial proportion of unsaturated hy
In a specific embodiment of the present inven
desirably
retained
for
drocarbons which are
tion, a crude petroleum oil, or other petroleum
Would
be
anti-detonating purposes, and which
oil containing kerosenehydrocarbons, is heated
removed by a rigorous refining agent. The re
in a tube still to a temperature of about 500°
650° F., and then flashed into a fractionating
45 action between a refining agent, such as sul
phuric acid, and the unsaturated and aromatic
sub
hydrocarbons of a cracked gasoline produces
stantial heat by exothermic reaction, such that
a loss in more volatile constituents of the gaso
stream
line results. Consequently, the split
of
cracked
lighter
fraction
method of treating a
gasoline with only a mild alkaline reagent, while
treating a heavier fraction of cracked gasoline
with sulphuric acid followed by neutralization,
'.55 >and then blending the treated fractions, has been
tower provided with steam stripping and reflux
return so that adequate fractionation is effective
in securing sharp cuts.
The top temperature
of the fractionating tower is controlled to con
50
dense the kerosene hydrocarbons, and perhaps a
heavier gasoline fraction, in the upper portion of
the tower. Two separate kerosene fractions of
different boiling range are rem‘oved as side
streams from the tower. Theseseparated frac
55
2
2,109,446
tions are then separately refined and later blend
ed in the manner above described.
refining apparatus indicated diagrammatically
Referring to the drawing, in which the single
ñgure is a diagrammatic illustration of a pre
ferred form of apparatus for carrying out the
method of the present invention, a conventional
tube still is indicated at I0 having a heating coil
I I to which a crude oil, or other petroleum oil
containing kerosene hydrocarbons, is supplied by
10 a pump (not shown) through the pipe I2.
The
confined stream of oil is heated under pressure to
a temperature which is suiiiciently elevated to
effect vaporization of the kerosene hydrocarbons
when flashed at a lower pressure into the frac
tionating tower I4, which may be maintained
substantially at atmospheric pressure. Where a
crude oil is being treated, this may be the first
stage of a two-stage atmospheric-vacuum treat
ment, wherein the oil is heated in the first stage
20 to a temperature of about 500°-650° F. and then
flashed into an atmospheric fractionating tower
where gasoline, kerosene and gas oil distillates
are obtained. Residuum from the atmospheric
tower then passes to the second stage where the
25 oil is heated in a second tube still (not shown) to
a higher temperature and then flashed into a
vacuum fractionating tower (not shown) where
lubricating fractions are removed.
As shown, the heated oil passes by pipe I5
30 containing pressure reducing valve I6, and is
discharged into an intermediate zone of the frac
tionating tower I4, which may contain a plural
ity of superposed trays I1 of the conventional
bubble cap type. A portion of the oil flashes
35 into vapor which passes upwardly through the
tower, the unvaporized oil flowing downwardly
from tray to tray counter-current to stripping
steam introduced at I8, and residuuin escapes
from the base of the tower by the valve con
40 trolled line I9.
Vapors escape from the top of
the tower by line 20 to a partial condenser 2I
lcooled by any suitable means to a controlled top
temperature to effect a partial condensation to
provide reflux which is returned to the tower
by the line 22. Any excess over the reiiux re
quirements passes to storage by the branch line
23, and uncondensed vapors pass by line 24 to ad
ditional condensing equipment (not shown).
Any suitable number of trays I1 may be pro
vided within the fractionating tower, and all
or any number of the trays equipped with liquid
withdrawals for side stream removal. As shown,
four valve controlled pipes 26-29 are arranged at
various elevations along the height of the tower.
A gas oil distillate may be removed by the line
29, and a heavy gasoline distillate by the line 26.
In place of removing a single kerosene fraction
by an intermediate side stream, two separate dis
tillates consisting essentially of hydrocarbons
60 boiling within the kerosene range are removed by
the lines 21 and 28 respectively. It is Vto be
understood that the positioning of the side
streams 21 and 28 coupled with the reñuxing
within the tower may be so controlled as to ob
65 ,tain fairly sharp cuts of any desired and variable
boiling ranges, whereby a lighter kerosene frac
tion is removed at 21 and a heavier kerosene frac
tion at 28. If desired, either or both of the sep
arate kerosene fractions may be further treated
70 with steam in kerosene strippers (not shown)
to increase the sharpness of the cuts.
'I‘he separate kerosene fractions are delivered
to storage tanks 30 and 3I respectively. The
light kerosen'e fraction is passed from storage
75 tank 30 through line 32 containing pump 33 to- a
at 34.
’I‘he heavy kerosene ydistillate is passed
through line 36 containing pump 31 to a relin
ing apparatus 38.
The refining apparatus for
each fraction may be of any suitable conven
tional construction, either adapted for batch or
continuous operation. As shown, an agitating
tank is illustrated adapted to be supplied with
chemical through line 4I from branch lines 42
and 43. Each refining tank is also provided with 10
a sludge withdrawal line 44. 'I‘he kerosene frac
tion is here treated with a strong refining chem
ical adapted to remove aromatic and sulphur hy
drocarbons. Very satisfactory results are secured
where the kerosene fraction is first agitated with
fuming sulphuric acid, allowed to settle, the
sludge withdrawn; and then to remove products
of sulphonation the treated oil is agitated with
weaker sulphuric acid, such as recovered sul
phuric acid obtained from the fuming acid sludge. 20
The treated oils are then withdrawn, ‘for ex
ample, by the line 46 in the case of the lighter
distillate from tank 34, and by the line 41 in
the case of the heavier distillate from tank 38.
'I‘he treated oil from each tank may then be passed 25
to a second tank where it is treated with alkali,
or any other refining treatment desired, such as
contact filtration. As this is entirely conventional
procedure, involving the use of conventional
apparatus, no attempt has been made to illus 30
trate the particular apparatus employed, which
may vary widely in construction. 'I'he additional
refining apparatus, if such is employed, is con
nected to the lines 46 and 41, at the points indi
cated by the breaks therein. If desired, the al
kali treatments may be carried out in the same
tanks 34 and 48 used for the acid treatments.
The reñned light kerosene distillate then
passes by line 50 to either a valve controlled
branch pipe 5I leading to a suitable storage re
ceptacle or valve controlled line 52 leading to a 40
blending tank 53 having outlet 54. 'I'he heavy
kerosene distillate passes by line 55 to either a
valve controlled line 56 leading to a storage tank
or valve controlled line 51 emptying into the
blending tank 53.
The two kerosene distillates
are mixed in predetermined or controlled pro
portions in the blending tank 53 to produce a
burning oil of the desired character and test.
By way of example, the refining treatment of
a Los Angeles basin crude to produce a kerosene 50
or burning oil boiling between 360°-485° F., and
which meets the required 18 hour “burn test”,
is herein described. In conventional practice,
wherein the entire kerosene cut boiling within
the range specified is treated with acid, it is
found necessary to apply 18 pounds of 15% fum
ing sulphuric acid per barrel of oil, followed by '7
pounds of recovered sulphuric acid (80% H2SO-4)
per barrel. In accordance with the present in
vention, this kerosene distillate is split into two 60
streams 21 and 28 in the manner previously de
scribed. The lighter distillate preferably has a
boiling range between 360°-435° F., and repre
sents approximately 50% by weight of the en
tire kerosene distillate of the desired boiling
range obtainable from the fractionating tower.
'I'he heavier kerosene fraction boils between 435°
490° F., and represents the other 50% of the
kerosene distillate. 'The light distillate is then
treated with approximately 4 pounds of 15%
iurning sulphuric acid and approximately 9
pounds of recovered acid per barrel. The heavy
kerosene distillate, which contains a larger pro
portion of the aromatic and sulphur hydrocar
75
3
2,109,446
bons, is severely treated with approximately 20
pounds of 15% fuming sulphuric acid and ap
proximately 5 pounds of recovered sulphuric
I claim: »
l. >The process of preparing a marketable
burning oil consisting essentially of hydrocar
acid per barrel. This gives a net consumption on
bons of the kerosene range boiling between sub
the total kerosene distillate of approximately 12
pounds of fuming sulphuric acid and ’7 pounds
of recovered acid per barrel, thereby effecting
a saving of approximately 33.3% of fuming sul
phuric acid over that used in the conventional
10 treatment. The light and heavy cuts, after treat
ment, are then blended in the proportion of their
production, which is about 48% by weight of the
heavy kerosene distillate to 52% by weight of
the light kerosene distillate. This is found to
produce a burning oil of the desired boiling range
between BGN-485° F., and which has a burn test
at least equivalent to that formerly produced by
treating the entire kerosene cut with the sub
stantially larger quantity of acid specified above.
It is believed that this greater eñiciency of
20
the refining acid in the split stream treatment is
stantially 360°-490° F., which comprises' sepa
rating from a petroleum oil by non-cracking
due to the following reasons, although I do not
iiash distillation a lighter kerosene distillate frac
tion boiling between substantially 360°-435° F.
and a heavier kerosene distillate fraction boiling
between substantially 435°-490° F., treating the 10V
lighter kerosene fraction with substantially 4
pounds of fuming sulphuric acid per barrel of
oil followed by treating with substantially 9
pounds of recovered sulphuric acid per barrel of
oil, treating the heavier kerosene fraction with 15
substantially 20 pounds of fuming sulphuric acid
per barrel of oil followed by treating with sub
stantially 5 pounds of recovered sulphuric acid
per barrel of oil, and blending the treated kero
sene fractions to produce without redistillation 20
a burning oil of the desired boiling range having
a burn test at least equivalent to that produced
by treating a mixture of the said kerosene frac
wish to be bound thereby. First, the light kero
sene distillate contains a smaller proportion of
25 the aromatic and sulphur hydrocarbons and
therefore requires less acid for refining to a
good burn test. Second, the heavier kerosene dis
tillate contains the larger proportion of th‘e aro
matic and sulphur hydrocarbons, and therefore
30 requires the larger proportion of the refining acid.
Third, the heavier distillate receives a more con
centrated treatment, due to the fact that there
is a greater concentration of acid to aromatic and
sulphur hydrocarbons. In other words, the light
35 kerosene fraction acts in the nature of a diluent,
thus diluting the refining acid and reducing its
e?ciency, so that normally a larger quantity of
acid is required to effect an equivalent reñning
action. The more concentrated treatment of the
40 present invention is responsible for more efficient
sulphonation of the aromatics and polymeriza
tion of the sulphur hydrocarbons, whereby a
smaller quantity of acid is more efficiently uti
. lized. Finally, by splitting the kerosene distillate
into two streams as specified, a larger proportion
of acid on the weight of the oil treated thereby,
can be utilized for the heavier fraction, and still
obtain the net saving in acid for the treatments
of both fractions.
In this manner, a more eco
nomical sulphonation and polymerization with
fuming sulphuric acid is accomplished by remov
ing that part of the chain of hydrocarbons of
lower boiling point that contains less of the un
desirable hydrocarbons, and concentrating the
treatment upon that part which requires a sub
stantial refining.
tions with substantially 18 pounds of fuming sul
phuric acid per barrel of oil followed by substan 25
tially ’7 pounds of recovered sulphuric acid per
barrel of oil, whereby a substantial saving in the
consumption of fuming sulphuric acid is effected.
2. The process of preparing a maketable burn
ing oil from a. crude mineral oil of the character 30
having substantial quantities of aromatic hydro
carbons throughout the kerosene boiling range,
which comprises heating a confined stream of the
mineral oil to a temperature not substantially
exceeding 650° F. but which is sufficiently elevat
edto vaporize kerosene hydrocarbons with a por
tion at least of the gas oil content, flashing the
heated oil into a fractionating zone where gaso
line vapors are removed overhead and kerosene
distillates are removed as side streams, reñux 40
ing the vapors in the fractionating zone to ob
tain sharp cuts, removing from different levels
of the fractionating zone .separate side streams
each consisting of hydrocarbons of the kerosene
range, an upper side stream being a lighter ker 45
osene> distillate fraction having a boiling range
of the order of S60-435° F. and a lower side stream
being a heavier kerosene distillate fraction having
a boiling range of 435-490" F., separately treat
ing the said kerosene fractions with predeter
mined amounts of fuming sulfuric acid capable
of removing aromatic hydrocarbons followed
Without intermediate distillation by treatment
with recovered sulfuric acid to remove products
of sulphonation, the said lighter kerosene frac 55
tion being treated with a relatively smaller quan
tity and the said heavier kerosene fraction be
ing treated with a relatively larger quantity of
the fuming sulfuric acid, and blending Without
It is to be understood that the proportions into
which the kerosene stream is split can be varied redistillation the separately treated kerosene
widely, and still obtain the advantages of the fractions to produce directly a burning oil hav 60
present invention. Further, the invention is not ing a boiling range of the order of 360-485" F.,
limited to the use of any deiinite quantity or 'the' fractionation into sharp cuts being predeter
kind of refining agent. For example, other rigor
mined in accordance with the fuming acid re
ous refining agents may be employed with bene
quirements of the said separated kerosene frac
ñcial results in accordance with the principles tions to produce after recombining of the treat 65
set forth above, such agents including sulphur ed fractions a blended burning oil having a burn
trioxide, liquid sulphur dioxide, metallic chlo
rides such as aluminum chloride, zinc chloride
and the like.
Obviously many modifications and variations of
the invention, a_s hereinbefore set forth, may be
made without departing from the spirit and scope
thereof, and therefore only such limitations
should be imposed as are indicated in the ap
pended claims.
test at least equivalent to that produced by treat
ing the entire kerosene content without splitting
thereof with a substantially greater quantity of
fuming sulfuric acid than the combined amountsv '
of fuming sulfuric acid employed in treating both
of the separated kerosene fractions such as to
produce a net saving of fuming sulfuric acid of
the order of 30% or more.
MARCUS T. KENDALL.
75
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