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Патент USA US3051657

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1
305L648
Patented Aug. 28, 1962
2
the effective surface area of the catalyst which is avail
able for treatment of the hydrocarbon distillate. The
3,051,648
STABILITY OF, HYDROCARBON DISTILLATE
aluminum phosphate catalyst may be present on the sup
Frederick G. HessfCranbur-y, and Walter C. Bradbury,
porting material in any suitable quantities such as between
Union, N.J., assignors to Cities Service Research and
Development Company, New York, N.Y., a corpora 5 about 0.5 and about 10 Iweight percent based on aluminum
phosphate. In order to assist in distributing the alumi
tion of New Jersey
No Drawing. Filed Apr. 29, 1960, Ser. No. 25,565
8 Claims. (Cl. 208-297)
num phosphate over as large a surface area as possible
it is preferred that the supporting material be ?nely di
vided with material capable of passing through a 10 mesh
This invention relates to the catalytic treatment of 10 or smaller screen being preferred. Material of 10 to 50
hydrocarbons and more particularly relates to a novel
mesh size is especially suitable. Asuitable catalyst may
process for improving the stability of hydrocarbon distil
be prepared by wetting ?ne silica gel with a concentrated
late.
solution of aluminum sulfate and then treating with an
Hydrocarbon distillate fuels treated in accordance with
excess of ammonium hydroxide to precipitate aluminum
the present invention include generally fuels having boil 15 hydroxide. Phosphoric acid may then be added to form
ing ranges between about 100 and about 1200“ F. and
aluminum phosphate and the catalyst may then be water
may include gasolene, kerosene, diesel fuels, heating fuels,
jet fuels and the like. Such distillates may be obtained
washed and dried to remove water.
It is preferred that the treatment of hydrocarbon distil
from any suitable source such as by fractionation of crude
late in accordance with the present invention be carried
oils or may be obtained from any of the various hydro 20 out in the absence of water in order to prevent the cata
carbon conversion or re?ning processes commonly used
in the treatment of hydrocarbon oils. Such processes in
clude, for instance, catalytic or thermal cracking or re
lyst from becoming dissolved in water and being thereby
dissociated into free ions. The treatment may be carried
out under any suitable conditions of temperature and
forming, coking, alkylation, polymerization and the like.
pressure, but it is preferred that the distillate being treated
The process of the present invention is especially appli 25 be maintained in the liquid phase and be treated at a
cable to kerosene and to fuel mixtures containing sub
temperature above about 400° F., preferably between
stantial portions of kerosene. Fuels containing substan
about 450° and about 600° F. Any suitable pressures
tial amounts of kerosene include, for instance, jet fuels
may be used, but pressures su?icient to maintain the dis
which frequently contain from 30 to 60 volume percent
tillate in the liquid phase are preferred. Temperatures
or more of kerosene and frequently have boiling ranges 30 between about 450° and about 600° F. and pressures of
between about 100 and 600° F. The invention is also
between about 5 and about 200 psi. have been found to
applicable to fuel compositions containing substantial
be suitable although higher pressures may, of course, be
amounts, such as at least 30 volume percent, of hydro
used.
carbon distillates of the type described above.
The mechanism by which stability of hydrocarbon dis
Distillates such as those described above have a strong 35 tillate fuels is increased by the treatment of the present
tendency to form gums and sediments, especially after
prolonged periods of storage or exposure to high tempera
invention is not completely understood, but it is believed
that such improved stability is the result of the removal
tures.
of undesirable sulfur compounds as well as the removal
of other undesirable compounds such as certain oxygen
Such gums and sediments are highly undesirable
and may clog fuel lines, valves, meters, ?lters, etc., as
well as form deposits in internal combustion engines or 40 and nitrogen compounds by the catalytic action of the
fuel burners. In order to prevent the formation of such
aluminum phosphate catalyst.
'
sediment and gums for as long a period as possible, vari
In treating distillate fuels in ‘accordance with the pres
ous additives or inhibitors are commonly added to distil
ent invention it is preferred to follow the catalytic treat
late fuels. While the use of such additives has proved
ment of the invention with a caustic or clay neutralizing
effective in substantially increasing the stability of distil 45 treat-ment in accordance with the conventional re?ning
late fuels by preventing the formation of sediment or
practice. If desired, the distillate fuel treated in accord
gums for substantial periods of time, such additives are
ance with the invention may also have been sweetened
expensive and are not always as effective as might be
for removal of obnoxious sulfur compounds by conven
desired.
tional processes such as with a doctor solution or with an
It is an object of the present invention to provide a 50 alkaline hypchlon'te such as sodium hypochlorite. It is
method of treating hydrocarbon distillate fuels to im
prove the stability thereof.
-It is another object of the invention to provide a novel
process for improving the stability of hydrocarbon distil
also contemplated that the distillate may be sweetened
following the catalytic treatment of the present invention.
The following speci?c examples will illustrate the ap
plication and bene?ts of the present invention in the treat
ment
of hydrocarbon distillate.
55
EXAMPLE 1
ent invention, hydrocarbon distillate fuel is treated for
In order to evaluate the treatment of the present inven
improvement of stability by contacting the same in the
tion a suitable catalyst was prepared by wetting 255 grams
liquid phase at a temperature of ‘at least about 400° F.
of l4—20 mesh silica gel with a concentrated aqueous
with a supported aluminum phosphate catalyst.
60
The aluminum phosphate catalyst with which hydro
solution of aluminum sulfate containing 16 grams of
carbon distillate is treated in accordance with the inven
Al2(SO4)3.18I-I2O. This was then treated with a slight
tion is preferably supported on suitable supporting ma
excess of dilute ammonium hydroxide solution to precipi
terial such as silica gel or neutral clay in order to increase
tate .aluminum hydroxide. After water Washing, phos
late fuels without the use of additives.
In accordance with a preferred embodiment of the pres
3,051,648
3
4
phoric ‘acid was added to form aluminum phosphate.
After washing with water to remove excess phosphoric
acid, the silica gel was dried in an oven and then heated
minum phosphate or any other catalyst. The results of
the CFR coker test on this control sample of kerosene
are shown in Table I below.
in a mu?ie furnace at 930° F. for 1 hour.
The kerosene treated with this catalyst had the follow
ing properties prior to treatment:
Table I
RESULTS OF CFR GOKER TEST
ASTM distillation:
IBP ___________________________ __°
10% evap ______________________ __°
20% evap ______________________ __°
30% evap ______________________ __°
F__
F__
F__
F__
Pressure
Difference
(111- He)
Deposit
Rating
Time
(mm.)
322
366
389 10
398
Control _________________________ __
40% evap"; __________________ _...° F__‘
407
Example 1 ______________________ __
50%
60%
70%
80%
90%
Max.
419
427
From Table I it is clear that the treatment of the pres
438 15
ent invention is extremely effective in increasing the sta
450
bility of hydrocarbon distillate fuels. It will be noted
469
that the control sample of kerosene which was not treated
501
evap ______________________ __°
evap ______________________ .._°
evap ______________________ __°
evap ______________________ __°
evap ______________________ __°
F__.
F__
F__
F__
F__
° F__
Recovered ______________________ _..percent_ ...
Residue
97
do.____
2
Loss _____________________________ __do____
1
Gravity
°API__
44.2
Freezing point______________________ __° F__ —50.4
Gums:
Existent ____________________ __percent.._
Potential _____________________ ___do____
Sulfur ______________________ __wt. percent__
FIA analysis:
-
Aromatic _____________________ __do____
Ole?n
do“..-
Saturates _____________________ __do____
Run
'
25.0
3
108
0
0
300
with ‘aluminum phosphate catalyst produced a pressure
difference of 25.0 inches of mercury across the ?lter and
a deposit rating of 3 during a CFR coker test of only
108 minutes while the kerosene which was treated in
accordance with the invention as described above pro
duced substantially no pressure drop across the ?lter and a
2.0 25 deposit rating of O'during a CFR coker test of 300 minutes
duration. These results make it clear not only that the
thermal stability of the fuel is substantially increased by
treatment in ‘accordance with the present invention, but
also that such treatment produces distillate fuel entirely
14.0
0.3 30 suitable for commercial use. Furthermore, such treatment
appears to be more economical than conventional acid
85.7
2.8
0.07
Naphthalenes _____________________ __do____
2.38
Smoke point (min) ______________________ __
25
treatment in improving the stability of hydrocarbon dis
tillates.
While the invention has been described above with re
A reactor measuring 1/2 inch in diameter by 18 inches 35 spect to certain preferred embodiments, thereof, it will be
long was ?lled with the catalyst described above and the
understood by those skilled in the art that various changes
kerosene described above was treated by passing the
.and modi?cations may be made Without departing from
same through the reactor at an inlet temperature of 5 00°
the spirit and scope of the invention and it is intended
F. ‘at the rate of 51 milliliters per minute. The pressure
that all such changes and modi?cations be covered by
was regulated between 50 and 125 psig. by means of 40 the appended claims.
a spring loaded valve. The hot distillate coming from
We claim:
the reactor was then passed through a cooler. The prod
1. The process for improving the stability of hydro
uct from this treatment was sour to the doctor test and
carbon distillate fuel which comprises contacting the same
was yellow in color. It was, therefore, sweetened by
in the liquid phase in an anhydrous atmosphere with a
means of doctor solution and sulfur at 130° F. This 45 supported aluminum phosphate catalyst.
was followed by treatment with 1 lb. per barrel of ?ne
v2. The process for improving the stability of hydro
Attapulgus clay.
carbon distillate fuel which comprises contacting the
The treated product obtained as described above was
same in the liquid phase in an anhydrous atmosphere at
then tested 1for stability by means of the standard CFR
a temperature of at least about 400° F. with a supported
coker test. In this test the thermal stability of a distillate
aluminum phosphate catalyst.
fuel is measured by heating the fuel to 400° F. while
3. The process for improving the thermal stability of
passing the fuel through a conduit surrounding a coaxial
hydrocarbon distillate fuel which comprises contacting
inner tube. The color of the inner tube following the
the same in the liquid phase in an anhydrous atmosphere
testis then compared with a standard color chart to'
at a temperature between about 450° and about 600°
determine the deposit rating of the fuel. A deposit rat 55 F. with a supported aluminum phosphate catalyst.
ing'of 0 signi?es a clear color and correspondingly high
4. The process for improving the thermal stability of a
stability fuel while increasing deposit ratings up to 4
hydrocarbon base fuel comprising at least about 30
signify increasing discoloration of the tube and corre~
volume percent kerosene which comprises contacting the
spondingly lower stability of the fuel tested. During
same in the liquid phase in an anhydrous atmosphere at
the CFR coker test the distillate being tested is passed
a temperature of at least about 400° F. with a supported
through a standard ?lter at a temperature of 500° F.
following passage through the conduit described above
‘and the pressure 'drop across the ?lter is measured and
considered as another measure of stability with relative
aluminum phosphate catalyst.
5. The process for improving the thermal stability of i
a hydrocarbon base fuel comprising at least about 30
volume percent kerosene which comprises contacting the
ly higher pressure drops indicating deposits of gums and
same in the liquid phase in an anhydrous atmosphere at
65
sediments and, therefore, lower stability. The results of
a temperature greater than about 400° F. with a catalyst
the CFR coker test on the kerosene treated with alumi
comprising between about 0.5 and about 10 weight per
num phosphate catalyst as described above are shown
cent aluminum phosphate deposited on an inert carrier.
in Table I below.
6. The process for improving the stability of a hydro
EXAMPLE 2
70 carbon base fuel comprising at least about 30 volume
percent kerosene which comprises contacting the same in
In order to provide a comparison as to the effectiveness
the liquid phase in an anhydrous atmosphere at a tem
of the treatment described above, a control sample of
the same kerosene used in the run described above was
perature between about 450° and about 600° F. and a
doctor sweetened, clay treated and subjected to the CFR
pressure between about 5 and about 200 p.s.i.g. with a
coker ‘test described above, but was not treated with alu 75 catalyst comprising between about 0.5 and about 10
5
53,051,648
weight percent aluminum phosphate deposited on silica
6
gel;
between about 5 and about 200 p.s.i.g. with a catalyst
comprising between about 0.5 and about 10 weight per
7. The process for improving the thermal stability of
hydrocarbon distillate fuel which comprises contacting
cent aluminum phosphate on an inert support.
the same in the liquid phase in an anhydrous atmosphere
at a temperature between about 450° and about 600° F.
and a pressure between about 5 and about 200 p.s.i.g.
with a catalyst comprising between about 0.5 and about
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,826,145
1,947,869
10 weight percent aluminum phosphate on silica gel.
8. The process for improving the thermal stability of 10 2,104,791
kerosene which comprises contacting the same in the
liquid phase in an anhydrous atmosphere at a temperature
between about 450° and about 600° F. and a pressure
Lachman ____________ .. Oct. 6, 1931
Morrell et al. . _________ __ Feb. 20, 1934
2,646,390
Craig _______________ __ Jan. 11, 1938
Arnold et a1 __________ _._ July 21, 1953
2,666,021
Milson ______________ __ Ian. 12, 1954
2,872,413
Elliott et al. ____J______‘__ Feb. 3, 1959
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