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Патент USA US2412371

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Patented Dec. 10, 1946
2,412,371 '
UNITED STATES PATENT OFFICE,
MANUFACTURE OF GASOLINE
John W. Teter, Chicago, Ill., assignor to Sinclair
Re?ning Company, New York, N. Y.-, a corpora
tion of Maine
No Drawing. Application December 19, 1940,
Serial No. 370,837
6 Claims.
(Cl. 19.6—54)
1
2.
This invention relates'to improvements in the
manufacture of gasoline by a cracking process of
the catalytic type. More particularly the inven
tion relates to an improved catalytic cracking
process of the class wherein the cracking catalyst
is of the type which functions by adsorption,
activation and desorption as distinguished from
or oil vapors and the mixture, passed through a
heating zone in which the desired temperature
clays, acid-treated clays and synthetic catalysts
only when supplied in the anhydrous state.
is maintained.
‘
'
Aluminum?uoride is quite stable and has a
melting point of 1040° 0., far in excess of the
temperatures at which it is'most effective. How=
ever, when supplied in the anhydrous state it
cracking catalysts which, like anhydrous alumi
appears to have little catalytic activity. In these
num chloride, function in the Friedel-Crafts type
respects it differs from aluminum chloride which
of reaction. Examples of cracking catalysts of 10 sublimes at a temperature of approximately 179°
the type ?rst mentioned are naturally occurring
C. and which has signi?cant catalytic activity
comprising silica and alumina, or silica and alu
The following examples illustrate the effect of
mina together with other metal oxides.
my aluminum ?uoride catalyst, as compared to
Prior to the discovery of the invention herein 15 thermal cracking and to the effect of the syn
described, the most active of the catalysts of the
thetic silica-alumina catalyst previously de
?rst type known to me was a powdered synthetic
scribed. In each of the following operations the
catalyst composed of 90% silica and 10% alumina
charging oil was a Pennsylvania gas oil having
by weight, prepared by precipitating aqueous so
the following characteristics:
dium silicate with hydrochloric acid in the pres 20
Gravity ____ _'_ _____ A ____________ __°API__. 37.8
ence of added sodium chloride, adding aluminum
Distillation:
'
,
chloride solution and precipitating with ammo
Initial __________________________ __°F__' 4'72
nium hydroxide, washing, drying at 250° F.,
10% ____________________________ __Y_°F__ 572
crushing and sizing. Cracking in the presence
50% ____________________________ __°F-_ 598
of this catalyst has been found to produce a
90% ___________________________ __°F__ 648
marked improvement both‘ in the anti-knock
End point ______________________ __°F__~ 674
value of the gasoline produced and in the gaso
line yield, together with a substantial decrease in
In each operation the oil, alone or admixed with
the amount of gas formed.
_
a. predetermined percentage of catalyst by weight
I have now found that crystalline aluminum
based on .the oil, was passed through a heating
?uoride, either by itself or together with metal
coil of the same length and at substantially the
oxides such as alumina, is an active cracking cat
same feed rate. During passage therethroug'h
alyst of even greater activity than the most active
of the synthetic silica-alumina catalyst hereto
fore employed. The aluminum fluoride employed
the oil was ?rst heated to, and then maintained
in the process of my invention is used in pow
dered form and may contain varying amounts of
combined and uncombined water. It may be rep
resented by the formula AIFS‘XHZO. In the
cracking process of my invention I merely subject
the oil to be cracked, in the presence of the
aluminum ?uoride catalyst. to a temperature ap~
proximating 900—1050°
preferably about 1000°
F., for a period of time sufficient-t0 effect a sub
stantial amount of cracking. Substantial super
atmospheric pressure may be applied to the oil
during treatment if desired. However, I prefer
at, the desired predetermined temperature.
; Pressure was controlled to maintain the desired
predetermined pressure at the outlet of the heat
ing coil. The total products discharged from the
coil were cooled to condense all normally liquid
hydrocarbons ‘in the form of a synthetic crude.
After separation of the catalyst, by hot ?ltration,
the ‘gasoline fraction was recovered from the syn
thetic crude by ‘distillation and stabilization.
Thus the gasoline yields are those obtained, by
a single once-through treatment, all recycling
being avoided in order to eliminate errors in Oh
taining comparative results.
rd
Three operations with no catalyst were ?rst
to use a pressure not substantially above thirty
carried out at temperatures of 950° F., 10009 F.
pounds per square inch asthe use of higher pres
and 1050" F., respectively, and with a coilloutlet
sures impairs the anti-knock properties of the 50 pressure of 30 pounds per square inch to cali
resultant gasoline. The aluminum fluoride cat
alyst may be arranged in a ?xed bed and the oil
brate the apparatus for thermal cracking with
respect to the particular oil used. Three similar
additional operations were then‘ carried out ‘un
to be cracked vaporized and passed therethrough
at the desired temperature, or the catalyst in
der the same three sets of operating conditions
powdered form may be dispersed through the oil 55 but with 1% by weight of ?nely divided crystal
2,412,371
3
.
line aluminum ?uoride of reagent grade admixed
amount of gas produced as compared to the sil
with the oil. A fresh sample of the crystalline '
aluminum ?uoride catalyst used in these oper
ations was completely dehydrated in a mu?le
furnace and the weight loss indicated an original
water content of 2.35 Hzo'AlFs. The octane
number of the produced gasoline was determined
in each instance both by the motor method
ica-alumina catalyst.
(M. M.) and by the research method (Res. M.).
The following table gives the results obtained: ‘
Temperature ________________ __° F_-
950
Pressure ______________ _ .pounds. _
30
Gasoline yield pe
Thermal.
1, 000 ‘
1,050
30
cent on charge:
.
21.0
17. 5
23. 2
991
1, 632
r " "
.
Thermal
. __.._
.
._____
363
M.):
_ _ _ __
_ _ _ __
‘
2, 686
906
2, 340
67. 7-80‘ 0
69. 5-822
'
63. 7-74. 4
‘
24.6
_
Octane number (M.
10 with 1% of this heterogeneous aluminum ?uoride
catalyst. dispersed in the oil.
The results ob
tained, together'with those obtained under 'sim-'
ilarconditionsbut using the reagent grade of
(aluminum ?uoride as the catalyst, are given'in
a 28.8
Gas, cu. ft./bbl. of gasoline:
a1 ______________________ __
scribed, was made at a temperature of 1000" F.
and at a pressure of 30 pounds per square inch
. .
11.8
v
aqueous hydro?uoric acid to yield a 50:50 mix- 7
_ ture of AlFsZAlzOa. A test, using the same charg
ing oil and same procedure as previously de- "
30
'
____________________ __
1% AIFa-XHzO _______________ __
'
A heterogeneous aluminum ?uoride catalyst
was prepared by treating alumina with su?icient
15 the following "table:
1
.
1%A1F3-XHgO _______________ __ 76. 9-89. 5 76. 1-90. 0 72. 4-85. 4
Gasoline
Gas‘,7 ' Octane number
7‘
'
cu‘
pcrbgent perobbl. (M‘ MrReS' M_)
Catalyst
Another operation with the same charging oil '
20
volume
was carried out at 1000?;F. with 1% of the crys
talline aluminum ?uoride" catalyst but with a
coil discharge pressure of -'75 pounds per square
inch. _ The following results were obtained;
gasoline
'
mrrxmmreagcnt grade); 7
23. 2
V 1 toe
76.1-90.0
iMF3:AlzOs(50I50) _________ _.
25. 5
'936
76. 2-89. 1
‘
It will be noted that the heterogeneous aluminum
Gasoline yield __‘__t;__r_ _____ _____per cent" 28.5
Gas, cubic feet per barrel of gasoline_r_____ 1,240 25 ?uoride catalyst produced a greater gasoline yield
than did the reagent grade aluminum ?uoride
Qctanenumber 1M. M.—~Bes. M.)____ 73.2-86.0
catalyst, the anti-knock value of the gasoline be
Comparison of these results with those obtained
ing substantially the'ws‘ame' in both instances. Yet
at a pressure .of‘30 pounds per square inch but
alumina alone has very little activity as a crack
at the sameoperating temperature shows that 30
the increase in gasoline yield obtained by in
I claim:
creasing the operating pressure is accompanied
1. The improvement in cracking hydrocarbon‘ '
by a decrease in the anti-knock value of the gas
oils for the production of high anti-knock gaso
lines which comprises subjecting the oil to crack
Two additionaltests were carried out at pres 35 ing temperature in the presence of ?nely divided
ing
oline.i
.
1.
>
I
catalyst.
’
'
-
‘
.
'
'
l
>
.
sures of'30 pounds per square inch and at tem
peratures of 950° F. and 1000° F.,' respectively,
crystalline aluminum ?uoride.
'
2. The improvement in cracking hydrocarbon
with‘i1% of the previously. described synthetic
oils for the production of high anti-knock gaso
silica-alumina catalyst dispersedin the oil. The
line which comprises subjecting the oil to crack
charging oil and the pressure employed were the 40 ing temperature in the presence of ?nely divided‘
sameas in vthe tests previously described.- The
aluminum ?uoride containing combined moisture.
results obtained, together with those obtained
‘3. The improvement in‘. cracking hydrocarbon
underisir'nilar operating conditions but with 1%
oils for the production of high anti-knock gaso
of the aluminum ?uoride catalyst, aregiven in
line which comprises dispersing a, small amount
the permeable i1 1
of a ?nely-divided crystalline aluminum ?uoride
Temperature: _______ _7 ___________ ___‘______° F_.
950
n 1,000
in the oil tolbe cracked ‘and subjecting the mixture
Pressure . . ______ _‘_ _____ ._' ________ __pounds_.
“30'
3O
Gasoline yield per cent on charge:
‘
r
‘
"1% silica-alumina catalyst.‘
___________ _-
1% aluminum ?uoride catalyst . _ _ _ _ _
_ _ __
20. 9
for a period of time su?icient to convert a sub
17. 5
23. 2
stantial proportion of the oil into high anti-knock
576
1, 234
363
906
Gas cu. l'tJbbl. of gasoline:
~ " 1% silica-alumina catalyst _______________ _;
;
1% aluminum ?uoride catalyst; _________ __
Octane M. M. and Res. M.:
.
.
, to a temperature approximating 950° F.—1000° F.
13.9
'
_
gasoline.
'
.
'
7
,
I
>
.
I
4. ‘The, improvement in cracking ‘hydrocarbon
oils for the production of high anti-knock gaso
line which comprises dispersing a small amount
-~ As the foregoing tests illustrate, the results
of ?nely+divided crystalline aluminum ?uoride in
obtained with the aluminum ?uoride catalyst are 55 the oil to be cracked and subjecting the mixture
markedly superior to those obtainable with ther
to a temperatureapproximating 9v5_0r°—l000° F. at '
mal cracking at temperatures ranging from be
a pressure not substantially. exceeding 30 pounds
low. 950° F. to upwards of 1050° F. from the stand
per square inchfor a period of time su?icient to‘
point or“ the gasoline yield, the amount of gas
convert a, substantial proportion of the oil into
produced'and the anti-knockvalue of the gas 60 high. octane gasoline.
'
'l
'
oline. However, when the temperature substan
5. The improvement in'_ cracking hydrocarbon
tially'e'xceeds 1000° F. the» resulting increase in
oils for the production of. high anti-knock gaso
gasolinefyield isobtained only at the expense of
line which comprises subjecting the oil to a cracka substantial increase in gas production and a 65 ing temperature‘ in the presence. of a finely-di
vided catalyst comprising alumina and crystalline
reduction in the anti-knock value of the gaso
’
~-1%'silica-alumina catalyst. ,_-.;_ _ ; .7. ._ __,-; 76. 5-89. 7
75. 7-87. 9
V 1% aluminum ?uoridecatalyst __________ .4 76. 9—89. 5
76.1-90.0
line.
The tests further illustrate the fact that
aluminum
?uoride.
j
.
.
'
‘
r
*
‘ v6.'The improvement in cracking hydrocarbon
oils for the’ production of high anti-knock‘ gaso
?uoride catalyst are as good or better than those 70 line whichcomprises subjecting the oil to crack
ing temperature in thenpresence vof aluminum
obtainable with the synthetic silica-alumina
?uoride containing combinedmoisture.;; '
‘
catalyst, while With the aluminum ?uoride cat
within the preferred operating range the anti
knock values obtainable with the aluminum
alyst there is a substantial increase in the gas
oline yield and a substantial decrease in the
' ' JOHN ‘W. TETER.
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