U.S. patent number 3,755,141 [Application Number 05/114,721] was granted by the patent office on 1973-08-28 for catalytic cracking.
This patent grant is currently assigned to Texaco, Inc.. Invention is credited to James H. Colvert, Gerald V. Nelson, Douglas J. Youngblood.
United States Patent |
3,755,141 |
Youngblood , et al. |
August 28, 1973 |
CATALYTIC CRACKING
Abstract
A process for the production of high octane motor gasoline
stocks by catalytic cracking in which a distillate charge stock
boiling above about 400.degree. F is subjected to catalytic
cracking in a catalytic cracking unit at limited per pass
conversion not exceeding 80 volume percent of the charge stock,
430.degree. F + gas oil product of the catalytic cracking operation
is subjected to hydrogen treatment to lower its polycyclic aromatic
content, as indicated by ultraviolet absorption to a concentration
approximating that of the fresh charge stock to the catalytic
cracking unit, and liquid effluent of the hydrogen treatment step
is passed to the catalytic cracking unit as part of the feed
thereto, producing exceptionally high yields of high octane naphtha
suitable as motor gasoline blending stock.
Inventors: |
Youngblood; Douglas J. (Groves,
TX), Colvert; James H. (Chatterton, TX), Nelson; Gerald
V. (Nederland, TX) |
Assignee: |
Texaco, Inc. (New York,
NY)
|
Family
ID: |
22357034 |
Appl.
No.: |
05/114,721 |
Filed: |
February 11, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
687283 |
Dec 1, 1967 |
|
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Current U.S.
Class: |
208/56;
208/120.3; 208/120.35; 208/67 |
Current CPC
Class: |
C10G
69/04 (20130101); C10L 1/06 (20130101) |
Current International
Class: |
C10G
69/04 (20060101); C10G 69/00 (20060101); C10L
1/00 (20060101); C10L 1/06 (20060101); C10g
037/06 () |
Field of
Search: |
;208/67,120,56 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levine; Herbert
Parent Case Text
This application is a continuation-in-part of our copending U. S.
Pat. application, Ser. No. 687,283, filed December 1, 1967 now
abandoned.
Claims
We claim:
1. A process for the conversion of a gas oil feed stock boiling
above about 430.degree. F. and containing polycyclic aromatic
compounds to gasoline in a yield of at least 80 volume per cent
which comprises subjecting said gas oil feed stock to catalytic
cracking under conditions to effect a conversion of between 30 and
80 volume per cent, separating the effluent from the catalytic
cracking zone into a cracked naptha and lighter fraction having an
end point of about 430.degree. F. and a cracked 430.degree. F+ gas
oil fraction having a higher polycyclic aromatic compound content
than said gas oil feed stock, recovering from said cracked naphtha
and lighter fraction as product of the process a catalytically
cracked gasoline having a boiling range of about
115.degree.-430.degree. F., subjecting at least a portion of said
cracked 430.degree.F.+ gas oil fraction to hydrogen treatment under
conditions to reduce the polycyclic content thereof to a
concentration not appreciably greater than that of said gas oil
feed stock, said portion having an initial boiling point of about
430.degree. F., separating the effluent from the hydrogenation zone
into a normally gaseous portion and a normally liquid portion and
introducing substantially all of said normally liquid portion with
fresh gas oil feed stock into said catalytic cracking zone.
2. The process of claim 1 in which the catalytic cracking
conversion is between 40 and 80 volume per cent.
3. The process of claim 1 in which a debutanized naphtha is
recovered from said naphtha and lighter fraction, the C.sub.3
-C.sub.4 olefins of said naphtha and lighter fraction are subjected
to alkylation with isobutane and the resulting alkylate combined
with said debutanized naphtha to form a high anti-knock motor
fuel.
4. The process of claim 1 in which the catalytic cracking is
carried out in the presence of a catalyst comprising a
hydrogen-exchanged zeolite, a silica-alumina base and a rare earth
metal.
5. The process of claim 1 in which the hydrogenation of monocyclic
aromatic compounds is minimized.
6. The process of claim 3 in which the yield of gasoline is at
least 90 volume per cent basis gas oil feed stock.
7. The process of claim 1 in which the hydrogenation product has a
polycyclic aromatic content of less than 20 weight per cent.
8. The process of claim 1 in which the total aromatic content of
the hydrogenation product is at least 75 percent of the total
aromatic content of the cracked 430.degree. F+ gas oil fraction.
Description
CATALYTIC CRACKING
(D#70,282-Cl)
This invention relates to an improved process for the production of
motor fuel gasoline from catalytic cracking feed-stocks. The
process is particularly applicable to the production of maximum
yields of motor gasolines from catalytic cracking unit feedstocks
without hydrocracking. The process is applicable to existing
catalytic cracking units.
When combined with conversion of C.sub.3 -C.sub.4 hydrocarbons to
gasoline blending components, e.g. by alkylation, the process of
this invention is capable of producing a quantity of debutanized
gasoline stock substantially equal to that of the feedstock charged
to a catalytic cracking unit. For example, by combination of
catalytic cracking, hydrogen treatment, and alkylation, catalytic
cracking feestocks, e.g., virgin gas oil boiling above about
430.degree. F, may be made to yield 95 to 110 volume percent
debutanized gasoline (basis fresh feed charge).
The process of this invention consists essentially of (1) catalytic
cracking of feedstock boiling above about 430.degree. F, (2)
subjecting at least a portion of the 430.degree. F+ gas oil product
of the catalytic cracking unit to hydrogen treatment for
significant reduction of its polycyclic aromatic content, and (3)
recycling normally liquid effluent of the hydrogen treatment, also
referred to herein as a hydrotreater, to the catalytic cracking
unit together with the fresh feedstock. Debutanized naphtha from
the catalytic cracking unit is a primary product of the process. In
a preferred embodiment, all or a substantial portion of the C.sub.3
-C.sub.4 olefins from the catllytic cracking unit are subjected to
alkylation and the resulting alkylate blended with the naphtha
fraction from the catalytic cracking unit to give yields of high
octane gasoline in the vicinity of 100 volume percent, basis the
fresh feed charged to the catalytic cracking unit. This process
permits substantially complete conversion of catalytic cracking
unit feedstocks to gas and motor gasoline products.
It has been proposed heretofore to subject catalytic cracking
feedstocks to hydrogen treatment as a means for improving the
yields and quality of motor gasolines. It has also been known for
some time that hydrocracking operations, as distinguished from
hydrogen treatment, will produce nearly 100 percent yields of
gasoline from virgin gas oil feestocks. Many existing refinery
facilities, however, do not have sufficient hydrogen for
hydrocracking processes and, in addition, have already existing
large facilities for catalytic cracking. Such catalytic cracking
units are not suitable for hydrocracking operations.
The term "hydrotreating" or "hydrogen treatment," as used herein,
refers to treatment with hydrogen under conditions which result in
little or no cracking of the hydrocarbons supplied to the hydrogen
treating unit and little or no production of lower boiling range
products. "Hydrocracking," on the other hand, refers to cracking
the hydrocarbons in the presence of hydrogen to produce lower
boiling range products.
It is an object of this invention to provide an improved process
for converting catalytic cracking unit charge-stocks to gasoline
motor fuel components. Still another object of this invention is to
provide an improved process for the production of motor fuel
gasolines of high octane value from the catalytic cracking
feestocks boiling in the range of about 430.degree. F and
higher.
The FIGURE is a schematic flow diagram illustrating the process of
this invention with reference to various petroleum refinery process
units.
With reference to the flow diagram of the FIGURE, fresh catalytic
cracking unit feedstock, e.g. virgin gas oil havin a boiling range
above about 400.degree. F, e.g. 450.degree. to 850.degree. F, from
a suitable source is supplied to the process through line 5,
blended with hydrogen treated mixed hydrocarbons as described
hereinafter, and passed through line 6 to a catalytic cracking unit
7. The catalytic cracking unit 7 may comrrise either a fluidized
catalyst or moving bed type catalytic cracking unit, both of which
are well known. Fluidized catalyst units may be of either bed type
or riser type.
Effluent from the catalytic cracking unit 7 is passed via line 8 to
a fractionation system 9 where it is separated into a plurality of
fractions. As illustrated in the specific embodiment illustrated in
the FIGURE, the catalytic cracking unit product is separated into a
fraction boiling below about 430.degree. F at atmospheric pressure,
e.g. hydrogen to 430.degree. F, which is discharged through line
11; a light gas oil fraction, e.g. one having a 50 percent point of
about 530.degree. F, which is discharged through line 12; an
intermediate gas oil fraction, e.g. one having a 50 percent point
of about 650.degree. F which is discharged through line 13; and a
heavy gas oil fraction, e.g. one having a 50 percent point of about
680.degree. F, which is discharged through line 14.
The naphtha and lighter fraction from line 11 is passed to a
recovery section 16 where it is separated into various fractions,
for example, a fuel gas fraction discharged through lien 17; a
C.sub.3 -C.sub.4 fraction discharged through line 18; and a
debutanized naphtha fraction discharged through line 19. The
debutanized naphtha fraction from line 19 is the principal product
of the process and is useful as base blending stock for motor
gasoline.
The C.sub.3 -C.sub.4 fraction discharged through line 18 contains
C.sub.3 and C.sub.4 olefins and isobutane. This stream is passed to
an alkylation unit 20 wherein the olefins are alkylated with
isobutane to high octane gasoline blending components or alkylate
which is discharged from unit 20 to line 21 for blending into
gasoline product. Those C.sub.3 -C.sub.4 olefins in excess of
isobutane available in the C.sub.3 -C.sub.4 fraction may be
discharged through line 22 to a suitable use, for example, as feed
for petrochemical operations. Alternatively, isobutane may be
supplied from a suitable source through line 23 to alkylation unit
20 for conversion to alkylate blending components for motor fuel
gasoline.
The various gas oil fractions discharged from the fractionator
through lines 12, 13 and 14 may be passed through line 13 to
hydrogen treater unit 26. Light gas oil may be supplied to line 13
by way of a line 27 as controlled by valve 28. Similarly, heavy gas
oil withdrawn from fractionator 9 through line 14 may be supplied
via lines 29 and 31 as controlled by valve 32 to line 13 as feed to
hydrogen treater unit 26. Part or all of the light gas oil may be
taken from line 12 as product, or part or all may be passed through
line 33 as controlled by valve 34 to line 35 for recycle to
catalytic cracking unit without hydrogen treatment. Similarly, part
or all of the heavy gas oil may be withdrawn as product through
line 14 or passed through line 36 as controlled by valve 37 to line
35 for the recycle directly to catalytic cracking unit 7. Provision
is also made for return of part of the intermediate gas oil
fraction, if desired, to the catalytic cracking unit via lines 38
and 35 as controlled by valve 39. Fresh feedstock may be supplied
from line 5 through line 41, if desired, as controlled by valve 42,
to line 13 as feed to the hydrogen treater unit 26.
The effluent from the hydrogen treater unit is discharged through
line 43 to a separation unit 44 in which gaseous components are
separated from normally liquid components. A gaseous fraction
consisting primarily of hydrogen is discharged from separator 44
through line 46 and returned to hydrogen treater 26 through line
47. Make-up hydrogen from a suitable source is supplied to line 47
from line 48. Normally liquid product of hydrotreater 26, including
naphtha fractions, is discharged from separator 44 to line 35,
mixed with fresh feedstock from line 5, and supplied to the
catalytic cracking unit 7 through line 6.
Preferably, and for highest gasoline yields, the cracking catalyst
comprises a molecular sieve or crystalline alumino-silicate base
carrying catalytic metal additives, for example, rare earth metals,
particularly cerium and lanthanum, their oxides or sulfides.
Preferred catalysts are molecular sieve cracking catalysts of the
well known commercial varieties, e.g. Davison XZ-25, Aerocat Triple
S-4, Nalcat KSF, Houdry HZ-1, etc. These catalysts are made up of a
silica-alumina-zeolite base in particle sizes suitable for
fluidization or formed into beads or pellets, usually of a size
range of 1/32 to 3/8 inch, suitably 1/16 to 1/8 inch, and
containing rare earth metal oxides. Fluid catalysts usually have
particle sizes of 50 to -325 mesh U. S. Standard Sieve Series.
Typical compositions of preferred catalysts are the following:
Davison XZ-25, a product of Davison Chemical Company, is a mixed
silica-alumina-zeolite cracking catalyst containing about 30-35
weight percent alumina, 18 weight percent zeolite X, and about 2
weight percent cerium and 1 weight percent lanthanum. Aerocat
Triple S-4, a product of American Cyanamid Company, is a
silica-alumina-zeolite cracking catalyst containing about 32 weight
percent alumina, 3 weight percent zeolite Y, 0.5 weight percent
cerium and 0.1 weight percent lanthanum. Nalcat KSF, a product of
Nalco Chemical Co., is a silica-alumina-zeolite cracking catalyst
containing about 31-35 weight percent alumina, 11 percent zeolite
X, about 1 percent cerium and 0.3 percent lanthanum.
The catalytic cracking unit is operated at a temperature in the
range of 800.degree. to 1,100.degree. F, preferably 850.degree. to
1,000.degree. F, with a space velocity, basis the total feed to the
catalytic cracking unit, of 0.2 to 300 pound of hydrocarbon
feedstock per hour per pound of catalyst at a reactor pressure
within the range of 0 to 200 psig, preferably of the order of 25
psig. The variable reaction conditions, i.e., temperature and sapce
velocity, are controlled to produce a per pass conversion of 30 to
80 volume percent. The relatively wide space velocity range
indicated is subject to considerable variation and depends upon the
particular reactor design under consideration, e.g., whether a
riser type or bed type catalytic cracking unit is employed. The
important consideration is the controlled per pass conversion which
preferably is in the range of 30 to 65 volume percent to obtain
maximum gasoline yield. Optimum conditions of space velocity and
per pass conversion may be established for any given commercial
unit by known test methods and economic evaluation.
To realize the full benefits of this invention, the catalytic
cracking unit should be operated near 100 percent ultimate
conversion of the feedstock to lighter products. Thus it is
generally desirable to convert all of the 430.degree. F+ product
from the catalytic cracking unit to naphtha and lighter products.
Preferably all of the heavy gas oil and a substantial portion or
all of the intermediate gas oil and of the light gas oil should be
hydrogen treated and recycled to the catalytic cracking unit.
Determination of the feed stream supplied to the hydrogen treater
is based on two factors. The first is that the composite recycle
stream returned to the catalytic cracking unit 7 through line 35
and admixed with fresh feed from line 5 is processed so that its
cracking characteristics are similar to those of the fresh
feedstock supplied through line 5. Hydrogen treatment of all of the
gas oils, i.e., all of the 430.degree. F gas oil from the catalytic
cracking unit results in the highest yield of motor gasoline. The
second factor is the market demand for catalytic cracking unit gas
oils. It is recognized that it may not always be desirable to
recycle all of the various gas oil fractions to extinction,
depending upon available market for gas oils, usually for the heavy
gas oil fraction and for the light gas oil fraction.
Since the heavy gas oil has the greatest polycyclic aromatic
content, in some cases it may be desirable to hydrogen treat only
the heavier fractions to reduce the hydrotreating requirements of
the system. In other instances it may be desirable to recycle some
of the heavy gas oil from line 29 directly to the catalytic
cracking unit via lines 35 and 36 to maintain the proper
reactor-regenerator heat balance in the catalytic cracking
unit.
The hydrotreater design is based on providing the catalytic cracker
recycle charge stock with a feed having a polycyclic aromatics
content approaching that of the fresh feed (normally below 20
weight percent polycyclic aromatics). Total liquid product from the
hydrotreater, including the gasoline produced is supplied to the
catalytic cracking unit as part of the feedstock therefor.
Hydrogen used in the process of the present invention may be
obtained from any suitable source. The term hydrogen as used in the
present specification and claims includes dilute hydrogen. The
hydrogen need not be pure but preferably a gas containing at least
about 70 percent hydrogen is used. Suitable sources of hydrogen are
catalytic reformer by-product gas and hydrogen produced by steam
reforming of hydrocarbons or by partial oxidation of carbonaceous
material followed by shift conversion and removal of carbon
dioxide. Since the efficiency of hydrogen treatment depends to some
extent on the partial pressure of the hydrogen, it is generally
advantageous to employ hydrogen rich gas of relatively high
hydrogen content for the hydrogen treatment.
Preferred catalysts for the hydrogen treatment are alumina base
hydrogenation catalysts in the form of pellets or extrudates of a
size range of 1/32 to 3/8 inch, suitably 1/16 to 1/8 inch. Oxides
of boron, cobalt, molybdenum, nickel and tungsten, and their
resulting sulfides formed prior to or during the use of the
catalyst, are effective hydrogen treatment catalysts when deployed
on suitable base supports, e.g. on high purity eta aluminas.
Suitable catalysts are well known, for example, commercial
catalysts Aero HDS-3, Harshaw Ni-4303, Harshaw Ni-4305 and Harshaw
Ni-4309. Aero HDS-3, produced by American Cyanamid Company, is a
nickel oxide-molybdenum oxide on alumina hydrogenation catalyst
containing about 10 weight percent molybdenum and about 2 weight
percent nickel, reported as the metals. Harshaw Ni-4303, produced
by Harshaw Chemical Company, is a nickel tungsten catalyst on an
alumina base comprising about 6 weight percent nickel and about 20
weight percent tungsten reported as the metals. Harshaw Ni-4305 and
Ni-4309 are nickel-tungsten catalysts on boria-alumina base,
Harshaw Ni-4305 contains about 5 weight percent nickel and 10
weight percent tungsten, reported as metals, and about 10 weight
percent boria (B.sub.2 O.sub.3). Harshaw Ni-4309 contains about 5
weight percent nickel, about 10 weight percent tungsten, reported
as metals, and about 10 weight percent boria.
The hydrotreating zone is maintained at between about 500.degree.
and 800.degree. F. and 400 and 3,000 psig. Preferred conditions are
650.degree.-725.degree. F. and 500-2,000 psig. The weight hourly
space velocity of the hydrocarbon feed may range betwen about 0.2
and 20 preferably 0.5 to 10 and the hydrogen rate between about
1,000 and 15,000 SCFB preferably 3,000 to 10,000 SCFB. The reaction
conditions particularly temperature, pressure and space velocity
are selected within the above ranges to effect reduction in the
polycyclic aromatic content while minimizing the reduction in total
aromatic content. The data in the following table are
illustrative.
AROMATIC REDUCTION
Charge: Light Cycle Gas Oil Catalyst: Nickel-Tungsten on Alumina
Operating Conditions Pressure, psig. 2000 500 Space velocity 1.0
1.0 Temperature, .degree.F. 700 700 Hydrogen rate, SCFB 6000 6000
Charge and Product Quality Charge API gravity 24.8 36.1 28.2 Total
aromatics, vol. % 59.7 11.7 57.9 Polycyclic aromatics, wt. % 35.4
0.3 1.6 Olefins, vol. % 5.3 1.3 1.6 Percent Reduction Total
aromatics 80 3 Polycyclic aromatics 99 95 Olefins 75 70
The same effect can be obtained by other combinations of
temperature, pressure and space velocity as indicated above.
Conventional procedures are used in the alkylation step.
SPECIFIC EXAMPLES
The following specific examples demonstrate the ability of the
process of this invention to produce abnormally high octane
gasoline by the combination of catalytic cracking hydrotreating and
alkylation.
A number of trial runs were made using virgin gas oil charge stock
having the following characteristics:
Fresh Charge Stock
Gravity, .degree.API 30.9 UV Absorbance at 285 mu 4.9 Polycyclic
Aromatics, wt. %.sup.1 15.2 Aromatics, Wt. % 32.5 X-Ray Sulfur, Wt.
% 0.53 Conradson Carbon Residue, Wt. % 0.05 Refractive Index at
25.degree.C 1.4824 ASTM Distillation, .degree.F. IBP 453 10 528 30
579 50 625 90 747 EP 760+ .sup.1 Polycyclic aromatics (PCA)
calculated by formula: PCA, Wt. % = UV Absorbance at 285
mu/0.323
Catalyst used in the fluidized bed catalytic cracking pilot unit
for these tests was simulated equilibrium Davison XZ-25 catalyst.
Aging of the catalyst was simulated for the runs by heat treating
fresh Davison XZ-25 at 1,480.degree. F. for 17 hours and blending
the heat treated catalyst with an equal weight of Davison High
Alumina cracking catalyst which had been heat treated 17 hours at
1,700.degree. F. Davison High Alumina cracking catalyst, a product
of Davison Chemical Company, is a silica-alumina catalyst
comprising about 25 weight percent alumina and about 75 weight
percent silica. Properties of the cracking catalyst are indicated
in the following table.
FCCU Test Cracking Catalyst
50% XZ-25.sup.1 and Catalyst 50% high alumina.sup.1 Composition,
wt. % Silica 69.3 Alumina 29.2 Cerium 1.0 Lanthanum 0.5 Zeolite
content, wt. % 5 Apparent Bulk Density Settled, lb./cu. ft. 31.8
Packed, lb./cu. ft. 38.5 Particle Size Distribution, wt. % 0-20
microns 2 20-40 microns 15 40-80 microns 57 80+ microns 26 .sup.1
Products of Davison Chemical Co. Davison High Alumina catalyst is a
silica-alumin a cracking catalyst containing 25 weight percent
alumina and 75 weight percent silica.
EFFECT OF PER PASS CONVERSION LEVEL
The effect of per pass conversion in the fluid catalytic cracking
unit (FCCU) on the volume of 430.degree. F+ gas oils from the unit
charged to the hydrogen treater unit (HTU) for 100 percent
conversion of catalytic cracking unit feedstock to motor fuel
(430.degree. F endpoint) and lighter products and on the polycyclic
aromatics content of the total 430.degree. F+ fractions are
indicated in the following table.
Per pass conversion, Vol. % 40 60 70 Total charge to HTU, basis
fresh feed to FCCU, Vol. % 150 66.7 42.8 Polycyclic aromatic
content of 430.degree.F+ fractions from FCCU, wt. % 26.6 37.5
49.0
Effect of Polycyclic Aromatics
The effect of the polycyclic aromatics content of charge stock to
the fluid catalytic cracking unit on the yield of debutanized
naphtha produced by the unit at a conversion level of 60 volume
percent per pass with the above blend of catalysts is shown in the
following table.
Polycyclic aromatics, wt. % 7.0 15.0 29.3 44.3 Debutanized naphtha
yield, vol. % 39.5 38.4 31.5 27.6
EXAMPLES 1 AND 2
In the following runs, virgin gas oil having the above
characteristics was charged to a fluid catalytic cracking unit
under conditions indicated below to give conversion levels of about
55 volume percent (Example 1) and about 65 volume percent (Example
2).
Example No. 1 2 Conversion Level 54.3 66.6 Reactor Temperature,
Ave., .degree.F 919 918 Pressure Atm.+ Atm.+ Space Velocity
lbs./hr./lb. catalyst 6.72 3.88 Catalyst/Oil, Wt. ratio 1.45 2.54
Feed Preheat Temp., .degree.F, Ave. 809 830 Regenerator Regenerator
Outlet Temp. .degree.F 1060 1064 Stripper, Ave. Temp. .degree.F 928
938 Carbon on Catalyst To Regenerator, Wt. % 1.02 1.19 To Reactor,
Wt. % 0.10 0.09 Yields, basis total feed Coke, Wt. % 1.2 2.3 Dry
Gas, Wt. %.sup.1 5.1 6.0 Isobutane, Vol. %.sup.2 4.6 (45.5) 8.3
(50) Normal Butane, Vol. %.sup.2 0.9 (9) 2.1 (13) Butylenes, Vol.
%.sup.2 4.6 (45.5) 6.2 (37) Total C.sub.4 's, Vol. % 10.1 16.6
C.sub.5 Hydrocarbons, Vol. % 6.4 12.2 Depentanized Naphtha, Vol. %
39.8 41.5 Product Quality Tests Light Gasoline
(115.degree.-250.degree.F) Gravity, .degree.API 66.4 67.1 ASTM
Octane RON, Clear, +3cc TEL 88.0,97.9 85.8,96.8 MON, Clear, +3cc
TEL 76.5,86.8 76.8,87.1 Heavy Gasoline (250.degree.-430.degree.F)
Gravity, .degree.API 41.6 41.5 ASTM Octane RON, Clear, +3cc TEL
86.1,92.0 87.5,93.9 MON, Clear, +3cc TEL 74.6,82.2 77.8,84.4 Gas
Oil (430.degree.F+) Gravity, .degree.API 28.1 25.1 UV Absorption at
285 mu 11.8 14.4 Polycyclic Aromatics, Wt. %.sup.3 36.5 44.6 .sup.1
Includes H.sub.2 and C.sub.1 -C.sub.3 hydrocarbons .sup.2 Numbers
shown in parentheses are individual C.sub.4 hydrocarbon as a
percentage of total C.sub.4 's. .sup.3 Calculated form UV
absorbance at 285 mu
EXAMPLES 3 AND 4
Two 430.degree.F+ gas oils from catalytic cracking test runs
comparable to those of Examples 1 and 2 were subjected to hydrogen
treatment. The hydrogen treatment catalyst was Aero HDS-3 in the
form of 1/8 inch pellets. The hydrotreater catalyst was sulfided to
about 5 weight percent sulfur prior to use by charging gas oil
containing sufficient added carbon disulfide to give a total sulfur
content of about 2 weight percent over the catalyst at 400.degree.
F for 3 hours and at 600.degree. F for an additional 3 hours to a
hydrogen sulfide level in the reactor off-gas of at least 500
grains per 100 cubic feet. Operating conditions for and results of
the hydrogenation treatment are shown in the following table in
which the charge stock for Example 3 was a 430.degree. F gas oil
obtained from catalytic cracking of virgin gas oil having the
characteristics indicated above at 51.5 volume percent conversion
and the charge stock for Example 4 was a 430.degree. F gas oil
obtained from catalytic cracking of the virgin gas oil at 63.0
volume percent conversion.
Hydrogen Treatment Unit
Example 3 4 Reactor Temperature, .degree.F. 706 680 Pressure, psig
1000 1000 Space Velocity Wo/Hr/Wc 1.96 1.25 Hydrogen/Hydrocarbon
Ratio 7.63 6.91 Total Reactor Feed Gas, SCF/Bb1 4120 3914 Vol. %
H.sub.2 in Reactor Feed Gas 97.7 98.4 Hydrogen Consumption, SCF/Bb1
750 1464 Charge to HTU Gravity, .degree.API 28.8 25.2 UV Absorbance
at 285 mu 11.13 15.25 Polycyclic Aromatics, Wt. %.sup.1 34.5 47.2
Aromatics, Wt. % 41.2 51.8 X-Ray Sulfur, Wt. % 0.51 0.60 Conradson
Carbon Residue, Wt. % 0.17 0.11 Refractive Index at 25.degree.C
1.5002 1.5304 ASTM Distillation, .degree.F IBP 440 10 481 30 516 50
549 90 EP HTU Product Gravity, .degree.API 33.0 30.8 UV Absonce at
285 mu 3.32 4.64 Polycyclic Aromatics, Wt. %.sup.1 10.3 14.4
Aromatics, Wt. % 32.9 X-Ray Sulfur, Wt. % 0.029 0.039 Conradson
Carbon Residue, Wt. % 0.02 0.03 Refractive Index at 25.degree.C
1.4768 1.4894 ASTM Distillation, .degree.F IBP 382 180 10 467 465
30 504 500 50 539 528 90 636 642 EP 720 721 .sup.1 Calculated from
UV absorbance at 285 mu
EXAMPLES 5 AND 6
Hydrogen treated product from Examples 3 and 4 were blended with
virgin gas oil of the characteristics listed above to produce a
blend of 51.5 volume percent virgin gas oil and 48.5 volume percent
of HTU product from Example 3 as charge stock to the fluid
catalytic cracking pilot unit (Example 5), and to produce a blend
of 63.0 volume percent virgin gas oil and 37.0 volume percent of
the HTU product of Example 4 as charge stock for the fluid
catalytic cracking pilot unit (Example 6) to simulate commercial
conditions and illustrate the benefits of the method of this
invention.
Catalytic Cracking Unit
Example 5 6 Charge to FCCU Gravity, .degree.API 31.8 30.7 UV
Absorbance at 285 mu 4.68 4.72 Polycyclic Aromatics, Wt. %.sup.1
14.5 14.6 Aromatics, Wt. % 32.7.sup.2 28.3 X-Ray Sulfur, Wt. % 0.32
0.39 Conradson Carbon Residue, Wt. % 0.06 0.10 Refractive Index at
25.degree.C 1.4798 1.4834 ASTM Distillation, .degree.F IBP 410 422
10 490 494 30 534 540 50 578 584 90 724 732 EP 760+ 760+ Products
from FCCU Yields, basis total feed Coke, wt. % 1.3 2.1 Dry Gas, Wt.
%.sup.3 4.1 5.5 Propylenes, Vol. % 3.9 4.8 Isobutane, Vol. %.sup.4
6.6 (47) 7.5 (50) Normal Butane, Vol. %.sup.4 1.5 (11) 2.1 (14)
Butylenes, Vol. %.sup.4 5.9 (42) 5.3 (36) C.sub.4 's, Vol. % 14.0
14.9 C.sub.5 's, Vol. % 8.2 11.7 Depentanized Naphtha, Vol. % 37.8
41.5 Tests Light Gasoline (115.degree.-250.degree.F) 66.9 66.4
Gravity, .degree.API ASTM Octane RON, Clear, +3 cc TEL 86.2,96.7
81.6,95.3 MON,Clear, +3 cc TEL 76.5,87.2 75.0,87.6 Heavy Gasoline
(250.degree.-430.degree.F) Gravity, .degree.API 40.9 38.0 ASTM
Octane RON, Clear, +3 cc TEL 86.4,92.3 89.0,95.8 MON, Clear, +3 cc
TEL 76.3,84.0 78.7,84.2 Gas Oil (430.degree.F+) Gravity,
.degree.API 27.8 24.2 UV Absorbance at 285 mu 13.4 15.0 Polycyclic
Aromatics, Wt. %.sup.1 41.5 46.4 .sup.1 Calculated from UV
Absorbance at 285 mu .sup.2 Calculated .sup.3 Includes H.sub.2,
C.sub.1, C.sub.2 =, C.sub.2, C.sub.3 =, C.sub.3 .sup.4 Numbers
shown in parenteses are individual butanes as a percentage of total
butanes.
Overall Yield Data
Yields, basis fresh feedstock charged to the fluid catalytic
cracking unit with all of the charge stock ultimately converted to
debutanized naphtha and lighter are shown in the following
table.
Yields Basis Fresh Feed to FCCU (100% Ultimate Conversion) Coke,
Wt. % 2.3 3.2 Dry Gas, Wt. % 7.3 8.5 H.sub.2 Consumption, SCF/Bb1
Fresh Feedstock 706 860 Propylenes, Vol. % 7.0 7.4 Isobutane, Vol.
% 11.8 11.6 Normal Butane, Vol. % 2.7 3.2 Butylenes, Vol. % 10.5
8.2 Debutanized Naphtha, Vol. % 82.3 81.9 Research Octane, +3 cc
TEL 95.9 96.5 Motor Octane, +3 cc TEL 87.9 88.4 Road Octane Index,
+3 cc TEL 95.7 96.3 With Alkylation Debutanized Naphtha &
Alkylate (No excess isobutane), Vol. % 98.3 97.7 Research Octane,
+3 cc TEL 97.4 97.9 Motor Octane, +3 cc TEL 90.6 91.0 Road Octane
Index, +3 cc TEL 97.8 98.2 Debutanized Naphtha + Alkylate (Excess
isobutane), Vol. % 111.1 107.5 Research Octane, +3 cc TEL 98.4 98.6
Motor Octane, +3 cc TEL 92.2 92.2 Road Octane Index, +3 cc TEL 99.0
99.1 Excess isobutane required, Vol. % 9.2 7.0
The foregoing examples illustrate the high yields of high octane
motor fuels which may be produced by the method of this
invention.
Obviously, many modifications and variations of the invention, as
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 appended claims.
* * * * *