U.S. patent number 3,891,540 [Application Number 05/457,310] was granted by the patent office on 1975-06-24 for combination operation to maximize fuel oil product of low pour.
This patent grant is currently assigned to Mobil Oil Corporation. Invention is credited to Edward J. Demmel, Donald M. Nace, Hartley Owen, Edward J. Rosinski.
United States Patent |
3,891,540 |
Demmel , et al. |
June 24, 1975 |
Combination operation to maximize fuel oil product of low pour
Abstract
A combination operation is described comprising catalytic
cracking and ZSM-5 type crystalline aluminosilicate catalyst
upgrading of light fuel oil product under selected conditions
designed to particularly increase the yield of light fuel oil
product of desired low pour point.
Inventors: |
Demmel; Edward J. (Pitman,
NJ), Nace; Donald M. (Woodbury, NJ), Owen; Hartley
(Belle Mead, NJ), Rosinski; Edward J. (Deptford, NJ) |
Assignee: |
Mobil Oil Corporation (New
York, NY)
|
Family
ID: |
23816228 |
Appl.
No.: |
05/457,310 |
Filed: |
April 2, 1974 |
Current U.S.
Class: |
208/77;
208/DIG.2; 208/70; 208/152; 208/68; 208/149; 208/155 |
Current CPC
Class: |
C10G
11/18 (20130101); C10G 69/04 (20130101); Y10S
208/02 (20130101); C10G 2400/06 (20130101) |
Current International
Class: |
C10G
11/18 (20060101); C10G 11/00 (20060101); C10G
69/04 (20060101); C10G 45/64 (20060101); C10G
69/00 (20060101); C10G 45/58 (20060101); C10g
037/06 (); C01b 033/28 () |
Field of
Search: |
;208/77,70,68,111 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Attorney, Agent or Firm: Huggett; Charles A. Farnsworth;
Carl D.
Claims
1. A method for improving the yield of low pour light fuel oil
product which comprises,
catalytically cracking a mixture comprising fresh gas oil feed and
heavy cycle oil product of cracking in a first conversion zone
under conditions selected to restrict conversion to less than 45
volume percent,
separating the product of said first conversion zone to recover
gasoline and lower boiling components from a light fuel oil
fraction, an intermediate cycle oil fraction and a heavy cycle oil
fraction, recycling the heavy cycle oil fraction to said first
conversion zone,
passing the intermediate cycle oil fraction to a second conversion
zone and restricting catalytic conversion thereof to increase the
yield of desired light fuel oil,
separating the product of the intermediate cycle oil conversion
operation to recover gasoline and lower boiling components from
light fuel oil and higher boiling cycle oil and
reducing the pour point of the light fuel oil fraction of the
combination catalytic cracking operation by contacting it with a
ZSM-5 type crystalline zeolite under hydrodewaxing conditions.
2. The method of claim 1 wherein conversion of the intermediate
cycle oil fraction is restricted to less than 30 volume
percent.
3. The method of claim 1 wherein conversion of the hydrocarbon
feeds is accomplished with a catalyst of restricted activity within
the range of 20-40 FAI.
4. The method of claim 1 wherein limited cracking of the
intermediate cycle oil is accomplished in the presence of
naphtha.
5. The method of claim 1 wherein the recovered light fuel oil
product of the cracking operation boils in the range of from about
320.degree.F. up to about 700.degree.F. at its 90 percent ASTM
distillation point.
6. The method of claim 1 wherein a faujasite conversion catalyst of
restricted activity is employed in each of said conversion
zones.
7. The method of claim 6 wherein the faujasite conversion catalyst
is combined with from 1 to 10 weight percent of a ZSM-5 type or a
mordenite type of crystalline zeolite.
8. The method of claim 1 wherein ZSM-5 type crystalline zeolite is
cascaded from the ZSM-5 hydrodewaxing operation to the cracking
operation at intervals when regeneration of ZSM-5 catalyst is
required.
9. The method of claim 1 wherein freshly regenerated catalyst is
passed to each conversion zone and the ratio to catalyst to oil in
the first conversion zone is about 6 based on fresh feed.
10. The method of claim 1 wherein the hydrodewaxing operation is
accomplished at a temperature within the range of 500.degree. to
900.degree.F. and cracking of the fresh and recycle oils charged to
the first conversion zone is accomplished at a temperature below
950.degree.F. in a riser conversion zone providing a relatively
short hydrocarbon residence time.
11. A method for converting high boiling hydrocarbons to light fuel
oil product which comprises,
converting relatively high boiling hydrocarbon materials and
recycle conversion products thereof higher boiling than a desired
light fuel oil product with a faujasite containing crystalline
zeolite cracking catalyst of 20 to 40 FAI activity under conditions
restricting fresh feed conversion to less than 45 volume
percent,
separating a light fuel oil product of conversion from a gasoline
product with a boiling point of about 700.degree.F. at its 90
percent ASTM distillation point, and
reducing the pour point of said desired light fuel oil product by
contact with a ZSM-5 type crystalline zeolite under hydrodewaxing
conditions.
12. The method of claim 11 wherein a crystalline zeolite of the
class selected from a ZSM-5 type crystalline material or a
mordenite type of crystalline material is in admixture with said
faujasite crystalline zeolite.
13. The method of claim 11 wherein an intermediate cycle oil
boiling between said desired light fuel oil product and a heavier
cycle oil product is separately converted to desired light fuel oil
product.
14. The method of claim 13 wherein a fresh gas oil feed and a
higher boiling recycle product of conversion are converted in a
zone separate from the intermediate cycle oil conversion zone.
15. The method of claim 14 wherein the fresh gas oil feed is
converted in a zone separate from a conversion zone for the
intermediate cycle oil and higher boiling recycle product.
16. The method of claim 11 wherein the desired light fuel oil
product has an initial boiling point within the range of
320.degree.F. to about 400.degree.F.
Description
BACKGROUND OF THE INVENTION
Cracking operations to produce a variety of useful products have
been practiced since early 1940. A prior art patent of particular
interest directed to restricted conversion operations is that of
Jewell 2,882,218. Naturally occurring clay type catalysts were
initially employed and subsequently replaced with synthetic
silica-alumina amorphous type cracking catalysts. These catalysts
were more active for accomplishing the desired conversion reactions
and thus permitted many processing variations and equipment
changes. The development of a crystalline alumino-silicate
conversion catalyst has provided additional opportunity to develop
more efficient conversion operations as well as substantially
improving the equipment in which employed. The present invention is
concerned with processing crude oil and distillation products
thereof under conditions to improve the recovery of fuel oil
boiling range products of desired pour point.
SUMMARY OF THE INVENTION
The present invention is concerned with a processing combination
comprising a hydrocarbon conversion operation designed particularly
for the increased production of a light fuel oil product. More
particularly, the present invention is concerned with the cracking
of cude oil and distillation products thereof such as gas oil and
higher boiling hydrocarbons with catalysts of selected activity
characteristics maintained under conditions particularly promoting
the formation of relatively large yields of fuel oil boiling range
product which is selectively converted with a small pore
crystalline zeolite under conditions to reduce the pour point of
the fuel oil product of cracking.
The fluid cracking operation of this invention is a relatively mild
conversion operation as compared with an operation primarily
directed to the production of gasoline. It is particularly
accomplished under conversion conditions restricted to less than 45
vol. percent in the presence of recycle material. More
particularly, it is preferred to restrict a first pass conversion
of fresh feed passed to the cracking operation to less than 40 vol.
percent and more usually to within the range of 25 to 35 vol.
percent. Under these restricted conditions, conversion is defined
as the volume percent of gas oil converted to material boiling in
the gasoline boiling range or lighter. Gasoline as referred to
herein is defined as a debutanized hydrocarbon with 90 vol. percent
of the material boiling below 400.degree.F. in an ASTM atmospheric
distillation still.
In the limited conversion fluid cracking operation of this
invention, the product effluent thereof is separated in a product
fractionation zone to recover a desired light cycle oil product
from lighter and heavier oil product material of the conversion
operation. The light cycle oil will normally boil to include
materials boiling above gasoline product up to about 700.degree.F.
at its 90 percent ASTM distillation point. Higher boiling material
recovered from the fractionation zone as heavy cycle oil is
recycled to the cracking operation for further conversion to lower
boiling desired product. Recycle rates will usually be in the range
of 1.5 to about 1.8 or less than 2.2 but greater than about 1.25.
The fluid cracking operation herein discussed is preferably carried
out in one or more riser conversion zones for fresh and recycle
hydrocarbon feed materials maintained at predetermined selected
conversion temperature conditions less than about 1000.degree.F.,
preferably not above about 950.degree.F. and more usually in the
range of 800.degree.F. to about 900.degree.F. Operating pressure
conditions may be in the range of atmospheric up to about 100
psig.
The catalyst employed in the riser cracking operation herein
described may comprise an amorphous silica-alumina cracking
catalyst, a faujasite type of crystalline zeolite of the "X" or "Y"
type or mixtures thereof provided with an activity level based on
the FAI (fluid activity index) test within the range of about 18 to
about 45, it being preferred to restrict the catalyst activity to
within the range of 20-40 FAI. The fluid cracking catalyst may be
an amorphous cracking component alone or a Y type of crystalline
faujasite alone or a combination thereof. Furthermore, either one
or both of these cracking components may be combined with a
relatively small amount up to about 10 weight percent of a ZSM-5
type of crystalline zeolite or a mordenite type of crystalline
zeolite. A crystalline zeolite cracking component in the form of a
rare earth exchanged Y crystalline zeolite may be in an amount
within the range of 1 to about 15 weight percent dispersed in a
suitable silica containing matrix material. A ZSM-5 type
crystalline zeolite component within the range of 1 to about 10
weight percent may be combined with the faujasite catalyst. The Y
type crystalline zeolite cracking component may also be combined
with a mordenite type of crystalline zeolite in a suitable support
matrix material in which composition the mordenite component may be
within the range of 1 to 10 weight percent. On the other hand, a
ZSM-5 type of crystalline zeolite may be used alone as herein
provided dispersed in a silica-clay matrix using from about 2 to
about 15 weight percent of the zeolite.
A catalyst composition suitable for use in the combination
operation of this invention comprises a mixture of crystalline
zeolites varying in pore size, structure and silica to alumina
ratio. For example, the catalyst composition employed in the fluid
cracking operation of this invention may comprise a crystalline
zeolite of at least 8 A. pore size of the X or Y faujasite type of
crystalline zeolite material activated by a rare earth exchange
material. The faujasite cracking component is used in a minor or
major proportion in combination with equal, a smaller, or a larger
amount of a crystalline zeolite of a generally smaller pore size
such as a ZSM-5 type of crystalline zeolite or a mordenite type of
crystalline zeolite which vary in structure and silica-alumina
ratio from the larger pore faujasite type material. The crystalline
zeolites whether used alone or together as herein discussed are
dispersed in a porous matrix material suitable for encountering the
high operating temperatures to which they will be exposed. The
smaller pore crystalline zeolite used in the combination operation
of this invention either alone or in admixture with a larger pore
material of the X or Y faujasite type material is preferably a
ZSM-5 type of catalyst composition. A ZSM-5 type catalyst
composition is described in U.S. Pats. Nos. 3,702,886 and 3,729,409
and the description thereof is incorporated herein by reference
thereto. A more complete description of a large pore crystalline
zeolite suitable for use in this invention may be found in U.S.
Pat. No. 3,556,988 issued Jan. 17, 1971. The description of such
catalyst compositions is incorporated herein by reference.
By porous matrix material it is intended to include inorganic and
organic compositions which may be catalytically active or
substantially inactive to the hydrocarbon conversion reactions
encountered. A preferred porous matrix may be selected from the
group comprising clay, acid treated clay, silica, alumina and
mixtures thereof. A silica-alumina cracking catalyst of a selected
and relatively low activity may be used as the primary or major
catalyst component with or without the presence of a faujasite
crystalline zeolite, a ZSM-5 type zeolite or a mordenite type
zeolite in the fluid cracking operation, as suggested above.
As suggested above, the cracking catalyst may include a mordenite
type of crystalline zeolite of the large or small pore variety
discussed in the prior art. In this catalyst combination, the
mordenite component will usually be only a fraction of the
faujasite component and selected from within the range of 1 to 10
weight percent.
The light fuel oil product of catalytic cracking obtained by the
fluid cracking operation particularly defined herein, normally will
boil in the range of about 320.degree.F. up to 400.degree.F. as its
initial boiling point up to about 700.degree.F. at its 90 percent
ASTM distillation level, and will have a pour point within the
range of -30 to about + 40.degree. F. depending upon the kind or
type of hydrocarbon feed used. To selectively improve or reduce the
pour point of the light fuel oil product of catalytic cracking
obtained as herein defined, the separated light fuel oil product is
thereafter passed in contact with a ZSM-5 type of crystalline
zeolite conversion catalyst alone maintained under selective
hydrodewaxing conditions particularly designed to further reduce
the light fuel oil product pour point. The ZSM-5 type zeolite
catalyst may be employed in a fixed or fluid bed of catalyst or as
an upflowing fluid mass of catalyst such as in a riser conversion
zone. In this hydrodewaxing operation, conversion of the separated
light fuel oil product of the fluid cracking operation is promoted
by contact with a ZSM-5 type of crystalline aluminosilicate
catalyst at a temperature maintained within the range of
500.degree. to about 900.degree.F., more preferably within the
range of 600 to about 800.degree.F. at a pressure in the range of
200 to 600 psig and a liquid hourly space velocity within the range
of 0.5 to 2.0 v/v/hr. It is preferred to conduct the pour point
reduction operation in the presence of hydrogen in an amount
sufficient to maintain a hydrogen to hydrocarbon mole ratio in the
range of 2 to 10/1.
In the combination catalytic operation above described, it is
contemplated providing a hydrotreating operation before or after
the ZSM-5 catalyst hydrodewaxing operation for the purpose of
removing sulfur from the light fuel oil material to about 3 weight
percent. However, high levels of sulfur may be tolerated in the
ZSM-5 conversion operations and it may not be necessary to reduce
the sulfur level. Also the cracking feedstock may be a low sulfur
material which does not need to be desulfurized.
As mentioned above, the fluid cracking operation of this invention
may be conducted in the presence of a faujasite crystalline zeolite
conversion catalyst in combination with a ZSM-5 type of crystalline
zeolite material. The ZSM-5 type component for the cracking
operation may be provided by cascading this component from the
downstream hydrodewaxing operation to the fluid cracking operation
periodically as required to maintain a desired level of this ZSM-5
crystalline zeolite component activity in the fluid faujasite
cracking catalyst. Thus, in a fluid catalyst hydrodewaxing
operation, the ZSM-5 zeolite catalyst component is transferred,
particularly when regeneration thereof is required, to the fluid
cracking operation at intervals as required. Makeup of this small
pore crystalline component to the overall combination is provided
through the hydrodewaxing operation alone or in combination with
the cracking operation. On the other hand, the hydrodewaxing
operation may include its own catalyst regeneration step thereby
precluding the necessity for cascading this catalyst component as
above discussed.
In the combination operation of this invention, it is to be noted
that with a given reactor configuration and catalyst composition,
the pour point of the light cycle oil (light fuel oil) is largely a
function of its ninety percent cut point and its initial boiling
point is set by the gasoline end point desired. The gasoline end
point may be in the range of 320.degree.F. up to about
400.degree.F. Using a hydrodewaxing operation as herein provided,
allows a much heavier end point to be selected than possible in
prior art processes for the light cycle oil product of this
invention. This wider boiling range light cycle oil material of
heavier end point and suitable as feed in the hydrodewaxing
operation also permits the use of a less severe fluid cracking
operation to produce a given volume of the wide boiling light fuel
oil product separated therefrom. In addition, the yield of light
fuel oil using the combination operation of this invention will
considerably increase for the same pour point and sverity
characteristics.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. I is a graph depicting the product selectivity obtained with
REY cracking catalysts at low conversion cracking of Durban fresh
feed.
FIG. II is a graph depicting the pour point and composition of
light fuel oil from low conversion cracking of Durban fresh feed
with REY catalysts.
FIG. III is a graph depicting the response in conversion to
temperature, contact time and catalyst to oil ratios for different
activity zeolite catalysts.
FIG. IV is a graph depicting the product selectivity obtained over
HZSM-5 containing catalyst compared to REY catalysts.
FIG. V is a graph depicting the properties of the 650.degree.F. (+)
cycle stock obtained by conversion of Durban fresh feed.
FIG. VI is a graph depicting the product selectivity obtained with
HZSM-5 containing catalysts compared to REY catalysts.
FIG. VII is a graph depicting the product selectivity obtained with
H-mordenite + REY compared with REY catalyst.
FIG. VIII is a graph depicting the pour point and composition of
light fuel oil from HZSM-5 containing catalysts compared to REY
catalyst.
FIG. IX is a graph depicting the pour point and composition of
light fuel oil from H-mordenite containing catalysts compared to
REY catalysts.
FIG. X is a graph depicting the pour point and composition of light
fuel oil obtained from coke deactivated REY catalysts compared with
a fresh clean burned REY catalyst.
FIG. XI is a schematic drawing in elevation of a combination
process comprising fluid catalytic cracking, product separation and
hydrodewaxing of a light fuel oil product of cracking.
In FIGS. IV, VI, VII, VIII, IX and X briefly defined, the results
obtained with REY catalysts is shown by a dotted line for
comparison with other results plotted. Further discussion of the
graphs will be provided below.
DISCUSSION OF SPECIFIC EMBODIMENTS
A Durban fresh gas oil feed defined below in Table I was subjected
to a series of low conversion cracking evaluation in the presence
of several different catalyst compositions. The operation
parameters studied were: temperature in the range of
850.degree.-950.degree.F.; hydrocarbon residence time in the range
of 2.5 to 4.5 seconds; and catalyst/oil ratios in the range of
2-20. FIG. III is a graphical representation of the response of
conversion to temperature, contact time and catalyst to oil ratio
for various catalysts.
The data and graphs referred to hereinafter identify the effects of
catalyst type and operating variables on product yields, product
compositions and product properties.
TABLE I ______________________________________ DURBAN FRESH FEED
______________________________________ Gravity, API 23.8 Sulfur, %
wt. 2.08 Nitrogen, % wt. 0.10 Conradsen Carbon, % wt. 0.23
Hydrogen, % wt. 12.3 Molecular wt. 357 Distillation, ibp,
.degree.F. 520 5% vol. 622 10% vol. 660 20% vol. 705 30% vol. 740
40% vol. 774 50% vol. 804 60% vol. 837 70% vol. 866 80% vol. 897
90% vol. 937 95% vol. 960 Composition, Paraffin % wt. 25.3
Naphthenes 27.3 Aromatics 47.4 % C, (Aromatic Ring Carbon) 19.0
______________________________________
Selectivity Comparison between Amorphous Silica/Alumina and REY
type Catalysts (Rare earth exchanged Y faujasite crystalline
zeolite).
The maximum light fuel oil (LFO) yields obtained by cracking with
an amorphous silica/alumina catalyst were found to be had at about
35 % conversion (to less than 430.degree.F. products) for a
650.degree.F. end boiling point (EBP) light fuel oil; at 30 %
conversion for a 690.degree.F. EBP light fuel oil and 20 percent
conversion for a 720.degree.F. EBP light fuel oil.
The maximum light fuel oil yields obtained by cracking with a (REY)
rare earth exchange Y faujasite type conversion catalyst, on the
other hand, were found to be had at 40 percent conversion for a
650.degree.F. end boiling point (EBP) light fuel oil; 35 percent
conversion for a 690.degree.F. EBP light fuel oil and at 25 percent
conversion for a 720.degree.F. EBP light fuel oil. Thus, the level
of conversion could be much higher with the faujasite conversion
catalyst than with the amorphous silica-alumina catalyst. Also, the
light fuel oil yields were found to be higher when the cracking
temperature is about 850.degree.F. instead of a higher temperature
of about 950.degree.F. FIG. I graphically reproduces the product
selectivity obtained by low conversion cracking of Durban fresh
feed (Table I) using REY catalysts and shows the 850.degree.F.
operation producing more fuel oil than the 950.degree.F.
operation.
Table II below provides a comparison of the yields obtained for the
silica-alumina and REY catalysts at a 30 wt. percent conversion
level.
Table II
__________________________________________________________________________
Silica/Alumina REY 850.degree.F. 950.degree.F. 850.degree.F.
950.degree.F.
__________________________________________________________________________
Coke 2.0 wt.% 1.5 wt.% 1.9 wt.% 1.1 wt.% Dry Gas 1.7 2.8 1.4 2.2
C.sub.4 's 4.1 3.5 3.0 3.0 C.sub.5 + Gasoline 22.2 22.2 23.7 23.7
430/650 LFO 27.5 25.5 28.0 27.3 430/690 LFO 34.9 33.6 35.7 34.4
430/720 LFO 41.2 40.0 43.0 41.6
__________________________________________________________________________
It will be observed from the above data, graphically presented in
FIG. V, that the REY type crystalline zeolite catalyst is more
selective for the production of gasoline and light fuel oil product
than the silica-alumina catalyst. Catalyst activity for the above
reported catalysts was identified as 23 to 32 FAI for the amorphous
silica-alumina catalyst and 40 to 68 FAI for the REY catalyst.
Properties and Composition of Light Fuel Oil Cuts
The pour point of the 430.degree.-650.degree. F;
430.degree.-690.degree. F. and 430.degree.-720.degree. F. fuel oil
cuts separated from a Durban fresh gas oil feed were reduced by
cracking at a relatively low conversion level. A relatively severe
cracking operation appears to have little effect on the light fuel
oil pour point obtained by either a silica-alumina or REY cracking
catalyst. FIG. II is a plot of the data obtained with the REY
catalysts. The data are essentially self-explanatory. For example,
the graph shows that the 650.degree.F. light fuel oil produced at
850.degree.F. with the REY catalyst has a lower point than the 690
or 720 light fuel oil produced at a higher temperature.
A comparison of the light fuel oil products of cracking obtained at
a 30 wt. % conversion level to 430.degree.F. minus products is
provided in Table III below.
Table III
__________________________________________________________________________
Uncracked Silica/Alumina REY Feed 850-950.degree.F.
850-950.degree.F.
__________________________________________________________________________
Pour Point 430/650.degree.LFO 20.degree. 5.degree. 2.degree. Pour
Point 430/690.degree.LFO 35.degree. 23.degree. 15.degree. Pour
Point 430/720.degree.LFO 40.degree. 30.degree. 32.degree. %
Aromatics in 650.degree. LFO 37% 56% 54% % Paraffin in 650.degree.
LFO 37% 23% 24% % Naphthenes in 650.degree. LFO 26% 21% 22% %
n-Paraffins in 650.degree. LFO 16% 8% 10%
__________________________________________________________________________
The cloud points of the light fuel oil products obtained at the 30
wt. percent conversion level are presented in Table IV below. It
will be noted from these data that there is a surprisingly small
difference between the pour point and the cloud point of these
different fuel oil fractions.
Table IV ______________________________________ Uncracked Silica/
PEY Feed Alumina ______________________________________ Cloud Point
430/650.degree.LFO 28.degree. 15.degree. 11.degree. Cloud Point
430/650.degree.LFO .about. 40.degree. 26.degree. 15.degree. Cloud
Point 430/720.degree.LFO 46.degree. 40.degree. 36.degree.
______________________________________
Properties of Heavy Cycle Oil
The hydrogen content and API gravity were determined for the
650.degree.F. plus heavy cycle oil product of the cracking
operations. The data obtained are plotted in FIG. V as a function
of the amount of heavy cycle oil remaining from the cracking
operation. In the figure, the severity of the cracking operation is
shown increasing from right to left. The heavy oil product obtained
with the REY catalyst is observed to be more aromatic than that
obtained with the silica-alumina catalyst as indicated by the lower
hydrogen content and lower API gravity of the product. The
1000.degree.F. temperature cracking runs with the silica-alumina
catalyst, on the other hand, produced a heavy cycle oil which is
more aromatic than that obtained at the 850.degree.F. and
950.degree.F. cracking conditions.
Effects of HZSM-5, H-Mordenite and Coke on REY type Conversion
Catalysts
The catalyst/oil ratio response of various catalyst compositions
was determined and a comparison thereof is plotted and shown in
FIG. III at two different riser residence times of 2.5 and 4.5
seconds. The figure is self-explanatory. An activity comparison of
the various catalysts tested using a fixed catalyst bed FAI test,
cracking a light East Texas gas oil at 850.degree.F. and with the
Durban charge stock at 850.degree.F. and a fixed catalyst/oil ratio
is provided in Table V. The activity of the several catalysts
tested is reported in the legend beneath the graphs of FIG.
III.
Table V
__________________________________________________________________________
Comparison of Low Activity Catalysts by FAI Test* Catalyst FAI Wt.%
C Wt.% Yields (Vol.% Conv.) on cat. Conv. C.sub.5 + Gaso. C.sub.4
's Dry Gas Coke
__________________________________________________________________________
Si/Al 22.7 0.16 22.2 16.6 3.36 1.85 0.36 10% Al.sub.2 O.sub.3 Si/Al
31.5 0.35 31.0 21.6 5.44 3.13 0.78 20% Al.sub.2 O.sub.3 2%
REY/Si-Clay- 40.0 0.104 39.3 31.7 4.57 2.79 0.23 Zi Spent Torr.
20.2 0.06 .DELTA. 19.9 16.7 2.06 1.01 0.14 (0.8% C) 2% REY + 2%
40.9 0.10 40.2 29.4 5.98 4.58 0.23 HZSM-5 on D10 matrix 2% REY +
10% HZSM-5 48.5 0.17 47.1 32.3 8.81 5.61 0.37 2% HZSM-5 17.7 0.06
17.3 12.3 2.79 2.01 0.14 2% REY + 2% H- Mord. 41.4 0.094 40.7 34.4
4.14 1.95 0.21 2% REY + 10% H- Mord. 38.6 0.095 37.8 33.8 2.32 1.47
0.22
__________________________________________________________________________
Comparison of Relative Catalyst Activities: LETGO in Dense Bed vs.
Durban Fresh Feed in Riser Catalyst LETGO at 850.degree. Durban at
850.degree. 2 C/O, 5 mm.t.sub.c 8 C/O, 41/2 sec. t.sub.c
__________________________________________________________________________
Wt.% Conv. Wt.% Cat. Wt.% Conv. Wt.% Cat. 2% HZSM-5 17.3 .06 22.7
.14 Spent Torrance FCC (.86%C) 19.9 .06 .DELTA. 23.0 .08 .DELTA.
Spent Ashland/Durban FCC (.92%C) -- -- 32.4 .17 .DELTA. 2% REY +
10% H-Mordenite 37.8 .10 37.6 .17 2% REY 39.3 .10 38.5 est. .18
est. 2% REY + 2% H-Mordenite 40.7 .10 39.0 .18 2% REY + 2% HZSM-5
40.2 .10 42.5 .20
__________________________________________________________________________
*LETGO, 850.degree.F., 5 mm. on-stream fixed bed.
From these activity comparison tests it has been observed that the
addition of 2 weight percent HZSM-5 or 2 and 10 weight percent
H-Mordenite to a 2 weight percent REY faujasite crystalline zeolite
dispersed in a silica-clay-zirconia matrix has little effect on
catalyst activity.
Selectivity Differences
Product yields obtained with two HZSM-5 catalysts are plotted in
FIG. IV and compared to a 2 weight percent REY alone catalyst. It
is found that the HZSM-5 type zeolite with and without a REY type
zeolite catalyst, lowers gasoline and light fuel oil selectivity by
increasing the dry gas and C.sub.4 yields. The dash line curves
identified at 850.degree.F. and 950.degree.F. for the REY alone
catalyst provide comparison with the results obtained with the
HZSM-5 containing catalysts at the 850.degree.F. and 950.degree.F.
temperature of conversion. Comparison at 30 weight percent
conversion to 430.degree.F. minus products is provided below in
Table VI.
Table VI
__________________________________________________________________________
2% REY + 2% REY 2% HZSM-5 2% HZSM-5 850.degree. 950.degree.
850.degree. 950.degree. 850.degree. 950.degree.
__________________________________________________________________________
Coke 1.9 wt.% 1.1 wt.% 1.2 wt.% 1.0 wt.% 1.7 wt.% 1.2 Dry Gas 1.4
2.2 3.0 3.3 3.5 4.9 C.sub.4 's 3.0 3.0 4.7 4.5 5.9 4.9 C.sub.5 +
Gasoline 23.7 23.7 21.1 21.1 19.0 19.0 430/650.degree. LFO 28.0
27.3 26.4 25.7 26.4 25.7 430/690.degree. LFO 35.7 34.4 34.7 33.6
34.7 33.6 430/720.degree. LFO 43.0 41.6 42.0 40.9 42.0 40.9
__________________________________________________________________________
Product yields obtained with two H-Mordenite type crystalline
zeolite catalysts combined with 2 weight percent REY are compared
with a 2 weight percent REY alone type zeolite cracking catalyst in
FIG. VII. It will be observed that the mordenite component has very
little effect on the light products and gasoline selectivity. Coke
make is slightly lower when H-Mordenite is present along with a
slight gasoline yield improvement. The mordenite containing
catalysts provided with an FAI of 41.4 and 38.6 (FIG. III) show a
definitely higher gasoline selectivity (solid line) over REY alone
(dashed line). FIG. VII also shows the presence of higher light
fuel oil yields (solid line) for each light fuel oil fraction as an
effect of the mordenite component on the catalyst. A comparison is
provided in Table VII below.
Table VII
__________________________________________________________________________
2% REY + 2% REY + 2% REY 2% H-Mordenite 10% H-Mordenite 850.degree.
950.degree. 850.degree. 850.degree. 950.degree.
__________________________________________________________________________
Coke 1.9 wt.% 1.1 wt.% 1.1 1.1 0.8 Dry Gas 1.4 2.2 1.5 1.5 1.9
C.sub.4 's 3.0 3.0 3.0 3.0 3.0 C.sub.5 + Gasoline 23.7 23.7 24.3
24.3 24.3 430/650 LFO 28.0 27.3 29.5 29.5 28.4 430/690 LFO 35.7
34.4 37.5 37.5 36.0 430/720 LFO 43.0 41.6 -- -- --
__________________________________________________________________________
Properties and Composition of Light Fuel Oil Cuts
FIGS. VIII and IX provide a plot of the data obtained showing the
pour point and the composition of the fuel oil cuts made by
cracking a Durban fresh feed defined above in Table I over
catalysts containing HZSM-5 type zeolites and H-Mordenite type
zeolites. The dashed line represents the results obtained with the
REY catalyst. The light fuel oil cuts obtained with the HZSM-5 and
Mordenite containing catalyst have higher pour point than the REY
produced product. In addition, a comparison of the results obtained
at a 30 weight percent conversion level to 430.degree.F. minus
product is provided in Table VIII below.
Table VIII
__________________________________________________________________________
Uncracked 2% REY HZSM-5 H-Mordenite Spent FCC Feed containing
containing Catalyst catalyst catalyst
__________________________________________________________________________
Pour Point 430/650 LFO 20.degree. 2.degree. 7.degree. 3.degree.
3.degree. Pour Point 430/690 LFO 35.degree. 15.degree. 21.degree.
22.degree. -- Pour Point 430/720 LFO 40.degree. 32.degree. -- -- --
% Aromatics in 650.degree. LFO 37% 54% 57% 54% 54% % Paraffins in
650.degree. LFO 37% 24% 22% 24% 24% % Napthenes in 650.degree. LFO
26% 22% 21% 22% 22% % n-Paraffins in 650.degree. LFO 16% 10% -- --
--
__________________________________________________________________________
A 650.degree.F. light fuel oil product of zeolite cracking
restricted to about 30 percent conversion with a REY-Mordenite
cracking catalyst and identified by FIG. IX as having a pour of +5
was selected as a charge for pour point reduction by contact with a
ZSM-5 crystalline zeolite hydrodewaxing catalyst. An estimated
reduction in pour of the above identified light fuel oil product
and operating conditions is provided in Table IX below.
Table IX ______________________________________ Calculated
Reduction of 650.degree.F. Light Cycle Oil of +5
______________________________________ Pour ZSM-5 Catalyst
Operating Conditions Pressure, psig. 550 LHSV, v/hr/v 1.5 H.sub.2
circulation, scf/b 2000 Temperature, .degree.F. 530-750.degree.F.
Age cycle Yields, % Wt. Vol. C.sub.1 0.05 -- C.sub.2 0.1 -- C.sub.3
0.5 -- C.sub.4 0.8 1.3 C.sub.5 0.9 1.3 C.sub.6 --330.degree.F.
Naphtha 3.2 4.0 330+.degree.F. Gas Oil 94.6 93.3 Total 100.15 99.9
Charge 330+ Btm. Product +5 Pour -10
______________________________________
The hydrodewaxing of light straight run petroleum fractions with
ZSM-5 type zeolites such as a light straight run material boiling
in the range of 350.degree.F. to about 550.degree.F. is disclosed
in U.S. Pat. No. 3,700,585 issued Oct. 24, 1972.
A straight run petroleum distillate boiling in the range of about
450.degree.F. to about 700.degree.F. was subjected to pour point
reduction by contact with a ZSM-5 crystalline zeolite. Table X
below presents the results obtained and operating conditions
employed in this operation.
Table X ______________________________________ LHSV 1.5 Pressure
400 H.sub.2 Circ. 2500 Temp., .degree.F. 530-750 Wt. Vol. C.sub.1
0.01 -- C.sub.2 0.04 -- C.sub.3 0.77 -- C.sub.4 's 1.97 2.85
C.sub.5 's 2.08 2.78 C.sub.6 --180.degree.F. 0.98 1.22
180-330+.degree.F. 2.06 2.40 330+.degree.F. Btm. 92.76 91.95 Total
100.70 101.20 Charge Product ______________________________________
350-700.degree.F. 330+.degree.F.Btm., API 32.7 (34) API +5 Pour
Point, .degree.F. -15 +10 Cloud Point, .degree.F. -5
______________________________________
In the combination operation of the present invention, it is thus
contemplated hydrodewaxing straight run petroleum distillates as
well as cracked products boiling in the light fuel oil boiling
range and combining the hydrodewaxed material to further improve
the yield of low pour light fuel oil product of relatively wide
boiling range.
Referring now to the drawing of the process combination, FIG. XI,
there is shown schematically in elevation one arrangement
comprising a fluid cracking operation followed by product
separation and hydrodewaxing of light fuel oil product to reduce
its pour point to a desired lower level. The drawing shows
schematically a regeneration vessel 2 wherein a fluid catalyst used
in a cracking operation is regenerated with oxygen containing gas
to remove deposited hydrocarbonaceous material by burning thereby
heating the catalyst to an elevated temperature up to about
1400.degree.F. and suitable for providing a substantial portion of
the endothermic heat required in a subsequent cracking operation.
Regeneration flue gases are removed from an upper portion of the
regeneration vessel by conduit 4. Regenerated catalyst at an
elevated temperature in the range of about 1100.degree. to
1350.degree.F. is removed from the regeneration zone by catalyst
transfer conduits 6 and 8 respectively for transfer to the lower
portion of riser reactor A and riser reactor B. A single riser
reactor system may be employed in place of the dual riser system
shown. However, the dual riser system provides greater flexibility
in operating conditions and arrangements and thus will be
specifically discussed.
In the dual riser cracking operation schematically depicted in the
drawing, riser "A" is employed for converting a mixture of fresh
gas oil feed and heavy cycle oil (HCO) at mix ratios discussed
above and cracking temperature conditions selected to restrict
conversion to less than about 45 vol. percent. Cracking of the
fresh feed and heavy cycle oil is accomplished by mixing hot
regenerated catalyst with the oil feed to form a suspension at a
catalyst to oil ratio of about 6 based on fresh feed and a
temperature within the range of 800.degree.F. to 950.degree.F. and
preferably not over 900.degree.F. The suspension thus formed is
passed upwardly through the riser conversion zone under velocity
conditions providing a hydrocarbon residence time less than 10
seconds before the suspension is cyclonically separated in vessel
10 adjacent the upper end of the riser. There may be a plurality of
interconnected cyclonic separating means provided for this purpose.
Riser "B" on the other hand, is employed for cracking of virgin
naphtha and/or recracking gasoline product of the cracking
operation either alone or in combination with a recycled
intermediate light cycle oil material. On the other hand, the dual
riser operation may be employed for separately cracking light gas
oil and heavy gas oils. In any event, a suspension of hydrocarbons
which at least includes the recycled intermediate light cycle oil
combined with regenerated catalyst and existing at a temperature
selected from within the range of 800.degree.F. to about
1000.degree.F. is passed upwardly through riser B under
predetermined limited conversion conditions preferably less than
about 30 volume percent. The suspension in riser B is separated in
cyclonic separating means provided at the end of riser B in vessel
10 into a hydrocarbon phase and a catalyst phase. Catalyst
separated by cyclonic means and recovered in vessel 10 is stripped
of entrained hydrocarbon in the lower portion of vessel 10 with
stripping gas before the catalyst is transferred to the
regeneration vessel by conduit 12. Hydrocarbon materials separated
from catalyst in vessel 10 and comprising products of conversion
separated from risers A and B and stripped products are conveyed by
conduit 14 to a product fractionator 16.
In fractionator 16, the hydrocarbon product of conversion is cooled
and separated into a clarified slurry oil (CSO) removed therefrom
by conduit 18, a heavy cycle oil (HCO) removed by conduit 20, an
intermediate cycle oil (ICO) removed by conduit 22 and a light
cycle oil (LCO) removed by conduit 24. Materials boiling lower than
light cycle oil and comprising gasoline product of the conversion
operation and lower boiling gasoline product of the conversion
operation and lower boiling gasiform material is removed from an
upper portion of fractionator 16 by conduit 26. The material in
conduit 26 is cooled in cooler 28 and then passed by conduit 30 to
a drum 32 wherein gasoline boiling material is separated from lower
boiling gaseous products. The gaseous products are withdrawn by
conduit 34. The separated gasoline is withdrawn by conduit 36 and a
portion thereof is recycled as reflux to the fractionator by
conduit 38. The remaining portion of the gasoline product is
recovered by conduit 40.
The intermediate cycle oil (ICO) in conduit 22 is withdrawn or
recycled by conduit 42 to the bottom or lower inlet of riser B. The
heavy cycle oil (HCO) in conduit 20 is withdrawn or recycled by
conduit 44 to the bottom or lower inlet of riser A. An
interconnecting conduit 46 with valve means connecting conduit 44
and 42 permits passing heavy cycle oil and intermediate cycle oil
to either riser inlet as desired.
The light cycle (fuel) oil (LCO) or No. 2 fuel oil in conduit 24 is
passed by pump 48 and conduit 50 to furnace 52 wherein it is heated
in the presence of hydrogen to a temperature within the range of
500.degree. to 900.degree.F. before being transferred by conduit 54
for contact with a hydrodewaxing catalyst bed 56 in vessel or zone
58. The ZSM-5 type zeolite hydrodewaxing catalyst maintained in
zone 58 is usually maintained at a pressure within the range of 100
to 800 psig. In the event that the light cycle oil product is
undesirably high in sulfur content, it is contemplated subjecting
it to a relatively mild hydrotreating operation which will reduce
the level of sulfur in the light fuel oil product not to exceed
about 3 weight percent. Typical hydrotreating operations known in
the art may be used for this purpose. Thereafter the hydrotreated
product is passed to zone 58. It is also contemplated and preferred
to effect hydrotreating the light fuel oil product of cracking
after hydrodewaxing thereof rather than before hydrodewaxing for
sulfur reduction. Catalyst bed 56 in zone 58 is preferably a dense
fluid bed of ZSM-5 type of crystalline zeolite catalyst
hereinbefore described. In catalyst bed 56 the light cycle oil or
No. 2 fuel oil is selectively converted or hydrodewaxed in the
presence of hydrogen so as to reduce its pour point a desired
amount and to within the range of -40.degree. to +15.degree.F.
Fresh ZSM-5 makeup catalyst may be added to bed 56 by conduit 60
when desired. The light fuel oil product of reduced pour point and
obtained by the selective conversion operation performed in vessel
58 is separated from catalyst in an upper portion thereof and
withdrawn from the vessel by conduit 62, cooled in cooler 64 and
conveyed by conduit 66 to drum 68. In drum 68, a hydrogen rich
recycle gas is separated from higher boiling condensed product. The
separated hydrogen rich gas is conveyed or recycled by conduit 70
for admixture with the light cycle oil feed in conduit 50. Hydrogen
make-up gas may be added to the hydrogen rich recycle gas by
conduit 72. Condensed liquid material is withdrawn from drum 68 by
conduit 74 communicating with separation vessel or fractionator 76.
In separator 76, a fuel oil product of desired low pour point is
separated from lower boiling components. The fuel oil is withdrawn
from the bottom of vessel 76 by conduit 78 as product of the
combination process. A portion of this fuel oil product is recycled
by conduit 80, cooler 82 and conduit 84 to maintain the temperature
in the bottom portion of vessel 76 of about 650.degree.F.
Components of the selective conversion operation and boiling below
the desired fuel oil product, that is, below about 400.degree.F.,
are withdrawn from the top of the tower by conduit 86. The material
in conduit 86 is cooled in cooler 88 and then conveyed by conduit
86 is cooled in cooler 88 and then conveyed by conduit 90 to drum
92. In drum 92 conditions of temperature and pressure are
maintained to separate a fuel gas product comprising C.sub.4 and
lower boiling hydrocarbons withdrawn by conduit 94 from higher
boiling material falling in the gasoline boiling range. Condensed
liquid is withdrawn by conduit 96 and a portion thereof is recycled
as reflux by conduit 98 to the top portion of separator vessel 76.
The remaining portion of the condensed liquid boiling below the
fuel oil product and comprising gasoline boiling range components
is withdrawn by conduit 100.
In the combination operation above described, the hydrodewaxing
operation in zone 58 is usually at a much higher pressure than the
cracking operation and within the range of about 200 to about 600
psig, and thus higher than that of fractionator 16 or vessel 10
wherein separated catalyst is collected and stripped before passage
to the catalyst regeneration zone. Thus, to provide and maintain a
crystalline zeolite cracking activity in the fluid cracking
operation depleted as by catalyst attrition, it is contemplated
passing the ZSM-5 type catalyst from the higher pressure vessel 58
by conduit 102 containing valve 104 to the bed of fluid cracking
catalyst collected in vessel 10. Thus regeneration of the cascaded
ZSM-5 catalyst component may be accomplished in zone 2 in addition
to maintaining a desired level of ZSM-5 type crystalline component
in the cracking catalyst. In this arrangement, zone 58 is provided
with fresh ZSM-5 catalyst by conduit 60.
Within the operating concepts of this invention, it has been
observed that the catalyst mixture of Y faujasite type crystalline
zeolite and mordenite type crystalline zeolites perform better at a
temperature of about 850.degree.F. than at 950.degree.F. within a
conversion level in the range of 20 to 45 vol. percent. Also, the
catalyst mixture was observed to perform better for the purpose
intended, that is, produce a desired light fuel oil product than a
Y faujasite crystalline zeolite alone. Furthermore, the mordenite
containing catalyst gives slightly higher gasoline yields along
with making less coke.
It will be understood by those skilled in the art that the
hydrocarbon materials charged to the combination operation of this
invention may vary considerably in boiling range and will vary with
the composition of the fresh feed. For example, a fresh gas oil
feed may boil in the range of 500.degree.F. to about 1050.degree.F.
and produce in addition to the light fuel oil and gasoline products
an intermediate cycle oil boiling in the range of 550.degree.F. to
about 800.degree.F. and a higher boiling cycle oil boiling in the
range of about 650.degree.F. to about 950.degree.F. Thus, since the
fractionation zone downstream of the cracking operation is
considered a relatively rough separation operation there will be
some considerable overlap in the boiling range of products
separated therefrom.
Having thus generally described the combination operation of the
present invention and discussed specific embodiments pertaining
thereto, it is to be understood that no undue restrictions are to
be imposed by reasons thereof except as defined by the following
claims. We claim:
* * * * *