U.S. patent number 3,803,027 [Application Number 05/310,762] was granted by the patent office on 1974-04-09 for process for conversion of residual oils.
This patent grant is currently assigned to Gulf Research & Development Company. Invention is credited to Robert D. Christman, Guglielmo Guelfi, Joel D. McKinney.
United States Patent |
3,803,027 |
Christman , et al. |
April 9, 1974 |
PROCESS FOR CONVERSION OF RESIDUAL OILS
Abstract
A process for hydrocracking petroleum stocks containing both
residual components and metallic contaminants employing a
particular catalyst. The catalyst is comprised of a metalliferous
hydrogenating component on a siliceous carrier and has a minimum
surface acidity and minimum Specific Volume of Pores, defined as an
inter-relationship of density, pore volume and pore-size
distribution.
Inventors: |
Christman; Robert D. (Penn
Hills, PA), Guelfi; Guglielmo (Milano, IT),
McKinney; Joel D. (Indiana Township, PA) |
Assignee: |
Gulf Research & Development
Company (Pittsburgh, PA)
|
Family
ID: |
26735667 |
Appl.
No.: |
05/310,762 |
Filed: |
November 30, 1972 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
56748 |
Jul 20, 1970 |
|
|
|
|
Current U.S.
Class: |
208/111.3;
208/111.35; 208/216R; 208/216PP |
Current CPC
Class: |
B01J
35/10 (20130101); C10G 47/12 (20130101); B01J
37/26 (20130101); B01J 35/1042 (20130101); B01J
35/1019 (20130101); B01J 35/1061 (20130101); B01J
35/1038 (20130101) |
Current International
Class: |
B01J
35/00 (20060101); B01J 37/26 (20060101); B01J
37/00 (20060101); B01J 35/10 (20060101); C10G
47/12 (20060101); C10G 47/00 (20060101); C10g
013/02 (); C10g 031/14 () |
Field of
Search: |
;208/111 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Parent Case Text
This application is a continuation-in-part of our copending
application Ser. No. 56,748, filed July 20, 1972, now abandoned.
Claims
1. A process for hydrocracking a petroleum oil containing residual
components and metallic contaminants, which process comprises
contacting the oil at hydrocracking conditions with hydrogen and a
catalyst comprising a metalliferous hydrogenating component
composited with a siliceous carrier containing at least about 15
percent by weight of silica based upon the carrier, the carrier
having a surface acidity of at least about 6 cc. of ammonia per
gram of carrier measured at a nominal temperature of 340.degree.F.,
and the catalyst having an inter-relationship of compacted density,
total pore volume and volume percent pore volume of pores having
radii in the range from 50 to 300 A
2. The process of claim 1 wherein the Specific Volume of Pores is
at least
3. The process of claim 1 wherein the compact density is in the
range from about 0.3 to about 0.8 grams per cc., the total pore
volume is in the range from about 0.4 to about 0.8 cc per gram and
the volume percent of the total pore volume in the form of pores
having radii in the range of
4. The process of claim 1 wherein at least 50 percent of the total
pore
5. The process of claim 1 wherein the ratio of pore volume of pores
having a radius from 50 to 100 A to the pore volume of pores having
a radius from
6. The process of claim 1 wherein the catalyst carrier contains
from about
7. The process of claim 1 wherein the carrier has a surface acidity
greater
8. The process of claim 1 wherein the metalliferous hydrogenating
component is selected from the group consisting of Group VI and
Group VIII metals,
9. The process of claim 1 wherein the petroleum oil contains at
least about
10. The process of claim 1 wherein the petroleum oil contains at
least about 10 parts per million by weight of contaminant metals.
Description
Our invention relates to a process for hydrocracking petroleum
stocks containing residual components and metallic contaminants.
More particularly, our invention is directed to such a process
employing a siliceous catalyst having a particular surface acidity
and a particular inter-relationship of density, pore volume and
pore-size distribution.
Residual petroleum oil fractions are relatively less valuable than
lighter distillate fractions and thus the desirability of
converting the comparatively higher boiling residual materials to
lower boiling, more valuable products, such as gasoline and furnace
oil, is well recognized. While the hydrocracking of such residual
stocks has previously been suggested, such previous hydrocracking
techniques suffer from the deficiency of comparatively short
catalyst life. It is believed that the shortened catalyst life
obtained in the hydrocracking of residual stocks is due to a very
great extent to contamination of the catalyst by deposition of
metals on the catalyst surface. The seriousness and magnitude of
this problem will be realized from a consideration of the following
items. First, it has generally been found that the degree of metals
removal from a hydrocarbon stock and thus the amount of metals
available for deposition on the catalyst is related to the extent
of the hydrocracking. Next, the severity of the conditions required
in treatment of a residual stock is quite high in order to effect
the extensive hydrocracking necessary to produce a satisfactory
yield of lower boiling materials. Finally, the residual components
of a petroleum stock are comprised of the larger, metals-containing
molecules and thus the preponderant portion of, if not the total,
metals content of a full crude is concentrated in the residual
fraction. It will be seen, therefore, that catalyst deactivation
due to deposition of contaminant metals on the catalyst presents a
severe obstacle to the extension of catalyst life in hydrocracking
residual stocks.
We have discovered a process for hydrocracking a petroleum oil that
contains residual components and metallic contaminants, while
effecting a decreased level of demetallization of feed stock but a
satisfactorily high level of conversion, which process comprises
contacting the oil at hydrocracking conditions with hydrogen and a
particular type catalyst. The particular catalyst to be employed in
our invention comprises a metalliferous hydrogenating component
composited with a siliceous carrier containing at least about 15
percent by weight of silica based upon the carrier. The siliceous
carrier must also have a surface acidity of at least about 6 cc. of
ammonia per gram of carrier (measured at a nominal temperature of
340.degree.F.) Additionally, the overall catalyst composite, i.e.,
hydrogenating components and siliceous carrier, must have a
particular inter-relationship of compacted density (D.sub.c)
expressed in grams per cc. (g/cc.), total pore volume (V.sub.t) of
pores having a radius in the range from 7 to 300 A expressed as cc.
per gram (cc/g) and volume per cent of the total pore volume in the
form of pores having radii in the range from 50 to 300 A (Z). This
inter-relationship is termed the Specific Volume of Pores (SVP) and
can be represented by the equation SVP = D.sub.c .times. V.sub.t
.times. Z.
The particular catalyst of our invention must have an SVP of at
least 20 and preferably at least about 22. Generally, the maximum
feasible value for SVP is considered to be about 40, although we
prefer to employ catalysts having an SVP no greater than about
35.
While the SVP itself is a determining factor in the selection of a
catalyst in accordance with our invention, the values of the
individual physical characteristics of the catalyst contributing to
the SVP are also important. Generally, the value of D.sub.c will be
greater than about 0.3 grams per cc. and preferably will be greater
than 0.4 grams per cc. Similarly, the value for D.sub.c generally
will not exceed about 0.8 grams per cc. and usually will be less
than about 0.7 grams per cc. We prefer, however, to employ
catalysts having a compacted density in the range from about 0.5 to
about 0.6 g/cc. The total pore volume (V.sub.t) will usually be at
least about 0.4 cc./g and preferably will be greater than 0.5 cc.
per gram. Generally, however, the value of V.sub.t will not be
greater than about 0.8 cc./g. The value for Z will generally be at
least about 50 per cent, preferably at least about 60 per cent, and
more preferably at least about 70 per cent or greater.
Additionally, we prefer that at least about 50 percent of the total
pore volume (V.sub.t) be in pores having radii in the range from 50
to 200 A and that the ratio of pore volume of pores having a radius
from 50 to 100 A to the pore volume of pores having a radius from
100 to 200 A be in the range from about 0.75:1 to about 1.5:1.
While the carrier employed in the catalyst of our invention must
have a silica content of at least 15 percent by weight based upon
the carrier, we prefer to employ a carrier containing at least 20
percent by weight silica and more preferably containing at least 30
percent by weight silica. Usually the maximum silica content of the
catalyst carrier of our invention will not exceed about 90 percent
by weight and generally the silica content will be less than 80
percent by weight. In this connection it should be noted that we
have found carriers having a silica content of less than about 70
percent to be quite satisfactory. Further, we prefer to employ
carriers having a surface acidity greater than 8 cc./g and
preferably greater than about 10 cc./g.
The metalliferous hydrogenating component employed in the catalyst
in our invention can be any of such materials well known in the art
or combinations of two or more of such materials. Generally, the
hydrogenating component can be any one or more of the Group VI or
Group VIII metals, their oxides or their sulfides, such as, for
example, nickel, cobalt, molybdenum, tungsten or Group VIII noble
metals. Usually combinations of these metalliferous components are
quite satisfactory, such as, for example, nickel-cobalt-molybdenum,
nickel-molybdenum, cobalt-molybdenum, and nickel-tungsten.
Additionally, the catalyst composites employed in our invention can
be promoted with a small quantity of a halogen such as, for
example, fluorine. Usually the halogen content can be in the range
from about 0.1 to 10 percent by weight based upon the total
catalyst and preferably from about 0.5 to 5 percent by weight. We
particularly prefer to employ fluorine as the halogen promoter in
the quantity from about 1 percent to about 3 percent by weight
based upon the total catalyst.
Catalysts of the type described above and suitable for employment
in our invention will have a surface area of at least about 100
M.sup.2 /g. and preferably will have a surface area in the range
from about 150 to about 300 M.sup.2 /g.
In the practice of our invention we prefer to employ catalysts of
comparatively small particle size, i.e., particles having a
smallest dimension of less than about 1/8 inch, preferably less
than about 1/16 inch, and more preferably about 1/32 inch or less.
Although it is not necessary that the entire catalyst bed be
composed of these small size particles, the proponderant portion of
the bed is preferably comprised of such small catalyst
particles.
Although it is not believed it is necessary to prepare the
catalysts required by our process in any particular manner,
satisfactory catalysts can be prepared by first synthesizing a
silica-alumina carrier in accordance with the general technique
described in U.S. Pat. No. 2,469,314. Broadly, the technique of
this patent comprises forming a silica sol which upon aging sets as
a firm hydrogel. This hydrogel is then admixed with a solution of
an aluminum salt and precipitation from the mixture is effected. In
keeping with the general teachings of U.S. Pat. No. 2,469,314,
particularly preferred procedures such as those described in U.S.
Pat. No. Re-issue 23,438 can also be employed to provide a suitable
silica-alumina carrier. After formation of this siliceous material,
it can be formed into particles of desired size and shape through
known techniques, such as, for example, extrusion. The
metalliferous hydrogenating components required by our process can
then be composited with the siliceous carrier by any of the
techniques well known in the catalyst art, such as, for example,
impregnation. It is believed that various other techniques for
producing catalysts of required characteristics will be evident to
those skilled in the catalyst art upon being informed of the
required physical properties to be possessed by the catalyst
employed herein.
The feed stock suitable for employment in our invention includes
any petroleum hydrocarbon stock containing a significant quantity
of residual components and metallic contaminants. As used herein
the terms "residual," "residue" and "residual fraction or
component" are meant to describe the most difficultly vaporizable
components of a petroleum oil which normally cannot be vaporized at
temperatures below that at which thermal decomposition or cracking
would occur at atmospheric pressure. These materials encompass the
highest boiling components of a crude oil. Generally, these
residual components or fractions can be separated from the lighter,
lower boiling components of a crude oil by employment of a vacuum
distillation. Normally a residue can be described as boiling above
about 1,050.degree.F. or 1,100.degree.F. Illustrative of petroleum
oils containing a significant quantity of residual components are
vacuum tower bottoms, atmospheric tower bottoms and reduced or
topped crudes.
Since the catalysts of the class disclosed herein appear to have
both the ability to effect extensive hydrocracking with diminished
demetallization of the treated stock and an especially high
tolerance for metallic contaminants normally tending to act as
catalyst poisons, the present process is particularly advantageous
in connection with the treatment of petroleum oils containing a
significant quantity of metallic components as are present in
residual fractions. This is not to say that the process of our
invention is not operative in the treatment of non-residual
containing distillate stocks, but the particular advantages
provided in accordance with our invention are not obtained when
hydrocracking completely distillate charge stocks. Accordingly,
therefore, the charge stock to our process is comprised of at least
10 percent by volume residual material and preferably at least
about 25 percent by volume residuals. It will be understood, of
course, that the process of our invention provides increasingly
advantageous results with increasing residual content of the charge
and that the maximum advantage is obtained when treating a 100
percent residual charge stock. Similarly, the charge stock to our
process will contain at least about 10 p.p.m. weight of contaminant
metals, such as for example, nickel and vanadium, and usually will
contain at least about 25 p.p.m. total metals content. Our
invention is particularly suitable for the treatment of residual
containing stocks which contain more than about 50 p.p.m. metals
and especially stocks which contain more than about 75 p.p.m.
metals.
The operating conditions employed in the hydrocracking operation of
our invention include a temperature in the range from about
650.degree.F. to about 900.degree.F., preferably in the range from
about 700.degree. to 850.degree.F. The pressure employed in this
process can be in the range from about 1,000 to 10,000 psig.
Preferably, we employ a hydrogen partial pressure in the range from
about 1,500 to about 5,000 psia with hydrogen partial pressures in
the range of 2,000 to about 3,000 psia being particularly
preferred. In this connection it should be pointed out that while
it is preferred to employ hydrogen of comparatively high purity
such as for example 85 percent by volume or greater, it is quite
satisfactory to employ hydrogen containing gas streams of the type
normally found in a refinery operation, such as for example,
reformer off gas, containing a minimum hydrogen concentration of
about 65 percent by volume. Generally, the hydrogen feed rate will
be in the range from about 2,000 to about 30,000 standard cubic
feet per barrel (SCF/B), preferably in the range from about 5,000
to about 15,000 SCF/B and more preferably in the range from 6,000
to about 12,000 SCF/B.
Normally, the amount of hydrogen consumed during our hydrocracking
operation will be at least about 300 SCF/B and can range up to
about 3,000 SCF/B, usually, however, hydrogen consumption will be
in the range from about 500 SCF/B up to about 1,500 to 2,000 SCF/B.
It will be understood, of course, that hydrogen consumption will
vary somewhat based upon the composition of the particular feed
stock being treated as well as, to a certain extent, upon the
selection of operating conditions.
In the hydrocracking operation of our invention, we also employ a
liquid hourly space velocity (LHSV) in the range from about 0.1 to
10 volumes of charge stock per volume of catalyst per hour.
Preferably, we employ an LHSV in the range from about 0.1 up to
about 1.0 or 2.0, with space velocities in the range from about 0.2
to about 0.5 being particularly preferred.
In order to illustrate our invention in greater detail, reference
is made to the following examples.
EXAMPLE I
In this example, a vacuum residue having the inspections shown in
Table 1 below was subjected to hydrocracking in two separate runs
employing an alumina-supported catalyst in one run and a
silica-alumina catalyst, as required by this invention, in the
other run.
Table 1 ______________________________________ Inspections Gravity
.degree.API 4.7 Sulfur, wt.% 5.61 Nitrogen, wt.% 0.44 Carbon
residue, ASTM D-524 wt.% 23.12 Nickel, PPM 38 Vanadium, PPM 142
Carbon, wt.% 83.68 Hydrogen, wt.% 9.88 Oxygen, wt.% 0.39
______________________________________
Both of the catalysts were 1/32 inch extrudates and were comprised
of nickel, cobalt and molybdenum as the hydrogenating
components.
The silica-alumina catalyst required in this invention was prepared
by first forming a silica sol at a pH of less than 7 and aging of
the sol to form a silica hydrogel, after which the hydrogel was
suspended in a solution of an aluminum salt and precipitation then
effected to produce a material containing about 25 percent by
weight alumina. This preparative technique is in accordance with
the disclosure of U.S. Pat. No. 2,469,314. This silica-alumina
material was then extruded to provide the 1/32 inch extrudates
mentioned above and the metalliferous hydrogenating components were
added by impregnation of the extrudates. More specifically, the
extrudates were first impregnated with a solution of ammonium
paramolybdate and then dried. After drying, the
molybdenum-containing extrudate was subjected to a second
impregnation with a solution of nickel and cobalt nitrates.
Subsequent to the second impregnation, the material was dried and
then calcined at 1,000.degree.F. Inspection data for both the
alumina supported catalyst and the silica-alumina catalyst required
in this invention are shown in Table 2 below.
Table 2
__________________________________________________________________________
Inspections Alumina Silica-alumina of this invention
__________________________________________________________________________
Compacted density, g/cc. 0.765 0.569 Surface acidity cc NH.sub.3 /g
(measured on support) at 342.degree.F. 9.48 11.26 Surface area
M.sup.2 /g 146.9 208.9 Pore vol. cc./g 0.47 0.58 Pore size
distribution, % of pore volume 200-300 A radius 4.0 ) 5.5 ) ) )
100-200 A radius 36.2 ) 78.1 27.9 ) 72.3 ) ) 50-100 A radius 37.9 )
38.9 ) 40-50 A radius 7.0 9.1 30-40 A radius 7.6 8.2 20-30 A radius
7.3 10.4 7-20 A radius 0.0 0.0 Specific vol. of pores cc./100 cc.
28.0 23.8
__________________________________________________________________________
After start up, both runs were continued for a period sufficient to
take the edge off the catalyst and to achieve lined out
operation.
The present discussion is directed to the main conversion portion
or lined out portion of the runs. At a throughput of about 130
volumes of feed per volume of catalyst, the temperature required to
maintain a 50 percent conversion was about 770.degree.F. for the
alumina based catalyst and about 775.degree.F. for the
silica-alumina based catalyst. At this same point in the runs the
alumina based catalyst removed about 98 weight per cent of the
metals, i.e. nickel and vanadium, present in the feedstock while
the silica-alumina based catalyst removed only about 88 percent of
the metals present in the feedstock. Both runs were continued and
the operating temperature of each run was adjusted so as to
maintain the 50 percent conversion. At a throughput of
approximately 200 volumes of feed per volume of catalyst the
temperature required to maintain the 50 percent conversion in the
run employing the alumina based catalyst had increased to about
775.degree.F. while the temperature required in the run employing
the silica-alumina based catalyst had increased to only about
778.degree.F. At this point in the runs, the alumina based catalyst
was still effective to remove approximately 98 percent of the
metals in the fresh feed while metals removal with the
silica-alumina supported catalyst had declined to about 84 percent.
Throughout the balance of the run the metals removal effected with
the alumina based catalyst remained substantially constant in the
range from about 97.5 to 98 percent metals removal. On the other
hand, however, the metals removal effected with the silica-alumina
based catalyst continued to decline to a level of about 55 percent,
or just slightly greater, at a throughput of about 740 volumes per
volume and then appeared to stabilize at about this level until the
run was terminated at a throughput of about 1,000 volumes per
volume.
During the operation of these runs the data further indicated that
the temperature required for maintenance of the 50 percent
conversion level with both catalysts was substantially equal at a
level of about 780.degree.F. in the period encompassing a
throughput from about 250 to about 260 volumes of feed per volume
of catalyst. Thereafter, temperature increase required to maintain
the 50 percent conversion in each of the runs continued at the same
rate that had previously been established so that the temperature
required to maintain the 50 percent conversion level with the
silica-alumina catalyst was only 782.degree.F. at a throughput of
340 volumes per volume, while a temperature of 786.degree.F. was
required at the same throughput with the alumina based catalyst.
From extrapolation of these data it can be determined that the
alumina based catalyst will reach a cut off temperature of
800.degree.F. in order to maintain a 50 percent conversion before
achieving a throughput of 550 volumes per volume, while the silica
alumina catalyst will require an operating temperature of only
788.degree.F. at a throughput of 550 volumes per volume. In fact
the run with the silica alumina based catalyst was continued and
required a temperature of 793.degree.F. to maintain the 50 percent
conversion at 600 volumes per volume throughput.
From this example it can be seen that, although the large-pored
alumina based catalyst may provide some temperature advantage over
the large-pored silica alumina based catalyst of this invention
during the earlier stages of operation, such temperature advantage
is rapidly lost. Further it can be seen that the overall rate of
deactivation of the alumina catalyst is substantially greater than
the deactivation rate of the silica-alumina catalyst of this
invention, thus showing that the silica-alumina based catalyst of
this invention will provide a substantially greater catalyst life
than that obtainable with the alumina based catalyst. It will also
be seen that this deactivation rate appears to be due primarily to
the greater metals removal effected by the alumina based catalyst
as compared to that produced by the silica-alumina based catalyst.
Moreover, it should be noted that the level of metals removal
achieved by the alumina catalyst is substantially constant
throughout the main conversion portion of the run while the level
of metals removal achieved with the silica-alumina based catalyst
of this invention advantageously decreases as the run progresses
and it is believed that this lower and decreasing rate of metals
removal of the silica-alumina based catalyst is effective to
increase further the life of such catalyst.
EXAMPLE II
In this example the same vacuum residue as employed in Example I
was subjected to hydrocracking in two separate runs employing the
silica-alumina catalyst of this invention as described in Example I
in one run and a second silica-alumina catalyst representative of
typical commercially available silica-alumina hydrocracking
catalysts in the other run. The catalysts employed in the runs of
this example were 1/32 inch extrudates comprised of nickel, cobalt
and molybdenum as the hydrogenating components. The inspection data
for the typical commercial silica-alumina catalyst are shown in
Table 3 below.
Table 3 ______________________________________ Inspections
Commercial Silica-alumina ______________________________________
Compacted density, g/cc. 0.757 Surface acidity cc NH.sub.3 /g
(measured on support) at 342.degree.F. 11.14 Surface area M.sup.2
/g 217.5 Pore vol. cc/g. 0.46 Pore size distribution, % of pore
vol. 200-300 A radius 2.0 ) ) 100-200 A radius 7.7 ) 54.4 ) 50-100
A radius 44.7 ) 40-50 A radius 14.9 30-40 A radius 13.4 20-30 A
radius 12.7 7-20 A radius 4.4 Specific vol. of pores cc/100 cc 19.0
______________________________________
Both of the runs of this example were conducted employing the
operating conditions of temperature, pressure and space velocity
shown in Table 4 below. Table 4 also shows the inspection data
obtained at various times during the course of the runs of this
example.
Table 4
__________________________________________________________________________
Silica-alumina of this Invention Catalyst Age:Days 9 33.5 66.5
109.5 121 LHSV vol./hr./vol. 0.35 Reactor temperature .degree.F.
775 780 790 815 820 (95% H2) Pressure:psig 2500 2500 2500 2800 2800
Inspections Gravity: .degree.API 18.7 18.1 14.5 12.7 12.7 Sulfur,
wt% 0.50 0.88 2.60 3.78 3.75 Nickel, ppm 5.1 8.4 22 21 -- Vanadium,
ppm 7.9 16 49 38 -- Distillation, vacuum 5% 507 492 489 454 448 10%
610 590 586 539 538 30% 896 868 877 862 843 40% 986 967 -- 999 --
Commercial Silica-Alumina Catalyst Age:Days 10.8 34.0 LHSV
vol./hr./vol. 0.35 0.35 Reactor temperature .degree.F. 775 790 (95%
H2) Pressure:psig 2500 3000 Inspections Gravity:.degree.API 23.3
13.7 Sulfur, wt% 0.31 3.46 Nickel:ppm 8.1 -- Vanadium:ppm 21 --
Distillation, vacuum 5% 508 536 10% 585 562 20% 712 747 30% 826 --
50% 1009 --
__________________________________________________________________________
From the data shown in Table 4 above, it will be seen that although
at a very early stage of operation (i.e., 9 days vs. 10.8 days) the
amount of metals removed employing the silica-alumina catalyst of
this invention was noticeably greater than the metals removal
provided by the commercial silica-alumina, the commercial
silica-alumina had become so deactivated by 34 days of operation
that a 15.degree. increase in operating temperature together with a
500 pound increase in pressure was ineffective to provide adequate
cracking activity to warrant continuation of the run. This can be
seen from the change in API gravity of product from 23.3 to 13.7
and an increase of the sulfur content of the product from 0.31 up
to 3.46 percent. During a comparable period of operation up to 33.5
days the silica-alumina catalyst of the present invention required
only a 5.degree.F. increase in operating temperature with no
alteration in pressure in order to maintain substantially a
constant level of conversion. This can be seen from the fact that
the API gravity and sulfur content of the product changed only
slightly. Quite significantly, however, it will be seen that the
amount of metals removal effected with the catalyst of this
invention had declined substantially from a total metals content in
the product of 13 ppm up to 24.4 ppm.
Further examination of the above data will show that at 66.5 days
of operation the silica-alumina catalyst of this invention required
a temperature of only 790.degree.F. and a pressure of 2,500 psig in
order to provide a conversion level noticeably greater than that
obtained after only 34 days of operation with the commercial
silica-alumina. Additionally, it will be noted that a further
decrease in metals removal was effected during the period from 33.5
to 66.5 days.
The remaining data regarding the run employing the silica-alumina
catalyst of this invention demonstrate the continued sufficiency of
activity of such catalyst so as to permit operation for a period
extending through 120 days. Thus, it can be seen that the
silica-alumina based catalyst of this invention, although showing a
somewhat higher metals removal during earlier stages of operation
as compared to the commercial silica-alumina, demonstrates a
reduction in the rate of metals removal as the time on stream
progresses and tends to stabilize at this reduced rate of metals
removal. Further, it would appear that the silica-alumina catalyst
of this invention is capable of retaining its cracking activity
while tolerating a greater quantity of metal deposition. On the
other hand, however, the commercial silica-alumina, although
showing an initial lower rate of metals deposition, evidently
deactivates extremely rapidly apparently due to the fact that such
catalyst cannot tolerate any significant quantity of deposited
metals before showing a decline in activity to a completely
unsatisfactory level.
EXAMPLE III
In this example the same vacuum residue as employed in Examples I
and II was subjected to hydrocracking in two separate runs
employing in one run the silica-alumina catalyst of this invention
as described in Example I and in the other run a second
silica-alumina catalyst of comparable specific volume of pores but
with a low surface acidity, outside the range required by the
present invention. Again as in Examples I and II, the catalysts
employed in the runs of this example were 1/32 inch extrudates
comprised of nickel, cobalt and molybdenum as the hydrogenating
components. The inspection data for the low surface acidity
silica-alumina catalyst are shown in Table 5 below.
Table 5
__________________________________________________________________________
Inspections Low Acidity Silica-Alumina
__________________________________________________________________________
Compacted density, g/cc 0.768 Surface acidity cc NH.sub.3 /g
(measured on support) at 342.degree.F. 4.7 Surface area M.sup.2 /g
128.6 Pore vol. cc/g 0.41 Pore size distribution % of pore vol.
200-300 A radius 1.5 ) ) 100-200 A radius 18.7 ) 81.9 ) 50-100 A
radius 61.7 ) 40-50 A radius 9.1 30-40 A radius 6.3 20-30 A radius
2.5 7-20 A radius 0.0 Specific vol. of pores cc/100 cc 25.8
__________________________________________________________________________
It will be recalled that the silica-alumina of this invention
described in Example I had a surface acidity of 11.26 and a
specific volume of pores of 23.9.
The particular operating conditions employed for the two runs of
this example together with charge stock and products inspections
are set forth in Table 6 below.
Table 6
__________________________________________________________________________
Silica-alumina Silica-alumina low surface Catalyst of this
Invention acidity
__________________________________________________________________________
Age: Days 9 7.7 LHSV vol./hr./vol. 0.35 0.35 Reactor temperature:
.degree.F. 775 775 (95% H.sup.2) Pressure: psig 2500 2500
Inspections Charge Gravity: .degree.API 4.7 18.7 16.9 Sulfur: wt.%
5.61 0.50 0.48 Nitrogen: wt.% 0.44 0.19 0.19 Carbon Residue: wt.%
23.12 6.89 6.70 Nickel: ppm 28 5.1 3.9 Vanadium: ppm 142 7.9 6.0
Distillation vacuum, .degree.F. 5% 507 543 10% 610 637 20% 776 776
30% 896 894 40% 986 1001
__________________________________________________________________________
From the data of Table 6 above it will be seen that under
substantially comparable operating conditions the silica-alumina
catalyst of the present invention was effective at 9 days of
operation to provide a satisfactory degree of hydrocracking as
indicated by the product API gravity of 18.7 and the production of
substantial quantities of lower boiling components. As
distinguished from this, the silica-alumina catalyst of low surface
acidity, after a comparatively shorter period of operation, had a
noticeably lower cracking activity than the catalyst of this
invention as can be seen from the API gravity of the product (16.9)
as well as the smaller quantity of lower boiling components in the
product. Furthermore, it will be noted that the product obtained
with the low surface acidity silica-alumina catalyst contained
somewhat less than 10 parts per million of metals while the product
obtained with the catalyst of our invention contained 13 parts per
million of metals.
* * * * *