U.S. patent application number 13/715959 was filed with the patent office on 2014-06-19 for hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units.
The applicant listed for this patent is Julie Chabot, Bo Kou, Alexander Kuperman. Invention is credited to Julie Chabot, Bo Kou, Alexander Kuperman.
Application Number | 20140166541 13/715959 |
Document ID | / |
Family ID | 49725334 |
Filed Date | 2014-06-19 |
United States Patent
Application |
20140166541 |
Kind Code |
A1 |
Chabot; Julie ; et
al. |
June 19, 2014 |
HYDROPROCESSING CO-CATALYST COMPOSITIONS AND METHODS OF
INTRODUCTION THEREOF INTO HYDROPROCESSING UNITS
Abstract
A hydroprocessing co-catalyst composition may comprise in an
embodiment a first component comprising co-catalyst particles and a
liquid carrier, and a second component comprising a dispersant and
a dispersant diluent. The co-catalyst particles may be in the
micron size range, and the dispersant may promote dispersion of the
co-catalyst particles in materials such as the liquid carrier, the
dispersant diluent, and combinations thereof. Methods of
introducing a hydroprocessing co-catalyst composition into a
hydroprocessing system are also disclosed.
Inventors: |
Chabot; Julie; (Novato,
CA) ; Kou; Bo; (Richmond, CA) ; Kuperman;
Alexander; (Richmond, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chabot; Julie
Kou; Bo
Kuperman; Alexander |
Novato
Richmond
Richmond |
CA
CA
CA |
US
US
US |
|
|
Family ID: |
49725334 |
Appl. No.: |
13/715959 |
Filed: |
December 14, 2012 |
Current U.S.
Class: |
208/213 ;
208/251H; 208/254H; 208/264 |
Current CPC
Class: |
C10G 45/04 20130101;
C10G 45/16 20130101 |
Class at
Publication: |
208/213 ;
208/251.H; 208/254.H; 208/264 |
International
Class: |
C10G 45/04 20060101
C10G045/04 |
Claims
1. A method of introducing co-catalyst particles into a
hydroprocessing system, the method comprising: a) providing a
composition A comprising the co-catalyst particles and a liquid
carrier; b) providing a composition B comprising a dispersant and a
dispersant diluent; c) combining composition B with composition A
to form a composition C, wherein composition C comprises a
suspension of the co-catalyst particles; and d) after step c),
contacting the co-catalyst particles with a hydrocarbon feed of the
hydroprocessing system.
2. The method of claim 1, wherein step d) comprises contacting the
co-catalyst particles with the hydrocarbon feed such that the
co-catalyst particles are entrained with the hydrocarbon feed
within the hydroprocessing system.
3. The method of claim 1, wherein the dispersant comprises
polyisobutylene succinimide.
4. The method of claim 3, wherein the dispersant further comprises
a material selected from the group consisting of carboxylic acids,
dicarboxylic acids, and combinations thereof.
5. The method of claim 3, wherein the dispersant further comprises
oleic acid.
6. The method of claim 1, wherein: the co-catalyst particles have a
mean particle size between about 2 microns and 100 microns, and the
co-catalyst particles comprise a support comprising a material
selected from the group consisting of alumina, aluminosilicates,
silica, boria, magnesia, titania, and combinations thereof.
7. The method of claim 1, wherein the co-catalyst particles have a
mean particle size between about 4 microns and 40 microns.
8. The method of claim 1, wherein composition A comprises from
about 5 wt. % to 50 wt. % of the co-catalyst particles and from
about 50 wt. % to 95 wt. % of the liquid carrier.
9. The method of claim 1, wherein the liquid carrier comprises
oil.
10. The method of claim 9, wherein: the co-catalyst particles are
hydrophilic, and step a) comprises suspending the co-catalyst
particles in the liquid carrier.
11. The method of claim 1, wherein the liquid carrier comprises a
material selected from the group consisting of vacuum gas oil,
light vacuum gas oil, heavy vacuum gas oil, lube oil base stock,
heavy diesel, and combinations thereof.
12. The method of claim 1, wherein the hydrocarbon feed comprises
heavy oil feedstock having a boiling range up to at least about
650.degree. F.
13. The method of claim 1, wherein during step d) the hydrocarbon
feed is at a temperature in the range from about 350.degree. F. to
750.degree. F.
14. The method of claim 1, further comprising: e) prior to step d),
diluting composition C with a catalyst introduction diluent to
provide a diluted suspension of the co-catalyst particles.
15. The method of claim 14, wherein: the catalyst introduction
diluent comprises oil having a boiling range from about 350.degree.
F. to 1125.degree. F., and during step e) the catalyst introduction
diluent is at a temperature in the range from about ambient
temperature to 700.degree. F.
16. A method of introducing co-catalyst particles into a
hydroprocessing system, the method comprising: a) providing a
composition A comprising the co-catalyst particles and a liquid
carrier, wherein the co-catalyst particles have a mean particle
size between about 2 microns and 100 microns, and the liquid
carrier comprises oil; b) providing a composition B comprising a
dispersant and a dispersant diluent; c) combining composition A
with composition B to form a composition C; and d) contacting
composition C with a hydrocarbon feed of the hydroprocessing
system.
17. The method of claim 16, wherein: the hydrocarbon feed comprises
heavy oil feedstock having a boiling range up to at least about
650.degree. F., and during step d) the hydrocarbon feed is at a
temperature in the range from about 350.degree. F. to 750.degree.
F.
18. The method of claim 16, wherein step d) comprises contacting
composition C with the hydrocarbon feed such that the co-catalyst
particles are entrained with the hydrocarbon feed within the
hydroprocessing system.
19. A method of introducing co-catalyst particles into a
hydroprocessing system, the method comprising: a) providing a
composition A comprising the co-catalyst particles and a liquid
carrier, wherein the co-catalyst particles comprise a support
comprising a material selected from the group consisting of
alumina, aluminosilicates, silica, boria, magnesia, titania, and
combinations thereof, and the co-catalyst particles have a mean
particle size between about 2 microns and 100 microns; b) providing
a composition B comprising a dispersant and a dispersant diluent;
c) combining composition B with composition A to form a composition
C, wherein composition C comprises a suspension of the co-catalyst
particles; and d) contacting composition C with a hydrocarbon feed
of the hydroprocessing system such that the co-catalyst particles
are entrained with the hydrocarbon feed within the hydroprocessing
system.
20. The method of claim 19, wherein composition C is miscible with
the hydrocarbon feed, and the hydrocarbon feed comprises heavy oil
feedstock having a boiling range up to at least about 650.degree.
F.
Description
TECHNICAL FIELD
[0001] The present invention relates to hydroprocessing co-catalyst
compositions and methods of introduction thereof into
hydroprocessing units.
BACKGROUND
[0002] Heavy feedstocks, such as vacuum gas oils and residuum,
contain relatively high concentrations of S-, N-, O-, and
polynuclear aromatic containing compounds, as well as complex Ni-
and V-containing compounds and asphaltenes. As a result, heavy oil
is particularly difficult to upgrade in refinery operations. Metals
contained in the oil tend to rapidly deactivate catalysts with
which they come in contact during the upgrading process. In
addition, sulfur and nitrogen are difficult to remove to the extent
necessary for further processing of the upgraded products from
heavy oil processing.
[0003] Furthermore, heavy oil components thermally crack during
processing to form free radicals, which quickly combine to make
sediment and coke precursors unless suppressed by active catalysis.
During conventional hydroprocessing of heavy oils, high molecular
weight coke precursors and contaminants that are deposited on
catalysts quickly reduce catalytic activity.
[0004] One type of conventional heavy oil processing uses an
ebullated bed system, in which the catalyst is maintained in a
fluidized state within the reaction zone. At periodic intervals, a
portion of the fluidized bed of catalyst, along with a small
portion of fluidizing liquid, is removed from the system. A
comparable amount of catalyst is added to the system to maintain a
constant quantity of catalyst in the system at any one time.
[0005] In conventional heavy oil upgrading, e.g., using an
ebullated bed system that relies solely on a conventional
pelletized hydroprocessing catalyst, poorly converted or
unconverted feed may precipitate as sediment or sludge. Sediment
can then plug equipment leading to shorter runtime and/or
operational issues, as well as poor product quality. The formation
of sediment or sludge typically increases with conversion and feed
difficulty. For this reason, the conversion or ability to process a
flexible array of feeds is limited in these units.
[0006] Thus, there is a need for improved hydroprocessing catalyst
systems that are more efficient, permit an increase in conversion
and/or the use of a wider range of feedstocks in a cost-effective
manner, as compared with the prior art. There is a further need for
methods of introducing a co-catalyst into a hydroprocessing
unit.
SUMMARY
[0007] One embodiment of the invention is a hydroprocessing
co-catalyst composition comprising a liquid carrier comprising oil
and co-catalyst particles in admixture with the liquid carrier,
wherein the co-catalyst particles are hydrophilic and have a mean
particle size between about 2 microns and 100 microns.
[0008] Another embodiment of the invention is a hydroprocessing
co-catalyst composition comprising co-catalyst particles having a
mean particle size between about 2 microns and 100 microns, and a
liquid carrier in admixture with the co-catalyst particles, wherein
the composition comprises from about 5 wt. % to 50 wt. % of the
co-catalyst particles, and the liquid carrier comprises oil.
[0009] A further embodiment of the invention is a hydroprocessing
co-catalyst composition comprising a liquid carrier comprising oil
having a boiling range from about 350.degree. F. to 1125.degree.
F., and co-catalyst particles having a mean particle size between
about 4 microns and 40 microns; wherein the composition comprises
from about 5 wt. % to 50 wt. % of the co-catalyst particles and the
co-catalyst particles comprise a support comprising a material
selected from alumina, aluminosilicates, silica, boria, magnesia,
titania, and combinations thereof.
[0010] In yet another embodiment, the invention is a
hydroprocessing co-catalyst comprising a composition A comprising a
liquid carrier and co-catalyst particles having a mean particle
size between about 2 microns and 100 microns, and a composition B
comprising a dispersant and a dispersant diluent.
[0011] In still a further embodiment, the invention is a
hydroprocessing co-catalyst comprising a liquid carrier,
co-catalyst particles having a mean particle size between about 2
microns and 100 microns, a dispersant, and a dispersant diluent,
wherein the hydroprocessing co-catalyst comprises from about 3 wt.
% to 50 wt. % of the co-catalyst particles.
[0012] In yet a further embodiment, the invention is a
hydroprocessing co-catalyst prepared by a method comprising the
steps of providing a composition A comprising co-catalyst particles
and a liquid carrier, providing a composition B comprising a
dispersant and a dispersant diluent, and combining composition A
with composition B to provide a suspension of the co-catalyst
particles.
[0013] In another embodiment, the invention comprises a method of
introducing co-catalyst particles into a hydroprocessing system,
the method comprising providing a composition A comprising the
co-catalyst particles and a liquid carrier; providing a composition
B comprising a dispersant and a dispersant diluent; combining
composition B with composition A to form a composition C, wherein
composition C comprises a suspension of the co-catalyst particles;
and after the combining step, contacting the co-catalyst particles
with a hydrocarbon feed of the hydroprocessing system.
[0014] In a further embodiment the invention is a method of
introducing co-catalyst particles into a hydroprocessing system,
the method comprising providing a composition A comprising the
co-catalyst particles and a liquid carrier, wherein the co-catalyst
particles have a mean particle size between about 2 microns and 100
microns, and the liquid carrier comprises oil; providing a
composition B comprising a dispersant and a dispersant diluent;
combining composition A with composition B to form a composition C;
and contacting composition C with a hydrocarbon feed of the
hydroprocessing system.
[0015] In yet another embodiment the invention is a method of
introducing co-catalyst particles into a hydroprocessing system,
the method comprising providing a composition A comprising the
co-catalyst particles and a liquid carrier; providing a composition
B comprising a dispersant and a dispersant diluent; combining
composition B with composition A to form a composition C, wherein
composition C comprises a suspension of the co-catalyst particles;
and contacting composition C with a hydrocarbon feed of the
hydroprocessing system such that the co-catalyst particles are
entrained with the hydrocarbon feed within the hydroprocessing
system. The co-catalyst particles may comprise a support comprising
a material selected from alumina, aluminosilicates, silica, boria,
magnesia, titania, and combinations thereof, and the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns.
[0016] As used herein, the terms "comprising" and "comprises" mean
the inclusion of named elements or steps that are identified
following those terms, but not necessarily excluding other unnamed
elements or steps.
DETAILED DESCRIPTION
[0017] The upgrading of residuum and other heavy feedstocks in
hydroprocessing units is an important process in petroleum refining
for producing higher value products. One type of heavy oil
hydroprocessing unit uses an ebullated bed system, in which the
catalyst is maintained in a fluidized state within the reaction
zone.
[0018] An ebullated bed heavy oil processing system that employs a
dual catalyst system for heavy oil hydroprocessing is disclosed,
for example, in commonly assigned co-pending U.S. patent
application Ser. No. 13/331,479, Hydroprocessing catalysts and
methods for making thereof filed Dec. 20, 2011, the disclosure of
which is incorporated by reference herein in its entirety.
[0019] Disclosed herein are new co-catalyst compositions, which
greatly augment the catalytic activity of conventional pellet
hydroprocessing catalysts to enhance the performance of
hydroprocessing units, such as LC-Fining and H-Oil ebullated bed
units, for processing heavy oil feedstocks. In contrast to the
prior art, micron-sized solid particles of co-catalyst may be
suspended in, and move with, the residuum feed stream, such that
the co-catalyst particles may percolate not only through the
ebullated bed reaction zone, but also throughout the
hydroprocessing unit. Because particles of the co-catalyst
disclosed herein can migrate with the feed stream through the
hydroprocessing unit, the co-catalyst provides substantial
additional catalytic activity to enhance residuum conversion, while
minimizing the formation of undesirable sediment or sludge.
[0020] In addition, the co-catalyst particles provide additional
surface area and pore volume to adsorb contaminants from the
residuum feed, resulting in reduced aging of the ebullated bed
portion of the hydroprocessing catalyst system and a much longer
runtime for the hydroprocessing unit.
[0021] Accordingly, the addition of the co-catalyst to an ebullated
bed hydroprocessing unit allows for improved operation, including
increased heavy oil feedstock conversion, and/or the ability to
process more difficult (e.g., heavier and/or more contaminated)
feeds.
[0022] In an embodiment, the performance of the co-catalyst, e.g.,
in an ebullated bed hydroprocessing unit, may be increased by
achieving good dispersion of the micron-sized solid co-catalyst
particles into the hydrocarbon feed (e.g., residuum). Such
dispersion of the co-catalyst particles in the feed may be enabled
not only by various chemical and physical attributes of the
co-catalyst composition, but also by novel methods and approaches,
as disclosed herein, for introducing the co-catalyst into the
hydroprocessing unit.
[0023] In an embodiment, the co-catalyst composition may be
miscible with a catalyst introduction diluent comprising a
hydrocarbonaceous oil, and the catalyst introduction diluent may be
combined with the co-catalyst composition before introducing the
diluent/co-catalyst mixture into the residuum feed. In another
embodiment, the co-catalyst composition may be miscible with the
residuum feed itself. In an embodiment, compositions as disclosed
herein may be safely and conveniently handled and transported.
[0024] Therefore, the co-catalyst compositions as provided herein
provide many advantages for heavy oil hydroprocessing as compared
with the prior art, including the major economic advantage of
enhancing the conversion and/or allowing for more difficult
feedstocks to be processed without the typical increase in sediment
or sludge make associated with such more severe operation.
[0025] As used herein, "heavy oil" feed or feedstock refers to
heavy and ultra-heavy crudes, including but not limited to resids,
coals, bitumen, tar sands, oils obtained from the
thermo-decomposition of waste products, polymers, biomasses, oils
deriving from coke and oil shales, and the like. Heavy oil
feedstock may be liquid, semi-solid, and/or solid. Examples of
heavy oil feedstock include but are not limited to Canada Tar
sands, vacuum resid from Brazilian Santos and Campos basins,
Egyptian Gulf of Suez, Chad, Venezuelan Zulia, Malaysia, and
Indonesia Sumatra. Other examples of heavy oil feedstock include
residuum left over from refinery processes, including "bottom of
the barrel" and "residuum" (or "resid"), atmospheric tower bottoms,
which have a boiling point of at least 650.degree. F. (343.degree.
C.), or vacuum tower bottoms, which have a boiling point of at
least 975.degree. F. (524.degree. C.), or "resid pitch" and "vacuum
residue" which have a boiling point of 975.degree. F. (524.degree.
C.) or greater.
Co-Catalyst Compositions for Hydroprocessing
[0026] In an embodiment, a hydroprocessing co-catalyst composition
may comprise a first component comprising co-catalyst particles and
a second component comprising a dispersant. Herein, the first
component may be referred to as Composition A, and the second
component may be referred to as Composition B.
i) Composition A
[0027] In an embodiment we provide a Composition A, which may
comprise a liquid carrier and co-catalyst particles. The
co-catalyst particles may be in admixture with the liquid carrier.
In an embodiment, the liquid carrier may comprise oil. Such oil may
comprise, for example, petroleum derived oil. In an embodiment, oil
comprising the liquid carrier may have a boiling range from about
350.degree. F. to 1125.degree. F., or from about 550.degree. F. to
1100.degree. F., or from about 550.degree. F. to 950.degree. F. As
a non-limiting example, the liquid carrier may comprise a material
selected from vacuum gas oil, light vacuum gas oil, heavy vacuum
gas oil, lube oil base stock, heavy diesel, and combinations
thereof.
[0028] In an embodiment, the co-catalyst particles may be
hydrophilic. The co-catalyst particles may comprise a support. The
support may comprise a material selected from alumina,
aluminosilicates, silica, as well as other refractory inorganic
oxides, including boria, magnesia, titania, and the like and
combinations thereof. The co-catalyst support of the present
invention can be manufactured by any conventional techniques. In an
embodiment, the co-catalyst particles may further comprise one or
more metal components. In an embodiment, the support or base may
contain catalytic metals, in particular metals from Group VIB of
the Periodic Table, including molybdenum and/or tungsten, and/or
from Group VIII of the Periodic Table, in particular nickel and/or
cobalt. Catalytic metals may be placed onto the support by
conventional techniques, including comulling, impregnation, and the
like.
[0029] In an embodiment, the co-catalyst particles may be
synthesized, ground or milled to achieve co-catalyst particles
having a particle size in the range from about 1 micron (.mu.m) to
100 microns, or from about 2 microns to 60 microns, or from about 2
microns to 30 microns. In another embodiment, the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns, or between about 4 microns and 40 microns, or between
about 4 microns and 30 microns.
[0030] In an embodiment, the co-catalyst particles may be suspended
in the liquid carrier. In an embodiment, the co-catalyst particles
may be suspensible in the liquid carrier in the absence of an
extrinsic dispersant. In an embodiment, a liquid carrier may itself
contain one or more intrinsic dispersive agents that promote
dispersion of the co-catalyst particles in the liquid carrier, such
that the liquid carrier is inherently capable of suspending the
co-catalyst particles therein without the addition of an extrinsic
dispersant to the liquid carrier or to the co-catalyst
particles.
[0031] In an embodiment, Composition A may comprise from about 5
wt. % to 50 wt. % of the co-catalyst particles, in another
embodiment from about 10 wt. % to 40 wt. %, or in a further
embodiment from about 15 wt. % to 30 wt. %. In an embodiment,
Composition A may comprise from about 50 wt. % to 95 wt. % of the
liquid carrier, or from about 60 wt. % to 90 wt. %, or from about
70 wt. % to 85 wt. %.
[0032] In an embodiment, the co-catalyst particles may be
synthesized or prepared, e.g., by grinding, milling, and the like,
using techniques and equipment known in the art, including but not
limited to: hammer mill, roller mill, ball mill, jet mill,
attrition mill, grinding mill, media agitation mill, and the like,
or utilizing synthesis techniques known in the art, including
precipitation, atomization, gelling and the like. The co-catalyst
particles may be sorted to provide suitable size distributions,
e.g., according to a particular requirement or application of a
co-catalyst composition.
[0033] In an embodiment, Composition A may have a viscosity, at
about 70.degree. F., in the range from about 1000 centipoise to
5000 centipoise, in another embodiment from about 1500 centipoise
to 4000 centipoise, or in a further embodiment from about 2000
centipoise to 3500 centipoise.
ii) Composition B
[0034] In an embodiment, Composition B may comprise a dispersant
and a dispersant diluent. In an embodiment, the dispersant may be
in admixture with the dispersant diluent. As an example, the
dispersant may comprise one or more components that are capable of
promoting dispersion of co-catalyst particles in a lipophilic
liquid. Such component(s) may comprise, for example, surface active
materials, such as non-ionic, anionic, cationic, or amphoteric
surfactants.
[0035] In an embodiment, the dispersant may be added to the
dispersant diluent in an amount such that Composition B may
comprise from about 10 wt. % to 95 wt. % of the dispersant, or from
about 20 wt. % to 80 wt. %, or from about 30 wt. % to 70 wt. %. In
one embodiment, the dispersant may be in the liquid state over a
broad temperature range, for example, from about 65.degree. F. to
500.degree. F., or from about 70.degree. F. to 350.degree. F.
[0036] In an embodiment, the dispersant may comprise a plurality of
components. In an embodiment, the dispersant may comprise
polyisobutylene succinimide. In an embodiment, the dispersant may
further comprise a material selected from carboxylic acids,
dicarboxylic acids, and combinations thereof. In one embodiment,
the dispersant may comprise polyisobutylene succinimide and a
carboxylic acid such as oleic acid. In a sub-embodiment,
Composition B may comprise from about 10 wt. % to 30 wt. % of
polyisobutylene succinimide and from about 30 wt. % to 65 wt. % of
oleic acid.
[0037] In an embodiment, the dispersant diluent may comprise oil.
In an embodiment, oil comprising the dispersant diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the dispersant
diluent may comprise a material selected from vacuum gas oil, light
vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavy
diesel, and combinations thereof.
iii) Composition C
[0038] In another embodiment we provide a Composition C, which may
comprise a hydroprocessing co-catalyst composition for introduction
or incorporation into a hydroprocessing system. In an embodiment.
Composition C may be used, for example, as an adjunct to a
conventional catalyst in a hydroprocessing (e.g., ebullated bed)
system for hydroprocessing a heavy hydrocarbon feed.
[0039] Composition C may comprise Composition A (supra) and
Composition B (supra). In an embodiment, Composition A and
Composition B may be provided in separate containers or vessels. As
an example, Composition A may be provided, or contained, in a first
vessel, and Composition B may be provided, or contained, in a
second vessel. In another embodiment, Composition C may comprise
Composition A in admixture with Composition B.
[0040] Composition A may comprise a liquid carrier and co-catalyst
particles, as described hereinabove. Composition B may comprise a
dispersant and a dispersant diluent, also as described hereinabove.
Composition C may be prepared by combining Composition A with
Composition B. In an embodiment, Composition A and Composition B
may be combined at a Composition A/Composition B volume ratio in
the range from about 1:20 to 60:1, or from about 1:10 to 50:1, or
from about 1:5 to 45:1, to provide Composition C. In an embodiment,
the liquid carrier of Composition A may be miscible with the
dispersant diluent of Composition B to form a single phase
homogeneous liquid.
[0041] In another embodiment, Composition C may be prepared by
separately combining one or more dispersant components with
Composition A. As an example, one or more materials selected from
polyisobutylene succinimide, carboxylic acids, and dicarboxylic
acids, may be added separately to Composition A.
[0042] Composition C may comprise a suspension of the co-catalyst
particles dispersed in a mixture of the liquid carrier and the
dispersant diluent. In an embodiment, Composition C may comprise a
slurry. Composition C may have a viscosity, at a temperature of
about 70.degree. F. in the range from about 100 centipoise to 3000
centipoise, or from about 150 centipoise to 2000 centipoise, or
from about 200 centipoise to 1000 centipoise. In an embodiment,
each of the liquid carrier and the dispersant diluent may comprise
oil.
[0043] In an embodiment, the co-catalyst particles may comprise a
support. The support may comprise a material selected from alumina,
aluminosilicates, silica, as well as other refractory inorganic
oxides, including boria, magnesia, titania, and the like, and
combinations thereof. The co-catalyst support of the present
invention can be manufactured by any conventional techniques. In an
embodiment, the co-catalyst particles may further comprise one or
more active metal components. In an embodiment, the support or base
may contain catalytic metals, in particular metals from Group VIB
of the Periodic Table, including molybdenum and/or tungsten, and/or
from Group III of the periodic Table, in particular nickel and/or
cobalt. Catalytic metals may be placed onto the support by
conventional techniques, including comulling, impregnation, and the
like.
[0044] In an embodiment, the co-catalyst particles may have a
particle size in the range from about 1 micron (.mu.m) to 100
microns, or from about 2 microns to 60 microns, or from about 2
microns to 30 microns. In another embodiment, the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns, or between about 4 microns and 40 microns, or between
about 4 microns and 30 microns. In an embodiment, Composition C may
comprise from about 3 wt. % to 50 wt. % of the co-catalyst
particles, or from about 5 wt. % to 40 wt. %, or from about 10 wt.
% to 30 wt. %.
[0045] The dispersant may comprise polyisobutylene succinimide. In
an embodiment, the dispersant may comprise a plurality of
components. In an embodiment, the dispersant may comprise a
material selected from carboxylic acids, dicarboxylic acids, and
combinations thereof. In a sub-embodiment, the dispersant may
comprise polyisobutylene succinimide and oleic acid.
[0046] In an embodiment, the dispersant diluent may comprise oil.
In an embodiment, oil comprising the dispersant diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the dispersant
diluent may comprise a material selected from vacuum gas oil, light
vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavy
diesel, and combinations thereof.
[0047] In an embodiment, the dispersant diluent may be miscible
with the liquid carrier to form a single phase homogeneous liquid.
In an embodiment, the dispersant diluent may comprise a first oil,
and the liquid carrier may comprise a second oil. The first oil and
the second oil may be the same or different. In another embodiment,
each of the first oil and the second oil may comprise vacuum gas
oil or lube oil base stock.
[0048] In another embodiment, Composition C may comprise
co-catalyst particles, a liquid carrier, a dispersant, and a
dispersant diluent. The liquid carrier may be miscible with the
dispersant diluent to form a single phase homogeneous liquid, and
Composition C may comprise a suspension of the co-catalyst
particles dispersed in the homogeneous liquid. In an embodiment,
each of the liquid carrier and the dispersant diluent may comprise
oil.
[0049] In an embodiment, Composition C may comprise from about 3
wt. % to 50 wt. % of the co-catalyst particles, or from about 5 wt.
% to 40 wt. %, or from about 10 wt. % to 30 wt. %. In an
embodiment, the co-catalyst particles may have a particle size in
the range from about 1 micron (.mu.m) to 100 microns, or from about
2 microns to 60 microns, or from about 2 microns to 30 microns. In
another embodiment, the co-catalyst particles may have a mean
particle size between about 2 microns and 100 microns, or between
about 4 microns and 40 microns, or between about 4 microns and 30
microns.
[0050] In an embodiment, the co-catalyst particles may comprise a
support. The support may comprise a material selected from alumina,
aluminosilicates, silica, as well as other refractory inorganic
oxides, including boria, magnesia, titania, and the like and
combinations thereof. The co-catalyst support of the present
invention can be manufactured by any conventional techniques.
[0051] In another embodiment a hydroprocessing co-catalyst
composition, such as Composition C, may be prepared by a method
comprising the steps of: i) providing a Composition A comprising
co-catalyst particles and a liquid carrier, ii) providing a
Composition B comprising a dispersant and a dispersant diluent; and
iii) combining Composition A with Composition B to provide a
suspension of the co-catalyst particles. In an embodiment, step i)
may comprise combining the co-catalyst particles with the liquid
carrier to provide a suspension of the co-catalyst in the liquid
carrier.
[0052] In an embodiment, Composition C may comprise from about 3
wt. % to 50 wt. % of the co-catalyst particles, or from about 5 wt.
% to 40 wt. %, or from about 10 wt. % to 30 wt. %. In an
embodiment, Composition C may comprise from about 50 wt. % to 90
wt. % of the liquid carrier, or from about 60 wt. % to 85 wt. %, or
from about 65 wt. % to 80 wt. %.
[0053] In an embodiment, the co-catalyst particles may have a
particle size in the range from about 1 micron (.mu.m) to 100
microns, or from about 2 microns to 60 microns, or from about 2
microns to 30 microns. In another embodiment, the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns, or between about 4 microns and 40 microns, or between
about 4 microns and 30 microns.
[0054] In an embodiment, the co-catalyst particles may be
hydrophilic. In an embodiment, the co-catalyst particles may
comprise a support. The support may comprise a material selected
from alumina, aluminosilicates, silica, as well as other refractory
inorganic oxides, including boria, magnesia, titania, and the like
and combinations thereof. The co-catalyst support of the present
invention can be manufactured by any conventional techniques. In an
embodiment, the co-catalyst particles may further comprise one or
more active metal components. In an embodiment, the support or base
may contain catalytic metals, in particular metals from Group VIB
of the Periodic Table, including molybdenum and/or tungsten, and/or
from Group III of the periodic Table, in particular nickel and/or
cobalt. Catalytic metals may be placed onto the support by
conventional techniques, including comulling, impregnation and the
like.
[0055] In an embodiment, the dispersant provided in Composition B
may comprise one or more components for promoting the dispersion of
the co-catalyst particles. In an embodiment, the dispersant may
comprise, for example, a surface active material, such as a
non-ionic, anionic, cationic, or amphoteric surfactant. In an
embodiment, the dispersant may be added to the dispersant diluent
in an amount such that Composition C may comprise from about 2 wt.
% to 60 wt. % of the dispersant, or from about 4 wt. % to 40 wt. %,
or from about 5 wt. % to 20 wt. %. In one embodiment, the
dispersant may be in the liquid state over a broad temperature
range, for example, from about 65.degree. F. to 500.degree. F., or
from about 70.degree. F. to 350.degree. F.
[0056] In an embodiment, the dispersant may comprise a plurality of
components. In an embodiment, the dispersant may comprise
polyisobutylene succinimide. In an embodiment, the dispersant may
further comprise a material selected from carboxylic acids,
dicarboxylic acids, and combinations thereof. In one embodiment,
the dispersant may comprise polyisobutylene succinimide and a
carboxylic acid such as oleic acid. In an embodiment, Composition C
may comprise from about 0.5 wt. % to 10.0 wt. % of polyisobutylene
succinimide, or from about 1.0 wt. % to 7.5 wt. %, or from about
1.5 wt. % to 5.0 wt. % of polyisobutylene succinimide. In an
embodiment, Composition C may further comprise from about 1.0 wt. %
to 15.0 wt. % of oleic acid, or from about 2.0 wt. % to 10.0 wt. %,
or from about 3.0 wt. % to 7.5 wt. % of oleic acid.
[0057] In an embodiment, the dispersant diluent may comprise oil.
In an embodiment, oil comprising the dispersant diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the dispersant
diluent may comprise a material selected from vacuum gas oil, light
vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavy
diesel, and combinations thereof.
[0058] In an embodiment, the liquid carrier may be miscible with
the dispersant diluent to form a single phase homogeneous liquid,
and Composition C may comprise a suspension of the co-catalyst
particles dispersed in the homogeneous liquid. In an embodiment,
the dispersant may promote dispersion of the co-catalyst particles
in the homogeneous liquid. The dispersant may prevent or delay
aggregation or flocculation of the co-catalyst particles in
Composition C, and may prevent or delay sedimentation or settling
of the co-catalyst particles. In an embodiment, the dispersant may
also promote dispersion of the co-catalyst particles in a refinery
stream or a hydrocarbon feed to a hydroprocessing unit.
[0059] While not being bound by any theory, in an embodiment a
plurality of dispersant molecules may be adsorbed by, or otherwise
associated with, each of the co-catalyst particles. In an
embodiment, the dispersant molecules may each have an elongated or
sterically bulky portion extending from the co-catalyst particles,
thereby preventing direct contact between adjacent co-catalyst
particles such that flocculation of the suspended co-catalyst
particles does not occur.
[0060] In one embodiment, Composition C may comprise a slurry. In
an embodiment, Composition C may have a viscosity, at about
70.degree. F., in the range from about 100 centipoise to 3000
centipoise, in another embodiment from about 150 centipoise to 2000
centipoise, or in a further embodiment from about 200 centipoise to
1000 centipoise. In an embodiment, the solids (particulate) content
of Composition C may be varied, for example, to optimize the
catalytic activity thereof. In another embodiment, the viscosity of
one or more of Compositions A, B, and C may be varied, for example,
to facilitate production, transport, pumpability, and/or storage
thereof.
[0061] In an embodiment, the viscosity of Composition C may be
varied, for example, by selecting a more or less viscous liquid
carrier, by selecting a more or less viscous dispersant diluent, by
varying the solids content, or by a combination thereof. In an
embodiment, the composition of Composition C may be adjusted to
provide a co-catalyst composition that not only has good catalytic
activity, but that is also convenient to transport, handle, and
introduce into the hydroprocessing unit.
[0062] In an embodiment, Composition C may be injected into the
hydroprocessing system directly. In another embodiment, Composition
C may be combined with a catalyst introduction diluent to provide a
Composition C/diluent mixture preparatory to the introduction of
the co-catalyst particles into a hydroprocessing system. The
Composition C/diluent mixture may be referred to herein as
Composition D. In an embodiment, the dispersant may promote
dispersion of the co-catalyst particles in the catalyst
introduction diluent or Composition D. In another embodiment, the
dispersant may promote dispersion of the co-catalyst particles in
the hydrocarbon feed.
[0063] The catalyst introduction diluent may comprise, for example,
petroleum derived oil. The catalyst introduction diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 450.degree. F. to 1100.degree. F., or from about 650.degree.
F. to 1000.degree. F. In an embodiment, the catalyst introduction
diluent may comprise, for example, a refinery stream or a feedstock
for a refinery process. Exemplary catalyst introduction diluents
may include, without limitation, vacuum gas oil, light gas oil,
diesel, light cycle oil, medium cycle oil, decant oil, flush oil,
cutter stocks, and combinations thereof.
[0064] In an embodiment, Composition C may be miscible with the
catalyst introduction diluent over a broad range of Composition
C/diluent proportions to give a homogeneous liquid dispersion
medium. In an embodiment, Composition C may be combined with the
catalyst introduction diluent at a diluent/Composition C volume
ratio in the range from about 1:1 to 200:1, or from about 2:1 to
100:1, or from about 3:1 to 50:1. In an embodiment, Composition C
may be miscible with the catalyst introduction diluent over a broad
temperature range. For example, Composition C may be miscible with
the catalyst introduction diluent at a temperature in the range
from about 150.degree. F. to 700.degree. F., or from about
200.degree. F. to 500.degree. F.
[0065] In an embodiment, the Composition C/diluent mixture may be
contacted with a hydrocarbon feed to a hydroprocessing system for
the efficacious dispersion of the co-catalyst composition into the
hydrocarbon feed. In an embodiment, the hydrocarbon feed may
comprise, for example, atmospheric or vacuum residuum or other
heavy oil feed to a hydroprocessing unit. In an embodiment, the
co-catalyst particles of Composition C may be sized for entrainment
in the hydrocarbon stream through at least a portion of an
ebullated bed hydroprocessing unit in one embodiment, or throughout
the entire course of an ebullated bed hydroprocessing unit in
another embodiment.
Methods for Making Co-Catalyst Compositions
[0066] In another embodiment we provide methods for making
co-catalyst compositions. In an embodiment, a hydroprocessing
co-catalyst composition, such as Composition C, may be prepared by
a method comprising the steps of providing a Composition A, which
comprises co-catalyst particles and a liquid carrier; and providing
a Composition B, which comprises a dispersant and a dispersant
diluent.
[0067] The co-catalyst particles may be in admixture with the
liquid carrier in Composition A. In an embodiment, the co-catalyst
particles may be combined with the liquid carrier using one or more
techniques known in the art for mixing liquids with particulate
solids. In an embodiment, Composition A may be prepared by
combining the co-catalyst particles with the liquid carrier so as
to form a suspension of the co-catalyst particles. In an
embodiment, the liquid carrier may comprise oil. Such oil may
comprise, for example, petroleum derived oil. In an embodiment, oil
comprising the liquid carrier may have a boiling range from about
350.degree. F. to 1125.degree. F., or from about 550.degree. F. to
1100.degree. F., or from about 550.degree. F. to 950.degree. F. As
a non-limiting example, the liquid carrier may comprise a material
selected from vacuum gas oil, light vacuum gas oil, heavy vacuum
gas oil, lube oil base stock, heavy diesel, and combinations
thereof.
[0068] In an embodiment, the co-catalyst particles may be combined
with the liquid carrier at a suitable temperature, which may be at,
below, or above ambient temperature. In embodiments wherein the
liquid carrier may comprise a viscous liquid, the co-catalyst
particles may be combined with the liquid carrier at substantially
above ambient temperature. In an embodiment, the co-catalyst
particles may be combined with the liquid carrier at a temperature
in the range from about 60.degree. F. to 200.degree. F., or from
about 75.degree. F. to 150.degree. F.
[0069] In an embodiment, the co-catalyst particles may have a
particle size in the range from about 1 micron (.mu.m) to 100
microns, or from about 2 microns to 60 microns, or from about 2
microns to 30 microns. In another embodiment, the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns, or between about 4 microns and 40 microns, or between
about 4 microns and 30 microns.
[0070] In an embodiment, the co-catalyst particles may be
hydrophilic. The co-catalyst particles may comprise a support. The
support may comprise a material selected from alumina,
aluminosilicates, silica, as well as other refractory inorganic
oxides, including boria, magnesia, titania, and the like, and
combinations thereof. The co-catalyst support of the present
invention can be manufactured by any conventional techniques. In an
embodiment, the co-catalyst particles may further comprise one or
more metal components. In an embodiment, the support or base may
contain catalytic metals, in particular metals from Group VIB of
the Periodic Table, including molybdenum and/or tungsten, and/or
from Group VIII of the Periodic Table, in particular nickel and/or
cobalt. Catalytic metals may be placed onto the support by
conventional techniques, including comulling, impregnation, and the
like.
[0071] In an embodiment, Composition B may be prepared by combining
the dispersant and the dispersant diluent such that the dispersant
may be in admixture with the dispersant diluent. In an embodiment,
the dispersant may comprise, for example, a surface active
material, such as a non-ionic, anionic, cationic, or amphoteric
surfactant.
[0072] The dispersant may serve to promote dispersion of the
co-catalyst particles of Composition A upon combining Composition A
with Composition B. In an embodiment, the dispersant may be added
to the dispersant diluent in an amount such that Composition B may
comprise from about 10 wt. % to 95 wt. % of the dispersant, or from
about 20 wt. % to 80 wt. %, or from about 30 wt. % to 70 wt. %. In
one embodiment, the dispersant may be in the liquid state over a
broad temperature range, for example, from about 65.degree. F. to
500.degree. F., or from about 70.degree. F. to 350.degree. F.
[0073] In an embodiment, the dispersant may comprise a plurality of
components. In an embodiment, the dispersant may comprise
polyisobutylene succinimide. In an embodiment, the dispersant may
comprise a material selected from carboxylic acids, dicarboxylic
acids, and combinations thereof. In one embodiment, the dispersant
may comprise polyisobutylene succinimide and a carboxylic acid such
as oleic acid. In a sub-embodiment. Composition B may comprise from
about 10 wt. % to 30 wt. % of polyisobutylene succinimide and from
about 30 wt. % to 65 wt. % of oleic acid.
[0074] In an embodiment, oil comprising the dispersant diluent may
have a boiling range from about 350.degree. F. to 1125.degree. F.,
or from about 550.degree. F. to 1100.degree. F. or from about
550.degree. F. to 950.degree. F. As a non-limiting example, the
dispersant diluent may comprise a material selected from vacuum gas
oil, light vacuum gas oil, heavy vacuum gas oil, lube oil base
stock, heavy diesel, and combinations thereof.
[0075] In an embodiment, Composition A and Composition B may be
provided, e.g., to a hydroprocessing unit or other refinery
location, in separate vessels or containers. That is to say, in an
embodiment, Composition C may be provided, e.g., to a
hydroprocessing unit, as its component parts, Composition A and
Composition B. In another embodiment, a method of making a
hydroprocessing co-catalyst composition may further comprise
combining Composition A with Composition B to provide Composition
C.
[0076] Composition C may comprise a suspension of the co-catalyst
particles dispersed in a mixture of the liquid carrier and the
dispersant diluent. Such mixture may comprise a homogeneous liquid
over a broad temperature range, e.g., from about 65.degree. F. to
650.degree. F., under hydroprocessing conditions (high pressure).
In an embodiment, Composition A may be combined with Composition B
at a Composition A/Composition B volume ratio in the range from
about 1:20 to 60:1, or from about 1:10 to 50:1, or from about 1:5
to 45:1, to provide Composition C.
[0077] In an embodiment, the co-catalyst particles may be prepared,
e.g., by grinding, milling, and the like. The co-catalyst particles
may be sorted to provide suitable size distributions for preparing
a co-catalyst composition having an appropriate level of catalytic
activity, a suitable viscosity, and/or other characteristics for a
particular hydroprocessing process or application. In an
embodiment, the co-catalyst particles may be ground, pulverized, or
crushed to the desired particle size using techniques known in the
art, e.g., via wet grinding or dry grinding, and using equipment
known in the art, including but not limited to: hammer mill, roller
mill, ball mill, jet mill, attrition mill, grinding mill, media
agitation mill, and the like. In an embodiment, the co-catalyst
particles may be synthesized to the desired size distributions
utilizing forming techniques known in the art, including but not
limited to precipitation, gelling, atomization, and the like.
[0078] In an embodiment, the co-catalyst particles may be
synthesized, ground or milled to achieve co-catalyst particles
having a particle size in the range from about 1 micron (.mu.m) to
100 microns, or from about 2 microns to 60 microns, or from about 2
microns to 30 microns. In another embodiment, the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns, or between about 4 microns and 40 microns, or between
about 4 microns and 30 microns.
[0079] In an embodiment, the dispersant may comprise a plurality of
components. In an embodiment, the dispersant may comprise
polyisobutylene succinimide. In an embodiment, the dispersant may
further comprise a material selected from carboxylic acids,
dicarboxylic acids, and combinations thereof. In one embodiment,
the dispersant may comprise polyisobutylene succinimide and a
carboxylic acid such as oleic acid. In a sub-embodiment,
Composition B may comprise from about 10 wt. % to 30 wt. % of
polyisobutylene succinimide and from about 30 wt. % to 65 wt. % of
oleic acid.
[0080] In an embodiment, an amount of the dispersant to be used in
preparing the hydroprocessing co-catalyst composition (e.g.,
Composition C) may be varied, for example, according to the total
surface area of the co-catalyst particles. In one embodiment, the
amount of dispersant in the hydroprocessing co-catalyst composition
may be proportional to the amount of co-catalyst particles in the
hydroprocessing co-catalyst composition. In an embodiment,
Composition C may comprise from about 2 wt. % to 60 wt. % of the
dispersant, or from about 4 wt. % to 40 wt. %, or from about 5 wt.
% to 20 wt. %.
[0081] In an embodiment, the dispersant may be combined with the
dispersant diluent at a suitable temperature, which may be at,
below, or above ambient temperature. In embodiments wherein the
dispersant diluent may comprise a viscous liquid, the dispersant
may be combined with the dispersant diluent at substantially above
ambient temperature, e.g., at a temperature in the range about
60.degree. F. to 200.degree. F., or from about 75.degree. F. to
150.degree. F.
[0082] In an embodiment, each of Composition A and Composition B
may be physically and chemically stable, and each of Composition A
and Composition B can be transported, moved, and manipulated, for
example, by pumping, either separately or following the combining
of Compositions A and B to form Composition C.
[0083] In another embodiment, Composition C may be prepared by
separately combining one or more dispersant components with
Composition A. As an example, one or more materials selected from
polyisobutylene succinimide, carboxylic acids, and dicarboxylic
acids, may be added separately to Composition A.
[0084] In another embodiment, the method of preparing a
hydroprocessing co-catalyst composition may further include
combining Composition C with a catalyst introduction diluent to
provide a Composition D, wherein Composition D may comprise a
diluted suspension of the co-catalyst particles. In an embodiment,
the catalyst introduction diluent may be miscible with the liquid
carrier and with the dispersant diluent. The catalyst introduction
diluent may be further miscible with a hydrocarbon feed having a
boiling range up to at least about 650.degree. F. The dispersant of
the co-catalyst composition may promote dispersion of the
co-catalyst particles in at least one material selected from the
liquid carrier, the dispersant diluent, the catalyst introduction
diluent, the hydrocarbon feed, and combinations thereof.
[0085] In an embodiment, the catalyst introduction diluent may
comprise a hydrocarbonaceous oil. The catalyst introduction diluent
may comprise, for example, petroleum derived oil. The catalyst
introduction diluent may have a boiling range from about
350.degree. F. to 1125.degree. F., or from about 450.degree. F. to
1100.degree. F., or from about 650.degree. F. to 1000.degree. F. In
an embodiment, the catalyst introduction diluent may comprise, for
example, a refinery stream or a feedstock for a refinery process.
Exemplary catalyst introduction diluents may include, without
limitation, vacuum gas oil, light gas oil, diesel, light cycle oil,
medium cycle oil, decant oil, flush oil, cutter stocks, and
combinations thereof.
[0086] In an embodiment, the catalyst introduction diluent may be
present in Composition D in an amount between about 50 vol. % and
99 vol. %, or between about 67 vol. % and 98 vol. %, or between
about 75 vol. % and 95 vol. %. In one embodiment, Composition C may
be combined with the catalyst introduction diluent at a
diluent/Composition C volume ratio in the range from about 1:1 to
100:1, or from about 2:1 to 50:1, or from about 3:1 to 20:1.
Methods for Introducing a Co-Catalyst Composition into a
Hydroprocessing System
[0087] In another embodiment, we provide a method of introducing
co-catalyst particles into a hydroprocessing system. The method may
include providing a Composition A comprising the co-catalyst
particles and a liquid carrier. In an embodiment, the co-catalyst
particles may be suspended in the liquid carrier. The co-catalyst
particles may be in the micron size range. In an embodiment, the
co-catalyst particles may have a particle size in the range from
about 1 micron (.mu.m) to 100 microns, or from about 2 microns to
60 microns, or from about 2 microns to 30 microns. In another
embodiment, the co-catalyst particles may have a mean particle size
between about 2 microns and 100 microns, or between about 4 microns
and 40 microns, or between about 4 microns and 30 microns.
[0088] In an embodiment, Composition A may comprise from about 5
wt. % to 50 wt. % of the co-catalyst particles, in another
embodiment from about 10 wt. % to 40 wt. %, or in a further
embodiment from about 15 wt. % to 30 wt. %. In an embodiment,
Composition A may comprise from about 50 wt. % to 95 wt. % of the
liquid carrier, or from about 60 wt. % to 90 wt. %, or from about
70 wt. % to 85 wt. %.
[0089] In an embodiment, the liquid carrier may comprise oil. Such
oil may comprise, for example, petroleum derived oil. In an
embodiment, oil comprising the liquid carrier may have a boiling
range from about 350.degree. F. to 1125.degree. F., or from about
550.degree. F. to 1100.degree. F., or from about 550.degree. F. to
950.degree. F. As a non-limiting example, the liquid carrier may
comprise a material selected from vacuum gas oil, light vacuum gas
oil, heavy vacuum gas oil, lube oil base stock, heavy diesel, and
combinations thereof.
[0090] In an embodiment, the liquid carrier may be miscible with a
liquid hydrocarbonaceous oil, such as that comprising a catalyst
introduction diluent or a hydrocarbon feed to a hydroprocessing
system. In an embodiment, the liquid carrier may be miscible with
the liquid hydrocarbonaceous oil over a broad temperature range.
For example, the liquid carrier may be miscible with the liquid
hydrocarbonaceous oil at a temperature in the range from about
150.degree. F. to 700.degree. F., or from about 350.degree. F. to
650.degree. F., under hydroprocessing conditions (high
pressure).
[0091] In an embodiment, the catalyst introduction diluent may
comprise a hydrocarbonaceous oil. The catalyst introduction diluent
may comprise, for example, petroleum derived oil. The catalyst
introduction diluent may have a boiling range from about
350.degree. F. to 1125.degree. F., or from about 450.degree. F. to
1100.degree. F., or from about 650.degree. F. to 1000.degree. F. In
an embodiment, the catalyst introduction diluent may comprise, for
example, a refinery stream or a feedstock for a refinery process.
Exemplary catalyst introduction diluents may include, without
limitation, vacuum gas oil, light gas oil, diesel, light cycle oil,
medium cycle oil, decant oil, flush oil, cutter stocks, and
combinations thereof.
[0092] The method of introducing co-catalyst particles into a
hydroprocessing system may further include providing a Composition
B comprising a dispersant and a dispersant diluent. Composition B
may comprise from about 10 wt. % to 95 wt. % of the dispersant, or
from about 20 wt. % to 80 wt. %, or from about 30 wt. % to 70 wt.
%.
[0093] In an embodiment, the dispersant may comprise a plurality of
components. In one embodiment, the dispersant may comprise a
polyisobutylene succinimide. In an embodiment, the dispersant may
further comprise a material selected from carboxylic acids,
dicarboxylic acids, and combinations thereof. In an embodiment, the
dispersant may comprise polyisobutylene succinimide and a
carboxylic acid such as oleic acid. In a sub-embodiment,
Composition B may comprise from about 5 wt. % to 40 wt. %, or from
about 10 wt. % to 30 wt. %, of polyisobutylene succinimide; and
Composition B may further comprise from about from about 5 wt. % to
70 wt. %, or from about 30 wt. % to 65 wt. %, of oleic acid.
[0094] In an embodiment, the dispersant diluent may comprise oil.
Such oil may comprise, for example, petroleum derived oil. In an
embodiment, oil comprising the dispersant diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the dispersant
diluent may comprise a material selected from vacuum gas oil, light
vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavy
diesel, and combinations thereof.
[0095] In an embodiment, the method of introducing co-catalyst
particles into a hydroprocessing system may still further include
combining Composition A with Composition B to form a Composition C,
wherein Composition C may comprise a suspension of the co-catalyst
particles. In an embodiment, Composition C may be agitated to
maintain the co-catalyst particles in suspension until Composition
C is to be used, e.g., diluted for introduction of the co-catalyst
particles into the hydroprocessing system. In an embodiment, the
combining step may comprise combining Composition A with
Composition B at a Composition A/Composition B volume ratio in the
range from about 1:20 to 60:1, or from about 1:10 to 50:1, or from
about 1:5 to 45:1.
[0096] In another embodiment, Composition C may be prepared by
separately combining one or more dispersant components with
Composition A. As an example, one or more materials selected from
polyisobutylene succinimide, carboxylic acids, and dicarboxylic
acids, may be added separately to Composition A.
[0097] The method of introducing the co-catalyst particles into a
hydroprocessing system may yet further include, after the formation
of Composition C, contacting the co-catalyst particles with a
hydrocarbon feed of the hydroprocessing system.
[0098] In another embodiment, prior to contacting the co-catalyst
particles with the hydrocarbon feed, the method may further
comprise diluting Composition C with the catalyst introduction
diluent to provide a Composition D comprising a diluted suspension
of the co-catalyst particles. In an embodiment, Composition D may
be suitable for introduction, e.g., via injection, into a
hydrocarbon feed to a hydroprocessing system. In an embodiment, the
contacting step may comprise contacting Composition D with the
hydrocarbon feed such that the co-catalyst particles are entrained
with the hydrocarbon feed within the hydroprocessing system.
[0099] Composition D could join the hydrocarbon feed at various
locations within the hydroprocessing unit. This could include
injecting Composition D directly into the hydrocarbon feed line,
ensuring that provisions were made to ensure that Composition D
will undergo sufficient mixing at the injection point to fully
disperse into the hydrocarbon feed, utilizing slurry flow
principles known in the art, including but not limited to proper
line sizing, geometry and orientation, utilization of a quill,
static mixer, or the like.
[0100] The catalyst introduction diluent may be in the liquid state
when combined with Composition C. In an embodiment, the catalyst
introduction diluent may be miscible with each of the liquid
carrier, the dispersant diluent, and the hydrocarbon feed to the
hydroprocessing system, and combinations thereof. The catalyst
introduction diluent may comprise, for example, petroleum derived
oil. The catalyst introduction diluent may have a boiling range
from about 350.degree. F. to 1125.degree. F., or from about
450.degree. F. to 1100.degree. F., or from about 650.degree. F. to
1000.degree. F. In an embodiment, the catalyst introduction diluent
may comprise, for example, a refinery stream or a feedstock for a
refinery process. Exemplary catalyst introduction diluents may
include, without limitation, vacuum gas oil, light gas oil, diesel,
light cycle oil, medium cycle oil, decant oil, flush oil, cutter
stocks, and combinations thereof.
[0101] In an embodiment, the catalyst introduction diluent may be
present in Composition D in an amount between about 50 vol. % and
99 vol. %, or between about 67 vol. % and 98 vol. %, or between
about 75 vol. % and 95 vol. %. For example, in one embodiment,
Composition C may be combined with the catalyst introduction
diluent at a diluent/Composition C volume ratio in the range from
about 1:1 to 100:1, or from about 2:1 to 50:1, or from about 3:1 to
20:1.
[0102] During the step of diluting Composition C with the catalyst
introduction diluent, the catalyst introduction diluent may be at a
temperature in the range from about ambient temperature to
700.degree. F., or from about 350.degree. F. to 650.degree. F., or
from about 450.degree. F. to 600.degree. F. In an embodiment,
Composition C may be maintained at about ambient temperature, prior
to combining the co-catalyst composition with the catalyst
introduction diluent. In another embodiment, Composition C may be
pre-heated prior to combining the co-catalyst composition with the
catalyst introduction diluent. During the contacting step, the
hydrocarbon feed may be at a temperature in the range from about
350.degree. F. to 750.degree. F., or from about 350.degree. F. to
650.degree. F., or from about 450.degree. F. to 600.degree. F. In
an embodiment, the hydrocarbon feed may comprise heavy oil, such as
vacuum residuum or atmospheric residuum, having a boiling range up
to at least about 650.degree. F.
[0103] The dispersant may promote dispersion of the co-catalyst
particles in at least one of the liquid carrier, the dispersant
diluent, the catalyst introduction diluent, the hydrocarbon feed,
or combinations thereof. In an embodiment, the dispersant may
comprise polyisobutylene succinimide. In an embodiment, the
dispersant may further comprise a material selected from carboxylic
acids, dicarboxylic acids, and combinations thereof. In an
embodiment, the dispersant may comprise polyisobutylene succinimide
and oleic acid. In an embodiment, Composition C may comprise from
about 0.5 wt. % to 10.0 wt. % of polyisobutylene succinimide, or
from about 1.0 wt. % to 7.5 wt. %, or from about 1.5 wt. % to 5.0
wt. % of polyisobutylene succinimide. In an embodiment, Composition
C may further comprise from about 1.0 wt. % to 15.0 wt. % of oleic
acid, or from about 2.0 wt. % to 10.0 wt. %, or from about 3.0 wt.
% to 7.5 wt. % of oleic acid.
[0104] In another embodiment, a method of introducing co-catalyst
particles into a hydroprocessing system may include providing a
Composition A comprising the co-catalyst particles and a liquid
carrier. Composition A may comprise from about 5 wt. % to 50 wt. %
of the co-catalyst particles and from about 50 wt. % to 95 wt. % of
the liquid carrier. In an embodiment, the liquid carrier may
comprise oil. Such oil may comprise, for example, petroleum derived
oil. In an embodiment, oil comprising the liquid carrier may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the liquid carrier
may comprise a material selected from vacuum gas oil, light vacuum
gas oil, heavy vacuum gas oil, lube oil base stock, heavy diesel,
and combinations thereof.
[0105] In an embodiment, the co-catalyst particles may have a
particle size in the range from about 1 micron (.mu.m) to 100
microns, or from about 2 microns to 60 microns, or from about 2
microns to 30 microns. In another embodiment, the co-catalyst
particles may have a mean particle size between about 2 microns and
100 microns, or between about 4 microns and 40 microns, or between
about 4 microns and 30 microns.
[0106] The co-catalyst particles may comprise a support. The
support may comprise a material selected from alumina,
aluminosilicates, silica, as well as other refractory inorganic
oxides, including boria, magnesia, titania, and the like, and
combinations thereof. The co-catalyst support of the present
invention can be manufactured by any conventional techniques. In an
embodiment, the co-catalyst particles may further comprise one or
more metal components. In an embodiment, the support or base may
contain catalytic metals, in particular metals from Group VIB of
the Periodic Table, including molybdenum and/or tungsten, and/or
from Group III of the periodic Table, in particular nickel and/or
cobalt. Catalytic metals may be placed onto the support by
conventional techniques, including comulling, impregnation, and the
like.
[0107] The method of introducing co-catalyst particles into a
hydroprocessing system may further include providing a Composition
B comprising a dispersant and a dispersant diluent. In an
embodiment, the dispersant may comprise polyisobutylene
succinimide. In an embodiment, the dispersant may further comprise
a material selected from carboxylic acids, dicarboxylic acids, and
combinations thereof.
[0108] In an embodiment, the dispersant diluent may comprise oil.
In an embodiment, oil comprising the dispersant diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the dispersant
diluent may comprise a material selected from vacuum gas oil, light
vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavy
diesel, and combinations thereof.
[0109] The method of introducing co-catalyst particles into a
hydroprocessing system may further include combining Composition A
with Composition B to form a Composition C, and combining
Composition C with a catalyst introduction diluent to provide a
composition D. The catalyst introduction diluent may be miscible
with Composition C. In an embodiment, the catalyst introduction
diluent may comprise oil.
[0110] The method of introducing co-catalyst particles into a
hydroprocessing system may still further include contacting
composition D with the hydrocarbon feed of the hydroprocessing
system. Composition D may be miscible with the hydrocarbon feed. In
an embodiment, Composition D may be combined with the hydrocarbon
feed such that the co-catalyst particles are entrained with the
hydrocarbon feed within the hydroprocessing system.
[0111] In yet another embodiment, a method of introducing
co-catalyst particles into a hydroprocessing system may include
providing a Composition A comprising the co-catalyst particles and
a liquid carrier. The co-catalyst particles may comprise a support
comprising a material selected from alumina, aluminosilicates,
silica, boria, magnesia, titania, and combinations thereof, and the
co-catalyst particles may have a mean particle size between about 2
microns and 100 microns.
[0112] The method of introducing co-catalyst particles into a
hydroprocessing system may further include providing a Composition
B comprising a dispersant and a dispersant diluent. In an
embodiment, the dispersant may comprise polyisobutylene
succinimide. In an embodiment, the dispersant may further comprise
a material selected from carboxylic acids, dicarboxylic acids, and
combinations thereof. In one embodiment, the dispersant may
comprise polyisobutylene succinimide and a carboxylic acid such as
oleic acid.
[0113] In an embodiment, the dispersant diluent may comprise oil.
In an embodiment, oil comprising the dispersant diluent may have a
boiling range from about 350.degree. F. to 1125.degree. F., or from
about 550.degree. F. to 1100.degree. F., or from about 550.degree.
F. to 950.degree. F. As a non-limiting example, the dispersant
diluent may comprise a material selected from vacuum gas oil, light
vacuum gas oil, heavy vacuum gas oil, lube oil base stock, heavy
diesel, and combinations thereof.
[0114] The method of introducing co-catalyst particles into a
hydroprocessing system may still further include combining
Composition A with Composition B to form a Composition C, wherein
Composition C comprises a suspension of the co-catalyst particles.
The method may yet further include diluting Composition C with a
catalyst introduction diluent to provide a composition D comprising
a diluted suspension of the co-catalyst particles, or direct
injection of Composition C into the hydroprocessing unit. The
catalyst introduction diluent may comprise oil, and the catalyst
introduction diluent may be miscible with Composition C.
[0115] After the diluting step, Composition D may be contacted with
a hydrocarbon feed of the hydroprocessing system, wherein
Composition D may be miscible with the hydrocarbon feed. The
hydrocarbon feed may have a boiling range >650.degree. F. and/or
>950.degree. F. In an embodiment, the contacting step may
comprise contacting the co-catalyst particles with the hydrocarbon
feed such that the co-catalyst particles are entrained with the
hydrocarbon feed within the hydroprocessing system.
[0116] According to methods and compositions disclosed herein,
co-catalyst particles introduced into a hydroprocessing system may
be present in the hydrocarbon feed at a concentration up to about
600 ppm, or from about 20 ppm to 500 ppm, or from about 100 to 400
ppm. In an embodiment, the co-catalyst particles may be entrained
with the hydrocarbon feed so as to freely migrate with the
hydrocarbon feed through at least a portion of the hydroprocessing
system, and in another embodiment the co-catalyst particles may be
entrained with the hydrocarbon feed so as to freely migrate with
the hydrocarbon feed throughout the entire hydroprocessing
system.
[0117] The hydrocarbon feed may be in the liquid state when
contacted with the co-catalyst particles. In an embodiment, when
the hydrocarbon feed is contacted with the co-catalyst particles
during the contacting step, the hydrocarbon feed may be at a
temperature in the range from about 350.degree. F. to 750.degree.
F., or from about 350.degree. F. to 650.degree. F., or from about
450.degree. F. to 600.degree. F. In an embodiment, and as a
non-limiting example, the hydrocarbon feed may comprise heavy oil
having a boiling range up to at least about 650.degree. F.
[0118] In one embodiment, fresh co-catalyst, e.g., in the form of a
Composition C/catalyst introduction diluent mixture, may be added
to the hydroprocessing system as a single addition; or in another
embodiment, the fresh co-catalyst may be added to the
hydroprocessing system intermittently; while in a further
embodiment, the fresh co-catalyst may be added to the
hydroprocessing system continuously.
[0119] In other embodiments fresh co-catalyst, e.g., in the form of
a Composition C only, may be added directly to the hydroprocessing
system in the absence of a catalyst introduction diluent, either as
a single addition, intermittently, or continuously.
[0120] During hydroprocessing, the dispersant may eventually
decompose to yield only species that are entirely compatible with
the hydroprocessing process and that will not interfere with the
products of hydroprocessing. In an embodiment, at least
substantially all of the dispersant may be converted or decomposed,
under hydroprocessing conditions in the hydroprocessing system, to
yield light hydrocarbons, for example, predominantly
C.sub.1-C.sub.4 hydrocarbons.
EXAMPLES
[0121] The following illustrative examples are intended to be
non-limiting.
Example 1
Preparation of a Suspension of Co-Catalyst Particles Using Vacuum
Gas Oil as Liquid Carrier
[0122] 43 g of co-catalyst particles were combined with 100 g of
vacuum gas oil (VGO) (see Table 1). The mixture was agitated for 5
minutes using a spatula to provide a co-catalyst composition in the
form of a slurry comprising a suspension of the co-catalyst
particles in the VGO. The co-catalyst solids content of the
co-catalyst composition of Example 1 was about 30 wt. %.
Example 2
Preparation of a Suspension of Co-Catalyst Particles Using Vacuum
Gas Oil as Liquid Carrier and Dispersants
[0123] 43 g of co-catalyst particles (per Example 1) were combined
with 100 g of VGO (see Table 1), 2.2 g of polyisobutylene
succinimide, and 5.4 g of oleic acid. The mixture was agitated for
5 minutes using a spatula to provide a co-catalyst composition in
the form of a slurry comprising a suspension of the co-catalyst
particles in the VGO and dispersants. The co-catalyst solids
content of the co-catalyst composition of Example 2 was about 28.6
wt. %. The addition of dispersants in Example 2 led to improved
solids dispersion (see Table 2), as measured using a Mettler-Toledo
Focused Beam Reflectance Measurement (FBRM) probe, relative to
Example 1.
Example 3
Preparation of a Co-Catalyst Containing Material Using Medium Cycle
Oil and Dispersants
[0124] 43 g of co-catalyst particles (per Example 1) were combined
with 100 g of medium cycle oil (MCO) (see Table 1), 2.2 g of
polyisobutylene succinimide, and 5.4 g of oleic acid. The mixture
was agitated as for Example 1. The use of MCO in the protocol of
Example 3, led to poor co-catalyst solids dispersion (see Table 2),
even in the presence of dispersants.
TABLE-US-00001 TABLE 1 Feed Description MCO VGO Feed ID ABQ0888
ABQ0297 Feed API 10.7 20.9 Feed Sulfur, wt % 0.3980 2.2130 Feed
Nitrogen, ppm 640 1247 Distillation wt % .degree. F. .degree. F.
0.5 403 567 5 480 694 10 490 741 15 499 770 20 517 788 25 524 802
30 532 814 40 546 832 50 568 849 60 583 865 70 606 882 75 620 892
80 630 903 85 651 917 90 669 934 95 699 961 99 762 1003 99.5 787
1014 650.degree. F.- 84.8 2.1 650-950.degree. F. .sup. 15.2 91.2
950.degree. F.+ 0.0 6.7
TABLE-US-00002 TABLE 2 Example 1 Example 2 Example 3 Co-Catalyst
Solids, g 43 43 43 Oil Carrier Type VGO VGO MCO Oil Carrier, g 100
100 100 Dispersant polylsobutylene 0 2.2 2.2 succinimide, g
Dispersant Oleic Acid, g 0 5.4 5.4 Solids Concentration, wt. % 30.1
28.6 28.6 ParticieSize Distribution 0-10 .mu.m (% Count) 91.9 96.0
80.7 10-20 .mu.m (% Count) 6.2 3.5 9.0 >20 .mu.m (% Count) 1.9
0.5 10.3
[0125] Where permitted, all publications, patents and patent
applications cited in this application are herein incorporated by
reference in their entirety, to the extent such disclosure is not
inconsistent with embodiments of the present invention.
[0126] For the purposes of this specification and appended claims,
unless otherwise indicated, all numbers expressing quantities,
percentages or proportions, and other numerical values used herein
are to be understood as being modified in all instances by the term
"about." It is noted that, as used in this specification and the
appended claims, the singular forms "a," "an," and "the," include
plural references unless expressly and unequivocally limited to one
referent.
[0127] Unless otherwise specified, the recitation of a genus of
elements, materials or other components, from which an individual
component or mixture of components can be selected, is intended to
include all possible sub-generic combinations of the listed
components and mixtures thereof. Also, "include" and its variants
are intended to be non-limiting, such that recitation of items in a
list is not to the exclusion of other like items that may also be
useful in the materials, compositions and methods disclosed
herein.
[0128] Numerous variations of the disclosed compositions and
methods may be possible in light of the teachings herein. It is
therefore understood that within the scope of the following claims,
embodiments of the invention may be practiced otherwise than as
specifically described or exemplified herein.
* * * * *