U.S. patent application number 12/510806 was filed with the patent office on 2010-01-28 for composition and methods for preferentially increasing yields of one or more selected hydrocarbon products.
Invention is credited to Paul Diddams, William Reagan, Darren Verrenkamp.
Application Number | 20100018898 12/510806 |
Document ID | / |
Family ID | 41567684 |
Filed Date | 2010-01-28 |
United States Patent
Application |
20100018898 |
Kind Code |
A1 |
Reagan; William ; et
al. |
January 28, 2010 |
COMPOSITION AND METHODS FOR PREFERENTIALLY INCREASING YIELDS OF ONE
OR MORE SELECTED HYDROCARBON PRODUCTS
Abstract
Methods and compositions to preferentially increase or decrease
the yield of at least a selected hydrocarbon product in one or more
fluidized units are provided. An embodiment includes: providing a
high activity component to a fluidized unit as physically separate
and distinct particles in an amount sufficient to preferentially
increase the yield of at least a selected hydrocarbon product
compared to another hydrocarbon product. Another embodiment
includes: providing a high activity component to a fluidized unit
as physically separate and distinct particles to preferentially
decrease the yield of at least a selected hydrocarbon product
compared to another hydrocarbon product. Another method includes:
providing at least a high activity component comprising a
contaminant inhibitor component to a fluidized unit as physically
separate and distinct particles to inhibit the adverse effects of
at least a contaminant in a feed stock.
Inventors: |
Reagan; William; (Pooler,
GA) ; Diddams; Paul; (Prague, CZ) ;
Verrenkamp; Darren; (Brisbane, AU) |
Correspondence
Address: |
PATTERSON & SHERIDAN, LLP / INTERCAT EQUIPMENT
3040 Post Oak Boulevard, Suite 1500
Houston
TX
77056-6582
US
|
Family ID: |
41567684 |
Appl. No.: |
12/510806 |
Filed: |
July 28, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61084129 |
Jul 28, 2008 |
|
|
|
Current U.S.
Class: |
208/113 |
Current CPC
Class: |
C10G 2400/04 20130101;
C10G 11/02 20130101; C10G 11/18 20130101; C10G 2400/02
20130101 |
Class at
Publication: |
208/113 |
International
Class: |
C10G 11/00 20060101
C10G011/00 |
Claims
1. A method comprising: providing at least a high activity
component to a fluidized unit as physically separate and distinct
particles in an amount sufficient to preferentially increase the
yield of at least a selected hydrocarbon product compared to
another hydrocarbon product.
2. The method of claim 1, further comprising: providing a high
activity component to a fluidized unit as physically separate and
distinct particles to preferentially increase the yield of LCO and
wherein the high activity component comprises from about 70% to
about 100% by weight LCO selective component.
3. The method of claim 2, further comprising providing a second
high activity component which differs from the high activity
component comprising LCO selective component in an amount
sufficient to at least partially reverse the preferential increase
in yield of LCO.
4. The method of claim 2, wherein providing the high activity
component comprising the LCO selective component as physically
separate and distinct particles preferentially increases LCO yield
compared to providing a base catalyst as a single particle
system.
5. The method of claim 1, further comprising: providing a high
activity component to a fluidized unit as physically separate and
distinct particles to preferentially increase the yield of gasoline
range product and wherein the high activity component comprises
about 40% to about 85% by weight a gasoline selective
component.
6. The method of claim 5, wherein gasoline selective component is
about 50% to about 85% by weight.
7. The method of claim 6, wherein the gasoline selective component
comprises at least 70% by weight.
8. The method of claim 5, further comprising providing a second
high activity component which differs from the first high activity
component in an amount sufficient to at least partially reverse the
preferential increase in yield of gasoline range product.
9. The method of claim 5, wherein providing the high activity
component comprising the gasoline selective component as physically
separate and distinct particles preferentially increases the yield
of gasoline range product compared to providing a base catalyst as
a single particle system.
10. The method of claim 1, further comprising: providing a high
activity component to a fluidized unit as physically separate and
distinct particles to preferentially increase the yield of the at
least a selected hydrocarbon product comprises preferentially
increasing the yield of LPG and wherein the high activity component
comprises from about 20% to about 85% by weight a LPG selective
component.
11. The method of claim 1, further comprising: providing a high
activity component to a fluidized unit as physically separate and
distinct particles to preferentially increase the yield of a
selected hydrocarbon product comprises preferentially increasing
the yield of gasoline range product or LPG and wherein the high
activity component comprises from about 70% to about 100% by weight
a contaminant inhibitor.
12. The method of claim 1, wherein the fluidized unit is selected
from a group consisting of unit for fluid catalyst cracking, unit
for residue cracking, unit for cracking gasoline into LPG, unit for
manufacture of pyridine and its derivatives, unit for manufacture
of acrylonitrile, and unit for cracking heavy feed into LPG.
13. The method of claim 1, further comprising providing the high
activity component to a plurality of units.
14. The method of claim 13, further comprising providing the high
activity component to a plurality of units sequentially.
15. The method of claim 13, further comprising providing the high
activity component to a plurality of units simultaneously.
16. The method of claim 1, further comprising providing a plurality
of high activity components which differ from each other to enhance
the preferentially increase the yield of the at least a selected
hydrocarbon product compared to than another product.
17. The method of claim 1, further comprising providing a plurality
of high activity components which differ from each other in an
amount sufficient to reverse the preferential yield of the at least
a selected hydrocarbon product.
18. A method comprising: providing at least a high activity
component comprising a contaminant inhibitor component to a
fluidized unit as physically separate and distinct particles to
inhibit the adverse effects of at least a contaminant in a feed
stock.
19. A method comprising: providing at least a high activity
component to a fluidized unit as physically separate and distinct
particles to preferentially decrease the yield of at least a
selected hydrocarbon product compared to another hydrocarbon
product.
20. The method of claim 19, further comprising providing a
plurality of high activity components which differ from each other
to enhance the preferentially decrease the yield of the at least a
selected hydrocarbon product compared to than another product.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to provisional application
61/084,129 filed Jul. 28, 2008 titled COMPOSITION AND METHODS FOR
INCREASING DIESEL YIELD AND OTHER PURE ADDITIVES AND METHODS OF
USE.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the invention generally relate to methods for
increasing or decreasing yields of one or more selected
hydrocarbons from one or more units. Particularly, the invention
relates to methods for increasing or decreasing yields of one or
more selected hydrocarbons from one or fluidized units.
[0004] 2. Description of the Related Art
[0005] FIG. 1 is a simplified schematic of a conventional fluid
catalytic cracking system 130. The fluid catalytic cracking system
130 generally includes a fluid catalytic cracking (FCC) unit 110
coupled to a catalyst injection system 100, a petroleum feed stock
source 104, an exhaust gas system 114 and a distillation system
116.
[0006] The FCC unit 110 includes a regenerator 150 and a reactor
152. The reactor 152 primarily houses the catalytic cracking
reaction of the petroleum feed stock and delivers the cracked
product in vapor form to the distillation system 116. Spend
catalyst from the cracking reaction is transfer from the reactor
152 to the regenerator 150 to regenerate the catalyst by removing
coke and other materials. The regenerated catalyst is then
reintroduced into the reactor 152 to continue the petroleum
cracking process.
[0007] The FCC unit is coupled to a catalyst injection system 100
that maintains a continuous or semi continuous addition of fresh
base catalyst to the inventory circulating between a regenerator
and a reactor.
[0008] During the catalytic cracking process, there is a dynamic
balance of the total amount of the base cracking catalyst, i.e.
catalyst inventory, within the FCC unit and desire to maintain the
activity level of the catalyst inventory. For example, fresh base
cracking catalyst is periodically added utilizing the catalyst
injection system to replace some base catalyst which is lost in
various ways such as through the distillation system, through the
exhaust gas exiting the regenerator and deactivation of the base
catalyst over time, which is normal. If the amount of base catalyst
within the FCC unit decreases significantly over time, the
performance and desired output of the FCC unit will diminish, and
in extreme cases the FCC unit may become inoperable. Conversely, if
the catalyst inventory in the FCC unit increases over time, the
catalyst bed level within the regenerator reaches an upper
operating limit. Such occurs when the catalyst addition rate for
maintenance of catalyst activity or inventory exceeds the lost
catalyst and the excess catalyst is periodically withdrawal from
the catalyst inventory.
[0009] In addition to the base cracking catalyst, other catalytic
components (such as additives) with various functionalities such as
to reduce sulfur or other contaminants etc. are often injected into
the FCCU to further influence the refining process by incorporating
these other catalytic components within or as part of the base
cracking catalyst. Incorporating other catalytic components within
or as part of the base cracking catalyst as a single particle
system is technically known either as `incorporation or in-situ" in
which the various parts of the base and other catalysts are
physically bound together. Incorporating other catalytic components
within or as part of the base cracking catalyst as a single
particle system provides dual or multiple functionalities within
the same single particle by virtue of the proximity of the
components. However, a base cracking catalyst with other catalytic
components incorporated within or as part of the base cracking
catalyst in a single particle system has limited ability and
flexibility to preferentially increase or control one or more
selected hydrocarbon products or conversely decrease one or more
less wanted hydrocarbon products is limited.
[0010] A need still remains for improved method and system for
enhanced process flexibility and or control to preferentially
increase or control one or more selected hydrocarbon products in
fluidized units and or conversely decrease one or more less wanted
hydrocarbon products.
BRIEF DESCRIPTION
[0011] The purpose and advantages of embodiments of the invention
will be set forth and apparent from the description of exemplary
embodiments that follows, as well as will be learned by practice of
the embodiments of the invention. Additional advantages will be
realized and attained by the methods and systems particularly
pointed out in the written description and claims hereof, as well
as from the appended drawings.
[0012] An embodiment of the invention provides a method. The method
includes: providing at least a high activity component to a
fluidized unit as physically separate and distinct particles in an
amount sufficient to preferentially increase the yield of at least
a selected hydrocarbon product compared to another hydrocarbon
product.
[0013] A second embodiment provides a method. The method includes:
providing at least a high activity component comprising a
contaminant inhibitor component to a fluidized unit as physically
separate and distinct particles to inhibit the adverse effects of
at least a contaminant in a feed stock.
[0014] A third embodiment provides a method. The method includes:
providing at least a high activity component to a fluidized unit as
physically separate and distinct particles to preferentially
decrease the yield of at least a selected hydrocarbon product
compared to another hydrocarbon product.
DESCRIPTION OF THE DRAWINGS
[0015] The accompanying figures, which are incorporated in and
constitute part of this specification, are included to illustrate
and provide a further understanding of the method and system of the
invention. Together with the description, the drawings serve to
explain the principles of the invention.
[0016] FIG. 1 is a schematic diagram of a conventional fluid
catalytic cracking system;
[0017] FIG. 2A is a schematic diagram of a high activity component
comprising a LCO (Light Cycle Oil) selective component in
accordance with an embodiment of the present invention;
[0018] FIG. 2B is a schematic diagram of a high activity component
comprising a gasoline selective component in accordance with an
embodiment of the present invention;
[0019] FIG. 2C is a schematic diagram of a high activity component
comprising a LPG (Liquefied Petroleum Gas) selective component in
accordance with an embodiment of the present invention;
[0020] FIG. 2D is a schematic diagram of a high activity component
comprising a contaminant inhibitor component in accordance with an
embodiment of the present invention;
[0021] FIG. 2E is a schematic diagram of a high activity component
comprising a combination of a contaminant inhibitor component and a
LCO selective component in accordance with an embodiment of the
present invention;
[0022] FIG. 3 is a schematic simulation graph of preferentially
increasing LCO yield by providing a high activity component
comprising a LCO selective component in accordance with an
embodiment of the present invention;
[0023] FIG. 4 is a schematic simulation graph of preferentially
increasing gasoline range product yield by providing a high
activity component comprising a gasoline selective component in
accordance with an embodiment of the present invention;
[0024] FIG. 5 is a schematic simulation graph of preferentially
increasing total surface area (TSA) which translates to increased
gasoline range product yield or LPG yield by providing a high
activity component comprising a contaminant inhibitor component in
accordance with an embodiment of the present invention; and
[0025] FIG. 6 is a schematic simulation graph of preferentially
increase yield of one or more selected hydrocarbon products by
providing a combination of high activity components in accordance
with an embodiment of the present invention.
[0026] To facilitate understanding, identical reference numerals
have been used, where possible; to designate identical elements
that are common to the figures, except that suffixes may be added,
when appropriate, to differentiate such elements. The images in the
drawings are simplified for illustrative purposes and are not
depicted to scale. It is contemplated that features or steps of one
embodiment may be beneficially incorporated in other embodiments
without further recitation.
DETAILED DESCRIPTION
[0027] In the following description, like reference characters
designate like or corresponding parts throughout the several views
shown in the figures. It is also understood that terms such as
"top," "bottom," "outward," "inward," and the like are words of
convenience and are not to be construed as limiting terms.
[0028] Reference will now be made in detail to exemplary
embodiments of the invention which are illustrated in the
accompanying figures and examples. Referring to the drawings in
general, it will be understood that the illustrations are for
describing a particular embodiment of the invention and are not
intended to limit the invention thereto.
[0029] Whenever a particular embodiment of the invention is said to
comprise or consist of at least one element of a group and
combinations thereof, it is understood that the embodiment may
comprise or consist of any of the elements of the group, either
individually or in combination with any of the other elements of
that group. Furthermore, when any variable occurs more than one
time in any constituent or in formula, its definition on each
occurrence is independent of its definition at every other
occurrence. Also, combinations of substituents and/or variables are
permissible only if such combinations result in stable
compounds.
[0030] An embodiment of the invention provides a method. The method
includes providing one or more high activity components to one or
more fluidized units. At least a high activity component is
provided as physically separate and distinct particles from a base
catalyst in an amount sufficient to preferentially increase the
yield of one more selected hydrocarbon product compared to another
hydrocarbon product or products. High activity component include
such as but not limited to one or more LCO selective components,
one or more gasoline selective components, one or more LPG
selective components, and one or more contaminant inhibitor
components, either individually or in a combination of two or more
thereof.
[0031] In an embodiment, providing a high activity component (as
schematically shown in FIG. 2A-2E) as physically separate and
distinct particles means providing at least a high activity
component which is not incorporated within or as part of the base
catalyst particle as a single particle system. For comparative
distinction, providing the high activity component as physically
separate and distinct particles from the base catalyst particle
(i.e. base cracking catalyst) is a multi-particle particle system
in contrast to incorporating the high activity component within or
as part of the base catalyst particle as a single particle system.
It should be appreciated that Applicant's embodiments of high
activity component provided as physically separate and distinct
particles from the base catalyst expressly allows trace or
contaminant or deminis base catalyst amount or function and is not
to be limited to a specified precise value, and may include values
that differ from the specified value. In one embodiment, a trace or
contaminant or deminis amount of base catalyst (base cracking
catalyst) may be incorporated within the high activity component,
which is distinct from incorporating the high activity component
within or as part of the base catalyst. High activity component
provided as physically separate and distinct particles expressly
includes the presence of trace or contaminant amounts of base
catalyst but does not require the presence of the base
catalyst.
[0032] In another embodiment, providing a high activity component
as physically separate and distinct particles means the high
activity component has a primary functionality which is distinct
from the base catalyst. For comparative distinction, when the high
activity component is incorporated within or as part of the base
catalyst particle in a single particle system instead of as
physically separate and distinct particles from the base catalyst
particle in a multi-particle particle system, dual or multiple
functionalities of the base catalyst and high activity component
co-exist within the same single particle by virtue of the proximity
of the components.
[0033] Base cracking catalyst is conventional and common in
fluidized units, and some fluidized units include base catalyst
particles which have other catalytic components incorporated within
or as part of base as single particle system with dual or multiple
functionalities of the base catalyst and high activity component.
Thus, it should be appreciated that some embodiments of the
invention may further include base catalyst particles which have
some high activity component or components incorporated within or
as part of the base catalyst particle since base cracking catalyst
is conventional and common in fluidized units, as long as at least
a high activity component is provided as physically separate and
distinct particles from the base catalyst particle in a
multi-particle particle system. Thus, since base cracking catalyst
is conventional and common in fluidized units, presence of base
catalyst particles which have or do not have high activity
component or components incorporated within or as part of the base
catalyst particle are included in embodiments of the invention, as
long as at least a high activity component is provided as
physically separate and distinct particles from the base catalyst
particle in a multi-particle particle system.
[0034] Embodiments of the invention include providing at least a
high activity component with a primarily functionality independent
of the base catalyst as physically separate and distinct particles
in a multi-particle particle regardless of whether some dual or
multi-natured base catalyst particle with high activity
component(s) incorporated within or as part of a base catalyst
particle are present in a fluidized unit.
[0035] Providing the high activity component as a separate and
distinct particle from the base catalyst may have one or more
advantages which are not attainable by incorporating the high
activity component within or as part of the base catalyst as a
single particle system such as but not limited to below.
[0036] When a high activity component is incorporated as part of or
within base catalyst, base catalyst comprises multiple elements
such as high activity component A, other elements such as the base
(B) etc. If refiner wants to increase the relative amount of the
high activity component A to increase yield of a specific product,
increasing the addition of the base catalyst with the incorporated
high activity component as a single particle system also inherently
increases B (base) etc. Thus, providing a base catalyst with the
incorporated high activity component as a single particle system
does not increase the relative amount of high activity component A
over B (base) and therefore does not change the relative
contributions to product yields because B (base) also is inherently
added.
[0037] Applicant's approach of providing the high activity
component A as physically separate and distinct particle from the B
(base) in a multi-particle particle system instead of a single
particle system allows high activity component A or a combination
of high activity components to be added specifically over and above
the B (base) and thereby increases the relative amount of high
activity component A over B (base) etc.
[0038] Furthermore, Applicant's embodiments of providing the high
activity component as physically separate and distinct particles
from the B (base) as a multi-particle particle prevents wastage of
"extra" base catalyst which is inherently added when the high
activity component is incorporated within or as part of the base
catalyst particle as a single particle system because Applicant's
embodiments allow high activity component A or a combination of
high activity components to be added specifically over and above or
without B (base) and thereby increases the relative amount of high
activity component A over B (base) etc.
[0039] In fact, the extra B (base catalyst) in this single particle
system may be detrimental by taking up volume or weight which may
be filled by the high activity component and thereby limit the
rates and amount available for a high activity catalyst.
[0040] Furthermore, providing the high activity component as
physically separate and distinct particles from the base as a
multi-particle particle allows a refiner to quickly alter
concentration of the base catalyst or a selected high activity
component with minimal waste of "unused" component because the
multi-particle particle system allows high activity component A or
a combination of high activity components to be added specifically
over and above or without the base and thereby increases the
relative amount of high activity component A over B (base) etc.
[0041] Furthermore, in a single particle system, the different
catalytic components deactivate (age) via thermal, hydrothermal and
other deactivation mechanisms, at different relative rates. Thus,
one component may be severely deactivated while the other component
still has some remaining activity or "useful life". In effect, the
herein described compositions and processes provide a method for
"using up" any remaining useful life in either of these two
components. Therefore, another advantage of applicant's
multi-particles system and method providing the high activity
component as a separate and distinct particle from the base
catalyst is to maximize usage of each of the components, regardless
of how the components age relative to each other in any given
industrial facility.
LCO Selective Component
[0042] FIG. 2A is a schematic representation of an embodiment of a
high activity component 201 to preferentially increase the yield of
one or more selected hydrocarbon products compared to another
hydrocarbon product or products. An example of a high activity
component 201 having one or more LCO selective components 211 is
Applicant's BCA.TM..
[0043] In one embodiment, the high activity component includes one
or more LCO (Light Cycle Oil) selective components 211 to
preferentially increase the yield of LCO. Non-limiting examples of
hydrocarbon products that may incorporate some LCO include diesel,
kerosene and aviation fuel. In a particular embodiment, the LCO
selective component 211 includes a diesel selective component to
preferentially increase the yield of LCO. Non-limiting examples of
LCO selective components 211, for illustration and not limitation,
include silica-alumina and active alumina matrix having an average
pore diameter between about 20 to about 500 A, either individually
or in a combination of two or more thereof.
[0044] In one embodiment, the high activity component 201 comprises
from about 70% to about 100% by weight LCO selective component 211.
In a particular embodiment, the LCO selective component 211 is
about 80% to about 100% by weight. In yet another embodiment, LCO
selective component is about 90% to about 100% by weight. In
another embodiment, LCO selective component 211 is about 100% by
weight, wherein the high activity component 201 essentially
consists of LCO selective component 211.
[0045] In one embodiment, the method of providing the high activity
component 201 having one or more LCO selective components 211 as
physically distinct and separate particles, versus incorporated as
part of or within a base catalyst as a single particle system,
preferentially increases LCO yield compared to providing as a
single particle.
[0046] In one embodiment, the method includes providing a plurality
of the high activity components 201. Furthermore, as depicted in
FIG. 2A, in one embodiment, a high activity component 201 may
include a plurality of LCO selective components 211 to
preferentially increase the yield of gasoline. The described
methods are not limited by a sequence of when and how the plurality
the high activity components 201 are provided. One embodiment
includes sequentially providing the plurality of high activity
components 201 to one or more fluidized units. Another embodiment
includes simultaneously providing the plurality of high activity
components 201 to one or more fluidized units. The method is also
not limited by the frequency of providing the plurality the high
activity components 201.
[0047] High activity component may also be referred as concentrated
catalyst, additive etc. Furthermore, properties of each high
activity component are independent of any other high activity
component.
[0048] Embodiments of the invention are not limited by how the high
activity component 201 is being delivered or the form, size or
shape of the high activity component 201. Non-limiting examples of
the form of high activity component 201 include liquid, powder,
formed solid shapes such as microspheres, beads, and extrudates,
either individually or in a combination of two or more forms.
Furthermore, the size or shape of the high activity component, may
have varying dimensions of depth, width, length and FIG. 2A depicts
the high activity component 201 with oval or circular cross-section
for illustration only.
[0049] Properties of each LCO selective component 211 are also
independent of any other LCO selective component 211 and
embodiments of the invention are also not limited by how the LCO
selective component 211 is delivered or the form, size or shape of
the LCO selective component 211. Non-limiting examples of the form
of LCO selective component 211 include liquid, powder, formed solid
shapes such as microspheres, beads, and extrudates, either
individually or in a combination of two or more forms. Furthermore,
the size or shape of the LCO selective component 211 may have
varying dimensions of depth, width, length and may independently
vary from embodiment to embodiment and FIG. 2A depicts LCO
selective component 211 with oval or circular cross-section for
illustration only.
[0050] It should also be appreciated that some embodiments of a
high activity component 201 also includes one or more products
resulting from the reaction of or between one or more elements or
reactants which comprise the high activity component. For example,
an embodiment of the high activity component 201 includes one or
more products resulting from LCO selective components reacting with
each other, or reacting with one or more other elements or
materials which comprise the high activity component.
[0051] In one embodiment, the method further includes providing a
second high activity component, which differs from a first high
activity component by reversing the preferential yield of a
selected hydrocarbon such as of gasoline vs. LCO. The described
methods are not limited by a sequence of when and how the differing
high activity component is provided. One embodiment comprises
sequentially providing the differing high activity component to a
fluidized unit to reverse or adjust yield based on market demand.
Another embodiment comprises simultaneously providing differing
high activity components to multiple fluidized units such that
distinct fluidized units preferentially yield different selected
hydrocarbon product(s) to meet varying market demand. For example,
high activity component with LCO selective component may be
provided to fluidized unit 1 while high activity component with
gasoline selective component may be sequentially or simultaneously
provided to fluidized unit 2 such that preferential yield of
different hydrocarbon product or combination of products by
different fluidized units are available to meet varying market
demand. The method is also not limited by the frequency of
providing differing high activity components to shift or reverse
the preferential hydrocarbon product yield based on market demand.
Thus, embodiments of the invention include providing at least a
second high activity component which differs from a first high
activity component in an amount sufficient to reverse the
preferential yield of hydrocarbon such as gasoline to LCO or
vice-versa as frequently as desired based on market demand.
Gasoline Selective Component
[0052] FIG. 2B is another schematic representation of an embodiment
of a high activity component 202 to preferentially increase the
yield of one or more selected hydrocarbon products compared to
another hydrocarbon product or products. An example of a high
activity component 202 having one or more gasoline selective
components 212 is Applicant's Hi-Y.TM..
[0053] In one embodiment, the high activity component 202 includes
one or more gasoline selective components 212 to preferentially
increase the yield of gasoline. Non-limiting examples of gasoline
selective component 212 for illustration and not limitation,
include ultrastable Y, proton exchanged zeolite Y(HY), rare earth
exchanged zeolite Y (HREY), calcined rare earth exchanged zeolite
Y(CREY), ultrastable zeolite Y (USY), rare earth exchanged
ultrastable zeolite Y (REUSY), and other zeolites known in the art,
either individually or in a combination of two or more thereof. In
one embodiment, the high activity component comprises from about
40% to about 85% by weight gasoline selective component 212. In a
particular embodiment, the gasoline selective component 212 is
about 50% to about 85% by weight. In yet another embodiment, the
gasoline selective component 212 comprises at least 70% by
weight.
[0054] In one embodiment, the method of providing the high activity
component 202 comprising the gasoline selective component(s) 212 as
physically separate and distinct particles preferentially increases
the yield of gasoline over LCO compared to providing the Y zeolite
or high activity component 202 comprising the gasoline selective
component(s) 212 as part of or incorporated within a base catalyst
because increasing gasoline selective component via increased
additions of the base catalyst maintains a fixed ratio of gasoline
selective component vs. other components rather than increasing the
ratio of gasoline selective component.
[0055] As discussed above, embodiments of the method optionally
include providing a plurality of the high activity components,
which may be the same or differ from each other. Embodiments of the
invention are not limited by how the high activity components are
delivered or the form, size or shape of the high activity
components and properties of each high activity component such as
201 and 202 are independent of any other high activity
component.
[0056] Furthermore, as depicted in FIG. 2B, in one embodiment, a
high activity component 202 may include a plurality of gasoline
selective components 212 to preferentially increase the yield of
gasoline. The described methods are not limited by a sequence of
when and how the plurality the high activity components 202 are
provided. One embodiment includes sequentially providing the
plurality the high activity components to one or more fluidized
units. Another embodiment includes simultaneously providing
plurality the high activity components to one or more fluidized
units. The method is also not limited by the frequency of providing
the plurality of high activity components 202.
[0057] As discussed above, embodiments of the invention are not
limited by how the high activity component 202 is delivered or the
form, size or shape of the high activity component and properties
of each high activity component are independent of any other high
activity component. Properties of each selective component, such as
LCO selective component 211 discussed above, gasoline selective
component 212, LPG selective component 213, contaminant inhibit
component 214, etc. are also independent of any other selective
component and embodiments of the invention are also not limited by
how the selective component, such as gasoline selective component
212 is delivered or the form, size or shape of the selective
component. It is understood that the form, size or shape of the
high activity and the selective component may be varied by one of
ordinary skill in the art to best suit the type of fluidized unit
and the preferential yield of the particular hydrocarbon product or
combination of products.
[0058] As discussed above, it should also be appreciated that some
embodiments of a high activity component also includes one or more
products resulting from the reaction of or between one or more
elements or reactants which comprise the high activity component.
For example, an embodiment of the high activity component 202
includes one or more products resulting from gasoline selective
components 212 reacting with each other, or reacting with one or
more other elements or materials which comprise the high activity
component.
[0059] In one embodiment, the method further includes providing at
least a second high activity component which differs from a first
high activity component 202 comprising the gasoline selective
component 212 in an amount sufficient to reverse the preferential
yield of gasoline. The method is also not limited by the frequency
of providing differing high activity components to shift or reverse
the preferential increased yield of one or more hydrocarbon
products based on market demand. Thus, embodiments of the invention
include providing at least a second high activity component which
differs from a first high activity component in an amount
sufficient to reverse the preferential yield of one or more
hydrocarbon products such as gasoline to LCO or vice-versa as
frequently as desired based on market demand.
LPG Selective Components
[0060] FIG. 2C is another schematic representation of an embodiment
of a high activity component 203 to preferentially increase the
yield of a selected hydrocarbon product compared to another
hydrocarbon product. In one embodiment, the high activity component
includes one or more LPG selective components 213 to preferentially
increase the yield of LPG. Non-limiting examples of LPG selective
component 213, for illustration and not limitation, include
Silicalite, Beta (BEA), EU-1, (EUO), ZSM-5(MFI), ZSM-11 (MEL),
ZSM-12 (MTW), ZSM-18 (MEI), ZSM-22 (TON), ZSM-23 (MTT), ZSM-35,
ZSM-39 (MTN), ZSM-48, ZSM-57 (MFS), ALPO-41 (AFO), ALPO-11 (AEL),
Boggsite (BOG), Dachiardite (DAC), Epistilbite (EPI), Ferrierite
(FER), Laumontite (LAU), Montesommaite (MON), Mordenite (MOR),
NU-87 (NES), Offretite (OFF), Partheite (PAR), Stilbite (STI), and
Weinebeneite (WEN), either individually or in a combination of two
or more thereof. In one embodiment, the high activity component
comprises from about 20% to about 85% by weight of an LPG selective
component 213. In a particular embodiment, the LPG selective
component 213 is about 30% to about 85% by weight. In yet another
embodiment, LPG selective component 213 is about 40% to about 85%
by weight.
[0061] In one embodiment, the method of providing at least a high
activity component 203 having the LPG selective component as a
separate and distinct particle from incorporated as part of or
within a base catalyst as a single particle system preferentially
increases LPG yield compared to providing as a single particle.
[0062] In one embodiment, the method further includes providing a
second high activity component which differs from a first high
activity component 203 comprising the LPG selective component 213
in an amount sufficient to reverse the preferential yield of LPG.
The method is also not limited by the frequency of providing
differing high activity components to shift or reverse the
preferential hydrocarbon product yield based on market demand.
Thus, embodiments of the invention include providing at least a
second high activity component which differs from a first high
activity component in an amount sufficient to reverse the
preferential yield of hydrocarbon such as gasoline to LPG or
vice-versa as frequently as desired based on market demand.
[0063] As discussed above, it should also be appreciated that some
embodiments of a high activity component also includes one or more
products resulting from the reaction of or between one or more
elements or reactants which comprise the high activity component.
For example, an embodiment of the high activity component 203
includes one or more products resulting from LPG selective
components 213 reacting with each other, or reacting with one or
more other elements or materials which comprise the high activity
component.
Contaminant Inhibitor Component
[0064] FIG. 2D is another schematic representation of an embodiment
of a high activity component 204. Examples of contaminant inhibitor
component 214 include Applicant's CAT-Aid.TM. comprising calcium
oxide supported on mixed metal oxide such as MgO and
Al.sub.2O.sub.3, and other metals traps such as MgO or Rare Earth
oxides, strontium titanate, barium titanate, sepiolite, etc.,
either individually or in a combination of two or more thereof.
[0065] In one embodiment, the high activity component 204 includes
one or more contaminant inhibitor components 214 to preferentially
increase the yield of one or more selected hydrocarbon products
compared to another hydrocarbon product or products. In one
embodiment, the method of providing the high activity component 204
comprising the contaminant inhibitor component 214 as separate and
distinct particles instead of incorporated as part of or within a
single particle base catalyst system preferentially increases
yields of LPG and or gasoline compared to providing as a single
particle system. Non-limiting examples of contaminant inhibitor
components 214, for illustration and not limitation, include nickel
traps, vanadium traps, either individually or in a combination of
two or more thereof. In one embodiment, the high activity component
204 comprises from about 70% to about 100% by weight a contaminant
inhibitor component 214. In a particular embodiment, the
contaminant inhibitor component 214 is about 80% to about 100% by
weight. In yet another embodiment, contaminant inhibitor component
214 is about 90% to about 100% by weight. In yet another
embodiment, contaminant inhibitor component 214 is about 95% by
weight. In another embodiment, contaminant inhibitor component 214
is about 100% by weight, wherein the high activity component 204
essentially consists of contaminant inhibitor component 214.
[0066] Another embodiment includes providing one or more high
activity components 204 comprising one or more contaminant
inhibitor components 214 to one or more fluidized unit as
physically separate and distinct particles instead of incorporated
as part of or within a single particle base catalyst system to
inhibit the adverse effects of one or more contaminants in a feed
stock. Examples of contaminants inhibited by contaminant inhibitor
component 214 include such as but not limited to vanadium, nickel,
copper, sodium, calcium, and iron, either individually or in a
combination of two or more thereof.
[0067] Another embodiment includes providing one or more high
activity components 204 comprising one or more contaminant
inhibitor components 214 to one or more fluidized unit as
physically separate and distinct particles instead of incorporated
as part of or within a single particle base catalyst system to
preferentially decrease the yield of one or more selected
hydrocarbon products compared to another hydrocarbon product or
products. Examples of selected hydrocarbon products for which yield
is decreased include such as but not limited to the dry gas, coke,
heavy cycle oil, bottoms, either individually or in combinations of
two or more thereof.
[0068] In a particular embodiment, preferentially decreasing yield
of one or more selected hydrocarbon products results in
preferentially increasing yields of LPG and or gasoline because
contaminant inhibitor components 214 shifts the product range from
dry gas, coke, and heavy cycle oil, either individually or in
combinations of two or more thereof to a product range of LPG and
or gasoline.
[0069] Properties of each contaminant inhibitor 214 component are
also independent of any other contaminant inhibitor components 214
and embodiments of the invention are also not limited by how the
contaminant inhibitor component 214 is delivered or the form, size
or shape of the contaminant inhibitor component and FIG. 2D depicts
contaminant inhibitor components 214 with trapezoid or rectangular
cross-section for illustration only.
[0070] It should also be appreciated that some embodiments of a
high activity component also includes one or more products
resulting from the reaction of or between one or more elements or
reactants which comprise the high activity component. For example,
an embodiment of the high activity component 204 includes one or
more products resulting from contaminant inhibitor components 214
reacting with each other, or reacting with one or more other
elements or materials which comprise the high activity
component.
Combination of Selective Components
[0071] In one embodiment, a plurality of high activity components
which differ from each other, such as respectively high activity
component 202 comprising gasoline selective components 212 and high
activity component 204 comprising one or more contaminant
inhibitors 214, are provided to preferentially have a synergistic
unexpected combined effect of enhancing the preferential yield of
one or more selected hydrocarbon products such as gasoline. Another
embodiment of a combination of differing high activity components
with unexpected synergistic effect includes high activity component
201 comprising LCO selective components 211 and high activity
component 204 comprising one or more contaminant inhibitors 214, to
preferentially have a synergistic unexpected combined effect of
enhancing the preferential yield of one or more selected
hydrocarbon products such as LCO.
[0072] The method further includes providing at least a second high
activity component (such as high activity component comprising
gasoline selective component) which differs from a first high
activity component comprising the contaminant inhibitor components
214 in an amount sufficient to reverse or alter preferential yields
of one or more selected hydrocarbon products based on market
demand. The method is also not limited by the frequency of
providing the combination of differing high activity components
with unexpected synergistic effect to reverse or alter i.e. adjust
the preferential yield of one or more hydrocarbon products based on
market demand. Thus, an embodiment includes providing a combination
of differing high activity components (such as high activity
components respectively comprising gasoline selective component and
contaminant inhibitor component) with unexpected synergistic effect
to enhance the preferential yield of one or more selected
hydrocarbon products; and another embodiment includes providing a
second combination of differing high activity components (such as
high activity components respectively comprising LCO selective
component and contaminant inhibitor component) with unexpected
synergistic effect in an amount sufficient to reverse or shift the
preferential yield of one or more selected hydrocarbon products
(such as from gasoline to LCO and vice versa) from the first
combination of differing high activity components as frequently as
desired based on market demand.
[0073] Just as how a plurality of high activity components which
have respectively differing selective components may be provided to
have synergistic unexpected combined effect, differing selective
components such as gasoline 211 and contaminant inhibitors 214 may
also be provided in a single high activity component.
[0074] FIG. 2E is another schematic representation of an embodiment
of a high activity component 205 comprising a plurality of
selective components which differ from each other, such as gasoline
selective components 212 and contaminant inhibitors 214. Another
embodiment of a high activity component 205 having a plurality of
selective components which differ from each other includes LCO
selective components 211 and contaminant inhibitor 214.
[0075] Furthermore, in an embodiment, the high activity component
205 includes a plurality of selective components which differ from
each other to preferentially have a synergistic combined unexpected
effect such as the combination of gasoline selective components 212
and contaminant inhibitors 214 depicted in FIG. 2E. The described
methods are not limited by a sequence of when and how the high
activity component 205 comprising the plurality of selective
components such as gasoline selective components 212 and
contaminant inhibitors 214. One embodiment comprises sequentially
providing the high activity component 205 comprising the plurality
of selective components to one or more fluidized units. Another
embodiment comprises simultaneously providing the high activity
component 205 comprising the plurality of selective components to
one or more fluidized units. The method is also not limited by the
frequency of providing the plurality of high activity
components.
[0076] The method further optionally includes providing at least a
second high activity component 205 which differs from a first high
activity component 205 comprising the plurality of differing
selective components in an amount sufficient to shift or reverse a
preferential yield of one or more hydrocarbon products. The second
high activity component may also comprise a plurality of selective
components which differ from each other. The method is also not
limited by the frequency of providing the differing high activity
components 205 to shift or reverse the preferential yield of
hydrocarbon product(s) based on market demand. Thus, embodiments of
the invention include providing at least a second high activity
component 205 (with a plurality of selective components which
differ from each other) which differs from a first high activity
component 205 (comprising a plurality of selective components which
differ from each other) such as first high activity component 205
comprising a combination of gasoline selective components 212 and
contaminant inhibitors 214 versus second high activity component
205 comprising a combination of LCO selective components 211 and
contaminant inhibitors 214 to reverse the preferential yield of one
or more hydrocarbon products as frequently as desired based on
market demand.
[0077] As discussed above, it should also be appreciated that some
embodiments of a high activity component also includes one or more
products resulting from the reaction of or between one or more
elements or reactants which comprise the high activity component.
For example, an embodiment of the high activity component 205
includes one or more products resulting from selective components
reacting with each other, or reacting with one or more other
elements or materials which comprise the high activity component
205.
[0078] Approximating language, as used herein throughout the
specification and claims, may be applied to modify any quantitative
or qualitative representation that could permissibly vary without
resulting in a change in the basic function to which it is related.
Accordingly, a value modified by a term such as "from about" or "to
about" is not to be limited to a specified precise value, and may
include values that differ from the specified value. In at least
some instances, the approximating language may correspond to the
precision of an instrument for measuring the value. Furthermore,
"providing high activity component in an amount sufficient to" may
be used in combination with quantitative value, and include a
varying amount of high activity component and is not to be limited
to a specified precise quantitative value, and may include values
that differ from a specified value.
[0079] It should be appreciated that an embodiment of the method
and systems may further include presence of or providing dual or
multi-natured base catalyst particles which have some high activity
component or components incorporated within or as part of the base
catalyst particle since base cracking catalyst is conventional and
common in fluidized units, as long as at least a high activity
component is provided as physically separate and distinct particles
from the base catalyst particle in a multi-particle particle
system.
[0080] In an embodiment, the high activity component is provided to
one or more units such as, but not limited to, an FCC unit, fixed
bed or moving bed unit, bubbling bed unit, units suitable for the
manufacture of pyridine and its derivatives, units suitable for the
manufacture of acrylonitrile, and other units suitable for
industrial processes, etc., either individually or in a combination
of two or more. In a particular embodiment, the high activity
component is provided to a plurality of units that are FCC units.
The FCC unit is adapted to promote catalytic cracking of feed stock
provided from a source and may be configured in a conventional
manner. In another embodiment, the high activity component is
provided to units designed to crack gasoline range feed stocks into
Liquefied Petroleum Gas (LPG) such as but not limited to
Superflex.TM. process or crack heavy feed into LPG instead of
gasoline such as but not limited to Indmax.TM. process. In another
particular embodiment, the high activity component is provided to
an unit for processing acrylonitrile. An example of a unit suitable
for the manufacture of acrylonitrile is a fluidized bed process.
Similar units are also used for manufacturing other chemicals such
as pyridine.
[0081] The following examples serve to illustrate the features and
advantages of the invention and are not intended to limit the
invention thereto.
EXAMPLE 1
High Activity Component 201 Comprising LCO Selective Component
211
[0082] Not to be bound by theory, feed generally consists of large
molecules which are too large to enter into the pores of gasoline
selective component such as Y zeolite pores. In contrast, LCO
selective component pores are larger than the pores of gasoline
selective component. Thus, large hydrocarbon molecules can enter
the larger pores of the LCO selective component and be cracked to
form LCO range molecules.
[0083] Below is an example of Applicant's unexpectedly superior
result of providing high activity component 201 comprising LCO
selective component 211 as physically separate and distinct
particles versus incorporated as part of or within the base
catalyst as a single particle system.
[0084] Not to be bound by theory, providing the high activity
component 201 comprising the LCO selective component 211 as
physically separate and distinct particles instead of incorporating
the LCO selective component as part of or within the base catalyst
as a single particle system appears to preferentially increase LCO
yield by decreasing the zeolites-to-matrix ratio (the matrix is
referred as LCO selective component).
[0085] Zeolite-to-Matrix Ratio (Z/M) is the measure of the ratio of
the Zeolite Surface Area/Matrix Surface Area (or ZSA/MSA).
Measurement was conducted via a multi-point N2 BET isotherm--where
the surface area is split into two parts: ZSA<20 Angstroms pore
diameter and MSA>20 Angstroms pore diameter.
[0086] Specifically, providing the high activity component 201
comprising the matrix as physically separate and distinct particles
in a multiple particle system instead of incorporating the matrix
as part of or within the base catalyst as a single particle system
more effectively increases matrix (i.e. decreases the Z/M ratio) by
selectively providing matrix over and above or without the unwanted
zeolite etc. and thereby increasing the ratio of matrix relative to
zeolite instead of maintaining a fixed ratio of Z/M, as discussed
above in benefits of Applicant's multiple particle system. FIG. 3
is a schematic simulation demonstrating providing the high activity
component comprising a LCO selective component such as BCA.TM. as
physically separate distinct particles preferentially increases LCO
yield.
[0087] The Y axis represents the path from Feed Injectors (near the
bottom of the Riser) to the Riser Termination (or Riser Outlet, or
Riser Exit--where Catalyst and most of the Product are finally
separated) i.e. where the oil is in contact with the catalyst; thus
the base of the Y axis represents the feed injection zone and the
top of the Y axis is the riser termination. The X axis plots the wt
% of a specific product to the total feed product mix at as that
particular point in the riser. For example, the feed is 100% of
this mix at the feed injection zone, falling rapidly in the initial
movement up the riser as the matrix converts the feed to
intermediates, with conversion tailing off towards the riser
termination so that all that is left is unconverted feed which is
recovered as a non-distilling fraction in the distillation system
usually referred as "bottoms" but also commonly called Decanted
Cycle Oil (DCO).
[0088] Providing the matrix as part of or within the base catalyst
as a single particle system increases the LCO volume by converting
the feed into LCO until at some point up the riser, the LCO reaches
a maximum concentration (represented by the star in the diagram).
LCO reaches a maximum concentration because the creation of more
LCO is outweighed by the conversion of LCO to gasoline range
material by Y zeolites higher up the riser.
[0089] In contrast, providing the high activity component 201
comprising the LCO selective component 211 as physically separate
distinct particles increases the formation of LCO from feed in
terms of rate and amount of LCO formation compared to incorporating
the matrix as part of or within the base catalyst as a single
particle system. Hence the LCO peak is larger and occurs at a
greater distance up the riser. Additionally, providing the LCO
selective component as separate distinct particles lowers the
concentration of unwanted zeolite because Applicant's multiple
particle addition system allows LCO selective component (matrix) to
be added specifically over and above or without zeolite and thereby
increases the relative amount of matrix over zeolite etc. which
leads to a slower rate of undesired zeolite promoted conversion of
LCO to gasoline, shown graphically by a less steep slope in the
curve compared to the catalyst-only LCO line.
[0090] The comparative improvement in preferentially increasing LCO
yield by providing the high activity component 201 comprising the
LCO selective component 211 as physically separate distinct
particles vs. incorporating the matrix as part of or within the
base catalyst as a single particle system is represented by the
area between the curves at the riser termination (top of the
diagram). Thus, providing the high activity component 201
comprising the LCO selective component 211 as physically separate
distinct particles preferentially increases LCO yield compared to
traditional method of incorporating such as part of or within the
base catalyst as a single particle system.
[0091] Table 1 demonstrates effects of providing the high activity
component 201 comprising LCO selective component 211 as physically
separate distinct particles compared to traditional method of
incorporating the high activity component comprising LCO selective
component as part of or within the base catalyst in a single
particle system. For example, Table 1 shows providing BCA-105.TM.,
a high activity component comprising 201 LCO selective component
211, as physically separate distinct particles increased LCO range
yield from 24.8 to 29.4 when 30% BCA-105.TM. was provided.
Simulation was based on several conducted trials.
TABLE-US-00001 TABLE 1 Effects of high activity component
comprising LCO Selective Component upon product yield Base Catalyst
+10% +20% +30% (and % 0 high BCA-105 .TM. BCA-105 .TM. BCA-105 .TM.
activity (high activity (high activity (high activity component
component component component comprising comprising comprising
comprising LCO LCO LCO LCO Product selective selective selective
selective Yields component) component) component) component) Dry
Gas 7.57 7.57 7.56 7.56 LPG 15.84 15.50 15.06 14.59 Gasoline 38.46
38.28 37.62 36.49 LCO 24.80 26.05 27.58 29.39 Bottoms 6.62 5.89
5.47 5.25 Coke 6.71 6.70 6.70 6.69 ECat MAT 74.0 73.0 71.9 70.7
Regenerator 1385 1382 1379 1376 Temp (Deg F.)
[0092] Table 2 is a summary of 36 commercial trials of BCA.TM.
(high activity component 201 comprising LCO selective component
211). Table 2 shows BCA.TM. has been commercially proven to
increase LCO yield (average +0.8 wt %) via reduction of Bottoms
(average -1.7 wt %) in a wide range of FCC unit designs such as
operating in full and partial burn mode and processing light and
heavy feeds.
TABLE-US-00002 TABLE 2 Minimum Average Maximum Feed Quality Density
0.882 0.912 0.936 Sulphur 0.03 0.99 2.30 Conradson Carbon Residue
0.1 1.7 4.9 Nitrogen 200 787 1822 Operations Reactor Temp 490 521
542 Regenerator Temp 658 712 754 Catalyst adds, tpd 0.8 4.8 25.0
BCA .TM. (high activity 3.0 8.4 15.0 component 201 comprising LCO
selective component) concentration, % Equilibrium Catalyst MAT 60
67 73 Ni 100 1697 5700 V 100 1719 7500 Yield Selectivities Dry gas
-0.90 -0.11 0.71 LPG -1.6 0.6 4.7 Gasoline -1.2 1.1 5.0 LCO -3.0
0.8 5.0 HCO -1.5 -0.4 0.6 Bottoms -4.5 -1.7 0.0 Coke -0.9 -0.1 0.5
Base Bottoms Density 0.98 1.06 1.12
[0093] An embodiment of the invention includes providing one or
more high activity components to a fluidized unit as physically
separate and distinct particles in an amount sufficient to
preferentially increase the yield of LCO compared to another
hydrocarbon or combination of hydrocarbon products by greater about
10% (based on wt % of feed product). Another embodiment includes
providing one or more high activity components to a fluidized unit
as physically separate and distinct particles in an amount
sufficient to preferentially increase the yield of LCO compared to
another hydrocarbon or combination of hydrocarbon products by
greater than about 8%, by greater than about 7%, and great than
about 5%. Yet another embodiment of the invention includes
providing one or more high activity components to a fluidized unit
as physically separate and distinct particles in an amount
sufficient to preferentially increase the yield of LCO compared to
another hydrocarbon or combination of hydrocarbon products by
greater than about 4%, by greater than about 3%, by greater than
about 2%, and by greater than about 1.0%. Embodiments of the
invention expressly includes providing one or more high activity
components as physically separate and distinct particles to one or
more fluidized unit in an amount sufficient to preferentially
increase the yield of LCO compared to another hydrocarbon or
combination of hydrocarbon products, and is not limited to a
specified precise value, and may include values that differ from
the specified value.
EXAMPLE 2
High Activity Component 202 Comprising Gasoline Selective Component
212
[0094] Applicant's Hi-Y.TM. is an example of high activity
component 202 comprising one or more gasoline selective component
212 to preferentially increase gasoline yield. In one embodiment,
high activity component 202 comprising one or more gasoline
selective components 212 includes a high concentration of y
zeolite; Applicant's Hi-Y.TM. high activity component includes a
high concentration of zeolite such as Y zeolites to provide high
zeolite functionality with relatively little amount of other
materials in the high activity component.
[0095] FIG. 4 is schematic simulation of providing high activity
component 202 comprising one or more gasoline selective component
212. FIG. 4 shows the changes in FCC unit's catalyst inventory
(including all the catalyst and additives being used) plotted
against feeds with varying quality (often referred to as
heaviness--heavier feeds being more difficult to crack). The total
surface area of the catalyst in the unit (also called equilibrium
catalyst or ECat) is commonly used to monitor the activity level of
the catalyst in the unit (total surface area being proportional to
activity). FIG. 4 shows catalyst surface area increases when a high
activity component 201 comprising gasoline selective component is
added (dashed line).
[0096] The area between the two catalyst lines/curves represents
the increase in total surface area (TSA) that may be achievable by
providing high activity component. The increased TSA directly
resulted in increased preferential yield of gasoline. In one
embodiment, the increased surface area of the high activity
component comprising one or more gasoline selective component 202,
which is typically greater than 380 m.sup.2/g, increases the
magnitude and rapidity of the yield slate changes versus those of a
second grade of catalyst. Furthermore, the lighter the feed, the
higher the concentration of high activity component that can be
used, which results in even greater increase in gasoline range
product yield.
[0097] Table 3 shows the change in activity and increase in
gasoline range product yield (weight percent on feed basis) by
providing the high activity component 202 comprising gasoline
selective components 212 as physically separate distinct particles
preferentially compared to traditional method of incorporating such
as part of or within the base catalyst as a single particle system.
For example, Table 3 demonstrates providing 20% Hi-Y.TM. (high
activity component 202 comprising gasoline selective component 212)
as physically separate distinct particles increased gasoline range
product yield from 39.5 to 40.9, from 41.9 to 44.1 and 43.6 to 45
(weight percent on feed basis) in Trial 1-3 respectively. Trial 1-3
are samples from three commercial trials tested under standard
laboratory conditions. Table 3 also demonstrates providing 20%
Hi-Y.TM. as physically separate distinct particles increased
conversion (wt %, weight percent on feed basis) in Trial 1-3.
TABLE-US-00003 TABLE 3 Trial 1 Trial 2 Trial 3 20% 20% 20% Hi-Y
.TM. Hi-Y .TM. Hi-Y .TM. high high high activity activity activity
component component component Trial 1 Trial 2 Trial 3 202 202 202
Control Control Control comprising comprising comprising Base as
Base as Base as gasoline gasoline gasoline single single single
selective selective selective particle particle particle component
component component Low N2 Feed system system system 212 212 212
Run ID 26413-2 26414-2 26415-2 26431-2 26432-2 26433-2 Conversion,
54.8 58.7 62.0 57.2 61.8 63.9 w % Coke 2.1 2.3 2.7 2.2 2.5 2.7
C2-(dry gas) 0.9 0.9 1.0 1.0 1.0 1.1 Hydrogen 0.10 0.11 0.11 0.08
0.08 0.09 Methane 0.30 0.31 0.35 0.32 0.34 0.36 Ethane 0.2 0.2 0.2
0.2 0.2 0.3 Ethylene 0.3 0.3 0.3 0.3 0.4 0.4 C3 0.6 0.7 0.7 0.7 0.7
0.8 C3= 3.5 3.9 4.3 3.8 4.1 4.4 Total C3s 4.1 4.6 5.0 4.4 4.8 5.2
iC4 2.8 3.2 3.6 3.2 3.5 3.8 nC4 0.6 0.7 0.7 0.6 0.7 0.8 iC4= 1.3
1.4 1.5 1.3 1.4 1.5 nC4= 3.4 3.6 3.9 3.5 3.7 3.9 1- 1.1 1.2 1.2 1.1
1.2 1.2 Butene Cis-2- 1.0 1.0 1.1 1.0 1.1 1.1 Butene Trans- 1.3 1.4
1.5 1.4 1.5 1.6 2-Butene 1,3- 0.0 0.0 0.0 0.0 0.0 0.0 Butadiene
Total 4.8 5.1 5.3 4.8 5.1 5.4 Butenes Total C4s 8.2 9.0 9.6 8.6 9.3
9.9 LPG 12.3 13.5 14.7 13.0 14.2 15.1 Isopentane 2.2 2.3 2.4 2.4
2.4 2.5 n-Pentane 0.2 0.2 0.2 0.2 0.2 0.2 3-Methyl- 0.1 0.1 0.1 0.1
0.1 0.1 1-Butene Trans-2- 0.5 0.5 0.5 0.5 0.4 0.5 Pentene 2-Methyl-
0.5 0.5 0.5 0.5 0.5 0.5 2-Butene 1-Pentene 0.2 0.2 0.2 0.2 0.2 0.2
2-Methyl- 0.3 0.3 0.3 0.3 0.3 0.3 1-Butene cis-2- 0.2 0.2 0.2 0.2
0.2 0.2 Pentene Total C5 4.3 4.3 4.5 4.3 4.2 4.5 C6+ 1.6 1.5 1.6
1.5 1.4 1.5 Total C5+ in 6.0 5.8 6.1 5.8 5.6 6.0 Gasoline Liquid
33.5 36.1 37.5 35.1 38.5 39.0 Gasoline Gasoline 39.5 41.9 43.6 40.9
44.1 45.0 (C5-163C) LCO (163-282C) 22.3 21.8 21.2 21.7 20.7 20.3
MCO (282-382C) 13.5 12.0 10.8 12.6 10.8_10.2 LCO + MCO 35.8 33.8
32.0 34.3 31.5 30.4 (163-382C) Bottoms 9.4 7.5 6.0 8.6 6.7 5.7
(382C+) Total 100.0 100.0 100.0 100.0 100.0 100.0
[0098] In embodiment of the invention includes providing one or
more high activity components to one or more fluidized units as
physically separate and distinct particles in an amount sufficient
to preferentially increase the yield of gasoline range products
compared to another hydrocarbon or combination of hydrocarbon
products by greater about 10% (based on wt % of feed product).
Another embodiment includes providing one or more high activity
components to a fluidized unit as physically separate and distinct
particles in an amount sufficient to preferentially increase the
yield of gasoline range products compared to another hydrocarbon or
combination of hydrocarbon products by greater than about 8%, by
greater than about 7%, and great than about 5%. Yet another
embodiment of the invention includes providing one or more high
activity components to a fluidized unit as physically separate and
distinct particles in an amount sufficient to preferentially
increase the yield of gasoline range products compared to another
hydrocarbon or combination of hydrocarbon products by greater than
about 4%, by greater than about 3%, by greater than about 2%, and
by greater than about 1.0%. Embodiments of the invention expressly
includes providing one or more high activity components as
physically separate and distinct particles to one or more fluidized
unit in an amount sufficient to preferentially increase the yield
of gasoline range products compared to another hydrocarbon or
combination of hydrocarbon products, and is not limited to a
specified precise value, and may include values that differ from
the specified value.
EXAMPLE 3
High Activity Component 203 Comprising LPG Selective Component
213
[0099] As previously discussed in the preceding examples 1-2, not
to be bound by theory, a feed mainly consists of large hydrocarbon
molecules which are too large to enter into the pores of high
activity component 202 comprising gasoline selective component such
as Y zeolite pores. In contrast, LCO selective component pores are
larger than the pores of gasoline selective component. Thus, large
hydrocarbon molecules can enter the larger pores of the LCO
selective component and be cracked to form LCO range molecules.
[0100] LCO range molecules are now small enough to enter the pores
of the gasoline selective component such as Y zeolite pores and the
preceding examples disclosed cracking the LCO range molecules in
the smaller pores of the gasoline selective component such as Y
zeolite pores to preferentially increase yield of gasoline range
molecules.
[0101] Applicant has extended this principle to LPG selective
component such as ZSM-5 which has even smaller pores than gasoline
selective component of Zeolite Y and can further crack gasoline
range molecules down to LPG range.
[0102] Feed/bottoms range hydrocarbon molecules are cracked by high
activity component 201 comprising LCO selective component 211 such
as BCA.TM. which has the largest pores into LCO range
molecules.
[0103] LCO range molecules are cracked by high activity component
202 comprising gasoline selective component 212 such as Y zeolites,
which has smaller pores than LCO selective component, into gasoline
range molecules.
[0104] Gasoline range molecules are cracked by high activity
component 203 comprising LPG selective component 213 which has even
smaller pores than gasoline selective component into LPG range
molecules.
[0105] Thus, an embodiment of the invention includes providing a
high activity component 203 comprising LPG selective component 213
as physically separate and distinct particles from a base catalyst
to preferentially increase LPG yield by cracking gasoline range
molecules in the smaller pores of the LPG selective component 213
such as ZSM-5 because the gasoline range molecules are now small
enough to enter the pores the of LPG selective component.
[0106] In an embodiment, providing a high activity component 203
with 2-3% of LPG selective component 213 such as ZSM-5 crystals as
physically separate and distinct can substantially increase LPG
yield up to 2 wt % and increase gasoline octane (up to 1 RON
number) compared to single particle system with ZSM-5 incorporated
within the base catalyst particle.
[0107] Table 4 demonstrates effects of high activity component 203
comprising LPG selective component 213 as physically separate
distinct particles compared to traditional base catalyst. For
example, Table 4 shows LPG yield increased from 19.7 to 24.7 as
successive amounts of high activity component 203 comprising LPG
Selective Component 213 of up to 10%, was added as physically
separate distinct particles. Table 4 also shows conversion
increased from 67.3 to 67.5 as successive amounts of high activity
component 203 comprising LPG Selective Component 213 of up to 10%,
was added as physically separate distinct particles.
TABLE-US-00004 TABLE 4 high activity component comprising LPG
Selective Base Component ECat 1% 2% 3% 4% 5% 10% Conversion, w %
67.3 66.5 65.9 66.0 66.2 67.3 67.5 Coke 5.0 4.9 4.7 4.5 4.6 4.6 4.6
C2- 2.5 2.5 2.5 2.5 2.6 2.8 3.0 Hydrogen 0.1 0.1 0.1 0.1 0.1 0.1
0.1 Hydrogen Sulfide 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Methane 0.9 1.0
0.9 0.9 0.9 1.0 0.9 Ethane 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Ethylene 0.8
0.9 0.9 1.0 1.1 1.1 1.3 C3 1.5 1.7 1.6 1.7 1.8 1.9 2.1 C3= 5.9 6.3
6.7 7.0 7.3 7.6 8.3 Total C3s 7.4 8.0 8.3 8.6 9.1 9.5 10.4 iC4 4.9
5.3 5.3 5.4 5.8 5.8 6.3 nC4 1.2 1.3 1.2 1.2 1.2 1.2 1.2 iC4= 1.8
1.8 1.9 2.0 2.0 2.1 2.2 nC4= 4.4 4.4 4.4 4.4 4.5 4.7 4.6 1-Butene
1.1 1.1 1.1 1.1 1.1 1.2 1.2 Cis-2-Butene 1.7 1.6 1.7 1.7 1.7 1.8
1.7 Trans-2- 1.7 1.6 1.6 1.6 1.7 1.7 1.7 Butene 1,3-Butadiene 0.0
0.0 0.0 0.0 0.0 0.0 0.0 Total Butenes 6.2 6.2 6.3 6.4 6.4 6.7 6.8
Total C4s 12.3 12.8 12.9 13.0 13.4 13.8 14.3 LPG 19.7 20.8 21.2
21.7 22.5 23.3 24.7 Gasoline (C5-430F) 40.1 38.2 37.5 37.3 36.4
36.6 35.2 LCO (430-540F) 8.6 8.5 8.6 8.5 8.5 8.3 8.3 MCO (540-650F)
6.4 6.4 6.5 6.4 6.4 6.2 6.1 LCO + MCO 15.1 14.9 15.1 14.9 14.9 14.5
14.5 (430-650F) Bottoms (650F+) 17.7 18.7 19.0 19.1 18.9 18.2 18.0
Totals 100 100 100 100 100 100 100
[0108] An embodiment of the invention includes providing one or
more high activity components to one or more fluidized units as
physically separate and distinct particles in an amount sufficient
to preferentially increase the yield LPG compared to another
hydrocarbon or combination of hydrocarbon products by greater about
10% (based on wt % of feed product). Another embodiment includes
providing one or more high activity components to a fluidized unit
as physically separate and distinct particles in an amount
sufficient to preferentially increase the yield of LPG compared to
another hydrocarbon or combination of hydrocarbon products by
greater than about 8%, by greater than about 7%, and greater than
about 5%. Yet another embodiment of the invention includes
providing one or more high activity components to a fluidized unit
as physically separate and distinct particles in an amount
sufficient to preferentially increase the yield of LPG compared to
another hydrocarbon or combination of hydrocarbon products by
greater than about 4%, by greater than about 3%, by greater than
about 2%, and by greater than about 0.1%. Embodiments of the
invention expressly includes providing one or more high activity
components as physically separate and distinct particles to one or
more fluidized unit in an amount sufficient to preferentially
increase the yield of LPG compared to another hydrocarbon or
combination of hydrocarbon products, and is not limited to a
specified precise value, and may include values that differ from
the specified value.
EXAMPLE 4
High Activity Component 204 Comprising Contaminant Inhibitor
Component 214
[0109] Metals in feed deposit and accumulate on the catalyst
(equilibrium catalyst or ECat) and increase the tendency to make
coke and gas, which are unwanted. Traditionally, a refiner
decreased the level of such metals on the ECat by adding higher
levels of fresh base catalyst and withdrawing a greater quantity of
contaminated ECat from the catalyst inventory.
[0110] Applicants have unexpectedly discovered increasing the
addition rate of a fresh base catalyst may have little or no effect
on reducing the impact of contaminant metals, or increasing yield
of a selected hydrocarbon product. However, applicants have
unexpectedly discovered providing a high activity component 204
comprising contaminant inhibitor component 214 as physically
separate and distinct particles from a base catalyst inhibits the
adverse effects one or more contaminants in a feedstock.
[0111] A non-limiting example of the contaminant inhibitor
component 204 includes but is not limited to Applicant's
CAT-Aid.TM.. Not to be bound by theory or advantage, a non-limiting
advantage of providing a high activity component 204 comprising
contaminant inhibitor component 214 as physically separate and
distinct particles from a base catalyst may be that for a constant
level of vanadium, CAT-Aid.TM. maintains a higher surface area of
the circulating catalyst because CAT-Aid.TM. improves zeolite
stability with increasing metals content compared to a single
system base catalyst. CAT-Aid.TM. improves zeolite stability by
inhibiting destruction of zeolite surface area and greater surface
area relates to increase yield. Providing a high activity component
204 comprising contaminant inhibitor component 214 such as
CAT-Aid.TM. as physically separate and distinct particles from a
single system base catalyst uses some of the freed-up coke burn
capacity to increase catalytic activity without increasing catalyst
addition rates. Any reduction in Feed, Occluded or Contaminant coke
frees up coke burning capacity to be used to (a) increase the
Catalytic coke--which results in increased conversion or (b)
increase the heaviness of the feed which means reduction in feed
cost.
[0112] Table 5 results from a recent commercial trial demonstrate
these points. Providing Cat Aid.TM. at 10% of the catalyst
inventory as physically separate and distinct particles from a base
catalyst showed the following advantages: 1) Feed rate increased
such as from 40,000 up to 45,000; 2) Use of poorer or less
expensive quality feed increased such as rate of vacuum tower
bottoms (VTB or vacuum residue). 3) Conversion increased by over
two percent and proportion of VTB. For example, Table 5 shows
Contaminant inhibitor component increased conversion from 80.7 to
83. 4) Total catalyst makeup reduced from 24 tons to 12 tons.
TABLE-US-00005 TABLE 5 Catalyst inventory w/ Catalyst 10% Cat Aid
.TM. (high inventory activity component before Cat comprising
contaminant CAT-Aid .TM. inhibitor) Delta % Delta Fresh Cat 12
tons/day 12 tons/day -- ECat 12 tons/day 0 -12 tons/day Cat Aid --
1.2 tons/day +1.2 tons/day Feed Rate (bpd) 40,000 41,500 to 45,000
+1,500 to +4% to 12.5% 5,000 VTB's (bpd) 1,500 2,000 +500 +25% Feed
API 29.69 28.58 -1.11 -3.7% Feed Con Carbon 1.22 1.56 +0.35 +29% w
% Feed Vanadium ppm 6.07 6.89 +0.82 +14% Feed Nickel ppm 4.08 4.59
+0.51 +13% Conversion (wt %) 80.7 83.0 +2.3 +3% Operating Expense
-5% to -10%
[0113] An embodiment of the invention includes providing one or
more high activity components to one or more fluidized units as
physically separate and distinct particles in an amount sufficient
to inhibit the adverse effects of one or more contaminants, either
individually or in a combination of two or more, in a feed stock by
greater about 10 wt %. Another embodiment includes providing one or
more high activity components to one or more fluidized unit as
physically separate and distinct particles in an amount sufficient
to inhibit the adverse effects of one or more contaminants in a
feed stock by greater than about 8%, by greater than about 7%, and
greater than about 5%. Yet another embodiment of the invention
includes providing one or more high activity components to one or
more fluidized unit as physically separate and distinct particles
in an amount sufficient to inhibit the adverse effects of one or
more contaminants either individually or in a combination of two or
more by greater about 4%, by greater than about 3%, by 1 greater
than about 2%, and by greater than about 1.0%. Embodiments of the
invention expressly includes providing one or more high activity
components as physically separate and distinct particles to one or
more fluidized unit in an amount sufficient to inhibit the adverse
effects of one or more contaminant either individually or in a
combination of two or more and is not limited to a specified
precise value, and may include values that differ from the
specified value
[0114] Table 6 shows the effects of providing 10% CAT-Aid.TM., high
activity component 204 comprising contaminant inhibitor component
214, as physically separate distinct particles, compared to
traditional method of the base catalyst as a single particle
system. For example, Table 6 shows CAT-Aid.TM. increased conversion
from 69.5 to 71.7 and from 72 to 73.6 in standard laboratory test
data from two commercial trials. Table 6 also shows CAT-Aid.TM.
decreased coke yield from 8.2 to 7.2 and from 9.3 to 8.3 in the 2
laboratory test trials. Table 6 shows CAT-Aid.TM. increased LPG
yield from 12.8 to 14 and from 13.7 to 14.9 in the 2 laboratory
test trials.
TABLE-US-00006 TABLE 6 Trial 2 Trial 1 FCC before Trial 2 FCC
Catalyst Catalyst Cat Trial 1 W 10% CAT- before Cat Aid .TM. Aid
.TM. (high w/ 10% CAT- Aid .TM. (high (high activity Aid .TM. (high
activity activity component activity component component 204 204
component 204 204 comprising comprising comprising comprising
contaminant contaminant contaminant contaminant inhibitor inhibitor
inhibitor inhibitor Product component 214) component 214) component
214) component 214) Run ID 28521-1 28522-1 28530-1 28531-1 Cat/Oil
4.02 4.96 4.02 4.96 Conversion, w % 69.5 72.0 71.7 73.6 Coke 8.2
9.3 7.2 8.3 C2- 2.6 2.7 2.2 2.4 Hydrogen 0.9 0.8 0.6 0.6 Methane
0.8 0.8 0.6 0.7 Ethane 0.5 0.5 0.4 0.4 Ethylene 0.5 0.6 0.5 0.6 C3
0.7 0.8 0.7 0.8 C3= 3.8 4.1 4.1 4.4 Total C3s 4.6 4.9 4.9 5.3 iC4
2.4 2.7 2.9 3.2 nC4 0.6 0.6 0.6 0.7 iC4= 1.5 1.6 1.6 1.6 nC4= 3.7
3.9 4.0 4.1 1-Butene 1.1 1.2 1.2 1.2 Cis-2- 1.1 1.2 1.2 1.2 Butene
Trans-2- 1.5 1.6 1.6 1.7 Butene 1,3- 0.0 0.0 0.0 0.0 Butadiene
Total Butenes 5.2 5.6 5.6 5.7 Total C4s 8.2 8.9 9.1 9.6 LPG 12.8
13.7 14.0 14.9 Isopentane 2.7 2.9 3.2 3.5 n-Pentane 0.3 0.3 0.3 0.3
3-Methyl-1- 0.2 0.2 0.2 0.2 Butene trans-2- 0.8 0.8 0.8 0.8 Pentene
2-Methyl-2- 1.1 1.1 1.1 1.1 Butene 1-Pentene 0.3 0.3 0.3 0.3
2-Methyl-1- 0.6 0.6 0.6 0.6 Butene cis-2-Pentene 0.4 0.5 0.4 0.4
Total C5 6.4 6.8 6.8 7.2 C6+ 4.1 4.5 4.4 4.6 Total C5+ in Gas 10.6
11.4 11.2 11.8 Liquid Gasoline 35.3 34.9 37.2 36.2 Total Gasoline
45.9 46.3 48.4 48.0 (C5-221C) LCO (221-282C) 11.2 10.6 10.6 10.3
MCO (282-343C) 7.7 6.9 7.1 6.6 LCO + MCO 18.8 17.5 17.7 16.9
(221-343C) Bottoms (343C+) 11.6 10.5 10.6 9.5 Total 100.0 100.0
100.0 100.0
An embodiment of the invention includes providing one or more high
activity components to one or more fluidized units as physically
separate and distinct particles in an amount sufficient to
preferentially decrease the yield one or more hydrocarbons such as
coke or dry gas either individually or combination compared to
another hydrocarbon or combination of hydrocarbon products by less
about 10% (based on wt % of feed product). Another embodiment
includes providing one or more high activity components to a
fluidized unit as physically separate and distinct particles in an
amount sufficient to preferentially decrease the yield one or more
hydrocarbons such as coke or dry either individually or combination
compared to another hydrocarbon or combination of hydrocarbon
products by less than about 8%, by less than about 7%, and less
than about 5%. Yet another embodiment of the invention includes
providing one or more high activity components to a fluidized unit
as physically separate and distinct particles in an amount
sufficient to preferentially decrease the yield one or more
hydrocarbons such as coke or dry either individually or combination
compared to another hydrocarbon or combination of hydrocarbon
products by less than about 4%, by less than about 3%, by less than
about 2%, and by less than about 0.1%. Embodiments of the invention
expressly includes providing one or more high activity components
as physically separate and distinct particles to one or more
fluidized unit in an amount sufficient to preferentially decrease
the yield one or more hydrocarbons such as coke or dry either
individually or combination compared to another hydrocarbon or
combination of hydrocarbon products, and is not limited to a
specified precise value, and may include values that differ from
the specified value.
EXAMPLE 5
Combination of Differing High Activity Components
[0115] Applicant tested embodiments of providing high activity
component as physically separate and distinct particles in
conjunction with a major Refiner. The refiner supplied two feeds
(one heavy and one light) which spanned the feed range of that
particular unit. Base fresh catalyst used in the unit was also
supplied. 3 comparative test were performed by providing: [0116] 1)
base catalyst alone (with no high activity component) [0117] 2)
base catalyst and combinations of high activity component(s) as
physically separate and distinct particles from base catalyst
[0118] 3) high activity components as physically separate and
distinct particles (without base catalyst)
[0119] Table 7 was generated by testing a combination of multiple
high activity components on heavy feed. Conradson Carbon Residue of
this feed was 5.2 wt % and specific gravity of this feed was 0.934.
Fresh base catalyst and high activity components were deactivated
to simulate equilibrium catalyst. Protocol includes metallation to
2500 ppm Vanadium, 5000 ppm Ni by cyclic cracking and steam
deactivation (1400.degree. F.) to match e-cat surface area.
TABLE-US-00007 TABLE 7 Combination of multiple high activity
components to Heavy Feed CAT-Aid .TM. Hi-Y .TM. (high activity BCA
.TM. (high activity component (high activity component 204
comprising component 202 comprising contaminant 201 comprising
gasoline inhibitor LCO selective Base selective component component
Catalyst component 212 214) 211) Bottoms 85 15 0 0 25.2 80 20 0 0
23.9 70 30 0 0 21.2 70 20 10 0 14.9 0 67 15 18 10.6 0 50 20 30
12.6
[0120] Table 7 shows the bottoms yield decreasing with increasing
Hi-Y.TM. (high activity component 202 comprising gasoline selective
component 212). The bottoms yield metric was chosen as it is
routinely the lowest value product; hence, the lower the bottoms
yield the better the catalyst formulation performance. All testing
was performed at constant coke (6 wt %). Table 7 shows providing
30% Hi-Y.TM. (high activity component 202 comprising gasoline
selective component 212) reduced bottoms yield reduced from 25.2 to
21.2, thereby reflecting the increased activity and preferential
yield of providing Hi Y.TM. as physically separate distinct
particles.
[0121] 10 wt % CAT-Aid.TM. (high activity component 204 comprising
contaminant inhibitor component 214) was then combined with 20% Hi
Y.TM. (high activity component 202 comprising gasoline selective
component 212) which reduced bottoms yield 25.2 to 14.9. Thus,
table 7 shows the unexpected benefits of providing a combination of
high activity components as physically separate distinct particles
from base catalyst. Furthermore, table 7 demonstrates even greater
gains were achieved with just high activity components which had 0%
base catalyst. Better result was achieved when a combination of
three high activity components was tailored to match the fresh base
catalyst properties of TSA and RE.sub.2O.sub.3: a combination of
high activity components comprising 15wt % CAT-Aid.TM. (high
activity component 204 comprising contaminant inhibitor component
214); 67 wt % Hi Y.TM. (high activity component 202 comprising
gasoline selective component 212); and 18 wt % BCA.TM. (high
activity component 201 comprising LCO selective component 211)
reduced bottoms yield even more from 25.2 to 10.6. Thus, table 7
shows the unexpected benefits of providing high activity components
as separate distinct particles instead of as part of or within a
base catalyst in a single particle system and table 7 also shows
the unexpected benefits of a combination of high activity
components.
[0122] Testing with a light feed produced similar results.
Conradson Carbon Residue of this feed was 1.8 wt % and specific
gravity of this feed was 0.888. Table 8 was generated by testing a
combination of multiple high activity components on light feed.
Fresh base catalyst and high activity components were deactivated
to simulate equilibrium catalyst. Protocol includes metallation to
500 ppm vanadium and 1500 ppm nickel by cyclic cracking Fresh base
catalyst and high activity components were deactivated to simulate
equilibrium catalyst. Protocol includes metallation to 2500 ppm
Vanadium, 5000 ppm Ni by cyclic cracking and steam deactivation
(1400.degree. F.) to match e-cat surface area.
TABLE-US-00008 TABLE 8 Combination of multiple high activity
components to Light Feed CAT-Aid .TM. Hi-Y .TM. (high activity
(high activity component component 202 204 comprising comprising
contaminant Base gasoline selective inhibitor Catalyst component
212) component 214) Bottoms 100 0 0 15.0 85 15 0 12.4 80 20 0 11.6
70 30 0 9.6 70 20 10 10.9
[0123] Table 8 shows as Hi Y.TM. Hi-Y.TM. (high activity component
202 comprising gasoline selective component) concentration
increased to 30%, bottoms yield reduced from 15 to 9.6, thereby
reflecting the increased activity and preferential yield of
providing Hi-Y.TM. (high activity component 202 comprising gasoline
selective component) as physically separate distinct particles
instead of just a base catalyst in a single particle system.
[0124] When 10 wt % CAT-Aid.TM. (high activity component 204
comprising contaminant inhibitor component 214) was then combined
with 70 wt % fresh catalyst and 20 wt % Hi Y.TM. (high activity
component 202 comprising gasoline selective component 212), bottoms
yield reduced from 15 to 10.9. Providing CAT-Aid.TM. (high activity
component 204 comprising contaminant inhibitor component 214) did
not on further decrease bottoms yield because the loss of the
catalyst blend surface area due to the addition of lower activity
CAT-AID was greater than the surface area retention protection to
the zeolite that CAT-Aid.TM. could provide in the low metals
environment. Thus, table 8 shows the unexpected benefits of
providing high activity components as separate distinct particle
instead of as part of or within a base catalyst in a single
particle system and table 8 also shows the unexpected benefits of a
combination of high activity components since bottoms yield did
decrease. However, a universal one size fits all combination of
high activity components does not necessary provide the optimum
solution for a range of feeds processed; the combination of high
activity component or components must be dynamically adjusted to
changing feed conditions etc. such as but limited to heaviness of
feed, etc.
[0125] Because a universal one size fits all combination of high
activity components does not necessary provide the optimum solution
for a range of feeds processed, FIG. 6 is a simulation graph of
providing a combination of multiple high activity components as
feed quality changes. For each production run, the production
planner needs only to supply the value of the control parameter
(Concarbon in the below example). The engineer or control room
operator may then read from the graph (or input the Concarbon value
directly into a control scheme) to quickly and accurately modify
component addition rates and therefore on-line catalyst formulation
towards the optimum for the specific feed being processed on that
production run.
[0126] Optionally, the method may further include using physical
hardware allowing individual adding of each high activity component
in a reliable and controlled manner. Separate individual addition
control of each high activity components may be supplied with
Applicant's AIM.TM. Additive Inventory Management Technology and
addition systems.
[0127] It will be apparent to those skilled in the art that various
modifications and variations can be made in the method and system
of the present invention without departing from the spirit or scope
of the invention. Thus, it is intended that the present invention
include modifications and variations that are within the scope of
the appended claims and their equivalents.
[0128] While the invention has been described in detail in
connection with only a limited number of aspects, it should be
understood that the invention is not limited to such disclosed
aspects. Rather, the invention can be modified to incorporate any
number of variations, alterations, substitutions or equivalent
arrangements not heretofore described, but which are commensurate
with the scope of the claims. Additionally, while various
embodiments of the invention have been described, it is to be
understood that aspects of the invention may include only some of
the described embodiments. Accordingly, the invention is not to be
seen as limited by the foregoing description, but is only limited
by the scope of the appended claims.
* * * * *