US20100018898A1

US20100018898A1 - Composition and methods for preferentially increasing yields of one or more selected hydrocarbon products

Info

Publication number: US20100018898A1
Application number: US12/510,806
Authority: US
Inventors: William Reagan; Paul Diddams; Darren Verrenkamp
Original assignee: Individual
Current assignee: Johnson Matthey Process Technologies Inc
Priority date: 2008-07-28
Filing date: 2009-07-28
Publication date: 2010-01-28
Also published as: AU2009276694B2; AU2009276694A1; EP2307525A4; CN102165044A; CN102165044B; CA2732264C; CA2732264A1; WO2010014606A3; EP2307525A2; WO2010014606A2

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.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

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

1. Field of the Invention
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.
2. Description of the Related Art
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.
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.
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.
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.
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.
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

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.
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.
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.
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

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.

FIG. 1 is a schematic diagram of a conventional fluid catalytic cracking system;

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;

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;

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;

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;

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;

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;

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;

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

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.

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

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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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

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™.
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.
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.
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.
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.
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.
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.
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.
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.
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

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™.
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.
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.
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.
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.
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.
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.
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

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.
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.
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.
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

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™ comprising calcium oxide supported on mixed metal oxide such as MgO and Al₂O₃, 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.
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.
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.
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.
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.
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.
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

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.
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.
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.
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.
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.
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.
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.
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.
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.
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™ process or crack heavy feed into LPG instead of gasoline such as but not limited to Indmax™ 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.
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

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.
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.
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).
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.
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™ as physically separate distinct particles preferentially increases LCO yield.
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).
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.
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.
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.
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™, 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™ was provided. Simulation was based on several conducted trials.

TABLE 1

Effects of high activity component comprising LCO
Selective Component upon product yield

	Base Catalyst	+10%	+20%	+30%
	(and % 0 high	BCA-105 ™	BCA-105 ™	BCA-105 ™
	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.)

Table 2 is a summary of 36 commercial trials of BCA™ (high activity component 201 comprising LCO selective component 211). Table 2 shows BCA™ 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 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 ™ (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

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

Applicant's Hi-Y™ 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™ 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.
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).
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 m²/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.
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™ (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™ as physically separate distinct particles increased conversion (wt %, weight percent on feed basis) in Trial 1-3.

TABLE 3

				Trial 1	Trial 2	Trial 3
				20%	20%	20%
				Hi-Y ™	Hi-Y ™	Hi-Y ™
				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

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

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.
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.
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.
Feed/bottoms range hydrocarbon molecules are cracked by high activity component 201 comprising LCO selective component 211 such as BCA™ which has the largest pores into LCO range molecules.
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.
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.
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.
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.
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 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

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

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.
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.
A non-limiting example of the contaminant inhibitor component 204 includes but is not limited to Applicant's CAT-Aid™. 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™ maintains a higher surface area of the circulating catalyst because CAT-Aid™ improves zeolite stability with increasing metals content compared to a single system base catalyst. CAT-Aid™ 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™ 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.
Table 5 results from a recent commercial trial demonstrate these points. Providing Cat Aid™ 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 5

	Catalyst inventory w/
Catalyst	10% Cat Aid ™ (high
inventory	activity component
before Cat	comprising contaminant
CAT-Aid ™	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%

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
Table 6 shows the effects of providing 10% CAT-Aid™, 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™ 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™ 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™ increased LPG yield from 12.8 to 14 and from 13.7 to 14.9 in the 2 laboratory test trials.

TABLE 6

		Trial 2
	Trial 1	FCC before		Trial 2
	FCC Catalyst	Catalyst Cat	Trial 1	W 10% CAT-
	before Cat Aid ™	Aid ™ (high	w/ 10% CAT-	Aid ™ (high
	(high	activity	Aid ™ (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

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:

- 1) base catalyst alone (with no high activity component)
- 2) base catalyst and combinations of high activity component(s) as physically separate and distinct particles from base catalyst
- 3) high activity components as physically separate and distinct particles (without base catalyst)

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° F.) to match e-cat surface area.

TABLE 7

Combination of multiple high activity
components to Heavy Feed

		CAT-Aid ™
	Hi-Y ™	(high activity	BCA ™
	(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

Table 7 shows the bottoms yield decreasing with increasing Hi-Y™ (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™ (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™ as physically separate distinct particles.
10 wt % CAT-Aid™ (high activity component 204 comprising contaminant inhibitor component 214) was then combined with 20% Hi Y™ (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 RE₂O₃: a combination of high activity components comprising 15wt % CAT-Aid™ (high activity component 204 comprising contaminant inhibitor component 214); 67 wt % Hi Y™ (high activity component 202 comprising gasoline selective component 212); and 18 wt % BCA™ (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.
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° F.) to match e-cat surface area.

TABLE 8

Combination of multiple high activity components to Light Feed

			CAT-Aid ™
		Hi-Y ™	(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

Table 8 shows as Hi Y™ Hi-Y™ (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™ (high activity component 202 comprising gasoline selective component) as physically separate distinct particles instead of just a base catalyst in a single particle system.
When 10 wt % CAT-Aid™ (high activity component 204 comprising contaminant inhibitor component 214) was then combined with 70 wt % fresh catalyst and 20 wt % Hi Y™ (high activity component 202 comprising gasoline selective component 212), bottoms yield reduced from 15 to 10.9. Providing CAT-Aid™ (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™ 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.
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.
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™ Additive Inventory Management Technology and addition systems.
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.
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.

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.