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

Composition and methods for preferentially increasing yields of one or more selected hydrocarbon products Download PDF

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US20100018898A1
US20100018898A1 US12/510,806 US51080609A US2010018898A1 US 20100018898 A1 US20100018898 A1 US 20100018898A1 US 51080609 A US51080609 A US 51080609A US 2010018898 A1 US2010018898 A1 US 2010018898A1
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Prior art keywords
high activity
component
providing
activity component
yield
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William Reagan
Paul Diddams
Darren Verrenkamp
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Johnson Matthey Process Technologies Inc
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Individual
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Assigned to INTERCAT, INC. reassignment INTERCAT, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DIDDAMS, PAUL, REAGAN, WILLIAM J., VERRENKAMP, DARREN
Publication of US20100018898A1 publication Critical patent/US20100018898A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • 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.
  • 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 .
  • FCC fluid catalytic cracking
  • 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.
  • the total amount of the base cracking catalyst i.e. catalyst inventory
  • catalyst inventory i.e. catalyst inventory
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • TSA total surface area
  • 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.
  • 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.
  • providing a high activity component 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.
  • providing the high activity component as physically separate and distinct particles from the base catalyst particle 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.
  • 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.
  • a trace or contaminant or deminis amount of base 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.
  • 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.
  • the high activity component 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.
  • 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.
  • 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.
  • base catalyst 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.
  • 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.
  • 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.
  • 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.
  • the different catalytic components deactivate (age) via thermal, hydrothermal and other deactivation mechanisms, at different relative rates.
  • one component may be severely deactivated while the other component still has some remaining activity or “useful life”.
  • 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.
  • 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 BCATM.
  • the high activity component includes one or more LCO (Light Cycle Oil) selective components 211 to preferentially increase the yield of LCO.
  • LCO Light Cycle Oil
  • hydrocarbon products that may incorporate some LCO include diesel, kerosene and aviation fuel.
  • 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 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.
  • the high activity component 201 comprises from about 70% to about 100% by weight LCO selective component 211 .
  • the LCO selective component 211 is about 80% to about 100% by weight.
  • LCO selective component is about 90% to about 100% by weight.
  • LCO selective component 211 is about 100% by weight, wherein the high activity component 201 essentially consists of LCO selective component 211 .
  • 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.
  • the method includes providing a plurality of the high activity components 201 .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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-YTM.
  • the high activity component 202 includes one or more gasoline selective components 212 to preferentially increase the yield of gasoline.
  • 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.
  • the high activity component comprises from about 40% to about 85% by weight gasoline selective component 212 .
  • the gasoline selective component 212 is about 50% to about 85% by weight.
  • the gasoline selective component 212 comprises at least 70% by weight.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • the high activity component comprises from about 20% to about 85% by weight of an LPG selective component 213 .
  • the LPG selective component 213 is about 30% to about 85% by weight.
  • LPG selective component 213 is about 40% to about 85% by weight.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 2D is another schematic representation of an embodiment of a high activity component 204 .
  • contaminant inhibitor component 214 include Applicant's CAT-AidTM comprising calcium oxide supported on mixed metal oxide such as MgO and Al 2 O 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.
  • 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.
  • 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 include nickel traps, vanadium traps, either individually or in a combination of two or more thereof.
  • the high activity component 204 comprises from about 70% to about 100% by weight a contaminant inhibitor component 214 .
  • 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.
  • 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.
  • 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.
  • 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.
  • each contaminant inhibitor 214 component is 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.
  • 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.
  • 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.
  • 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.
  • a second high activity component such as high activity component comprising gasoline selective component
  • 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.
  • 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.
  • differing high activity components such as high activity components respectively comprising gasoline selective component and contaminant inhibitor component
  • second combination of differing high activity components such as high activity components respectively comprising LCO selective component and contaminant inhibitor component
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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 SuperflexTM process or crack heavy feed into LPG instead of gasoline such as but not limited to IndmaxTM process.
  • LPG Liquefied Petroleum Gas
  • 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.
  • High Activity Component 201 Comprising LCO Selective Component 211
  • feed generally consists of large molecules which are too large to enter into the pores of gasoline selective component such as Y zeolite pores.
  • LCO selective component pores are larger than the pores of gasoline selective component.
  • large hydrocarbon molecules can enter the larger pores of the LCO selective component and be cracked to form LCO range molecules.
  • 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).
  • Z/M Zeolite-to-Matrix Ratio
  • FIG. 3 is a schematic simulation demonstrating providing the high activity component comprising a LCO selective component such as BCATM 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.
  • 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).
  • bottoms but also commonly called Decanted Cycle Oil (DCO).
  • DCO Decanted Cycle Oil
  • LCO 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.
  • 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).
  • 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.
  • Table 1 shows providing BCA-105TM, 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-105TM was provided. Simulation was based on several conducted trials.
  • Table 2 is a summary of 36 commercial trials of BCATM (high activity component 201 comprising LCO selective component 211 ). Table 2 shows BCATM 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.
  • 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.
  • High Activity Component 202 Comprising Gasoline Selective Component 212
  • Applicant's Hi-YTM is an example of high activity component 202 comprising one or more gasoline selective component 212 to preferentially increase gasoline yield.
  • high activity component 202 comprising one or more gasoline selective components 212 includes a high concentration of y zeolite;
  • Applicant's Hi-YTM 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
  • ECat equilibrium catalyst
  • 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.
  • TSA total surface area
  • the increased TSA directly resulted in increased preferential yield of gasoline.
  • the increased surface area of the high activity component comprising one or more gasoline selective component 202 which is typically greater than 380 m 2 /g, increases the magnitude and rapidity of the yield slate changes versus those of a second grade of catalyst.
  • 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.
  • Table 3 demonstrates providing 20% Hi-YTM (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-YTM as physically separate distinct particles increased conversion (wt %, weight percent on feed basis) in Trial 1-3.
  • Trial 1 Trial 2 Trial 3 20% 20% 20% 20% Hi-Y TM Hi-Y TM Hi-Y TM high high high activity activity activity component component component component
  • Trial 1 Trial 2 Trial 3 202 202 202 202 202 202 202 Control Control comprising comprising Base as Base as gasoline gasoline gasoline single single single selective selective particle particle particle component component component
  • 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.
  • High Activity Component 203 Comprising LPG Selective Component 213
  • 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.
  • gasoline selective component such as Y zeolite pores.
  • LCO selective component pores are larger than the pores of gasoline selective component.
  • 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 BCATM which has the largest pores into LCO range molecules.
  • LCO selective component 211 such as BCATM 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 selective component 212 such as Y zeolites, which has smaller pores than LCO selective component
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • High Activity Component 204 Comprising Contaminant Inhibitor Component 214
  • 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.
  • 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-AidTM.
  • 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-AidTM maintains a higher surface area of the circulating catalyst because CAT-AidTM improves zeolite stability with increasing metals content compared to a single system base catalyst.
  • CAT-AidTM 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-AidTM 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 AidTM 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.
  • VTB vacuum tower bottoms
  • Table 5 shows Contaminant inhibitor component increased conversion from 80.7 to 83. 4) Total catalyst makeup reduced from 24 tons to 12 tons.
  • 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-AidTM, 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.
  • Table 6 shows CAT-AidTM 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-AidTM 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-AidTM increased LPG yield from 12.8 to 14 and from 13.7 to 14.9 in the 2 laboratory test trials.
  • 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.
  • 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:
  • 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 shows the bottoms yield decreasing with increasing Hi-YTM (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-YTM (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 YTM as physically separate distinct particles.
  • 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.
  • Table 8 shows as Hi YTM Hi-YTM (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-YTM (high activity component 202 comprising gasoline selective component) as physically separate distinct particles instead of just a base catalyst in a single particle system.
  • 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.
  • 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.
  • FIG. 6 is a simulation graph of providing a combination of multiple high activity components as feed quality changes.
  • 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.
  • 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 AIMTM Additive Inventory Management Technology and addition systems.

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AU2009276694B2 (en) 2015-08-06
EP2307525A2 (fr) 2011-04-13
WO2010014606A3 (fr) 2010-05-06
CN102165044B (zh) 2015-01-07
AU2009276694A1 (en) 2010-02-04
CA2732264C (fr) 2014-10-21
CN102165044A (zh) 2011-08-24
WO2010014606A2 (fr) 2010-02-04
CA2732264A1 (fr) 2010-02-04

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