Fluid Catalytic Cracking Patents – 2017, Part I: Catalytic Compositions/Synthesis

Posted on 06/15/2018 by William Reid, in Articles, Patent Trends & Activity

This is the first article in a review of patents issued in 2017 in the area of Fluid Catalytic Cracking (FCC).  The summary below covers six patents related to fluid cracking catalyst compositions/synthesis.

One technique for categorizing patents related to Fluid Catalytic Cracking is to group them in certain categories:  those related to catalyst zeolite, matrix or the catalyst per se, their synthesis or crossover patents directed to additive/FCC catalyst systems; catalyst additives per se, such as metals passivation catalysts, octane additives or combustion promoters; reactor internals; regenerator internals; FCC-related process conditions, operations, and treatment of FCC feed or products; or incorporation of the FCC in a broader process, and ancillary FCC-related processes.  In 2017, there was a concentration in the final category, with lighter representation in all other areas.

In this article dealing with catalyst systems and crossovers, half the patents: U.S. 9,605,213 (‘213 Patent), U.S. 9,783,743 (‘743 Patent), and U.S. 9,796,932 (‘932 Patent), deal with systems where additives are incorporated in the system itself.  Another patent U.S. 9,611,432 (‘432 Patent) deals with a particular manner of preparing a catalyst with improved activity and selectivity.  Still another, U.S. 9,682,366 (‘366 Patent), deals with a particular zeolite, and the final patent U.S. 9,617,480 (‘480 Patent) deals with a catalytic composition.  It is noteworthy that only the ‘480 Patent is directed to an innovation in the bare FCC catalyst composition itself.  The other three: the ‘213 Patent, ‘743 Patent and ‘932 Patent, describe blended systems with additives.

The patents related to FCC catalyst or catalyst systems are summarized below.  Table 1 below lists relevant information on the patents.  Table 2 contains a representative independent claim from each.

The following three patents illustrate blends of FCC catalysts with additives.  Two of the blends are with octane additives.  The third blend utilizes a metals trap/passivator.

U.S. Patent No. 9,605,213 relates to a process for cracking a heavy hydrocarbon feedstock with a catalyst system for producing higher propylene yields.  The patent contains a single independent claim with a total of 14 claims.  The conditions of cracking are: the reaction zone is maintained between 500 and 600°C, and the FCC itself is configured in “down-flow mode.”  The catalyst of the process contains 10% of a USY zeolite; 30% of a phosphorous modified sub-micron ZSM-5 having an average crystal size between 50 and 400 nm, and a silica/alumina ratio of 1:2 to 1:4; 20% of a pseudoboehmite alumina, and 40% by weight of kaolin.  The feedstock is typically hydrotreated or un-hydrotreated VGO.

U.S. Patent No. 9.783,743 relates to a process for cracking higher boiling feedstock with lower fuel gas yield.  The patent contains a single independent claim with a total of 8 claims.  The process uses a two-component catalyst system consisting of an FCC component based on a REY, REUSY, USY or beta zeolite, and an additive component based on a ZSM-5, ZSM-11, or ZSM-23 zeolite.  The FCC component contains 5-60 wt% of the zeolite, 10-40 wt% of clay, 5-40 wt% of binder, and 0.01 to 2.0 wt% rare earth.  The additive component contains 5-60 wt% of the zeolite, 10 to 40 wt% of a clay, 5 to 40 wt% of a binder, 0.01 to 2.0 wt% of an alkaline earth metal, and 4 to 16 wt% of a phosphorous compound in the form of P2O5.  The weight ratio of FCC/additive is 1:1 to 10:1.

U.S. Patent No. 9,796,932 relates to a two-component FCC catalyst composition for cracking resid feeds with high nickel and vanadium content.  The patent contains three independent claims (1, 14 & 15), with a total of 15 claims.  One component of the catalyst composition contains a boron oxide component as a metals trap/passivator, situated on a first matrix.  The second component contains 20 to 95 wt% of a zeolite, and a phosphorus component on a second matrix.  The boron oxide component is generally present in an amount of from 0.005 to 8.0 wt% on the basis of the total composition.

The following patent is directed to a catalyst system having a particular starting and aged activity.

U.S. Patent No. 9,611,432 relates to a catalyst composition containing 1 to 50% zeolite, 5 to 99% inorganic oxide and 0 to 70% of an optional clay.  The patent contains six independent claims (1, 5, 12, 18, 24 and 25), with a total of 26 claims. The zeolite can be either a medium or large pore zeolite.  The catalyst has three activity limitations:  a fresh activity of 81 to 96, an activity after aging of higher than 80, and an equilibrium activity of 35-60 as introduced into the FCC; and a self-balancing time of 0.1 to 50 hours.  The balancing time is defined as the time necessary for achieving the equilibrium activity by aging at 800°C and 100% steam.  The catalyst composition is intended to result in a more homogeneous catalyst inventory for improved product selectivity.

The following patent is directed to a catalyst system produced in a particular way to provide improved attrition resistance.

U.S. Patent No. 9,682,366 relates to an FCC catalyst produced in a particular manner to provide improved attrition resistance.  The patent contains two independent claims (1 and 11), with a total of 20 claims.  The FCC catalyst microsphere is produced from a slurry containing a matrix and zeolite-forming nutrients or zeolite crystals where a cationic polyelectrolyte in an amount from 0.005 to 0.5 wt% relative to a total weight of the matrix and the zeolite-forming nutrient or the zeolite crystals is present in the slurry.  The catalyst has a macropore volume in the pore range of 600 to 20,000 angstrom of 0.07 cc/g or more mercury intrusion.  The cationic polyelectrolyte is described as typically being used as bulking agents to flocculate hydrous kaolin such as polyamines, quaternary ammonium salts, diallyl ammonium polymer salts, and dimethyl dially ammonium chloride (polydadmacs).

As mentioned above, the following patent is directed to an innovation in the bare FCC catalyst composition itself.

U.S. Patent No. 9,617,480 relates to a process for producing a catalyst having improved zeolite stability and attrition resistance.  The patent contains two independent claims (1 and 19), with a total of 28 claims.  The catalyst is produced by combining peptized alumina, a yttrium compound in an amount from 0.5 to 15 wt%, and a rare earth-exchanged faujasite zeolite.  The yttrium compound is situated within the pores of the zeolite, and a ratio of the rare earth/yttrium is in a range of not more than 0.5.

Table 1: FCC Patents  —  FCC Catalyst Systems

Patent Number Inventor Assignee Title Issue Date
U.S. 9,605,213 Al-Ghrami et al. Saudi Arabian Oil Company Method For The Fluidized Catalytic Cracking Of A Heavy Hydrocarbon Feedstock March 28, 2017
U.S. 9,611, 432 Xu et al. CPCC Catalytic Cracking Catalyst Having A Higher Selectivity, Processing Method And Use Thereof April 4, 2017
U.S. 9,617,480 Shu et al. W.R. Grace & Co.-Conn. Process For Making Improved Zeolite Catalysts From Peptized Aluminas April 11, 2017
U.S. 9,682,366 Sigman, et al. BASF Corp. Method Of Producing FCC Catalysts With Reduced Attrition Rates June 20, 2017
U.S. 9,783,743 Dinda et al. Reliance Industries Ltd. Process And Composition Of Catalyst/Additive For Reducing Fuel Gas Yield In Fluid Catalytic Cracking (FCC) Process October 10, 2017
U.S. 9,796,932 Smith et al. BASF Corp. FCC Catalyst Compositions Containing Boron Oxide And Phosphorus October 24, 2017

 

Table 2: FCC Catalyst Systems

Patent Number Independent Claim
U.S. 9,605,213 Claim 1. A method for the fluid catalytic cracking of a heavy hydrocarbon feedstock, the method comprising: supplying the heavy hydrocarbon feedstock to a reaction zone comprising a catalyst, such that both the heavy hydrocarbon feedstock and the catalyst are in contact in a down-flow mode, wherein said contact between the heavy hydrocarbon feedstock and the catalyst takes place in a fluidized catalytic cracking apparatus comprising a separation zone, a stripping zone, and a regeneration zone; and maintaining the reaction zone at a temperature of between 500 and 600°C., such that the hydrocarbon feedstock converts into a cracked hydrocarbon effluent comprising light olefins, gasoline, and diesel, wherein the catalyst comprises 30% by weight of a phosphorous modified sub-micron ZSM-5, 10% by weight of an ultra-stable Y-type zeolite, 20% by weight of a pseudoboehmite alumina, and 40% by weight of kaolin, and wherein the phosphorous modified sub-micron ZSM-5 has an average crystal size between 50 and 400 nm, inclusive, and a silica to alumina ratio of 1:2 to 1:4, inclusive.
U.S. 9,611,432 Claim 1.  A catalytic cracking catalyst as introduced into a fluid catalytic cracking (FCC) reaction system, comprising: relative to a total weight of the catalyst, 1-50% by weight of a zeolite, 5-99% by weight of an inorganic oxide and 0-70% by weight of an optional clay, wherein the zeolite is a medium pore zeolite or a large pore zeolite, wherein the catalytic cracking catalyst is obtained by aging a fresh catalytic cracking catalyst in an aging medium, wherein the fresh catalytic cracking catalyst prior to aging has a fresh catalyst activity ranging from 81 to 96, wherein the catalytic cracking catalyst after aging has an initial activity of higher than 80, a self-balancing time of 0.1-50 h, and an equilibrium activity of 35-60 as introduced into the FCC reaction system at one or more locations chosen from a regenerator, a disengager, a riser, or a steam stripper, wherein the aging medium is a mixture of steam and a flue gas from the FCC reaction system, and wherein the fresh catalyst activity prior to aging, the initial activity of the catalytic cracking catalyst after aging, and the equilibrium activity of the catalyst cracking catalyst are measured according to RIPP 92-90.
U.S. 9,617,480 Claim 1.  A process for making a catalyst, the process comprising (a) combining peptized alumina, yttrium compound, and zeolite having catalytic activity in a fluid catalytic cracking process, and (b) forming an alumina-containing catalyst from the combination in (a), wherein the yttrium compound is present in an amount ranging from about 0.5% to about 15% by weight, measured as an oxide (Y2O3) of the zeolite, and wherein the zeolite is faujasite, the yttrium compound is located within pores of the zeolite, and a rare earth is present with a ratio of the rare earth to the yttrium compound in a range of not more than 0.5.
U.S. 9,682,366 Claim 1.  An FCC zeolite-containing catalyst microsphere, the microsphere comprising zeolite, the microsphere having been formed from a slurry comprising a matrix and at least one of a zeolite-forming nutrient or zeolite crystals, the slurry having been mixed with, prior to or during formation of the microsphere, a cationic polyelectrolyte in an amount from 0.005 to 0.5 wt. % relative to a total weight of the matrix and the zeolite-forming nutrient or the zeolite crystals in the slurry, wherein the FCC zeolite-containing catalyst microsphere comprises a macroporous structure having a macropore volume in the pore range of 600 to 20,000 Å of about 0.07 cc/gm or more mercury intrusion.
U.S. 9,783,743 A process for cracking of higher boiling point petroleum feedstock in the presence of a catalyst composition to reduce dry gas production without affecting the yield of LPG, light olefins and gasoline products; said process comprising contacting said feedstock under reaction conditions suitable for fluid catalytic cracking with the catalyst composition in a fluidized bed; wherein the catalyst composition comprises: (a) an FCC catalyst component comprising: at least one zeolite in an amount ranging between 5 and 60 wt %; at least one clay in an amount ranging between 10 and 40 wt %; at least one binder in an amount ranging between 5 and 40 wt %; at least one alkaline earth metal in an amount ranging between 0.01 and 2.0 wt %; and at least one rare earth metal selected from the group consisting of lanthanum, cerium, neodymium, samarium, gadolinium and yttrium in an amount ranging between 0.01 and 2.0 wt %; wherein, the zeolite present in the FCC catalyst component is selected from the group consisting of REY, REUSY, USY, beta and combinations thereof; all proportion being with respect to the weight of the FCC catalyst components; (b) an additive component comprising: at least one zeolite in an amount ranging between 5 and 60 wt %; at least one clay in an amount ranging between 10 and 40 wt %; at least one binder in an amount ranging between 5 and 40 wt %; at least one alkaline earth metal in an amount ranging between 0.01 and 2.0 wt %; and at least one phosphorous containing compound in the form of P2O5 in an amount ranging between 4 and 16 wt %, and wherein the zeolite present in the additive component is a medium pore size zeolite selected from the group consisting of ZSM-5, ZSM-11, ZSM-23 zeolite and combinations thereof; wherein the weight ratio of the amount of the FCC catalyst component and the amount of the additive component ranges between 1:1 and 10:1; all proportion being with respect to the weight of the respective FCC catalyst and additive components.
U.S.  9,796,932 An FCC catalyst composition for cracking hydrocarbons, the FCC catalyst composition comprising: a first particle type comprising one or more boron oxide components, and a first matrix component wherein the first particle type does not incorporate a zeolite; and a second particle type comprising a second matrix component, a phosphorus component, and 20% to 95% by weight of a zeolite component; wherein the second particle type is different from the first particle type and the first particle type and second particle type are mixed together.

 

– William Reid

[1] My thanks to Mr. Ken Peccatiello of Peccatiello Engineering (www.PeccatielloEngineering.com) for reviewing the text.


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