Fluid Catalytic Cracking Patents – 2018/2019: Catalyst Systems
This is an article in a series reviewing Fluid Catalytic Cracking (FCC) patents granted in approximately the last year. In particular, the patents highlighted here relate to FCC catalyst and additive systems. One take-away from this review is that the number of such patents as a percentage of the entirety of FCC-related patents, including those related to equipment, processes, feed treatment, environmental, etc., is down to less than a quarter. This may reflect a shift in research dollars away from the catalyst area, or at least a shift in those research dollars directed to acquiring patentable inventions. The second take-away is that the catalyst related patents are largely directed to integral multiple zeolite systems for increasing light olefins production, such as USY and ZSM-5. This was already a fairly crowded area, however, in U.S. Patent No. 10,173,206 assigned to Albemarle Europe SPL, an interesting approach was to combine a Y zeolite exchanged with a non-rare earth material selected from magnesium, calcium or strontium, with a ZSM-5 zeolite, where the ratio of the two zeolites was specified.
Of the catalyst patents not directed to increasing light olefins, U.S. Patent No. 10,300,466 assigned to Instituto Mexicano Del Petroleo, relates to a process for modifying a Faujasite Y-type zeolite to reduce sodium content and introduce mesoporosity. U.S. Patent No. 10,086,367 assigned to BASF Corporation, relates to a two-step phosphorous treatment of BASF’s in situ crystallized Y zeolite, which sandwich a rare earth treatment step. Finally, U.S. Patent No. 10,315,186 assigned to Indian Oil Corporation Limited, relates to an attrition resistant CO oxidation promotor support.
Attached Table 1 lists relevant information on the catalyst patents reviewed. Table 2 contains a representative independent claim from each.
U.S. Patent No. 10,086,367 contains two independent claims (claims 1 & 12), and generally relates to a method for producing a phosphorous-treated FCC catalyst system. The method involves first forming a precursor microsphere containing non-zeolitic material and alumina, crystallizing a Y zeolite in situ on the microsphere to form a zeolite containing microsphere, treating the zeolite containing microsphere with phosphorus, treating the phosphorous modified material with rare earth, and finally treating the rare earth treated material with phosphorous a second time.
U.S. Patent No. 10,130,943 has a single independent claim (claim 1), and generally relates to an FCC catalyst for improved olefin production while processing heavy feed containing high levels of metals. The catalyst is a dual zeolite integral catalyst also containing a metals trap and a bottoms-upgrading matrix component. The catalyst contains 3.5 to 15.5% of pentasil zeolite, 9 to 40% USY or REUSY zeolite, 0.3 to 3% of a metals trap, and 3.5 to 15% of a large pore active matrix. The metals trap is a rare earth treated silica-alumina. The large pore active matrix contains 40-60 wt% of alumina, 5-25 wt% silica, 20-60 wt% clay, 1-20 wt% PO4 and has a pore size in the range of 80Å to 200Å.
U.S. Patent No. 10,173,206 has two independent claims (claims 1 & 5), and generally relates to an FCC catalyst and process for increased propylene. The catalyst is again a dual zeolite system containing 5 to 50 wt% of a Y zeolite exchanged with a non-rare earth material selected from magnesium, calcium or strontium; and a second component is ZSM-5 present at 2 to 50 wt%, where the ratio of Y zeolite to ZSM-5 ranges from 1:2.5 to 1:6.
U.S. Patent No. 10,252,249 has a single independent claim (claim 1), and generally relates to an olefin/octane additive composition which is attrition resistant. The catalyst contains 10-70 wt% zeolite, chosen from mordenite, ZSM-5, beta, and ZSM-11; 5-20 wt% colloidal silica; 10-60 wt% clay; 1-10 wt% phosphate; and 1-15 wt% aluminum phosphate binder. The aluminum phosphate binder is a reaction product of mono aluminum phosphate and an aluminum compound present in the mole ratio of 1:1 to 1:2.5. Typically, the aluminum compounds are selected from salts of alumina such as alumina nitrate, alumina sulphate, alumina chloride, alumina acetate and alumina oxalate.
U.S. Patent No. 10,287,511 has three independent claims (claims 1, 12 & 18) and generally relates to a catalyst system for enhancing light olefins yield, a method for preparing it, and its use in an FCC. The catalyst is a multiple zeolite system containing 70-95 wt% non-zeolite material, 3-18 wt% of a first zeolite (zeolite-1) and 2-12 wt% of a second zeolite (zeolite-2). The non-zeolitic material contains active material such as alumina, and inactive materials such as binder and fillers such as clay. The first zeolite is an REUSY or a combination of REUSY+Beta, having a pore size of 7-8Å, and is rare earth exchanged such that the rare earth concentration of the entire catalyst is 0.3-1.0 wt%. The pore size of the second zeolite is 5-6 Å and is selected from ZSM-5, ZSM-11, ZSM-22 and SAPO-11.
U.S. Patent No. 10,300,466 has two independent claims (claims 1 & 6), and generally relates to a method of zeolite modification for producing a Faujasite Y-type zeolite having lower sodium with a mesoporous material. Such mesoporous materials are known to provide improved bottoms cracking capability. The process involves contacting the Faujasite Y-type zeolite with a specified amount of glycerol at a temperature of 180 to 200°C to form a gel, contacting the gel with a particular amount of ammonium salts to form a mixture, and then hydrothermally treating the mixture at 140 to 180°C for 10 to 20 hours, and then cooling. The solids formed are separated, washed and then dried. The dried solids are thermally treated at 480 to 520°C at a heating profile of 1 to 3°C/minute. The resultant zeolite is reduced in sodium content by 75%, and the has a mesoporous structure with a bimodal pore size distribution having an average pore size of 2 to 100 nm.
U.S. Patent No. 10,315,186 has three independent claims (claims 1, 5 & 12) and generally relates to a CO oxidation promoter support, a process for preparing it, and a process for producing the related CO oxidation promoter using the support. The support claim (claim 1) interestingly contains physical property limitations of the support, the process for producing it and the CO oxidation promotor additive into which it will be incorporated, which contains a group VIII B metal. The support is a pseudoboehmite alumina with a crystallite size from 10 to 20 Å, surface area from 200 to 405 m2/g, an average pore diameter of 35 to 45 Å and an average pore diameter of 0.2 to 0.6 cm3/g. The CO oxidation promoter additive has an ABD greater than 0.95 g/cc and an attrition of less than 5%, and has a conversion efficiency of 85-97 and CO2/CO ratio of 20-51. The support has self-binding properties and contains less than 0.2% of residual sodium oxide, and is prepared by reacting aluminum sulphate with sodium hydroxide at a particular pH and temperature, filtering, hydrothermally treating the resultant solids, slurrying with water, and peptizing with an organic acid.
Table 1: Fluid Catalytic Cracking Patents — Catalyst Systems
|Patent Number||Inventor||Assignee||Title||Issue Date|
|U.S. 10,086,367||Smith et al.||BASF Corporation||Phosphorus-Containing FCC Catalyst||October 2, 2018|
|U.S. 10,130,943||Velayutham et al.||Indian Oil Corporation Limited||Catalyst Composition For Fluid Catalytic Cracking, Process For Preparing The Same And Use Thereof||November 20, 2018|
|U.S. 10,173,206||Ludvig et al.||Albemarle Europe SPRL||Modified Y-Zeolite/ZSM-5 Catalyst For Increased Propylene Production||January 8, 2019|
|U.S. 10,252,249||Kuvettu et al.||Indian Oil Corporation Limited||Composition And A Process For Preparation Of Attrition Resistant Cracking Catalyst Suitable For Enhancing Light Olefins||April 9, 2019|
|U.S. 10,287,511||Kumar et al.||Hindustan Petroleum Corporation Ltd.||Catalyst Composition For Fluid Catalytic Cracking, And Use Thereof||May 14, 2019|
|U.S. 10,300,466||Herrera et al.||Instituto Mexicano Del Petroleo||Process For Modifying The Physical And Chemical Properties Of Faujasite Y-Type Zeolites||May 28, 2019|
|U.S. 10,315,186||Loganathan et al.||Indian Oil Corporation Limited||CO Oxidation Promoter And A Process For The Preparation Thereof||June 11, 2019|
Table 2: Fluid Catalytic Cracking — Catalyst Systems
|Patent Number||Independent Claim|
|U.S. 10,086,367||1. A method of manufacturing a fluid catalytic cracking (FCC) catalyst, the method comprising: pre-forming a precursor microsphere comprising a non-zeolitic material and alumina; in situ crystallizing a Y zeolite on the pre-formed microsphere to provide a zeolite containing microsphere; adding a first portion of a phosphorus component to the zeolite-containing microsphere to form a first phosphorus-modified microsphere; adding a rare earth component to the first phosphorus-modified microsphere to provide a rare earth-containing microsphere; and adding a second portion of the phosphorus component to the rare earth-containing precursor microsphere to provide a catalytic microsphere.|
|U.S. 10,130,943||1. A catalyst composition for use in a catalytic cracking process, said catalyst composition comprising 3.5 to 15.5% of pentasil zeolite, 9 to 40% of ultra-stable Y (USY) or rare earth exchanged USY (REUSY) zeolite, 3.5 to 15% of large pore active matrix based bottom up-gradation component and 0.3 to 3% of a metal trap component, the percentage being based on weight of the catalyst composition and wherein the large pore active matrix based bottom up-gradation component comprises 40-60 wt % alumina, 5-25 wt % silica, 20-60 wt % clay, 1-20 wt % PO4 and has a pore size in the range of 80 Å. to 200 Å.|
|U.S. 10,173,206||1. An FCC catalyst composition comprising a particulate, said particulate comprising catalytic components (a) and (b), wherein component (a) comprises a non-rare earth metal exchanged Y-zeolite in an amount in the range of about 5 to about 50 wt %, based upon the weight of the particulate; and component (b) consists of ZSM-5 zeolite in an amount in the range of about 2 to about 50 wt %, based upon the weight of the particulate, wherein (a) and (b) are present in the same particle, wherein the Y-zeolite:ZSM-5 weight ratio is in the range of about 1:2.5 to about 1:6, and wherein the non-rare earth metal is magnesium, calcium, or strontium.|
|U.S. 10,252,249||1. An attrition resistant hydrocarbon cracking catalyst additive composition comprising 10-70% wt % zeolite, 5-20 wt % colloidal silica, 10-60 wt % clay, 1-10 wt % phosphate and 1-15 wt % aluminium phosphate binder, wherein the aluminium phosphate binder is a reaction product of mono aluminium phosphate and an aluminium compound in the mole ratio of 1:1 to 1:2.5: wherein said zeolite is selected from mordenite, ZSM-5, beta, ZSM-11 with silica alumina ratio ranging from 8 to 500.|
|U.S. 10,287,511||1. A catalyst composition consisting essentially of: 70 wt. % to 95 wt. % of a non-zeolitic material; 3 wt. % to 18 wt. % of at least one zeolite-1 selected from the group consisting of rare earth exchanged USY (REUSY) zeolite and combinations of REUSY zeolite and Beta zeolite; and 2 wt. % to 12 wt. % of at least one zeolite-2, wherein: the at least one zeolite-1 contains sufficient rare earth content that the catalyst composition contains 0.3 wt. % to 1 wt. % rare earth content, and the respective percentages are based on the weight of the catalyst composition.|
|U.S. 10,300,466||1. A process for modifying the physical and chemical properties of Faujasite Y-type zeolites, comprising the steps of: a) contacting Faujasite Y-type zeolite with glycerol in an amount of 0.01 to 1 g per ml of glycerol at a temperature of 180°C. to 200°C. to form a gel; b) adding one or more ammonium salts to the gel of step a) in an amount of 0.01 to 3 g per gram of said zeolite at a temperature of 20°C. to 80°C. to form a mixture, hydrothermally treating said mixture at a temperature of 140°C. to 180°C. for 10 to 20 hours, and cooling the hydrothermally treated mixture to room temperature, and; c) recovering the product obtained in step b) by filtration and/or centrifugation, washing the resulting solid and drying at a temperature of 80 to 120°C., subjecting the dried solid to a thermal treatment in an air atmosphere at a temperature of 480°C. to 520°C. at a heating profile of 1 to 3°C./min to obtain a modified Faujasite Y-type zeolite, wherein a sodium is reduced up to 75% with respect to the Faujasite Y-type zeolite starting material, and said modified Faujasite Y-type zeolite has a mesoporous structure having a bimodal pore size distribution with an average pore size of 2 to 100 nm.|
|U.S. 10,315,186||1. An additive support for a CO oxidation promoter additive comprising pseudoboehmite alumina having a crystallite size in the range of 10 to 20Å, a surface area in the range of 200 to 450 m2/g, an average pore diameter in the range of 35 to 45Å, and an average pore volume in the range of 0.2 to 0.6 cm3/gm; wherein the additive support is having self-binding properties and less than 0.2% of residual sodium oxide; wherein the additive support is prepared by a process comprising: (a) reacting aluminium sulphate with sodium hydroxide by sequential addition of sodium hydroxide solution into solution of aluminium sulphate at a temperature of 25 to 100°C. to obtain a slurry, (b) continuing the reaction until pH of the slurry is reached to 9.5, (c) filtering the slurry to obtain a wet cake, (d) washing the wet cake with hot water, (e) hydrothermal treatment for crystallization of wet cake at a crystallization temperature of 70 to 130°C. for the duration in the range of 12 h-48 h and filter the crystallize material to obtain pseudoboehmite alumina support, (f) preparing a slurry by intimate mixing of pseudoboehmite alumina support and water, (g) peptizing with an organic acid under stirring, and (h) spray drying the slurry of step (g) to obtain microspheres of pseudoboehmite alumina support; wherein the CO oxidation promoter additive is having an apparent bulk density (ABD) above 0.95 g/cm3, and an attrition of less than 5%; wherein the CO oxidation promoter additive is having conversion efficiency in the range of 85-97 and CO2/CO ratio in the range of 20-51.|
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