This is the second article in a review of patents issued in 2015 in the area of Fluid Catalytic Cracking (FCC). The previous article covered FCC additives, and can be found HERE. The summary below covers seven patents relating to FCC catalysts and zeolites. Four of the seven, U.S. Patent No.’s 8,940,652, 8,951,498, 9,126,183, and 9,192,925, relate primarily to the preparation of the zeolite. Two others, U.S. Patent No.’s 8,993,469 and 9,056,308, relate to the overall catalyst. A seventh patent, U.S. Patent 9,175,230, relates to a catalyst having a particular combination of alumina’s. Three of the patents, U.S. Patent No.’s 8,940,652, 9,056,308, and 9,175,230 also recite limitations related to phosphorous. Finally, two of the patents, U.S. Patent No.’s 8,951,498 and 9,126,183, also relate to mesoporosity. Review of the collection of patents demonstrates that a substantial amount of research activity continues to be conducted in the area of catalysts and zeolites; in particular work focused on zeolite preparation for improving stability and mesoporosity.
U.S. Patent No. 8,940,652 relates to a process for preparing a catalyst with high hydrothermal stability and activity. The patent contains a single independent process claim and two independent product-by-process claims. The process includes exchanging an as-crystalized catalyst with an ammonium salt to reduce the Na2O content; treating the resultant material with a phosphate solution to add 0.5 to 2% P2O5 onto the catalyst; exchanging that material with ammonium ion to further reduce Na2O; and then finally contacting the material with a second phosphate solution to arrive at a catalyst with 2-4 wt% P2O5 on the catalyst.
U.S. Patent No. 8,951,498 relates to a process for preparing zeolite nanocrystals to form mesoporous aggregates having improved mass transport properties. The patent contains a single independent claim where a silicon source, a single mono-ammonium organic template and an aluminum source in a solvent are contacted to produce a zeolite gel. At least 50% of the solvent is evaporated from the zeolite gel, which is then heated at a temperature and pressure to produce mesoporous nanocrystalline zeolite crystals. The crystals are then separated, washed, dried and calcined.
U.S. Patent No. 8,993,469 relates to a process for preparing a catalyst having a particular average particle diameter (20 to 300 µm) and void area in the cross-section of the particle (0.3 or less relative to the cross-section of the particle). The catalyst contains an MFI (ZSM-5) type zeolite. The patent contains a single, independent process claim where a mixture of zeolite, colloidal silica and a water soluble compound (nitrate, acetate, carbonate or sulfate salt or a chloride) are spray-dried. The water soluble compound is present in a particular amount relative to the silica in the colloidal silica, and affects the mechanical strength of the catalyst particle.
U.S. Patent No. 9,056,308 relates to a catalyst for producing light olefins from cracking naphtha. The claims contain a single independent claim directed to a catalyst for cracking C4+ material with a boiling point of 30-200°C. The catalyst contains 1-50 wt% of zeolite, 21-70 wt% clay and 1-40 wt% of inorganic binder, where the zeolite contains ZSM-5. MnO2 and P2O5 are embedded on each of the zeolite, clay and inorganic oxide in amounts of 0.01-5.0 wt% and 1-15 wt%, respectively, by weight of the catalyst.
U.S. Patent No. 9,126,183 relates to a modified zeolite Y produced by a particular process. The patent contains two independent claims. One is directed to the modified zeolite, the other is directed to catalytic particles containing the zeolite. The zeolite contains an intracrystalline structure having micropores, small mesopores (2 to 5 nm) and large mesopores (10 to 50 nm), along with a defined range for the ratio of pore volume of the small mesopores to the pore volume of the large mesopores, as well as a defined Si/Al atomic ratio. The process to produce the zeolite includes treating the zeolite Y with a strong base at a concentration of 0.001 to 0.5 M. The treated material is filtered, washed with a solvent and optionally dried. Then, the material is treated with ammonium nitrate and washed to a neutral pH. Finally, the material is calcined and then recovered.
U.S. Patent No. 9,192,925 relates to a zeolite synthesis process, where the zeolite framework contains germanium, titanium, tin and aluminum. The zeolite can be an MFI (ZSM-5) type. The patent has two independent claims, each directed to a process. The process involves calcining the zeolite after its preparation, and then depositing a metal from Group 6, 7, 8, 9, or 10, where the metal is present only as deposited metal.
U.S. Patent No. 9,175,230 relates to a catalyst and processes for preparing it. The catalyst contains alumina, phosphorous, molecular sieve, η-alumina, χ-alumina and ϒ-alumina. η-alumina is present in an amount from 0.5 to 50 wt%. χ-alumina and ϒ-alumina together are present in an amount of less than 50 wt%. Rare earth is present in an amount from 0.1-2 wt%, and clay is present in an amount from greater than 0 to 75 wt%. Phosphorous is present in an amount of 0.1 to 5.5 wt%, and molecular sieve in an amount of 10-70 wt%. There are two independent claims directed to making the catalyst. The first involves a two-step drying process where an aluminum compound is dried between room temperature to 200°C, then rare earth and a phosphorus compound is added, and the material is calcined at a temperature from higher than 200°C to 750°C. The second involves adding a phosphorous compound to the aluminum-containing slurry, drying the slurry, and then calcining the dried slurry.
Table 1. — FCC Patents — Zeolites and Catalysts
Click here to view table.
Table 2. — FCC Zeolites & Catalysts
Click here to view table.
My thanks to Mr. Ken Peccatiello of Peccatiello Engineering (www.PeccatielloEngineering.com) for reviewing the text.