Recent Trends in Fluid Catalytic Cracking Patents, 2012-13

Fluid Catalytic Cracking Patents (I)  —  2012-2013[1]

Last year, we reviewed the 2012 patents in the area of Fluid Catalytic Cracking (FCC) specifically related to the FCC process.  The original intent, of course, had been to also summarize the 2012 patents for FCC catalysts and equipment.  Unfortunately, that goal met the same fate as several of my New Year’s resolutions.  A year’s passage, however, has brought sufficient wisdom not only to grasp the trend in my New Year’s resolutions, but to realize I now have two-year’s patents to review in those areas.

To evaluate patent activity in the FCC area during 2012-2013, a search of the patent database of the U.S. Patent & Trademark Office was conducted.  The search demonstrated that a number of patent applications in the area of fluid catalytic cracking were granted as patents during that time.  These patents relate to the full range of FCC operation: general process, equipment and catalysts, and reflect the decisions companies have made to protect their Intellectual Property assets.  In this and the next few articles, I’ll briefly summarize the patents in the area of FCC catalysts (additives, cracking catalyst, and zeolite) granted during 2012 & 2013.  The current article will cover patents relating to FCC catalyst additives.  In later articles, I’ll summarize FCC-related patents in the areas of equipment and process.  Table 1 lists relevant information on the FCC catalyst additive patents.  Tables 2(a)-(d) contain representative independent claims from each.

Six patents in the area of FCC additives were present.  This number is somewhat small compared to patents granted in other FCC areas during 2012-2013, and could be an indication that precious R&D dollars have been concentrated in other areas.  The patents can generally be arranged into several sub-categories.  Three of the patents: U.S. Patent Nos. 8,221,615, 8,409,428, and 8,449,762 relate to FCC gasoline sulfur reduction catalysts.  Another patent, U.S. Patent No. 8,444,941, relates to an additive for controlling flue gas emissions; still another, U.S. Patent No. 8,372,269, relates to a metals trap.  The last patent, U.S. Patent No. 8,501,657, (not a true additive in the conventional sense) relates to a sulfur-reduction catalyst for addition to the liquid gasoline itself.

I believe these patents reflect the realities of today’s FCC operations-related research.  First, the relatively few number of patents directed to gasoline sulfur reduction catalysts (or catalysts for addition to liquid gasoline, to reduce sulfur), compared to, e.g., those patents directed to zeolites and the cracking catalyst itself, indicates that this is not a heavy research area.  Sulfur reduction in most commercial FCC units is handled either upstream of the FCC in feed treatment units, such as gas-oil hydrotreaters, or downstream of the FCC in product treatment units, such as naphtha hyrdotreaters/desulphurizers.  The added advantage of a feed hydrotreater, of course, is that it also improves FCC yields.  Therefore, practical use of such additives is normally limited to smaller operating units lacking feed or product treatment capabilities, or in the event of hydrotreater upset or downtime.  Second, the primary use of metals traps is in niche situations where metals tolerance needs can’t be met by either feed treatment or through the design of the FCC catalyst itself.  Finally, SO_x/NO_x capture  technology is a fairly mature and stable area.[2]

The patents are summarized below.

Gasoline Sulfur Reduction

U.S. Patent No. 8,221,615 of Hu et al., assigned to W.R. Grace & Co.-Conn., generally relates to a process for reducing the sulfur content of a catalytically cracked petroleum fraction by contacting the feed (containing organosulfur compounds) at elevated temperature with a zeolite-containing cracking catalyst.  The catalyst has been rare earth-exchanged with yttrium, and at least one of Zn, Mg, and Mn.  The yttrium and the Zn, Mg, and Mn are exchanged onto the zeolite, and the yttrium is present in an amount of 0.1 to 12 wt%, measured as Y₂O₃.  The patent contains a single independent claim, which is listed in Table 2a.

U.S. Patent No. 8,409,428, assigned to Saudi Arabian Oil Company & King Fahd University of Petroleum and Minerals, generally relates to a method for using a gasoline sulfur reduction additive in an FCC process.  The sulfur reduction additive contains a porous montmorillonite clay support whose pores have incorporated a zirconium component to increase its surface area.  The support is impregnated with a Lewis acid compound selected from Group IIB of the Periodic Table.  The patent contains a single independent claim (claim 1) where the gasoline sulfur reduction additive is contacted with a hydrocarbon feedstock along with a conventional FCC catalyst.  Claim 1 is listed in Table 2a.

U.S. Patent No. 8,449,762, assigned to BASF Corporation, relates to a process for catalytic cracking a hydrocarbon feed to products, including gasoline, using a sulfur reduction catalyst containing a metal vanadate.  The patent contains a single independent claim which is listed in Table 2a.

Flue Gas Emissions Control

U.S. Patent No. 8,444,941, assigned to Intercat Equipment, Inc., generally relates to methods for using an additive material in an FCC exhaust outlet.  The additive material contains an active phase component and a collection enhancing component.  The active phase contains at least one of a SO_x emissions reducing component and a NO_x emission reducing component.  The collection enhancing component has a characteristic selected from increased magnetic susceptibility and low electric resistivity.  The patent contains three independent claims (1, 4 and 7) where the additive material is contacted with the FCC gas exhaust stream; the additive material is removed/collected from the exhaust stream; and a portion of the recovered additive material is recycled.  Claim 1 is listed in Table 2b.

Metals Trapping

U.S. Patent No. 8,372,269 of Willis et al., assigned to BASF Corporation, generally relates to magnesium-based (oxide or hydroxide) metal traps for FCC processing.  The metal trap is spray-dried from a mixture of kaolin, magnesium compounds and calcium carbonate.  The spray dried material is then calcined at a temperature from 1500°F to 1650°F.  The patent contains one independent claim (claim 1) directed to the metal trap, and one independent claim (claim 11) directed to a method for passivation using the metal trap.  Claim 1 is listed in Table 2c.

Gasoline Sulfur Reduction (through contact with gasoline)

U.S. Patent No. 8,501,657, assigned to Dalian Institute of Chemical Physics & Chinese Academy of Science, generally relates to a tungsten-based catalyst for the desulfurization and deodorization of gasoline.  The examples show mixing of the catalyst with FCC gasoline.  The patent contains a single independent claim (claim 1) where the catalyst is selected from [C₁₈H₃₇N(CH₃)₃]₁₀HNa[H₂P₂W₁₂O₄₈], [C₁₈H₃₇N(CH₃)₃]₇H₃Na₂[P₂W₁₅O₅₆], [C₁₈H₃₇N(CH₃)₃]₇H₂Na[P₂W₁₇O₆₁].  Claim 1 is listed in Table 2d.

 

Table 1
FCC Catalyst Additive Patents

Patent Number	Inventor	Assignee	Title	Issue Date
U.S. 8,221,615	Hu et al.	W.R. Grace & Co.-Conn.	Gasoline sulfur reduction catalyst for fluid catalytic cracking process	July 17, 2012
U.S. 8,372,269	Willis et al.	BASF Corporation	Heavy Metals Trapping Co-Catalyst For FCC Processes	February 12, 2013
U.S. 8,444,941	Evans et al.	Intercat Equipment, Inc.	Cracking Catalysts, Additives, Methods Of Making Them and Using Them	May 21, 2013
U.S. 8,409,428	Dean et al.	Saudi Arabian Oil Co.; King Fahd University of Petroleum and Minerals	Catalyst Additive For Reduction Of Sulfur In Catalytically Cracked Gasoline	April 2, 2013
U.S. 8,449,762	Gao et al.	BASF Corporation	Catalyst Composition For Reducing Gasoline Sulfur Content In Catalytic Cracking Process	May 28, 2013
U.S. 8,501,657	Li et al.	Dalian Institute of Chemical Physics, Chinese Academy of Science	Catalyst For Desulfurization Of Gasoline And Method For Preparation Of The Same And Use Thereof	August 6, 2013

 

Table 2a
Gasoline Sulfur Reduction

Patent Number	Independent Claim
U.S. 8,221,615	Claim 1.  A method of reducing the sulfur content of a catalytically cracked petroleum fraction, which comprises catalytically cracking a petroleum feed fraction containing organosulfur compounds at elevated temperature in the presence of a cracking catalyst comprising zeolite, yttrium, and at least one element selected from the group consisting of zinc, magnesium, and manganese, wherein the yttrium and the element are present as cations exchanged onto the zeolite; and further wherein the catalyst composition comprises 0.1 to about 12% by weight yttrium, measured as Y2O3.
U.S. 8,409,428	Claim 1.  A process for reducing the sulfur content of a gasoline fraction obtained from an FCC cracking process which comprises contacting a hydrocarbon feedstock with a conventional FCC cracking catalyst in combination with separate particles of sulfur reduction additive composition, said additive composition comprising a porous montmorillonite clay support material into the pores of which a zirconium component has been incorporated to thereby increase the surface area of the support material and the surface of which support material is subsequently impregnated with a Lewis acid compound selected from Group IIB of the Periodic Table.
U.S. 8,449,762	Claim 1.  A process for catalytically cracking a hydrocarbon feedstock to products comprising gasoline, said process comprising contacting said feedstock with a sulfur reduction catalyst comprising a metal vanadate compound.

 

Table 2b
Flue Gas Emissions Control

Patent Number

Independent Claim

U.S. 8,444,941

Claim 1.  A method comprising: routing a gaseous exhaust stream from an outlet of a fluid catalytic cracking (FCC) unit to an exhaust flue through an exhaust path; and introducing a downstream additive material to the gaseous exhaust stream, wherein the downstream additive material comprises (a) an active phase component, and (b) a collection enhancing component having a characteristic selected from the group consisting of increased magnetic susceptibility encouragement of clumping, and low electrical resistivity; and the active phase component comprises a SOx emission reducing component and/or a NOx emission reducing component.

 

Table 2c
Metals Trapping

Patent Number	Independent Claim
U.S. 8,372,269	Claim 1.  A metal trap particle used to passivate metals during FCC processing comprising a spray dried mixture of kaolin, magnesium oxide or magnesium hydroxide, and calcium carbonate, said spray dried mixture having been calcined at a temperature of from 1500°F. to less than 1650°F.

 

Table 2d
Gasoline Sulfur Reduction (through contact with gasoline)

Patent Number	Independent Claim
U.S. 8,501,657	Claim 1.  A catalyst for desulfurization and deodorization of gasoline selected from one or more of the following catalysts:  [C18H37N(CH3)3]10HNa[H2P2W12O48], [C18H37N(CH3)3]7H3Na2[P2W15O56], [C18H37N(CH3)3]7H2Na[P2W17O61].