CATALYTIC CRACKING PROCESS WITH BIO-REGENERATIVE FEEDS

Abstract

The fluidized bed catalytic cracking (FCC) process involves feedstocks comprising at least one biorenewable feedstock stream, including a step where feedstocks containing at least one hydrocarbon feedstock stream and at least one biorenewable feedstock stream are exposed to a catalytic cracking catalyst under FCC cracking conditions in which the catalytic cracking catalyst preparation consists of faujasite zeolite in amounts ranging from approximately 5% by weight to approximately 60% by weight of the total catalytic cracking catalyst preparation, total alumina in amounts ranging from approximately 30% by weight to approximately 70% by weight of the total catalytic cracking catalyst preparation, and yttrium in amounts ranging from approximately 0.5% by weight to approximately 6% by weight of Y2O3 and based on the total catalytic cracking catalyst preparation, and where the catalytic cracking catalyst has a surface area The substrate surface area (MSA) is larger than approximately 40 m2 / g.

Description

Atty. Dkt. No.: GRAC-10335 (W10335) PROCESSES FOR FLUID CATALYTIC CRACKING BIO-RENEWABLE FEEDS CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 593,936 filed on October 27, 2023, the contents of which are incorporated by reference herein in their entirety. FIELD

[0002] The present technology is generally related to a process for fluid catalytic cracking bio-renewable feeds. Specifically, the technology is related to using catalyst compositions that include faujasite zeolite, alumina, and yttrium, and methods of using such compositions. BACKGROUND

[0003] Increased attention has been given to the use of bio-renewable materials as a fuel source. Fluidized catalytic cracking (FCC), which has been widely used in the petroleum industry to convert high boiling petroleum-based hydrocarbon feedstocks to more valuable hydrocarbon products, has been reported as one process useful for converting non-petroleum based bio-renewable feeds to low molecular weight, low boiling hydrocarbon products, e.g. gasoline. There remains a need in the catalyst industry for improved processes for the conversion of feedstocks containing bio-renewable feeds.

[0004] The use of bio-based feeds, in the FCC unit, leads to higher levels and different types of impurities being deposited on and deactivating the FCC catalyst. These impurities include Na, K, alkaline earth (Ca and Mg) ions, as well as, phosphorus-compounds and transition metal ions. These impurities necessitate the development of new and improved FCC catalysts that tolerate the higher levels and different types of impurities.Atty. Dkt. No.: GRAC-10335 (W10335)

[0005] This disclosure addresses these needs by providing catalyst compositions that are useful in a process for fluid catalytic cracking bio-renewable feeds. Specifically, this process uses catalyst compositions that have a high matrix surface area and include yttrium stabilized zeolite. Such catalyst compositions provide improvements in metals tolerance, catalyst activity, and product yields. SUMMARY

[0006] In one aspect is a process for fluid catalytic cracking (FCC) of a feedstock comprising at least one bio-renewable feed, the process comprising: contacting a feedstock with at least one hydrocarbon feed and at least one bio-renewable feed with a catalytic cracking catalyst under FCC cracking conditions; wherein: the catalytic cracking catalyst composition comprises: about 5 wt% to about 60 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition; about 30 wt% to about 70 wt% total alumina based on the total weight of the catalytic cracking catalyst composition; and about 0.5 wt% to about 6 wt% yttrium measured as Y2O3and based on the total weight of the catalytic cracking catalyst composition; and the catalytic cracking catalyst has a matrix surface area (MSA) greater than about 40 m2 / g.

[0007] In some embodiments, the faujasite zeolite is a faujasite Y-type zeolite. In some embodiments, the catalytic cracking catalyst comprises about 15 wt% to about 30 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition.

[0008] In some embodiments, the total alumina is the alumina present in one or more of the faujasite zeolite, clay, matrix component(s), and / or catalyst binder(s). In some embodiments, the catalyst binder comprises peptized alumina, and the peptized alumina is based on pseudoboehmite or boehmite. In some embodiments, the catalytic cracking catalyst comprises about 45 wt% to about 60 wt% total alumina based on the total weight of the composition.Atty. Dkt. No.: GRAC-10335 (W10335)

[0009] In some embodiments, the catalytic cracking catalyst comprises about 0.5 wt% to about 2 wt% yttrium measured as Y2O3 and based on the total weight of the composition.

[0010] In some embodiments, the catalytic cracking catalyst has a MSA of about 50 m2 / g to about 200 m2 / g. In some embodiments, the catalytic cracking catalyst has a MSA of about 90 m2 / g to about 200 m2 / g. In some embodiments, the catalytic cracking catalyst has a ratio of zeolite surface area (ZSA) to matrix surface area (MSA) of less than about 2.

[0011] In some embodiments, the hydrocarbon feed comprises a petroleum-based feedstock. In some embodiments, the hydrocarbon feed is a petroleum-based feedstock selected from the group consisting of deep cut gas oil, vacuum gas oil (VGO), thermal oil, residual oil, cycle stock, whole top crude, tar sand oil, shale oil, synthetic fuel, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, hydrotreated feedstocks, and mixtures of any two or more thereof.

[0012] In some embodiments, the bio-renewable feed is a feedstock selected from the group consisting of canola oil, corn oil, soy oils, rapeseed oil, soybean oil, palm oil, colza oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, mustard oil, cotton seed oil, inedible tallow, inedible oil, yellow, brown greases, lard, train oil, fats in milk, fish oil, algal oil, tall oil, sewage sludge, tall oil, bio-derived pyrolysis oil, and mixtures of any two or more thereof.

[0013] In some embodiments, the process produces an equilibrium catalyst having faujasite containing catalyst particles comprising one or more of the following: greater than about 0.8 wt% Na2O; greater than about 0.3 wt% K2O; greater than about 0.5 wt% P2O5; greater than about 0.5 wt% CaO; and greater than about 0.7 wt% MgO.

[0014] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 1.0 wt% Na2O; greater than about 0.5 wt% K2O; greater than about 0.7 wt% P2O5; greater than about 0.7 wt% CaO; and greater than about 0.9 wt% MgO.Atty. Dkt. No.: GRAC-10335 (W10335)

[0015] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 1.2 wt% Na2O; greater than about 0.8 wt% K2O; greater than about 1.0 wt% P2O5; greater than about 1.0 wt% CaO; and greater than about 1.2 wt% MgO.

[0016] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising greater than about 2 wt% of the sum of the wt% Na2O, wt% K2O, wt% P2O, wt% MgO, and wt% CaO. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] FIG.1 depicts the effect of 0.6 wt% K2O on ZSA retention of Catalysts 1-4 as described in Example 5.

[0018] FIG.2 depicts the effect of 0.8 wt% Na2O on ZSA retention of Catalysts 1-4 as described in Example 6.

[0019] FIG.3 depicts the effect of 2 wt% CaO on ZSA retention of Catalysts 1-4 as described in Example 7.

[0020] FIG.4 depicts the effect of 2.5 wt% P2O5 on ZSA retention of Catalysts 3-4 as described in Example 8.

[0021] FIG.5 depicts the effect of 2.5 wt% P2O5and 1 wt% CaO on ZSA retention of Catalysts 3-4 as described in Example 9. DETAILED DESCRIPTION

[0022] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particularAtty. Dkt. No.: GRAC-10335 (W10335) embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0023] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.

[0024] As used herein, the term “bio-renewable” or “bio-feed” are used herein interchangeably, to designate any feed or fraction of a feed or feedstock that has a fat component derived from plant or animal oil. Typically, the feed or fraction comprises primarily triglycerides and free fatty acids (FFA). The tri-glycerides and FFAs contain aliphatic hydrocarbon chains in their structure having 14 to 22 carbons. Examples of such feedstocks include, but are not limited to, canola oil, corn oil, soy oils, rapeseed oil, soybean oil, palm oil, colza oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, mustard oil, cotton seed oil, inedible tallow, inedible oil, e.g. jatropha oil, yellow and brown greases, lard, train oil, fats in milk, fish oil, algal oil, tall oil, sewage sludge and the like. Another example of a bio-renewable feedstock that can be used in the present invention is tall oil. Tall oil is a by-product of the wood processing industry. Tall oil contains esters and rosin acids in addition to FFAs. Rosin acids are cyclic carboxylic acids. The triglycerides and FFAs of the typical vegetable or animal fat contain aliphatic hydrocarbon chains in their structure which have about 8 to about 24 carbon atoms. Pyrolysis oils, which are formed by the pyrolysis of cellulosic waste material, can also be used as a non-petroleum feedstock or a portion or fraction of the feedstock.

[0025] The phrase “fluid catalytic cracking conditions” or “FCC conditions” is used herein to indicate the conditions of a typical fluid catalytic cracking process, wherein a circulating inventory of a fluidized cracking catalyst is contacted with a heavy feedstock, e.g. hydrocarbon feedstock, bio-renewable feedstock, or a mixture thereof, at elevated temperature to convert the feedstocks into lower molecular weight compounds.Atty. Dkt. No.: GRAC-10335 (W10335)

[0026] The term “fluid catalytic cracking activity” is used herein to indicate the ability of a compound to catalyze the conversion of hydrocarbons and / or fat molecules to lower molecular weight compounds under fluid catalytic cracking conditions.

[0027] For purposes of this invention, the term “matrix” is used herein to indicate all mesoporous materials, i.e. materials having pores with a pore radii of at least 20 Å (angstrom) as measured by BET and t-plot (see Johnson, J. M. F. L., J. Cat 52, pgs 425-431 (1978)), comprising the catalytic cracking catalyst disclosed herein, including any binders and / or fillers, and excluding the catalytically active zeolite which typically will have pores in the micropore range, i.e. openings less than 20 Å (angstrom) as measured by BET and t-plot.

[0028] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0029] Using bio-based feeds or bio-renewable feeds, in the FCC unit, results in higher levels and different types of impurities being deposited on and deactivating the FCC catalyst. Such impurities include Na, K, alkaline earth (Ca and Mg) ions, as well as, phosphorus compounds and transition metal ions. As such, these impurities necessitate the development of new and improved FCC catalysts that tolerate these higher levels and different types of impurities.Atty. Dkt. No.: GRAC-10335 (W10335)

[0030] This disclosure provides catalyst compositions that are useful for the fluid catalytic cracking of bio-renewable feeds. Specifically, the FCC catalyst compositions described herein have a high matrix surface area and include yttrium stabilized zeolite. Also, provided herein is the use of the FCC catalyst compositions described herein with feeds that contain high and unique impurity metals present in ranges outside of typical for commercial units. Such catalyst compositions provide improvements in metals tolerance, catalyst activity, and product yields.

[0031] As demonstrated in the Examples, the incorporation of high matrix surface area (MSA) alumina, and the use of yttrium, instead of lanthanum, as the stabilizing ion for the Y zeolite component into an FCC catalyst improve metals tolerance, catalyst activity and product yields. As compared to lanthanum stabilized Y-zeolite FCC catalyst, yttrium stabilized Y-zeolite FCC catalyst is more Na, K, Mg, Ca, and P tolerant in the presence of either high or low matrix surface area. Additionally, incorporating higher matrix alumina levels, to give higher MSA, significantly enhances the metals tolerance, gives better activity retention, and better yield selectivity in the presence of either lanthanum or yttrium stabilized Y-zeolite catalyst. Combining both yttrium zeolite stabilization and high matrix leads to the best metals tolerance and provides the highest activity and the best selectivity.

[0032] Described herein is a process for fluid catalytic cracking (FCC) of a feedstock comprising at least one bio-renewable feed, the process comprising: contacting a feedstock with at least one hydrocarbon feed and at least one bio-renewable feed with a catalytic cracking catalyst under FCC cracking conditions; wherein: the catalytic cracking catalyst composition comprises: about 5 wt% to about 60 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition; about 30 wt% to about 70 wt% total alumina based on the total weight of the catalytic cracking catalyst composition; andAtty. Dkt. No.: GRAC-10335 (W10335) about 0.5 wt% to about 6 wt% yttrium measured as Y2O3and based on the total weight of the catalytic cracking catalyst composition; and the catalytic cracking catalyst has a matrix surface area (MSA) greater than about 40 m2 / g.

[0033] The catalytic cracking catalyst composition described herein may comprise any zeolite that has catalytic cracking activity under fluid catalytic cracking conditions. In some embodiments, the zeolite is faujasite zeolite, such as Y-type zeolite. In some embodiments, the zeolite is an ultra stable type Y-zeolite (USY), such as that disclosed in U.S. Pat. No.3,293,192.

[0034] The catalytic cracking catalyst composition comprises about 5 wt% to about 60 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition, including about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, and about 60 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition. In some embodiments, the catalytic cracking catalyst composition comprises about 15 wt% to about 30 wt%, including about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, about 20 wt%, about 21 wt%, about 22 wt%, about 23 wt%, about 24 wt%, about 25 wt%, about 26 wt%, about 27 wt%, about 28 wt%, about 29 wt%, and about 30 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition.

[0035] The catalytic cracking catalyst composition described herein comprises alumina, formed from alumina precursors such as peptized alumina, alumina hydrate, and aluminum chlorhydrol. The alumina precursors may further comprise boehmite or microcrystalline boehmite, also called pseudoboehmite. Peptized alumina refers to alumina precursors such as pseudoboehmite that have been treated with acid in a manner that fully or partially breaks up the aluminum oxide hydroxide into a particle size distribution with an increased number of particles that are less than one micron in size. The total alumina described herein may also comprise the alumina present in faujasite, clay and other matrix and binder components.Atty. Dkt. No.: GRAC-10335 (W10335)

[0036] In some embodiments, the total alumina is the alumina present in one or more of the faujasite zeolite, clay, matrix component(s), and / or catalyst binder(s). In some embodiments, the catalyst binder comprises peptized alumina. In some embodiments, the peptized alumina is based on pseudoboehmite or boehmite.

[0037] The catalytic cracking catalyst composition comprises about 30 wt% to about 70 wt% total alumina based on the total weight of the composition, including about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, and about 70 wt% total alumina based on the total weight of the composition. In some embodiments, the catalytic cracking catalyst composition comprises about 45 wt% to about 60 wt% total alumina based on the total weight of the composition.

[0038] The catalytic cracking catalyst composition described herein comprises yttrium that is partially or totally exchanged on the zeolite. Yttrium may be exchanged on the zeolite using conventional means, such as direct exchange onto the zeolite with a yttrium salt prior to the addition of any optional components. Suitable yttrium salts include yttrium halides (e.g., chlorides, bromides, fluorides and iodides), nitrates, sulfates, carbonates, and acetates. As used herein, yttrium not only refers to yttrium salt, but also yttrium cation such as that exchanged on zeolite. Weight measurements of yttrium refer to that reported as yttrium oxide (Y2O3) in elemental analysis techniques conventionally used in the art, including but not limited to, inductively coupled plasma (ICP) analytical methods.

[0039] The catalytic cracking catalyst composition comprises about 0.5 wt% to about 6 wt% yttrium measured as Y2O3and based on the total weight of the composition, including about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, about 5.5 wt%, and 6 wt% yttrium measured as Y2O3and based on the total weight of the composition. In some embodiments, the catalytic cracking catalyst comprises about 0.5 wt% to about 2 wt% yttrium measured as Y2O3 and based on the total weight of the composition.Atty. Dkt. No.: GRAC-10335 (W10335)

[0040] The catalytic cracking catalyst composition described herein has a high matrix surface area (MSA). “Matrix surface area” refers to the surface area attributable to the matrix material comprising the catalyst, which material will generally have a pore size of 20 Å (angstrom) or greater as measured by BET and t-plot method.

[0041] In some embodiments, the catalytic cracking catalyst has a MSA of greater than about 40 m2 / g, greater than about 50 m2 / g, greater than about 55 m2 / g, greater than about 60 m2 / g, greater than about 65 m2 / g, greater than about 70 m2 / g, greater than about 75 m2 / g, greater than about 80 m2 / g, greater than about 85 m2 / g, greater than about 90 m2 / g, greater than about 95 m2 / g, or greater than about 100 m2 / g.

[0042] In some embodiments, the catalytic cracking catalyst has a MSA of about 50 m2 / g to about 200 m2 / g, including about 50 m2 / g, about 60 m2 / g, about 70 m2 / g, about 80 m2 / g, about 90 m2 / g, about 100 m2 / g, about 110 m2 / g, about 120 m2 / g, about 130 m2 / g, about 140 m2 / g, about 150 m2 / g, about 160 m2 / g, about 170 m2 / g, about 180 m2 / g, about 190 m2 / g, and about 200 m2 / g. In some embodiments, the catalytic cracking catalyst has a MSA of about 90 m2 / g to about 200 m2 / g.

[0043] In some embodiments, the catalytic cracking catalyst has a ratio of zeolite surface area (ZSA) to matrix surface area (MSA) of less than about 2.

[0044] As described herein, using a non-standard feed, such bio-renewable feeds, in a FCC unit deposits higher levels of impurities and different impurities than are present in current FCC units. As described below, the average impurity level, on the faujasite zeolite containing catalyst particles in the equilibrium catalyst comprises one or more of the following: greater than about 0.8 wt% Na2O; greater than about 0.3 wt% K2O; greater than about 0.5 wt% P2O5; greater than about 0.5 wt% CaO; greater than about 0.7 wt% MgO; and greater than about 2 wt% of the sum of the wt% Na2O, the wt% K2O, the wt% P2O, the wt% MgO, and the wt% CaO.

[0045] In some embodiments, the equilibrium catalyst has faujasite zeolite containing catalyst particles comprising greater than about 0.8 wt% Na2O, greater than about 1.0 wt% Na2O,Atty. Dkt. No.: GRAC-10335 (W10335) or greater than about 1.2 wt% Na2O. In some embodiments, the equilibrium catalyst has faujasite zeolite containing catalyst particles comprising greater than about 0.3 wt% K2O, greater than about 0.5 wt% K2O, or greater than about 0.8 wt% K2O. In some embodiments, the equilibrium catalyst has faujasite zeolite containing catalyst particles comprising greater than about 0.5 wt% P2O5, greater than about 0.7 wt% P2O5, or greater than about 1.0 wt% P2O5. In some embodiments, the equilibrium catalyst has faujasite zeolite containing catalyst particles comprising greater than about 0.5 wt% CaO, greater than about 0.7 wt% CaO, or greater than about 1.0 wt% CaO. In some embodiments, the equilibrium catalyst has faujasite zeolite containing catalyst particles comprising greater than about 0.7 wt% MgO, greater than about 0.9 wt% MgO, or greater than about 1.2 wt% MgO.

[0046] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 0.8 wt% Na2O; greater than about 0.3 wt% K2O; greater than about 0.5 wt% P2O5; greater than about 0.5 wt% CaO; and greater than about 0.7 wt% MgO.

[0047] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 1.0 wt% Na2O; greater than about 0.5 wt% K2O; greater than about 0.7 wt% P2O5; greater than about 0.7 wt% CaO; and greater than about 0.9 wt% MgO.

[0048] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 1.2 wt% Na2O;Atty. Dkt. No.: GRAC-10335 (W10335) greater than about 0.8 wt% K2O; greater than about 1.0 wt% P2O5; greater than about 1.0 wt% CaO; and greater than about 1.2 wt% MgO.

[0049] In some embodiments, the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising greater than about 2 wt% of the sum of the wt% Na2O, the wt% K2O, the wt% P2O5, the wt% MgO, and the wt% CaO. FCC Units and Conditions

[0050] The FCC process described herein is performed in a FCC unit. The FCC unit is not particularly restricted as long as the unit contains a reaction zone, a separation zone, a stripping zone and a regeneration zone. The significant steps of the FCC process typically comprises: ^ (i) catalytically cracking a bio-renewable feed containing feedstock in a catalytic cracking zone, normally a riser cracking zone, operating at catalytic cracking conditions by contacting feed with a source of hot, regenerated cracking catalyst to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons; ^ (ii) discharging and separating the effluent, normally in one or more cyclones, into a vapor phase rich in cracked product and a solids rich phase comprising the spent catalyst; ^ (iii) removing the vapor phase as product and fractionating the product in the FCC main column and its associated side columns to form gas and liquid cracking products including gasoline; ^ (iv) stripping the spent catalyst, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst isAtty. Dkt. No.: GRAC-10335 (W10335) oxidatively regenerated in a catalyst regeneration zone to produce hot, regenerated catalyst, which is then recycled to the cracking zone for cracking further quantities of feed.

[0051] Within the reaction zone of the FCC unit, the FCC process is typically conducted at reaction temperatures of about 480° C to about 650° C with catalyst regeneration temperatures of about 600° C to about 800° C. As it is well known in the art, the catalyst regeneration zone may consist of a single or multiple reactor vessels.

[0052] A catalyst-oil-ratio of typically, about 3 to about 25, preferably, about 3 to about 15; a hydrocarbon partial pressure in the reactor of typically, 1 bar to about 4 bar, preferably about 1.75 bar to about 2.5 bar; and a contact time between the feedstock and the catalyst of 0.5 to 10 seconds, preferably 1 to 5 seconds. The term “catalyst-oil-ratio’ as used in the present invention refers to the ratio of the catalyst circulation amount (ton / h) and the feedstock supply rate (ton / h). The term “hydrocarbon partial pressure” is used herein to indicate the overall hydrocarbon partial pressure in the riser reactor. The term “catalyst contact time” is used herein to indicate the time from the point of contact between the feedstock and the catalyst at the catalyst inlet of the riser reactor until separation of the reaction products and the catalyst at the stripper outlet.

[0053] The outlet temperature of the reaction zone as used in the present invention refers to the outlet temperature of the fluidized riser reactor. Generally, the outlet temperature of the reaction zone in the present invention will range from about 480 °C to about 650 °C. It is also within the scope of the present invention that the FCC unit may comprise any device conventionally used for processing bio-renewable feeds. Feedstocks

[0054] Feedstocks useful herein in this disclosure comprise petroleum-based hydrocarbon feedstocks comprising at least one bio-renewable feed fraction. Petroleum based hydrocarbons feedstocks useful herein typically include, in whole or in part, a gas oil (e.g., light,Atty. Dkt. No.: GRAC-10335 (W10335) medium, or heavy gas oil) having an initial boiling point above about 120 °C, a 50% point of at least about 315 °C. The feedstock may also include deep cut gas oil, vacuum gas oil (VGO), thermal oil, residual oil, cycle stock, whole top crude, tar sand oil, shale oil, synthetic fuel, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, hydrotreated feedstocks derived from any of the foregoing, and the like. As will be recognized, the distillation of higher boiling petroleum fractions above about 400 °C must be carried out under vacuum to avoid thermal cracking. The boiling temperatures utilized herein are expressed in terms of convenience of the boiling point corrected to atmospheric pressure. Even high metal content resids or deeper cut gas oils having an end point of up to about 850 °C can be cracked using the invention.

[0055] Feedstocks described herein may be blended feedstocks, i.e., feedstocks comprising both hydrocarbon feed and bio-renewable feed fractions. Blended feedstocks useful in the process of the invention typically comprise from about 99 to about 25 wt % hydrocarbon feedstock and from about 1 to about 75 wt % bio-renewable feedstocks. In some embodiments, the blended feedstock comprises from about 97 to about 80 wt % hydrocarbon feedstock and from about 3 to about 20 wt % of a bio-renewable feedstock.

[0056] The feedstocks described herein may also be injected separately into the FCC riser reactor through different feed nozzles. The biofeed may be injected either upstream, downstream of, or at the same position as the hydrocarbon feed. The overall ratio of the feedstocks useful in the process of the invention typically comprise from about 99 to about 25 wt % hydrocarbon feedstock and from about 1 to about 75 wt % bio-renewable feedstocks. In some embodiments, the overall feedstock comprises from about 97 to about 80 wt % hydrocarbon feedstock and from about 3 to about 20 wt % of a bio-renewable feedstock.

[0057] In some embodiments, the hydrocarbon feed or fraction comprises a petroleum- based feedstock. In some embodiments, the hydrocarbon feed or fraction is a petroleum-based feedstock selected from the group consisting of deep cut gas oil, vacuum gas oil (VGO), thermal oil, residual oil, cycle stock, whole top crude, tar sand oil, shale oil, synthetic fuel, heavyAtty. Dkt. No.: GRAC-10335 (W10335) hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, hydrotreated feedstocks, and mixtures of any two or more thereof.

[0058] The bio-renewable feeds described herein contain animal and / or plant fats and / or oils alone. In some embodiments, the bio-renewable feed or fraction is a feedstock selected from the group consisting of canola oil, corn oil, soy oils, rapeseed oil, soybean oil, palm oil, colza oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, mustard oil, cotton seed oil, inedible tallow, inedible oil, yellow, brown greases, lard, train oil, fats in milk, fish oil, algal oil, tall oil, sewage sludge, tall oil, bio-derived pyrolysis oil, and mixtures of any two or more thereof.

[0059] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention. EXAMPLES

[0060] “CPS” is used herein to indicate a cyclic propylene steam deactivation procedure which uses propylene and air to simulate the oxidation-reduction cycles in addition to the steam deactivation effect. (See American Chemical Society Symposium Series, No.634, Page 171- 183(1996)).

[0061] “ACE” is used herein to mean the Advanced Cracking Evaluation Test as described in U.S. Pat. No.6,069,012, said reference being herein incorporated by reference.

[0062] The surface area as indicated herein was measured by N2BET and the t-plot method and chemical analysis was performed by ICP-OES analysis, standardized to National Institute of Science and Technology standards.Atty. Dkt. No.: GRAC-10335 (W10335)

[0063] Example 1. Lanthanum Stabilized Catalyst with low Matrix Surface Area (MSA) – Catalyst 1.

[0064] An aqueous slurry containing 40 wt% USY (0.9 wt% Na2O), 13 wt% alumina binder from aluminum chlorhydrol, 10 wt% alumina from large crystal boehmite, 2.0 wt% La2O3from LaCl3 solution, and clay was prepared and mixed. The slurry was then milled in a Drais mill and spray dried. The spray dried catalyst was then calcined for 1 hour at 593 °C to produce Catalyst 1. The properties of Catalyst 1 are shown in Table 1.

[0065] Example 2. Yttrium Stabilized Catalyst with low Matrix Surface Area (MSA) – Catalyst 2.

[0066] An aqueous slurry containing 40 wt% USY (0.9 wt% Na2O), 13 wt% alumina binder from aluminum chlorhydrol, 10 wt% alumina from large crystal boehmite, 1.4 wt% Y2O3from YCl3 solution, and clay was prepared and mixed. The slurry was then milled in a Drais mill and spray dried. The spray dried catalyst was then calcined for 1 hour at 593 °C to produce Catalyst 2. The properties of Catalyst 2 are shown in Table 1.

[0067] Example 3. Lanthanum Stabilized Catalyst with High Matrix Surface Area (MSA) – Catalyst 3.

[0068] An aqueous slurry containing 25 wt% USY (2 wt% Na2O), 30 wt% alumina from peptized pseudo-boehmite, 5 wt% colloidal silica, 2.0 wt% La2O3 from LaCl3 solution, and clay was prepared and mixed. The slurry was then milled in a Drais mill and spray dried. The spray dried catalyst was then calcined for 40 minutes at 399 °C and washed with an ammonium containing solution and water to remove Na2O to produce Catalyst 3. The properties of Catalyst 3 are shown in Table 1.Atty. Dkt. No.: GRAC-10335 (W10335)

[0069] Example 4. Yttrium Stabilized Catalyst with High Matrix Surface Area (MSA) – Catalyst 4.

[0070] An aqueous slurry containing 25 wt% USY (2 wt% Na2O), 30 wt% alumina from peptized pseudo-boehmite, 5 wt% colloidal silica, 1.4 wt% Y2O3from YCl3solution, and clay was prepared and mixed. The slurry was then milled in a Drais mill and spray dried. The spray dried catalyst was then calcined for 40 minutes at 399 °C and washed with an ammonium containing solution and water to remove Na2O to produce Catalyst 4. The properties of Catalyst 4 are shown in Table 1. Table 1. Catalyst Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4 PV, cm3 / g 0.42 0.42 0.43 0.42

[0071] Deactivation Technique for Examples 5-9.

[0072] Catalysts 1 to 4 were treated using a spray impregnation method to coat the impurities on the outer edge of the catalyst particle (Applied Catalysis A: General 462-463 (2013) 91-99). This technique, in combination with the subsequent Cyclic Propylene Steam deactivation (CPS) step, allows for distribution of contaminants in a very similar manner to Ecat. The spray impregnation is performed by spraying aqueous solutions of the metal salts into a hot fluidized bed of catalyst where the water evaporates when it contacts the hot catalyst surface.Atty. Dkt. No.: GRAC-10335 (W10335) Na2SO4, K2SO4, calcium acetate, and diammonium hydrogen phosphate (DAP) were utilized as the salts to deposit the impurities. After spray-coating the impurities, the catalysts were calcined for 2 hours at 593 °C. If nickel and vanadium were additionally used in the deactivation, they were added after the spray-coating and calcination of the other impurities. The catalysts were then deactivated using a CPS deactivation.

[0073] Example 5. Catalysts 1-4 were spray-coated with 0.5 wt% K2O as described in the general procedure above. The combination of the initial K2O on catalyst and the added K2O resulted in all catalysts having 0.6 wt% K2O. The catalysts were then aged using a CPS deactivation protocol without Ni and V. The BET and t-plot surface areas of the spray-coated, deactivated catalyst was compared to the base catalyst surface area to give a % zeolite surface area retention. The base catalyst surface area was measured before spray coating and deactivation. The results are shown in FIG.1. The data shows the yttrium ion stabilized catalysts have better ZSA retention than lanthanum ion stabilized catalysts. Additionally, Catalysts 3 and 4, with higher matrix surface, have better ZSA retention than the lower MSA Catalysts 1 and 2.

[0074] The Catalysts 1-4 were also tested in the ACE unit to measure the catalyst activity. Catalyst 1 was compared to Catalyst 2 and Catalyst 3 was compared to Catalyst 4 to differentiate the effectiveness of yttrium versus lanthanum stabilization of the zeolite. The results are shown in Table 2 at a constant conversion of 78 wt% of fresh feed. In both cases, the yttrium stabilized zeolite provides better catalyst activity (requires lower catalyst / oil ratio to give the same conversion). Table 2. Conversion 78, wt% of Fresh Feed (FF) %Atty. Dkt. No.: GRAC-10335 (W10335) Dry Gas, wt%FF 2.1 2.0 2.2 2.1 Gasoline, wt%FF 53.1 54.4 54.2 54.6

[0075] Example 6.

[0076] Catalysts 1-4 were spray coated with 0.5 wt% Na2O as described in the general procedure above. The combination of the initial Na2O on catalyst and the added Na2O led to all catalysts having from 0.7-0.8 wt% Na2O. The catalysts were then aged using a CPS deactivation protocol without Ni and V. The BET and t-plot surface areas of the spray-coated, deactivated catalysts were compared to the base catalyst surface area to give a % zeolite surface area retention. The base catalyst surface area was measured before spray coating and deactivation. The results are shown in FIG.2. The data shows the yttrium ion stabilized catalysts have better ZSA retention than lanthanum ion stabilized catalysts. Additionally, Catalysts 3 and 4, with higher matrix surface, have better ZSA retention than the lower MSA Catalysts 1 and 2.

[0077] The Catalysts 1-4 were also tested in the ACE unit to measure the catalyst activity. Catalyst 1 was compared to Catalyst 2 and Catalyst 3 was compared to Catalyst 4 to differentiate the effectiveness of yttrium versus lanthanum stabilization of the zeolite. The results are shown in Table 3 at a constant conversion of 75 wt% of fresh feed. In both cases, the yttrium stabilized zeolite provides better catalyst activity (requires lower catalyst / oil ratio to give the same conversion). Table 3. Conversion 75, wt% of Fresh Feed (FF) %Atty. Dkt. No.: GRAC-10335 (W10335) Catalyst to Oil 6.3 5.7 6.6 5.6 Ratio

[0078] Example 7.

[0079] Catalysts 1-4 were spray coated with 2 wt% CaO as described in the general procedure above. The combination of the initial CaO on catalyst and the added CaO led to all catalysts having 2 wt% CaO. The catalysts were then aged using a CPS deactivation protocol with 2000 mg / kg Ni and 3000 mg / kg V. The BET and t-plot surface areas of the spray-coated, deactivated catalysts were compared to the base catalyst surface area to give a % zeolite surface area retention. The base catalyst surface area was measured before spray coating and deactivation. The results are shown in FIG.3. The data shows the yttrium ion stabilized catalysts have better ZSA retention than lanthanum ion stabilized catalysts. Additionally, Catalysts 3 and 4, with higher matrix surface, have better ZSA retention than the lower MSA Catalysts 1 and 2.

[0080] The Catalysts 1-4 were also tested in the ACE unit to measure the catalyst activity. Catalyst 1 was compared to Catalyst 2 and Catalyst 3 was compared to Catalyst 4 to differentiate the effectiveness of yttrium versus lanthanum stabilization of the zeolite. The results are shown in Table 4 at a constant conversion of 68 wt% of fresh feed. In both cases, the yttrium stabilized zeolite provides better catalyst activity (requires lower catalyst / oil ratio to give the same conversion). Table 4.Atty. Dkt. No.: GRAC-10335 (W10335) Conversion 68, wt% of Fresh Feed (FF) Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4

[0081] Example 8.

[0082] Catalysts 3 and 4 were spray coated with 2.5 wt% P2O5 as described in the general procedure above. The catalysts were then aged using a CPS deactivation protocol with 2000 mg / kg Ni and 3000 mg / kg V. The BET and t-plot surface areas of the spray-coated, deactivated catalysts were compared to the base catalyst surface area to give a % zeolite surface area retention. The base catalyst surface area was measured before spray coating and deactivation. The results are shown in FIG.4. The data shows the yttrium ion stabilized catalyst has better ZSA retention than lanthanum ion stabilized catalyst.

[0083] The Catalysts 3 and 4, with added P2O5, were also tested in the ACE unit to measure the catalyst activity. Catalyst 3 was compared to Catalyst 4 to differentiate the effectiveness of yttrium versus lanthanum stabilization of the zeolite. The results are shown in Table 5, at a constant catalyst to oil ratio of 6. The yttrium stabilized zeolite provides significantly better catalyst activity (higher conversion at constant catalyst / oil ratio). Table 5. Cat to Oil 6Atty. Dkt. No.: GRAC-10335 (W10335) Catalyst 3 Catalyst 4 with 2.5 wt% with 2.5 wt%

[0084] Example 9.

[0085] Catalysts 3 and 4 were spray coated with 2.5 wt% P2O5and 1 wt% CaO as described in the general procedure above. The catalysts were then aged using a CPS deactivation protocol with 2000 mg / kg Ni and 3000 mg / kg V. The BET and t-plot surface areas of the spray- coated, deactivated catalysts were compared to the base catalyst surface area to give a % zeolite surface area retention. The base catalyst surface area was measured before spray coating and deactivation. The results are shown in FIG.5. The data shows the yttrium ion stabilized catalyst has better ZSA retention than lanthanum ion stabilized catalyst.

[0086] The Catalysts 3 and 4, with added P2O5and CaO, were also tested in the ACE unit to measure the catalyst activity. Catalyst 3 was compared to Catalyst 4 to differentiate the effectiveness of yttrium versus lanthanum stabilization of the zeolite. The results are shown in Table 6, at a constant catalyst to oil ratio of 6. The yttrium stabilized zeolite provides significantly better catalyst activity (higher conversion at constant catalyst / oil ratio). Table 6. Cat to Oil 6Atty. Dkt. No.: GRAC-10335 (W10335) with 2.5 wt% with 2.5 wt% P2O5 / 1 wt% CaO P2O5 / 1 wt% CaO

[0087] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0088] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.

[0089] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalentAtty. Dkt. No.: GRAC-10335 (W10335) methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, or compositions, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0090] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0091] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0092] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.Atty. Dkt. No.: GRAC-10335 (W10335)

[0093] Other embodiments are set forth in the following claims.

Claims

Atty. Dkt. No.: GRAC-10335 (W10335) WHAT IS CLAIMED IS:

1. A process for fluid catalytic cracking (FCC) of a feedstock comprising at least one bio- renewable feed, the process comprising: contacting a feedstock with at least one hydrocarbon feed and at least one bio-renewable feed with a catalytic cracking catalyst under FCC cracking conditions; wherein: the catalytic cracking catalyst composition comprises: about 5 wt% to about 60 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition; about 30 wt% to about 70 wt% total alumina based on the total weight of the catalytic cracking catalyst composition; and about 0.5 wt% to about 6 wt% yttrium measured as Y2O3 and based on the total weight of the catalytic cracking catalyst composition; and the catalytic cracking catalyst has a matrix surface area (MSA) greater than about 40 m2 / g.

2. The process of claim 1, wherein the faujasite zeolite is a faujasite Y-type zeolite.

3. The process of claim 1 or 2, wherein the catalytic cracking catalyst comprises about 15 wt% to about 30 wt% faujasite zeolite based on the total weight of the catalytic cracking catalyst composition.

4. The process of any one of claims 1-3, wherein the total alumina is the alumina present in one or more of the faujasite zeolite, clay, matrix component(s), and / or catalyst binder(s).

5. The process of claim 4, wherein the catalyst binder comprises peptized alumina, and the peptized alumina is based on pseudoboehmite or boehmite.

6. The process of any one of claims 1-5, wherein the catalytic cracking catalyst comprises about 45 wt% to about 60 wt% total alumina based on the total weight of the composition.Atty. Dkt. No.: GRAC-10335 (W10335) 7. The process of any one of claims 1-6, wherein the catalytic cracking catalyst comprises about 0.5 wt% to about 2 wt% yttrium measured as Y2O3 and based on the total weight of the composition.

8. The process of any one of claims 1-7, wherein the catalytic cracking catalyst has a MSA of about 50 m2 / g to about 200 m2 / g.

9. The process of claim 8, wherein the catalytic cracking catalyst has a MSA of about 90 m2 / g to about 200 m2 / g.

10. The process of any one of claims 1-9, wherein the catalytic cracking catalyst has a ratio of zeolite surface area (ZSA) to matrix surface area (MSA) of less than about 2.

11. The process of any one of claims 1-10, wherein the hydrocarbon feed comprises a petroleum-based feedstock.

12. The process of any one of claims 1-11, wherein the hydrocarbon feed is selected from the group consisting of deep cut gas oil, vacuum gas oil (VGO), thermal oil, residual oil, cycle stock, whole top crude, tar sand oil, shale oil, synthetic fuel, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, hydrotreated feedstocks, and mixtures of any two or more thereof.

13. The process of any one of claims 1-12, wherein the bio-renewable feed is selected from the group consisting of canola oil, corn oil, soy oils, rapeseed oil, soybean oil, palm oil, colza oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, mustard oil, cotton seed oil, inedible tallow, inedible oil, yellow, brown greases, lard, train oil, fats in milk, fish oil, algal oil, tall oil, sewage sludge, tall oil, bio-derived pyrolysis oil, and mixtures of any two or more thereof.

14. The process of any one of claims 1-13, wherein the process produces an equilibrium catalyst having faujasite containing catalyst particles comprising one or more of the following: greater than about 0.8 wt% Na2O;Atty. Dkt. No.: GRAC-10335 (W10335) greater than about 0.3 wt% K2O; greater than about 0.5 wt% P2O5; greater than about 0.5 wt% CaO; and greater than about 0.7 wt% MgO.

15. The process of any one of claims 1-14, wherein the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 1.0 wt% Na2O; greater than about 0.5 wt% K2O; greater than about 0.7 wt% P2O5; greater than about 0.7 wt% CaO; and greater than about 0.9 wt% MgO.

16. The process of any one of claims 1-15, wherein the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising one or more of the following: greater than about 1.2 wt% Na2O; greater than about 0.8 wt% K2O; greater than about 1.0 wt% P2O5; greater than about 1.0 wt% CaO; and greater than about 1.2 wt% MgO.

17. The process of any one of claims 1-16, wherein the process produces an equilibrium catalyst having faujasite zeolite containing catalyst particles comprising greater than about 2 wt% of the sum of the wt% Na2O, wt% K2O, wt% P2O, wt% MgO, and wt% CaO.

Images