Process for fluid catalytic cracking of biorenewable feedstocks

Abstract

A method of fluid catalytic cracking (FCC) of a feedstock comprising at least one biorenewable feed, comprising contacting a feedstock having at least one hydrocarbon feed and at least one biorenewable feed with a catalytic cracking catalyst under FCC cracking conditions; wherein the catalytic cracking catalyst composition comprises from about 5 wt% to about 60 wt% of zeolite, based on the total weight of the catalytic cracking catalyst composition, from about 30 wt% to about 70 wt% of total alumina, based on the total weight of the catalytic cracking catalyst composition, and from about 0.5 wt% to about 6 wt% of yttrium, measured as Y203, based on the total weight of the catalytic cracking catalyst composition; and wherein the catalytic cracking catalyst has a matrix surface area (MSA) of greater than about 40 m2 / g. 2 / g.

Description

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

[0002] field This technology generally relates to a method for fluidized catalytic cracking of biorenewable feedstocks. Specifically, the technology relates to the use of catalyst compositions comprising zeolite, alumina, and yttrium, and methods for using such compositions.

[0003] background The use of biorenewable materials as fuel sources has garnered increasing attention. Fluid catalytic cracking (FCC), already widely used in the petroleum industry to convert high-boiling petroleum-based hydrocarbon feedstocks into more valuable hydrocarbon products, has been reported as a useful method for converting non-petroleum-based biorenewable feedstocks into low-molecular-weight, low-boiling-point hydrocarbon products such as gasoline. In the catalyst industry, there remains a need for improved methods for converting feedstocks containing biorenewable materials.

[0004] The use of bio-based feeds in FCC units results in higher levels and different types of impurities depositing on the FCC catalyst and deactivating it. 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 to tolerate higher levels and different types of impurities.

[0005] This disclosure addresses these needs by providing useful catalyst compositions for a method of fluidized catalytic cracking of biorenewable feedstocks. Specifically, the method uses catalyst compositions with a high matrix surface area and incorporating yttrium-stabilized zeolites. Such catalyst compositions offer improvements in metal tolerance, catalyst activity, and product yield. Summary of the Invention

[0006] In one aspect, a method for fluidized catalytic cracking (FCC) of a feedstock comprising at least one biorenewable feedstock is provided. The method comprises, under FCC cracking conditions, contacting the feedstock having at least one hydrocarbon feedstock and at least one biorenewable feedstock with a catalytic cracking catalyst, wherein: the catalytic cracking catalyst composition comprises: about 5% to about 60% by weight of octahedral zeolite based on the total weight of the catalytic cracking catalyst composition; about 30% to about 70% by weight of total alumina based on the total weight of the catalytic cracking catalyst composition; and about 0.5% to about 6% by weight of yttrium as measured in Y₂O₃ based on the total weight of the catalytic cracking catalyst composition; and the catalytic cracking catalyst has a molecular weight greater than about 40 μm. 2 / g matrix surface area (MSA).

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

[0008] In some embodiments, the total alumina is alumina present in one or more of zeolite, clay, matrix components, and / or catalyst binder. In some embodiments, the catalyst binder comprises soluble alumina, and the soluble alumina is based on pseudoboehmite or boehmite. In some embodiments, the catalytic cracking catalyst comprises about 45% to about 60% total alumina based on the total weight of the composition.

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

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

[0011] In some embodiments, the hydrocarbon feedstock comprises a petroleum-based feedstock. In some embodiments, the hydrocarbon feedstock is selected from deep-cut gas oil, vacuum gas oil (VGO), thermal oil, residue oil, cycle stock, whole topcrude, tar sand oil, shale oil, synthetic fuels; destructively hydrogenated heavy hydrocarbon fractions derived from coal, tar, pitch, asphalt; hydrotreated feedstocks; and petroleum-based feedstocks of any two or more of these.

[0012] In some embodiments, the biorenewable feedstock is selected from canola oil, corn oil, soybean oils, rapeseed oil, soybean oil, palm oil, colzaoil, sunflower oil, hempseed oil, olive oil, flaxseed oil, coconut oil, castor oil, peanut oil, mustard oil, cottonseed oil, inedible tallow, non-edible oils, yellow and brown greases, lard, train oil, milk fat, fish oil, algae oil, tall oil, sewage sludge, tall oil, bio-derived pyrolysis oil, and any mixture of two or more thereof.

[0013] In some embodiments, the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite 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 method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite 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.

[0015] In some embodiments, the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite 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 method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite having a total weight of greater than about 2% by weight of Na2O, K2O, P2O, MgO, and CaO. Brief description of the attached diagram Figure 1 The effect of 0.6 wt% K2O as described in Example 5 on the ZSA retention of catalysts 1-4 was depicted.

[0018] Figure 2 The effect of 0.8 wt% Na2O as described in Example 6 on the ZSA retention of catalysts 1-4 was depicted.

[0019] Figure 3 The effect of 2% by weight CaO on the ZSA retention rate of catalysts 1-4, as described in Example 7, was depicted.

[0020] Figure 4 The effect of 2.5 wt% P2O5 as described in Example 8 on the ZSA retention of catalysts 3-4 was depicted.

[0021] Figure 5 The effect of 2.5 wt% P2O5 and 1 wt% CaO on the ZSA retention of catalysts 3-4, as described in Example 9, was depicted.

[0022] Detailed description Various implementation schemes are described below. It should be noted that the specific implementation schemes are not intended as an exhaustive description or as a limitation on the broader aspects discussed herein. An aspect described in conjunction with a particular implementation scheme is not necessarily limited to that scheme and can be implemented in conjunction with any other implementation scheme.

[0023] As used herein, “about” will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If the use of the term is unclear to one of ordinary skill in the art, “about” will mean at most plus or minus 10% of the particular term, taking into account the context in which it is used.

[0024] As used herein, the terms "biorenewable" or "biofeed" are used interchangeably to refer to any feed or feed fraction having a fatty component derived from vegetable or animal oils. Typically, such feed or fraction primarily comprises triglycerides and free fatty acids (FFA). These triglycerides and FFA contain aliphatic hydrocarbon chains having 14 to 22 carbon atoms in their structure. Examples of such feedstocks include, but are not limited to, canola oil, corn oil, soybean oil, rapeseed oil, palm oil, rapeseed oil, sunflower oil, hemp seed oil, olive oil, flaxseed oil, coconut oil, castor oil, peanut oil, mustard oil, cottonseed oil, non-edible animal fats, non-edible oils such as jatropha oil, yellow and brown fats, lard, marine animal oils, milk fat, fish oil, algae oil, tall oil, sewage sludge, etc. Another example of a biorenewable feedstock that can be used in this invention is tall oil. Tall oil is a byproduct of the wood processing industry. Besides FFA, tall oil also contains esters and abietic acid. Abietic acid is a cyclic carboxylic acid. Typical vegetable or animal fat triglycerides and FFA contain aliphatic hydrocarbon chains with approximately 8 to approximately 24 carbon atoms in their structure. Pyrolysis oils obtained from the pyrolysis of cellulose waste materials can also be used as non-petroleum feedstocks or as a portion or fraction of such feedstocks.

[0025] The phrase “fluidized catalytic cracking conditions” or “FCC conditions” is used herein to indicate the conditions of a typical fluidized catalytic cracking process in which a circulating stock of fluidized catalytic cracking catalyst is contacted with a heavy feedstock (e.g., a hydrocarbon feedstock, a biorenewable feedstock, or a mixture thereof) at elevated temperatures to convert the feedstock into compounds of lower molecular weight.

[0026] The term "fluidized catalytic cracking activity" is used in this paper to indicate the ability of a compound to catalyze the conversion of hydrocarbon and / or aliphatic molecules into lower molecular weight compounds under fluidized catalytic cracking conditions.

[0027] For the purposes of this invention, the term "matrix" is used herein to refer to all mesoporous materials, i.e., materials having pores with a pore size of at least 20 Å (angstroms) as measured by BET and t-plot (see Johnson, JMFL, J. Cat 52, pp. 425-431 (1978)), which constitutes the catalytic cracking catalyst disclosed herein, the matrix including any binder and / or filler and excluding catalytically active zeolite (catalytically active zeolite will generally have pores in the microporous range, i.e., openings less than 20 Å (angstroms) as measured by BET and t-plot).

[0028] In the context of describing elements (especially in the context of the appended claims), the terms “a”, “an”, and “the”, and similar references, shall be interpreted as encompassing both the singular and the plural, unless otherwise indicated herein or the context explicitly contradicts this. The enumeration of ranges of values ​​herein is intended only as a shorthand method for individually referring to each individual value falling within that range, unless otherwise indicated herein, and each individual value is incorporated into the specification as if it were individually enumerated herein. All methods described herein may be performed in any suitable order unless otherwise indicated herein or the context explicitly contradicts this. The use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better illustrate the embodiments and, unless otherwise stated, does not constitute a limitation on the scope of the claims. No language in the specification should be construed as indicating that any unclaimed element is essential.

[0029] Using bio-based or biorenewable feedstocks in FCC units can lead to higher levels and different types of impurities depositing on the FCC catalyst and deactivating it. These impurities include Na, K, alkaline earth metal (Ca and Mg) ions, as well as phosphorus compounds and transition metal ions. Therefore, there is a need to develop new and improved FCC catalysts that can tolerate these higher levels and different types of impurities.

[0030] This disclosure provides catalyst compositions for use in fluidized catalytic cracking of biorenewable feedstocks. Specifically, the FCC catalyst compositions described herein have a high matrix surface area and contain yttrium-stabilized zeolites. Furthermore, this disclosure provides the use of the FCC catalyst compositions described herein with feedstocks containing high levels and unique impurity metals (which are present outside the typical range of commercial plants). Such catalyst compositions offer improvements in metal tolerance, catalyst activity, and product yield.

[0031] As demonstrated in the examples, incorporating high matrix surface area (MSA) alumina and using yttrium instead of lanthanum as a stabilizing ion in the Y-zeolite component into the FCC catalyst improves metal tolerance, catalyst activity, and product yield. Compared to lanthanum-stabilized Y-zeolite FCC catalysts, yttrium-stabilized Y-zeolite FCC catalysts exhibit greater tolerance to Na, K, Mg, Ca, and P in both high and low matrix surface areas. Furthermore, incorporating higher matrix alumina levels to provide higher MSA significantly enhances metal tolerance, provides better activity retention, and offers better yield selectivity in the presence of lanthanum or yttrium-stabilized Y-zeolite catalysts. The combination of yttrium zeolite stabilization and a high matrix results in optimal metal tolerance, providing the highest activity and best selectivity.

[0032] This document describes a method for fluidized catalytic cracking (FCC) of a feedstock comprising at least one biorenewable feed, the method comprising: Under FCC cracking conditions, feedstock containing at least one hydrocarbon feedstock and at least one biorenewable feedstock is brought into contact with a catalytic cracking catalyst. in: The catalytic cracking catalyst composition comprises: Based on the total weight of the catalytic cracking catalyst composition, about 5% to about 60% of octahedral zeolite; Based on the total weight of the catalytic cracking catalyst composition, approximately 30% to approximately 70% total alumina; and Yttrium, measured as Y2O3 and based on the total weight of the catalytic cracking catalyst composition, is approximately 0.5 wt% to approximately 6 wt%; and This catalytic cracking catalyst has a molecular weight greater than approximately 40 m. 2 / g matrix surface area (MSA).

[0033] The catalytic cracking catalyst composition described herein may comprise any zeolite exhibiting catalytic cracking activity under fluidized bed catalytic cracking conditions. In some embodiments, the zeolite is an octahedral zeolite, such as a Y-type zeolite. In some embodiments, the zeolite is an ultrastable Y-type zeolite (USY), as disclosed in U.S. Patent No. 3,293,192.

[0034] Based on the total weight of the catalytic cracking catalyst composition, the catalytic cracking catalyst composition comprises about 5 wt% to about 60 wt% of zeolite, specifically 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% of zeolite. In some embodiments, based on the total weight of the catalytic cracking catalyst composition, the catalytic cracking catalyst composition comprises about 15 wt% to about 30 wt%, specifically 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% of zeolite.

[0035] The catalytic cracking catalyst composition described herein comprises alumina, which is formed from alumina precursors such as colloidal alumina, hydrated alumina, and aluminum chlorhydrol. This alumina precursor may further comprise boehmite or microcrystalline boehmite, also known as pseudoboehmite. Colloidal alumina refers to a precursor such as pseudoboehmite that has been acid-treated to completely or partially break down aluminum oxide hydroxide into particles with a size distribution less than 1 micrometer, thus increasing the number of such particles. The total alumina described herein may also include alumina present in zeolite, clay, and other matrix and binder components.

[0036] In some embodiments, the total alumina is alumina present in one or more of zeolite, clay, matrix components, and / or catalyst binders. In some embodiments, the catalyst binder comprises colloidal alumina. In some embodiments, the colloidal alumina is based on boehmite or boehmite.

[0037] Based on the total weight of the composition, the catalytic cracking catalyst composition comprises about 30 wt% to about 70 wt% of total alumina, specifically 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% of total alumina. In some embodiments, based on the total weight of the composition, the catalytic cracking catalyst composition comprises about 45 wt% to about 60 wt% of total alumina.

[0038] The catalytic cracking catalyst compositions described herein contain yttrium partially or completely exchanged onto the zeolite. Yttrium can be exchanged onto the zeolite using conventional methods, such as direct exchange with a yttrium salt before 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 refers not only to yttrium salts but also to yttrium cations, such as yttrium exchanged onto the zeolite. A gravimetric measurement of yttrium refers to a measurement reported as yttrium oxide (Y₂O₃) using elemental analysis techniques conventionally used in the art, including but not limited to inductively coupled plasma (ICP) analysis.

[0039] The catalytic cracking catalyst composition, measured by Y2O3 and based on the total weight of the composition, comprises about 0.5 wt% to about 6 wt% of yttrium, and, measured by Y2O3 and based on the total weight of the composition, comprises 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% of yttrium. In some embodiments, the catalytic cracking catalyst comprises about 0.5 wt% to about 2 wt% of yttrium, measured by Y2O3 and based on the total weight of the composition.

[0040] The catalytic cracking catalyst compositions described herein have high matrix surface area (MSA). “Matrix surface area” refers to the surface area attributable to the matrix material constituting the catalyst, which typically has a pore size of 20 Å or larger, as measured by BET and t-plot methods.

[0041] In some embodiments, the catalytic cracking catalyst has a molecular weight greater than about 40 m. 2 / g, greater than approximately 50 m 2 / g, greater than approximately 55 m 2 / g, greater than approximately 60 m 2 / g, greater than approximately 65 m 2 / g, greater than approximately 70 m 2 / g, greater than approximately 75 m 2 / g, greater than approximately 80 m 2 / g, greater than approximately 85 m 2 / g, greater than approximately 90 m 2 / g, greater than approximately 95 m 2 / g, or greater than approximately 100 m 2 / g MSA.

[0042] In some embodiments, the catalytic cracking catalyst has approximately 50 m 2 / g to approximately 200 m 2 / g, including approximately 50m 2 / g, approximately 60 m 2 / g, approximately 70 m 2 / g, approximately 80 m 2 / g, approximately 90 m 2 / g, approximately 100 m 2 / g, approximately 110 m 2 / g, approximately 120 m 2 / g, approximately 130 m 2 / g, approximately 140 m 2 / g, approximately 150 m 2 / g, approximately 160 m2 / g, approximately 170 m 2 / g, approximately 180 m 2 / g, approximately 190 m 2 / g, and about 200 m 2 / g MSA. In some embodiments, the catalytic cracking catalyst has approximately 90 m 2 / g to approximately 200 m 2 / g MSA.

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

[0044] As described herein, the use of non-standard feedstocks, such as biorenewable feedstocks, in FCC units results in the deposition of higher levels and different impurities than those present in current FCC units. As described below, the average impurity level on catalyst particles containing zeolite 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 a sum greater than about 2 wt% of Na₂O wt%, K₂O wt%, P₂O wt%, MgO wt%, and CaO wt%.

[0045] In some embodiments, the equilibrium catalyst has catalyst particles containing octahedral zeolite, comprising greater than about 0.8 wt% Na₂O, greater than about 1.0 wt% Na₂O, or greater than about 1.2 wt% Na₂O. In some embodiments, the equilibrium catalyst has catalyst particles containing octahedral zeolite, 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 catalyst particles containing octahedral zeolite, 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 catalyst particles containing octahedral zeolite, 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 balanced catalyst has catalyst particles containing octahedral zeolite, which contain more than about 0.7 wt% MgO, more than about 0.9 wt% MgO, or more than about 1.2 wt% MgO.

[0046] In some embodiments, the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising one or more of the following: Greater than approximately 0.8% by weight of Na₂O; Greater than approximately 0.3% by weight of K2O; Greater than approximately 0.5% by weight of P2O5; Greater than approximately 0.5% by weight of CaO; and Greater than approximately 0.7% by weight of MgO.

[0047] In some embodiments, the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising one or more of the following: Greater than approximately 1.0 wt% Na2O; Greater than approximately 0.5% by weight of K2O; Greater than approximately 0.7% by weight of P2O5; Greater than approximately 0.7% by weight of CaO; and Greater than approximately 0.9% by weight of MgO.

[0048] In some embodiments, the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising one or more of the following: Greater than approximately 1.2% by weight of Na₂O; Greater than approximately 0.8% by weight of K2O; Greater than approximately 1.0 wt% P2O5; Greater than approximately 1.0 wt% CaO; and Greater than approximately 1.2% by weight of MgO.

[0049] In some embodiments, the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite having a total weight of greater than about 2% by weight of Na2O, K2O, P2O5, MgO, and CaO.

[0050] FCC equipment and conditions The FCC method described in this article is carried out in an FCC facility. There are no particular limitations on the FCC facility, as long as it contains a reaction zone, a separation zone, a stripping zone, and a regeneration zone. The key steps of the FCC method typically include: (i) In a catalytic cracking zone (typically a riser cracking zone), the feedstock containing biorenewable feedstock is catalytically cracked by contacting the feedstock with a thermally regenerated cracking catalyst source to produce an effluent containing cracking products and spent catalyst containing coke and strippable hydrocarbons. (ii) The effluent is discharged and separated (typically in one or more cyclone separators) into a gas phase rich in cracking products and a solid phase containing spent catalyst. (iii) The gas phase is removed as a product and the product is fractionated in the FCC main column and its auxiliary side columns to form gaseous and liquid cracking products, including gasoline; (iv) The stripped catalyst (usually by steam) is stripped to remove occluded hydrocarbons from the catalyst. The stripped catalyst is then oxidatively regenerated in the catalyst regeneration zone to produce a thermally regenerated catalyst, which is then recycled to the cracking zone to crack a larger amount of feed.

[0051] Within the reaction zone of an FCC unit, the FCC process is typically carried out at a reaction temperature of approximately 480°C to approximately 650°C, with a catalyst regeneration temperature of approximately 600°C to approximately 800°C. As is known in the art, the catalyst regeneration zone may consist of a single or multiple reactor vessels.

[0052] The catalyst-oil ratio is typically from about 3 to about 25, preferably from about 3 to about 15; the partial pressure of hydrocarbons in the reactor is typically from 1 bar to about 4 bar, preferably from about 1.75 bar to about 2.5 bar; and the contact time between the feedstock and the catalyst is from 0.5 to 10 seconds, preferably from 1 to 5 seconds. As used herein, the term "catalyst-oil ratio" refers to the ratio of the catalyst circulation rate (tons / hour) to the feedstock supply rate (tons / hour). The term "partial pressure of hydrocarbons" is used herein to indicate the total partial pressure of hydrocarbons 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 the separation of the reaction products and the catalyst at the stripper outlet.

[0053] As used in this invention, the reaction zone outlet temperature refers to the outlet temperature of the fluidized bed reactor. Typically, the reaction zone outlet temperature range in this invention will be from approximately 480°C to approximately 650°C. The FCC unit may include any equipment conventionally used for processing biorenewable feedstocks and is also within the scope of this invention.

[0054] raw material The feedstocks available for use herein comprise petroleum-based hydrocarbon feedstocks containing at least one biorenewable feedstock fraction. Petroleum-based hydrocarbon feedstocks available herein typically comprise wholly or partially gas oils (e.g., light, medium, or heavy gas oils) with an initial boiling point above about 120°C and a 50% point of at least about 315°C. Feedstocks may also include deep-cut gas oils, vacuum gas oils (VGOs), heat transfer oils, residue oils, cycle oils, all-top crude oils, tar sands oils, shale oils, synthetic fuels, destructively hydrogenated heavy hydrocarbon fractions derived from coal, tar, bitumen, asphalt, etc.; hydrotreated feedstocks derived from any of the foregoing, etc. As will be appreciated, distillation of higher-boiling-point petroleum fractions with boiling points above about 400°C must be carried out under vacuum to avoid thermal cracking. Boiling temperatures used herein are expressed as boiling points corrected to atmospheric pressure for convenience. The present invention can even be used to crack residue oils with high metal content or deep-cut gas oils with a final boiling point of up to about 850°C.

[0055] The raw materials described herein can be blended raw materials, i.e., raw materials comprising both hydrocarbon feedstock and biorenewable feedstock fractions. Blended raw materials used in the methods of this invention typically comprise about 99 to about 25% by weight of hydrocarbon feedstock and about 1 to about 75% by weight of biorenewable feedstock. In some embodiments, the blended raw material comprises about 97 to about 80% by weight of hydrocarbon feedstock and about 3 to about 20% by weight of biorenewable feedstock.

[0056] The feedstocks described herein can also be injected into the FCC riser reactor via different feed nozzles. The biofeed can be injected upstream, downstream, or at the same location as the hydrocarbon feedstock. The total proportion of feedstocks usable in the methods of this invention typically comprises about 99 to about 25% by weight of hydrocarbon feedstock and about 1 to about 75% by weight of biorenewable feedstock. In some embodiments, the total feedstock comprises about 97 to about 80% by weight of hydrocarbon feedstock and about 3 to about 20% by weight of biorenewable feedstock.

[0057] In some embodiments, the hydrocarbon feedstock or fraction comprises a petroleum-based feedstock. In some embodiments, the hydrocarbon feedstock or fraction is selected from deep-cut gas oil, vacuum gas oil (VGO), heat transfer oil, residue oil, circulating oil, all-top crude oil, tar sands oil, shale oil, synthetic fuels; destructively hydrogenated heavy hydrocarbon fractions derived from coal, tar, bitumen, and asphalt; hydrotreated feedstocks; and petroleum-based feedstocks of any two or more of these.

[0058] The biorenewable feedstock described herein contains only animal and / or vegetable fats and / or oils. In some embodiments, the biorenewable feedstock or fraction is selected from canola oil, corn oil, soybean oil, rapeseed oil, palm oil, rapeseed oil, sunflower oil, hemp seed oil, olive oil, flaxseed oil, coconut oil, castor oil, peanut oil, mustard oil, cottonseed oil, non-edible animal fats, non-edible oils, yellow and brown fats, lard, marine animal oils, milk fat, fish oil, algal oil, tall oil, sewage sludge, tall oil, bio-derived pyrolysis oil, and mixtures of any two or more thereof.

[0059] Therefore, the invention generally described will be more readily understood by referring to the following embodiments, which are provided by way of illustration and are not intended to limit the invention.

[0060] Example “CPS” is used in this paper to refer to a cyclic propylene vapor deactivation procedure that uses propylene and air to simulate a redox cycle in addition to the vapor deactivation effect. (See American Chemical Society Symposium Series, No. 634, pp. 171-183 (1996)).

[0061] "ACE" is used herein to refer to the Advanced Cracking Evaluation Test, as described in U.S. Patent No. 6,069,012, which is incorporated herein by reference.

[0062] The surface areas indicated herein were measured using N2BET and t-Plot methods and chemically analyzed by ICP-OES, normalized to the standards of the National Institute of Science and Technology (NIST).

[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 chlorhydride, 10 wt% alumina from large-crystal boehmite, 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 at 593 °C for 1 hour 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 hydroxyaluminate chloride, 10 wt% alumina from large-crystal boehmite, 1.4 wt% Y2O3 from YCl3 solution, and clay was prepared and mixed. The slurry was then ground in a Drais mill and spray-dried. The spray-dried catalyst was then calcined at 593 °C for 1 hour 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 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 at 399 °C for 40 minutes and washed with an ammonium-containing solution and water to remove Na₂O, thus producing catalyst 3. The properties of catalyst 3 are shown in Table 1.

[0069] Example 4. A 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 soluble boehmite, 5 wt% colloidal silica, 1.4 wt% Y₂O₃ from 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 at 399 °C for 40 minutes and washed with an ammonium-containing solution and water to remove Na₂O, thus producing catalyst 4. The properties of catalyst 4 are shown in Table 1.

[0071] Table 1. .

[0072] Deactivation techniques in Examples 5-9.

[0073] Catalysts 1 through 4 were treated using a spray-coating method to coat impurities onto the outer edges of the catalyst particles (Applied Catalysis A: General 462-463 (2013) 91-99). This technique, combined with a subsequent circulating propylene vapor deactivation (CPS) step, allows for the distribution of contaminants in a manner very similar to that of the equilibrium catalyst (Ecat.). Spray-coating was performed by spraying an aqueous solution of a metal salt onto a hot fluidized catalyst bed, where the water evaporates upon contact with the hot catalyst surface. Na₂SO₄, K₂SO₄, calcium acetate, and diammonium hydrogen phosphate (DAP) were used as salts to deposit impurities. After spray-coating the impurities, the catalyst was calcined at 593 °C for 2 hours. If nickel and vanadium were additionally used in the deactivation, they were added after the spraying and calcination of the other impurities. The catalyst was then deactivated using CPS.

[0074] Example 5. Following the general procedure described above, catalysts 1-4 were sprayed with 0.5 wt% K2O. The combination of the initial K2O on the catalysts and the added K2O resulted in all catalysts containing 0.6 wt% K2O. The catalysts were then aged using a Ni and V-free CPS deactivation scheme. The BET and t-plot surface areas of the sprayed, deactivated catalysts were compared with the surface area of ​​the base catalyst to obtain the zeolite surface area retention percentage. The surface area of ​​the base catalyst was measured before spraying and deactivation. The results show... Figure 1 Data shows that yttrium ion-stabilized catalysts exhibit better ZSA retention rates than lanthanum ion-stabilized catalysts. Furthermore, catalysts 3 and 4, with higher matrix surface areas, demonstrate better ZSA retention rates than catalysts 1 and 2, which have lower MSA.

[0075] Catalysts 1-4 were also tested in the ACE unit to measure catalyst activity. Catalyst 1 was compared with catalyst 2, and catalyst 3 with catalyst 4 to differentiate the effectiveness of yttrium and lanthanum in zeolite stabilization. The results at a constant conversion of 78 wt% of fresh feed are shown in Table 2. In both cases, the yttrium-stabilized zeolite provided better catalyst activity (requiring a lower catalyst / oil ratio to achieve the same conversion).

[0076] Table 2. .

[0077] Example 6. Following the general procedure described above, catalysts 1-4 were sprayed with 0.5 wt% Na₂O. The combination of the initial Na₂O on the catalysts and the added Na₂O resulted in all catalysts containing 0.7-0.8 wt% Na₂O. The catalysts were then aged using a Ni- and V-free CPS deactivation scheme. The BET and t-plot surface areas of the sprayed, deactivated catalysts were compared with the surface area of ​​the base catalyst to obtain the zeolite surface area retention percentage. The surface area of ​​the base catalyst was measured before spraying and deactivation. The results are shown in... Figure 2 Data shows that yttrium ion-stabilized catalysts exhibit better ZSA retention rates than lanthanum ion-stabilized catalysts. Furthermore, catalysts 3 and 4, with higher matrix surface areas, demonstrate better ZSA retention rates than catalysts 1 and 2, which have lower MSA.

[0078] Catalysts 1-4 were also tested in the ACE unit to measure catalyst activity. Catalyst 1 was compared with catalyst 2, and catalyst 3 with catalyst 4 to differentiate the effectiveness of yttrium and lanthanum in zeolite stabilization. The results at a constant conversion of 75 wt% of fresh feed are shown in Table 3. In both cases, the yttrium-stabilized zeolite provided better catalyst activity (requiring a lower catalyst / oil ratio to achieve the same conversion).

[0079] Table 3. .

[0080] Example 7. Following the general procedure described above, catalysts 1-4 were sprayed with 2 wt% CaO. The combination of the initial CaO on the catalysts and the added CaO resulted in all catalysts containing 2 wt% CaO. The catalysts were then aged using a CPS deactivation scheme with 2000 mg / kg Ni and 3000 mg / kg V. The BET and t-plot surface areas of the sprayed, deactivated catalysts were compared with the surface area of ​​the base catalyst to obtain the zeolite surface area retention percentage. The surface area of ​​the base catalyst was measured before spraying and deactivation. The results are shown in... Figure 3 Data shows that yttrium ion-stabilized catalysts exhibit better ZSA retention rates than lanthanum ion-stabilized catalysts. Furthermore, catalysts 3 and 4, with higher matrix surface areas, demonstrate better ZSA retention rates than catalysts 1 and 2, which have lower MSA.

[0081] Catalysts 1-4 were also tested in the ACE unit to measure catalyst activity. Catalyst 1 was compared with catalyst 2, and catalyst 3 with catalyst 4 to differentiate the effectiveness of yttrium and lanthanum in zeolite stabilization. The results at a constant conversion of 68 wt% of fresh feed are shown in Table 4. In both cases, the yttrium-stabilized zeolite provided better catalyst activity (requiring a lower catalyst / oil ratio to achieve the same conversion).

[0082] Table 4. .

[0083] Example 8. Following the general procedure described above, catalysts 3 and 4 were sprayed with 2.5 wt% P₂O₅. The catalysts were then aged using a CPS deactivation scheme with 2000 mg / kg Ni and 3000 mg / kg V. The BET and t-plot surface areas of the sprayed, deactivated catalysts were compared with the surface area of ​​the base catalyst to obtain the zeolite surface area retention percentage. The surface area of ​​the base catalyst was measured prior to spraying and deactivation. The results are shown in... Figure 4 Data shows that yttrium ion-stabilized catalysts exhibit better ZSA retention rates than lanthanum ion-stabilized catalysts.

[0084] Catalysts 3 and 4, with added P2O5, were also tested in the ACE unit to measure catalyst activity. Catalyst 3 was compared with catalyst 4 to differentiate the effectiveness of yttrium and lanthanum in zeolite stabilization. The results at a constant catalyst / oil ratio of 6 are shown in Table 5. The yttrium-stabilized zeolite provided significantly better catalyst activity (higher conversion at a constant catalyst / oil ratio).

[0085] Table 5. .

[0086] Example 9. Following the general procedure described above, catalysts 3 and 4 were sprayed with 2.5 wt% P₂O₅ and 1 wt% CaO. The catalysts were then aged using a CPS deactivation scheme with 2000 mg / kg Ni and 3000 mg / kg V. The BET and t-plot surface areas of the sprayed, deactivated catalysts were compared with the surface area of ​​the base catalyst to obtain the zeolite surface area retention percentage. The surface area of ​​the base catalyst was measured prior to spraying and deactivation. The results are shown in... Figure 5 Data shows that yttrium ion-stabilized catalysts exhibit better ZSA retention rates than lanthanum ion-stabilized catalysts.

[0087] Catalysts 3 and 4, in which P2O5 and CaO were added, were also tested in the ACE unit to measure catalyst activity. Catalyst 3 was compared with catalyst 4 to differentiate the effectiveness of yttrium and lanthanum in zeolite stabilization. The results at a constant catalyst / oil ratio of 6 are shown in Table 6. The yttrium-stabilized zeolite provided significantly better catalyst activity (higher conversion at a constant catalyst / oil ratio).

[0088] Table 6. .

[0089] Although certain embodiments have been described and illustrated, it should be understood that changes and modifications may be made in accordance with common art without departing from the broader aspects of the technology as defined in the following claims.

[0090] The embodiments described herein can be suitably implemented in the absence of any one or more elements or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” should be interpreted broadly without limitation. Furthermore, the terms and expressions used herein have been used as descriptive rather than restrictive terms, and such terms and expressions are not intended to exclude any equivalents or portions thereof of the shown and described features, but it should be recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consistently composed of” will be understood to include those specifically listed elements as well as additional elements that do not materially affect the essential and novel features of the claimed technology. The phrase “consisting of” excludes any unspecified elements.

[0091] This disclosure is not limited to the specific embodiments described herein. Many modifications and variations are possible without departing from its spirit and scope, as will be apparent to those skilled in the art. In addition to those listed herein, functionally equivalent methods and compositions within the scope of this disclosure will be apparent to those skilled in the art based on the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure is limited only by the terms of the appended claims and the full scope of equivalents conferred by such claims. It should be understood that this disclosure is not limited to specific methods, reagents, compounds, or compositions, which can certainly be varied. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0092] Furthermore, when the features or aspects of this disclosure are described in accordance with the Markush Group, those skilled in the art will recognize that this disclosure is therefore also described in the form of any single member or subgroup of members of the Markush Group.

[0093] As those skilled in the art will understand, for any and all purposes, particularly for the purpose of providing a written description, all scopes disclosed herein also encompass any and all possible subscopes and combinations thereof. Any listed scope can be readily identified as sufficiently descriptive and capable of being decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can be readily decomposed into a lower third, middle third, and upper third, etc. As those skilled in the art will also understand, all language such as “at most,” “at least,” “greater than,” “less than,” etc., includes the stated numbers and refers to a scope that can subsequently be decomposed into subscopes as described above. Finally, as those skilled in the art will understand, a scope includes each individual member.

[0094] All publications, patent applications, granted patents, and other documents referenced in this specification are incorporated herein by reference as if each individual publication, patent application, granted patent, or other document were specifically and individually indicated as incorporated herein by reference in its entirety. Definitions contained in the text incorporated by reference are excluded to the extent that they contradict the definitions in this disclosure.

[0095] Other embodiments are set forth in the appended claims.

Claims

1. A method for fluidized catalytic cracking (FCC) of a feedstock comprising at least one biorenewable feed, the method comprising: Under FCC cracking conditions, feedstock having at least one hydrocarbon feedstock and at least one bio-renewable feedstock is brought into contact with a catalytic cracking catalyst; in: The catalytic cracking catalyst composition comprises: Based on the total weight of the catalytic cracking catalyst composition, about 5% to about 60% of octahedral zeolite; Based on the total weight of the catalytic cracking catalyst composition, approximately 30% to approximately 70% of total alumina, and Yttrium, measured as Y2O3 and based on the total weight of the catalytic cracking catalyst composition, is approximately 0.5 wt% to approximately 6 wt%; and The catalytic cracking catalyst has a molecular weight greater than approximately 40 m. 2 / g matrix surface area (MSA).

2. The method according to claim 1, wherein the octahedral zeolite is an octahedral zeolite Y-type zeolite.

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

4. The method according to any one of claims 1-3, wherein the total alumina is alumina present in one or more of zeolite, clay, matrix components and / or catalyst binders.

5. The method of claim 4, wherein the catalyst binder comprises soluble alumina, and the soluble alumina is based on boehmite or boehmite.

6. The method according to any one of claims 1-5, wherein the catalytic cracking catalyst comprises about 45% to about 60% total alumina based on the total weight of the composition.

7. The method according to any one of claims 1-6, wherein the catalytic cracking catalyst comprises about 0.5% to about 2% yttrium, measured in Y2O3 and based on the total weight of the composition.

8. The method according to any one of claims 1-7, wherein the catalytic cracking catalyst has about 50 μm 2 / g to approximately 200 m 2 / g MSA.

9. The method according to claim 8, wherein the catalytic cracking catalyst has a content of about 90 μm. 2 / g to approximately 200 m 2 / g MSA.

10. The method according to 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 method according to any one of claims 1-10, wherein the hydrocarbon feed comprises a petroleum-based feedstock.

12. The method according to any one of claims 1-11, wherein the hydrocarbon feedstock is selected from deep-cut gas oil, vacuum gas oil (VGO), heat transfer oil, residue oil, circulating oil, top-mounted crude oil, tar sands oil, shale oil, synthetic fuels; destructively hydrogenated heavy hydrocarbon fractions derived from coal, tar, bitumen, asphalt; hydrotreated feedstocks, and mixtures of any two or more thereof.

13. The method according to any one of claims 1-12, wherein the biorenewable feedstock is selected from rapeseed oil, corn oil, soybean oil, rapeseed oil, palm oil, rapeseed oil, sunflower oil, hemp seed oil, olive oil, flaxseed oil, coconut oil, castor oil, peanut oil, mustard oil, cottonseed oil, non-edible animal fats, non-edible oils, yellow and brown fats, lard, marine animal oils, milk fat, fish oil, algal oil, tall oil, sewage sludge, tall oil, bio-derived pyrolysis oil, and any mixture of two or more thereof.

14. The method according to any one of claims 1-13, wherein the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising one or more of the following: Greater than approximately 0.8% by weight of Na₂O; Greater than approximately 0.3% by weight of K2O; Greater than approximately 0.5% by weight of P2O5; Greater than approximately 0.5% by weight of CaO; and Greater than approximately 0.7% by weight of MgO.

15. The method according to any one of claims 1-14, wherein the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising one or more of the following: Greater than approximately 1.0 wt% Na2O; Greater than approximately 0.5% by weight of K2O; Greater than approximately 0.7% by weight of P2O5; Greater than approximately 0.7% by weight of CaO; and Greater than approximately 0.9% by weight of MgO.

16. The method according to any one of claims 1-15, wherein the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising one or more of the following: Greater than approximately 1.2% by weight of Na₂O; Greater than approximately 0.8% by weight of K2O; Greater than approximately 1.0 wt% P2O5; Greater than approximately 1.0 wt% CaO; and Greater than approximately 1.2% by weight of MgO.

17. The method according to any one of claims 1-16, wherein the method produces a balanced catalyst having catalyst particles containing octahedral zeolite, the catalyst particles containing octahedral zeolite comprising a sum greater than about 2 wt% of Na2O, K2O, P2O, MgO, and CaO.

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