FCC catalysts substantially free of clay having increased contaminant tolerance, their preparation and use

Abstract

A method of making a particulate FCC catalyst and a particulate FCC catalyst that increases contaminant tolerance and is substantially free of clay. Thus, in one embodiment, a particulate FCC catalyst composition is provided that includes one or more zeolites, at least one alumina component, at least one silica component and is substantially free of clay. In another embodiment, a particulate FCC catalyst composition is provided that includes at least two different types of alumina and at least one silica component and is substantially free of clay. The alumina component can be selected from the group of peptizable metaborrstone, non-peptizable microcrystalline boehmite phase, non-peptizable alpha phase or non-peptizable alumina containing gamma phase or non-peptizable alumina containing chi phase or gibbsite alumina. The silica component can be selected from the group of low sodium stabilized colloidal silica and acid or low sodium or ammonia stabilized colloidal silica or polysilicic acid.

Description

[0001] Cross-references to related applications

[0002] This application, filed October 29, 2021, claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 107,961, filed October 30, 2020, entitled “A substantially clay-free FCC catalyst having a variety of alumina, preparation thereof, and use thereof,” filed under 35 U.S. SC § 119(e), the entire contents and substance of which are hereby incorporated by reference as if fully set forth herein. Technical Field

[0003] This invention relates to a catalyst composition and its use in a method of cracking or converting feedstocks, such as those obtained from processing crude oil or >0% by weight vegetable oils (soybean, rapeseed, corn, palm, rapeseed, etc.), waste oil, tallow, biowaste, and / or blends of pyrolysis oils produced by any thermal treatment of biomass or plastics, exhibiting increased tolerance to contaminants. Background Technology

[0004] A common challenge in the design and production of heterogeneous catalysts is finding a good trade-off between the effectiveness and / or accessibility of active sites and the effectiveness of the immobilized matrix in imparting sufficient physical strength (i.e., abrasion resistance) to catalyst particles. In particular, FCC catalysts can become “poisoned” over time due to contaminants such as iron, Ca, P, Mg, and Si. For brevity, we will refer to Fe and Ca poisoning in this specification, but it should be understood that this includes other contaminants in the FCC feed that cause the same effect. Feedstock containing Fe, Ca, and other contaminants leading to FCC catalyst poisoning is a well-known problem that severely impacts catalyst accessibility, fluidization, activity, and bottom residue recovery capabilities. The ability to break down bottom residues in FCC catalysts is one of the most critical performance requirements, as it converts lower-value, heavier molecules into value-added products. Iron poisoning is known, but the introduction of tight oils has brought this issue to the forefront. Iron and calcium poisoning leads to surface blockage through vitrification and surface nodule formation, directly affecting activity and bottom residue recovery. The improved tolerance of the catalyst enables customers to process cheaper feedstocks containing high Fe / Ca ratios.

[0005] WO 02 / 098563 discloses a method for preparing an FCC catalyst with high wear resistance and high accessibility. The catalyst is prepared by slurrying zeolite, clay, and boehmite, feeding the slurry into a forming apparatus, and forming the mixture to form particles, characterized by destabilizing the mixture immediately prior to the forming step. This destabilization is achieved, for example, by increasing the temperature, increasing the pH, decreasing the pH, or by adding a gel inducing agent, such as a salt, phosphate, sulfate, or (partially) gelled silica. Prior to destabilization, any gelatinizable compounds present in the slurry must be fully dissolved.

[0006] WO 06 / 067154 describes FCC catalysts, their preparation, and uses. It discloses a method for preparing FCC catalysts with high abrasion resistance and high accessibility. The catalyst is prepared by: a) slurrying clay, zeolite, sodium-free silica source, quasicrystalline boehmite, and microcrystalline boehmite, provided that the slurry does not contain colloidal quasicrystalline boehmite; b) adding a monovalent acid to the slurry; c) adjusting the pH of the slurry to a value greater than 3; and d) shaping the slurry to form particles.

[0007] WO 19 / 140223 describes an FCC catalyst, its preparation, and its use. It discloses a method for preparing the catalyst and a catalyst comprising more than one type of silica. The catalyst is disclosed as a particulate FCC catalyst comprising about 5% to about 60% by weight of one or more zeolites, about 10% to about 45% by weight of quasi-crystalline boehmite (QCB), about 0% to about 35% by weight of microcrystalline boehmite (MCB), greater than about 0% to about 15% by weight of silica from sodium-stabilized colloidal silica, greater than about 0% to about 30% by weight of silica from ammonia-stabilized or low-sodium colloidal silica, and the balance being clay, and a method for its preparation. Summary of the Invention

[0008] This invention relates to an FCC catalyst intended for use in a method of cracking feedstock over a catalyst composition to produce conversion product hydrocarbon compounds (e.g., products containing high gasoline fractions) with a molecular weight lower than that of the feedstock hydrocarbons. Additionally, the feedstock may include a hydrocarbon feedstock and a blend of >0% by weight of vegetable oils (soybean, rapeseed, corn, palm, canola, etc.), waste oil, tallow, biowaste, and / or pyrolysis or other oils (e.g., Fischer-Tropsch liquids), said other oils being obtained through any thermal or other treatment of biomass, plastics, sewage, municipal waste, agricultural waste, or other suitable organic waste and combinations thereof. A unique feature of this invention is that the catalyst is substantially clay-free.

[0009] Unbound by any particular theory, it is believed that mobile silica present in clay leads to surface blockage and nodule formation by forming low-melting-point eutectic phases covering the outer surface of FCC catalysts with added iron, calcium, sodium, and / or other contaminants from the feed. Replacing clay containing mobile silica with alumina-based components has been found to improve the iron tolerance of the resulting catalysts. Since silica in zeolites is assumed to be immobile, clay is considered a major source of mobile silica. Alumina-based components are immobile, and therefore are believed to be suppressed by the formation of low-melting-point eutectic phases (glass layers) through reaction with iron and sodium. Different alumina, such as boehmite, gamma-alumina, alpha-alumina, x-alumina, gibbsite, and alumina trihydrate, are used to replace clay. Binder silica is used to improve the wear of these substantially clay-free catalysts. The present invention is a substantially clay-free catalyst with improved contaminant tolerance, as demonstrated by higher accessibility retention after iron deactivation. The higher bottom residue in performance testing reflects the benefits of the essentially clay-free catalyst in improving iron tolerance.

[0010] Therefore, in one embodiment, a particulate FCC catalyst composition is provided, comprising one or more zeolites, at least one alumina component, at least one silica component, and substantially free of clay. In another embodiment, a particulate FCC catalyst composition is provided, comprising at least two different types of alumina and at least one silica component, and substantially free of clay. The alumina component may be selected from the group consisting of soluble quasi-crystalline boehmite, insoluble microcrystalline boehmite phase, insoluble α phase or insoluble alumina containing γ phase or insoluble alumina containing χ phase or gibbsite alumina. The silica component may be selected from the group consisting of low-sodium stable colloidal silica and acid- or low-sodium or ammonia-stable colloidal silica or polysilicic acid. Therefore, the catalyst is generally a particulate FCC catalyst composition comprising one or more zeolites, at least one alumina component, at least one silica component, and substantially free of clay. Preferably, the particulate composition is an FCC catalyst comprising: about 1% to about 50% of one or more zeolites, about 1% to about 45% by weight of quasicrystalline boehmite; about 1% to about 45% by weight of microcrystalline boehmite, more than about 0-40% by weight of insoluble alumina including γ- or α- or χ-phase alumina or gibbsite, about 1% to about 20% by weight of sodium-stabilized silica, and about 0-20% by weight of low-sodium or acid or ammonia-stabilized colloidal silica or polysilicic acid, and is substantially free of clay.

[0011] In another embodiment, a method for cracking feedstock is provided, the method comprising the following steps:

[0012] a) Provides a particulate FCC catalyst composition comprising one or more zeolites, at least one alumina component, at least one silica component, and substantially free of clay;

[0013] b) Contact the FCC catalyst with the raw material at a temperature in the range of 400°C to 650°C for a residence time in the range of 0.5 to 12 seconds.

[0014] The raw materials may be hydrocarbon raw materials or hydrocarbons and vegetable oils (soybean, rapeseed, corn, palm, rapeseed, etc.), waste oil, tallow, biological waste and / or pyrolysis or other oils (e.g., Fischer-Tropsch liquids), said other oils being obtained by any thermal treatment or other treatment of biomass or plastics, sewage, municipal waste, agricultural waste or other suitable organic waste and combinations thereof.

[0015] These and other embodiments, advantages and features of the invention will become more apparent from the following detailed description, including the appended claims. Detailed Implementation

[0016] Unless otherwise stated, weight percentages (e.g., 1-10 wt%) used herein are based on the total dry weight of the product containing the specified substance or form of substance as an ingredient or component, or the percentage of the dry weight of the specified form of the substance. It should be further understood that when steps, components, or elements are described as preferred in a certain way herein, they were preferred up to the initial date of this disclosure, and these preferences may, of course, vary depending on the given circumstances or future developments in the art.

[0017] General Procedure

[0018] For example, in the first step of the manufacturing process, a slurry can typically be prepared by adding zeolite, alumina, and silica, along with optional other components, as dry solids to water. Alternatively, slurries containing individual materials can be mixed to form the slurry. Some materials can also be added as a slurry, while others are added as dry solids. Optionally, other components may be added, such as hydrated aluminum chloride, aluminum nitrate, Al₂O₃, Al(OH)₃, montmorillonite, sepiolite, barium titanate, calcium titanate, calcium silicate, magnesium silicate, magnesium titanate, mixed metal oxides, layered hydroxyl salts, other zeolites, magnesium oxide, alkalis or salts, and / or metal additives, such as compounds containing: alkaline earth metals (e.g., Mg, Ca, and Ba), Group IIIA transition metals, Group IVA transition metals (e.g., Ti, Zr), Group VA transition metals (e.g., V, Nb), Group VIA transition metals (e.g., Cr, Mo, W), Group VIIA transition metals (e.g., Mn), Group VIIIA transition metals (e.g., Fe, Co, Ni, Ru, Rh, Pd, Pt), Group IB transition metals (e.g., Cu), Group IIB transition metals (e.g., Zn), lanthanides (e.g., La, Ce), phosphorus, phosphates, or mixtures thereof. These compounds may be added in any order. All of these compounds may also be combined simultaneously.

[0019] The term "boehmite" is used in industry to describe alumina hydrates that exhibit X-ray diffraction (XRD) patterns close to those of alumina-hydroxyl [AlO(OH)]. Furthermore, the term boehmite is commonly used to describe various alumina hydrates containing varying amounts of hydrated water, possessing different surface areas, pore volumes, specific densities, and exhibiting different thermal properties upon heat treatment. However, although they exhibit characteristic boehmite [AlO(OH)] peaks, their XRD patterns typically vary in width and are also shifted in position. The sharpness and position of the XRD peaks have been used to indicate crystallinity, crystal size, and the number of defects.

[0020] Broadly speaking, boehmite alumina falls into two categories: quasicrystalline boehmite (QCB) and microcrystalline boehmite (MCB). In the prior art, quasicrystalline boehmite is also referred to as pseudo-boehmite and gel-like boehmite. Typically, compared to MCB, these QCBs have a higher surface area, larger pores and pore volume, and a lower specific density. They are readily dispersed in water or acid, have smaller crystal sizes than MCB, and contain a greater amount of hydrated water molecules. The degree of hydration of QCB can range from approximately 1.4 to approximately 2 moles of water per mole of Al, and they are typically ordered or otherwise intercalated between octahedral layers.

[0021] Microcrystalline boehmite (MCB) differs from QCB in its high crystallinity, relatively large crystal size, very low surface area, and high density. In contrast to QCB, MCB exhibits an XRD pattern with high peak intensity and a very narrow half-width. This is due to the relatively small number of intercalated water molecules, large crystal size, high crystallinity of the bulk material, and low crystal defect content. Typically, the amount of intercalated water molecules can vary from about 1 to about 1.4 per mole of Al.

[0022] MCB and QCB are characterized by powder X-ray reflection. ICDD contains entries for boehmite and confirms the presence of reflections corresponding to the (020), (021), and (041) planes. For copper radiation, such reflections appear at 14, 28, and 38 degrees 2-θ. The exact location of the reflection depends on crystallinity and the amount of embedded water: as the amount of embedded water increases, the (020) reflection shifts to lower values, corresponding to larger d-spacings. However, lines near the aforementioned locations indicate the presence of one or more types of boehmite phases. For the purposes of this specification, we define quasicrystalline boehmite as (020) reflection with a full width at half maximum (FWHH) of 1.5° or greater than 1.5° 2θ. Boehmite with (020) reflection having an FWHH less than 1.5° 2θ is considered microcrystalline boehmite. The slurry preferably contains about 1% to about 50% by weight, more preferably about 15% to about 35% by weight, of undissolved QCB based on the final catalyst. The slurry also contains about 1% to about 50% by weight, more preferably about 0% to about 35% by weight, based on the final catalyst.

[0023] The particulate composition of the present invention may include a third alumina source. The third alumina is typically an insoluble alumina containing a γ phase, an insoluble alumina containing an α phase, an insoluble alumina containing an χ phase, or gibbsite alumina. Based on the final catalyst, the present invention contains greater than about 0 to about 40% by weight of an insoluble alumina comprising γ, α, or χ phase alumina or gibbsite.

[0024] γ-alumina is understood as a transition phase of alumina. Boehmite or pseudo-boehmite can be converted to γ-alumina by applying heat treatment. Typically, boehmite or pseudo-boehmite is treated at 500-800 °C (preferably about 600-800 °C) for about 1 hour to about 4 hours. The γ-alumina phase is shown by XRD peaks at about 37.6 (311), 45.8 (400), and 67 (440) 2-θ.

[0025] χ is a metastable and insoluble phase of alumina. It exhibits characteristic XRD peaks with 2θ values ​​at approximately 37, 43, and 67 °C. It can be obtained by heat-treating gibbsite alumina in a moderate temperature range (300–700 °C).

[0026] Gibbsite is a mineral form of aluminum hydroxide and an important aluminum ore as it is one of the three main phases constituting rock bauxite. Its basic structure consists of stacked sheets of interconnected octahedrons. Each octahedron is formed by an aluminum ion bonded to six hydroxide ions, and each hydroxide ion is shared by two aluminum octahedrons. Insoluble gibbsite-alumina exhibits characteristic XRD peaks with 2θ values ​​at approximately 18, 20.3, and 38 degrees.

[0027] Alpha-alumina is the only stable phase of alumina and is insoluble. It can be obtained by high-temperature (above 1000°C) treatment of boehmite alumina. It has characteristic XRD peaks with 2θ values ​​at approximately 25.5, 35, 43.5, 57.5, and 69 degrees corresponding to the plane reflections of (012), (104), (115), (116), and (030).

[0028] The total amount of silica added, based on the final catalyst, is typically greater than about 0% to about 35% by weight. The silica component may be a single silica source or more than one silica source. The first silica source is typically a low-sodium silica source and is added to the initial slurry. Examples of such silica sources include, but are not limited to, potassium silicate, sodium silicate, lithium silicate, calcium silicate, magnesium silicate, barium silicate, strontium silicate, zinc silicate, phosphorus silicate, and barium silicate. Suitable examples of organosilicones are silicones (polyorganosiloxanes, such as polymethylphenylsiloxane and polydimethylsiloxane) and other compounds comprising a Si-OCO-Si structure and their precursors, such as methylchlorosilane, dimethylchlorosilane, trimethylchlorosilane, and mixtures thereof. Preferred low-sodium silica sources are sodium-stabilized alkaline colloidal silica. Based on the weight of the final catalyst, the slurry also contains greater than about 0% to about 30% by weight, more preferably greater than about 1% to about 20% by weight, of silica from the low-sodium silica source.

[0029] The second silica source is typically a low-sodium or sodium-free acidic colloidal silica, ammonia-stabilized silica, or polysilicic acid. Suitable silica sources added as a second silica source include (poly)silicic acid, sodium silicate, sodium-free silica sources, and organosilicon sources. One such second silica source is sodium-stabilized or sodium-free polysilicic acid, which is prepared online by mixing appropriate amounts of sulfuric acid and water glass. The amount of this second silica addition is greater than about 0 to 30% by weight, preferably greater than about 1% to about 20% by weight, and most preferably about 5% to about 20% by weight, based on the weight of the final catalyst.

[0030] If a second silica source is used, the choice of source can affect the timing of adding the material to the slurry. If acidic colloidal silica is used, it can be added at any step before the pH adjustment step. However, if the second silica source is sodium-stabilized or sodium-free polysilicic acid, it should be added after the zeolite addition but before the pH adjustment step. Additionally, due to the sodium content of polysilicic acid, washing the final catalyst may be necessary to remove excess sodium. Calcination of the final catalyst may also be required or desirable.

[0031] The unique feature of this invention is that, due to the binding properties of the aforementioned components, this catalyst does not require clay. Therefore, no clay is added to the slurry, and the resulting catalyst is substantially free of added clay. Without adding any clay to the slurry, impurity levels of clay may be present.

[0032] In the next step, a monovalent acid is added to the suspension to induce digestion. Organic and inorganic monovalent acids, or mixtures thereof, can be used. Examples of suitable monovalent acids are formic acid, acetic acid, propionic acid, nitric acid, and hydrochloric acid. The acid is added to the slurry in an amount sufficient to obtain a pH value below 7, more preferably between 1 and 4.

[0033] In the next step, one or more zeolites are added. The zeolites used in the method according to the invention preferably have a low sodium content (less than 1.5% by weight of Na₂O) or are sodium-free. Suitable zeolites present in the slurry of step a) include the following: for example, γ-zeolites, including HY, USY, dealuminated γ, RE-Y and RE-USY zeolites β, ZSM-5, phosphorus-activated ZSM-5, ion-exchanged ZSM-5, MCM-22 and MCM-36, metal-exchanged zeolites, ITQ, SAPO, ALPO and mixtures thereof. The slurry preferably contains one or more zeolites at 1% to about 50% by weight based on the final catalyst.

[0034] The slurry is then passed through a high-shear mixer, where it is destabilized by increasing the pH value. The pH of the slurry is then adjusted to a value of 3 or higher, more preferably 3.5 or higher, and even more preferably 4 or higher. The pH of the slurry is preferably not higher than 7, as slurries with higher pH values ​​may be difficult to process. The pH can be adjusted by adding an alkali (e.g., NaOH or NH4OH) to the slurry. The time interval between pH adjustment and molding is preferably 30 minutes or less, more preferably less than 5 minutes, and most preferably less than 3 minutes. In this step, the solids content of the slurry is preferably about 10% to about 45% by weight, more preferably about 15% to about 40% by weight, and most preferably about 25% to about 35% by weight.

[0035] The slurry is then shaped. Suitable shaping methods include spray drying, pulse drying, granulation, extrusion (optionally combined with kneading), beading, or any other conventional shaping method or combination thereof used in the field of catalysts and absorbents. Spray drying is the preferred shaping method. If the catalyst is shaped by spray drying, the inlet temperature of the spray dryer is preferably in the range of 300°C to 600°C, and the outlet temperature is preferably in the range of 105°C to 200°C.

[0036] The resulting catalyst

[0037] The catalyst thus obtained exhibits particularly good wear resistance and accessibility. Therefore, the present invention also relates to catalysts obtainable by the method according to the invention. The catalyst is typically a particulate FCC catalyst composition with increased iron tolerance, comprising one or more zeolites, at least one alumina component, at least one silica component, and is substantially free of clay. Additionally, the catalyst may typically comprise about 1 to about 50% of one or more zeolites, about 1 to about 45% by weight of quasicrystalline boehmite, about 1 to about 45% by weight of microcrystalline boehmite, greater than about 0-40% by weight of insoluble alumina comprising γ- or α- or χ-phase alumina or gibbsite, about 1% to about 20% by weight of sodium-stabilized silica, and about 0-20% by weight of low-sodium or acid- or ammonia-stabilized colloidal silica or polysilicic acid, and is substantially free of clay.

[0038] These catalysts can be used as FCC catalysts or FCC additives in hydrotreating catalysts, alkylation catalysts, reforming catalysts, gas-liquid conversion catalysts, coal conversion catalysts, hydrogen production catalysts, and automotive catalysts. Therefore, this invention also relates to the use of these catalysts, which can be obtained by the methods of this invention, as catalysts or additives in fluidized catalytic cracking, hydrotreating, alkylation, reforming, gas-liquid conversion, coal conversion, and hydrogen production, as well as as automotive catalysts.

[0039] The method of this invention is particularly applicable to fluidized catalytic cracking (FCC). In FCC methods (the details of which are generally known), the catalyst is typically present in the form of fine particles containing more than 90% by weight of particles ranging in diameter from about 5 to about 300 micrometers. In the reactor section, the hydrocarbon feedstock, as described above, is vaporized and directed upward through the reaction zone, such that the particulate catalyst is entrained and fluidized in the hydrocarbon feedstock stream. A hot catalyst from the regenerator reacts with the hydrocarbon feedstock vaporized and cracked by the catalyst. Typically, the temperature in the reactor is 400-650°C, and the pressure can be reduced, atmospheric, or ultra-atmospheric, typically from about atmospheric to about 5 atmospheres. The catalytic method can be a fixed bed, moving bed, or fluidized bed, and the hydrocarbon stream can flow in parallel or countercurrent with the catalyst stream. The method of this invention is also applicable to TCC (Thermofor Catalytic Cracking), DCC (Deep Catalytic Cracking), or HSFCC. Additionally, hydrocarbon feedstocks may include vegetable oils (soybean, rapeseed, corn, palm, canola, etc.), waste oil, tallow, biological waste, and / or blends of pyrolysis or other oils (e.g., Fischer-Tropsch liquids), obtained through any thermal or other treatment of biomass or plastics, sewage, municipal waste, agricultural waste, or other suitable organic waste and combinations thereof. A unique feature of this invention is that the catalyst is substantially clay-free and contains more than two alumina sources.

[0040] Example

[0041] The abrasion resistance of the catalyst is measured primarily using the ASTM 5757 standard test method for determining the wear and tear of powdered catalysts by air jet. The results show that when the material is tested using the above method, the greater the abrasion resistance of the catalyst, the lower the observed abrasion index value.

[0042] The accessibility of the catalyst prepared according to the following examples was measured by adding 1 g of catalyst to a stirred vessel containing 50 ml of vacuum gas oil diluted in toluene. The solution was circulated between the vessel and a spectrophotometer, during which the VGO concentration was continuously measured.

[0043] Before any laboratory testing, the catalyst must be deactivated to simulate the catalyst in a refining unit, typically using steam and metal contaminants. As described in previous literature (Applied Catalysis A: General 249 (2003) 69–80) (which is incorporated herein by reference), these catalysts are deactivated with Fe, Ni, V, and Ca contaminants in an improved cyclic deactivation mode with lower steam partial pressures and temperatures. Similar to cyclic deactivation, the catalyst is exposed to the cracking and regeneration cycles along with a feed containing metal contaminants. This is an industrially recognized deactivation procedure simulating laboratory-scale Fe deactivation.

[0044] Example 1

[0045] As shown in Table 1 below, Example 1 compares the use of additional insoluble microcrystalline boehmite and partially χ-phase alumina instead of clay. One example, Experiment-1, was conducted according to the invention and the methods disclosed herein. In addition to three types of alumina, sodium-stabilized colloidal silica and acid-stabilized colloidal silica were also used for bonding purposes. The resulting catalyst exhibited considerable wear and improved accessibility compared to a reference catalyst containing clay. The Fe tolerance of this catalyst was verified by laboratory-scale deactivation of Fe, Ca, Ni, and V metals as described in the literature (Applied Catalysis A: General 249 (2003) 69–80). The substantially clay-free catalyst showed higher accessibility than the reference catalyst after Fe deactivation, indicating better Fe tolerance. Better Fe tolerance of the substantially clay-free catalyst was revealed in the improved bottom residue upgrading in the ACE performance evaluation. The upgraded bottom residue was converted into high-value gasoline and LCO fractions, and all other key components were comparable to or better than the reference catalyst.

[0046] Table 1

[0047]

[0048] Example 2:

[0049] In the following examples, clay was replaced by gibbsite or α-alumina. Experiments 2 and 3 were conducted according to the invention and the methods disclosed herein. The experimental catalysts contained three different alumina (quasicrystalline boehmite, microcrystalline boehmite, and gibbsite or α-alumina) and two different colloidal silicas. These substantially clay-free catalysts exhibited higher iron tolerance, as indicated by greater accessibility compared to the reference catalyst after laboratory-scale deactivation with Fe, Ca, Ni, and V metals. Similarly, better bottom residue enhancement in the ACE performance evaluation confirms the benefit of higher accessibility in substantially clay-free catalysts.

[0050] Table 2

[0051]

[0052] Example 3:

[0053] In the following examples, clay was replaced by amorphous alumina and gibbsite containing the χ phase. Sodium-stabilized colloidal silica and sodium-stabilized polysilicic acid were used. Experiments 4 and 5 were conducted according to the invention and the methods disclosed herein. The experimental catalysts had three different alumina (quasicrystalline boehmite, microcrystalline boehmite, and gibbsite or χ alumina) and two different colloidal silica (sodium-stabilized colloidal silica and sodium-containing polysilicic acid). These substantially clay-free catalysts exhibited higher iron tolerance, as indicated by greater accessibility than the reference catalyst after laboratory-scale deactivation with Fe, Ca, Ni, and V metals. Better bottom residue improvement in ACE performance evaluation confirms the benefit of higher accessibility retention in substantially clay-free catalysts.

[0054] Table 3

[0055]

Claims

1. A particulate FCC catalyst composition with increased contaminant tolerance, said composition comprising 1% to 50% of one or more zeolites, 1% to 45% by weight of quasicrystalline boehmite, 1% to 45% by weight of microcrystalline boehmite, greater than 0 and less than or equal to 40% by weight of insoluble alumina comprising γ- or α- or χ-phase alumina or gibbsite, 1% to 20% by weight of sodium-stabilized silica, and greater than 0 and less than or equal to 20% by weight of low-sodium or acid or ammonia-stabilized colloidal silica or polysilicic acid, and free of clay.

2. The particulate FCC catalyst composition of claim 1, wherein the quasicrystalline boehmite has characteristic sharp XRD peaks with 2θ values ​​of about 14, 28, and 38 degrees corresponding to the plane reflections of (020), (021), and (041).

3. The particulate FCC catalyst composition of claim 1, wherein the microcrystalline boehmite has characteristic XRD peaks with 2θ values ​​of about 14, 28, and 38 degrees corresponding to the plane reflections of (020), (021), and (041).

4. The particulate FCC catalyst composition of claim 1, wherein the insoluble alumina comprising α-alumina has characteristic XRD peaks with 2θ values ​​of approximately 25.5, 35, 43.5, 57.5, and 69 degrees corresponding to plane reflections of (012), (104), (115), (116), and (030).

5. The particulate FCC catalyst composition of claim 1, wherein the insoluble alumina comprising γ-alumina has characteristic XRD peaks with 2θ values ​​of approximately 37.6, 45.8, and 67 degrees corresponding to the (311), (400), and (440) plane reflections.

6. The particulate FCC catalyst composition of claim 1, wherein the insoluble alumina comprising χ-phase alumina has characteristic XRD peaks with 2θ values ​​of about 37, 43, and 67 degrees.

7. The particulate FCC catalyst composition of claim 1, wherein the insoluble alumina comprising gibbsite has characteristic XRD peaks with 2θ values ​​of about 18, 20.3, and 38 degrees.

8. A method for cracking feedstock, the method comprising the following steps: a) Providing a particulate FCC catalyst composition according to any one of claims 1-7 with increased contaminant tolerance; b) Contact the FCC catalyst with the raw material at a temperature in the range of 400°C to 650°C for a residence time in the range of 0.5 to 12 seconds; wherein the raw material is a hydrocarbon raw material.

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