Essentially clay-free FCC catalyst with improved contaminant resistance, its preparation and use

Abstract

The particulate FCC catalyst and the method for preparing the particulate FCC catalyst have improved pollutant resistance and are essentially clay-free. Thus, in one embodiment, a particulate FCC catalyst composition is provided that includes one or more zeolites, at least one alumina component, and at least one silica component, and is essentially clay-free. In a further 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 essentially clay-free. The alumina component may be selected from the group consisting of peptized quasicrystalline boehmite, non-peptized microcrystalline boehmite phase, non-peptized alumina containing a non-peptized alpha or gamma phase, or non-peptized alumina containing a chi phase or gibbsite alumina. The silica component may be selected from the group consisting of low-sodium stabilized colloidal silica and acid- or low-sodium or ammonia-stabilized colloidal silica or pleuisilicate.

Description

Technical Field

[0001] Cross - reference to related applications Under 35 U.S.C.§119(e), this application filed on October 29, 2021, claims the benefit of U.S. Provisional Patent Application No. 63 / 107,961, filed on October 30, 2020, entitled "ESSENTIALLY CLAY FREE FCC CATALYST WITH MULTIPLE ALUMINA, ITS PREPARATION AND USE", and is hereby incorporated by reference in its entirety and in its entirety as if fully set forth herein.

[0002] The present invention relates to catalyst compositions showing improved resistance to contaminants and their use in processes for the decomposition or conversion of feeds, such as those obtained from the treatment of crude oil, or vegetable oils (soybean, canola, corn, palm, rapeseed, etc.) with more than 0 wt%, waste oils, animal fats, bio - waste, and / or pyrolysis oils obtained by any heat treatment of biomass or plastics.

Background Art

[0003] A common challenge in the design and manufacture of heterogeneous catalysts is finding a suitable compromise between the effectiveness and / or accessibility of the active sites and the effectiveness of the immobilization matrix in conferring sufficient physical strength, i.e., abrasion resistance, to the catalyst particles. In particular, FCC catalysts become "contaminated" over time with contaminants such as iron, Ca, P, Mg, and Si. For brevity, this specification refers to Fe and Ca poisoning, but it should be understood that this includes other contaminants in the FCC feed that cause the same effects. Poisoning of FCC catalysts with feedstocks containing Fe, Ca, and other contaminants is a well-known problem that significantly affects the catalyst's accessibility, fluidity, activity, and sediment improvement capabilities. The sediment decomposition capability of an FCC catalyst is one of the most important performance requirements, as it converts low-value heavy molecules into value-added products. Iron poisoning has been known for some time, but the introduction of tight oil has brought this problem to the surface. Iron and calcium poisoning leads to surface clogging due to vitrification and the formation of surface nodules, which directly affect activity and sediment improvement. The improved catalyst allows customers to process lower-cost, high-Fe / Ca-containing raw materials.

[0004] International Publication No. 02 / 098563 discloses a method for producing an FCC catalyst having both high wear resistance and high accessibility. The catalyst is prepared by slurring zeolite, clay, and boehmite, supplying the slurry to a molding apparatus, and molding the mixture to form particles, characterized in that the mixture is destabilized immediately before the molding step. This destabilization is achieved, for example, by raising the temperature, raising or lowering the pH, or by adding gel-inducing agents such as salts, phosphates, sulfates, and (partially) gelled silica. Prior to destabilization, any gelatinous compounds present in the slurry must be sufficiently deglutinated.

[0005] International Publication No. 06 / 067154 describes an FCC catalyst, its preparation and use. It discloses a method for producing an FCC catalyst having both high wear resistance and high accessibility. The catalyst is prepared by slurring clay, zeolite, a sodium-free silica source, quasicrystalline boehmite, and microcrystalline boehmite, wherein the slurry is slurred without defatted 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.

[0006] International Publication No. 19 / 140223 describes FCC catalysts, their preparation and use. It discloses a method for producing the catalyst and a catalyst containing two or more silicas. The catalyst disclosed is a particulate FCC catalyst and a method for producing the same, comprising about 5 to about 60 wt% of one or more zeolites, about 10 to about 45 wt% of quasicrystalline boehmite (QCB), about 0 to about 35 wt% of microcrystalline boehmite (MCB), about 0% to over 15 wt% of silica from sodium-stabilized colloidal silica, about 0% to over 30 wt% of silica from ammonia-stabilized or low-sodium colloidal silica, and balanced clay. [Overview of the project]

[0007] The present invention relates to an FCC catalyst intended for use in a process for the decomposition of feed on a catalyst composition to produce a conversion product hydrocarbon compound with a lower molecular weight than the feed hydrocarbon, such as a product containing a high gasoline fraction. Furthermore, the raw materials may include a mixture of hydrocarbon raw materials and other oils (e.g., Fischer-Tropsch liquid) obtained by any thermal or other treatment of more than 0 wt% of vegetable oil (soybean, canola, corn, palm, rapeseed, etc.), waste oil, animal fat, biowaste and / or thermal decomposition, or biomass, plastics, sewage, municipal waste, agricultural waste, or other suitable organic mass waste and combinations thereof. A unique feature of the present invention is that the catalyst is essentially clay-free.

[0008] While not bound by any particular theory, mobile silica present in clay is thought to be responsible for surface occlusion and nodule formation by forming a low-melting-point eutectic phase with added iron, calcium, sodium, and / or other contaminants from the feed covering the outer surface of the FCC catalyst. It has been found that replacing the mobile silica containing clay with an alumina-based component improves the iron resistance of the resulting catalyst. Since silica in zeolites is assumed to be immobile, clay is considered to be the primary source of mobile silica. Because alumina-based components are immobile, it is thought that the formation of a low-melting-point eutectic phase (glass layer) through reaction with iron and sodium is suppressed. Different aluminas such as boehmite, gamma alumina, alpha alumina, chi alumina, gibbsite, and aluminum trihydrate were used to substitute for clay. Binder silica was used to improve wear in these essentially clay-free catalysts. The present invention provides an essentially clay-free catalyst with improved contaminant resistance, as demonstrated by the retention of higher accessibility after deactivation with iron. The improved sediment quality in performance tests reflects the benefits of improved iron resistance in catalysts that are essentially clay-free.

[0009] Accordingly, in one embodiment, a particulate FCC catalyst composition is provided that comprises one or more zeolites, at least one alumina component, and at least one silica component, and is essentially clay-free. In a further embodiment, a particulate FCC catalyst composition is provided that comprises at least two different types of alumina and at least one silica component, and is essentially clay-free. The alumina component can be selected from the group of non-collapsible alumina comprising colloidal quasicrystalline boehmite, non-collapsible microcrystalline boehmite phase, non-collapsible alpha phase, or gamma phase, or non-collapsible alumina comprising kai 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 proisilicate. Thus, the catalyst is generally a particulate FCC catalyst composition comprising one or more zeolites, at least one alumina component, and at least one silica component, and is essentially clay-free. The particulate composition contains approximately 1 to 50% of one or more zeolites, approximately 1 to 45 wt% of quasicrystalline boehmite, approximately 1 to 45 wt% of microcrystalline boehmite, more than 0 to 40 wt% of non-collapsible alumina including gamma, alpha, or kai phase alumina or gibbsite, approximately 1 to 20 wt% of sodium-stabilized silica, and approximately 0 to 20 wt% of low sodium, acid, or ammonia-stabilized colloidal silica or polysilicic acid, and clay. It is preferable that the FCC catalyst does not essentially contain [the specified element].

[0010] In a further embodiment, a process for decomposing a raw material: a) To supply a particulate FCC catalyst composition comprising one or more zeolites, at least one alumina component, and at least one silica component, and essentially free of clay; b) A process is provided which includes contacting the FCC catalyst with the raw material at a temperature in the range of 400 to 650°C for a residence time in the range of 0.5 to 12 seconds. The raw materials may be hydrocarbon raw materials, or mixtures of hydrocarbons and vegetable oils (soybean, canola, corn, palm, rapeseed, etc.), waste oil, animal fat, biowaste and / or thermal decomposition, or other oils (e.g., Fischer Tropsch liquid) obtained by any thermal or other treatment of biomass, plastics, sewage, municipal waste, agricultural waste, or other suitable organic mass waste and combinations thereof.

[0011] These and further embodiments, advantages and features of the present invention will become even more apparent from the following detailed description, including the appended claims. [Modes for carrying out the invention]

[0012] Unless otherwise indicated, weight percentages (e.g., 1 to 10 wt%) used herein refer to the dry base weight percentage of a particular form of a substance, based on the total dry base weight of the product in which the particular substance or form of substance is a component or ingredient. Where a process or component or element is described herein as preferred in any way, it should be further understood that they are preferred as of the first date of this disclosure, and such preferences may naturally change depending on given circumstances or future developments in the art.

[0013] General procedure In the first step of the manufacturing process, for example, typically zeolite, alumina, and silica, as well as any other components, can be added to water as dry solids to form a slurry. Alternatively, slurries containing individual materials can be mixed to form a slurry. It is also possible to add some of the materials as a slurry and others as dry solids. Depending on the circumstances, other components may be added, such as aluminum chlorohydrol, aluminum nitrate, Al2O3, Al(OH)3, smectite, sepiolite, barium titanate, calcium titanate, calcium silicate, magnesium silicate, magnesium titanate, mixed metal oxides, layered hydroxy salts, additional zeolites, magnesium oxide, bases or salts, and / or metal additives, such as 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 VIA 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. The order of addition of these compounds is arbitrary. It is also possible to combine all of these compounds simultaneously.

[0014] The term "boehmite" is used in industry to describe alumina hydrates that exhibit an X-ray diffraction (XRD) pattern similar to that of aluminum hydroxide [AlO(OH)]. Furthermore, the term boehmite is generally used to describe a wide range of alumina hydrates that contain varying amounts of hydrate water, have varying surface areas, pore volumes, and specific densities, and exhibit varying thermal properties upon heat treatment. However, while their XRD patterns show characteristic boehmite [AlO(OH)] peaks, their widths typically vary, and their positions can also shift. The sharpness and position of the XRD peaks are used to indicate crystallinity, crystal size, and defect count.

[0015] Generally, boehmite alumina falls into two categories: quasicrystalline boehmite (QCB) and microcrystalline boehmite (MCB). In modern technology, quasicrystalline boehmite is also called pseudoboehmite and gelatinous boehmite. Typically, these QCBs have a higher surface area, larger pores and pore volume, and a lower specific density than MCBs. They disperse readily in water or acid, have smaller crystal sizes than MCBs, and contain more hydration water molecules. The degree of hydration of QCBs can have a wide range of values, usually regularly or otherwise intercalated between octahedral layers, for example, from about 1.4 to about 2 moles per mole of Al.

[0016] Microcrystalline boehmite is distinguished from QCB by its high crystallinity, relatively large crystal size, very low surface area, and high density. In contrast to QCB, MCB exhibits an XRD pattern with higher peak intensity and a very narrow full width at half maximum. This is due to a relatively small number of intercalated water molecules, a large crystal size, high crystallinity of the bulk material, and a small amount of crystal defects. Typically, the number of intercalated water molecules can vary in the range of about 1 to about 1.4 per mole of Al.

[0017] MCB and QCB are characterized by powder X-ray reflections. ICDD includes entries for boehmite and confirms the presence of reflections corresponding to the (020), (021), and (041) planes. For copper emission, such reflections appear at 2θ degrees 14, 28, and 38. The precise location of the reflections depends on the degree of crystallinity and the amount of intercalated water: as the amount of intercalated water increases, the (020) reflection shifts to lower values ​​corresponding to larger d intervals. Nevertheless, lines close to the above locations indicate the presence of one or more types of boehmite phases. For the purposes of this specification, quasicrystalline boehmite is defined as having a (020) reflection greater than 1.5° full width at half maximum (FWHH) or 1.5°2θ. Boehmite with a (020) reflection having an FWHH less than 1.5°2θ is considered microcrystalline boehmite. The slurry contains, based on the final catalyst, preferably about 1 to about 50 wt%, more preferably about 15 to about 35 wt%, of non-collectible QCB. The slurry also contains, based on the final catalyst, about 1 to about 50 wt%, more preferably about 0 to about 35 wt%, of MCB.

[0018] The particulate composition may contain a third alumina source. The third alumina is typically non-collapsible alumina containing a gamma phase, or non-collapsible alumina containing an alpha phase, or non-collapsible alumina containing a chi phase, or gibbsite alumina. Based on the final catalyst, the present invention contains about 0 to about 40 wt% or more of non-collapsible alumina containing gamma, alpha, or chi phase alumina or gibbsite.

[0019] Gamma alumina is understood to be the transition phase of alumina. Boehmite and pseudoboehmite can be converted to gamma alumina by heat treatment. Typically, boehmite or pseudoboehmite is treated at 500–800°C (preferably about 600–800°C) for about 1–4 hours. The gamma alumina phase is indicated by XRD peaks at 2θ of about 37.6 (311), 45.8 (400), and 67 (440).

[0020] Chi is a metastable and non-collapsible phase of alumina. It exhibits characteristic XRD peaks with 2θ values ​​at approximately 37, 43, and 67 degrees. It can be obtained from the heat treatment of gibbsite alumina in the moderate temperature range (300–700°C).

[0021] Gibbsite is a mineral form of aluminum hydroxide and an important aluminum ore in that it is one of the three main phases that make up rock bauxite. Its basic structure forms a layered sheet of linked octahedrons. Each octahedron is bonded to six hydroxide groups of aluminum Composed of aluminum ions, each hydroxide group is shared by two aluminum octahedra. Non-collective gibbsite-alumina has characteristic XRD peaks with 2θ values ​​at approximately 18, 20.3, and 38 degrees.

[0022] Alpha-alumina is the only stable phase of alumina, and it is non-collapsible. It can be obtained by high-temperature (over 1000°C) treatment of boehmite-alumina. It has characteristic XRD peaks with 2θ values ​​of approximately 25.5, 35, 43.5, 57.5, and 69 degrees, corresponding to (012), (104), (115), (116), and (030) plane reflections.

[0023] The total amount of silica added generally exceeds about 0 to about 35 wt% based on the final catalyst. The silica component can be either a single silica or two or more silica sources. 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. Examples of suitable organosilicates are silicones (polyorganosiloxanes such as polymethylphenylsiloxane and polydimethylsiloxane) and other compounds containing Si-O-C-O-Si structures, as well as their precursors such as methylchlorosilane, dimethylchlorosilane, trimethylchlorosilane, and mixtures thereof. A preferred low-sodium silica source is sodium-stabilized basic colloidal silica. The slurry further contains silica from a low-sodium silicon source in an amount of about 0 to more than about 30 wt%, more preferably more than about 1 to about 20 wt%, based on the weight of the final catalyst.

[0024] The second silica source is typically a low-sodium or sodium-free acidic colloidal silica or ammonia-stabilized silica or polysilicic acid. Suitable silicon sources added as the second silica source include (poly)silicic acid, sodium silicate, sodium-free silicon sources, and organosilicon sources. One such source for the second silica is sodium-stabilized polysilicic acid or sodium-free polysilicic acid produced in-line in the process by mixing an appropriate amount of sulfuric acid and water glass. This second addition of silica is added in an amount of about 0 to more than 30 wt%, preferably about 1 wt% to about 20 wt%, and most preferably about 5 to about 20% based on the weight of the final catalyst.

[0025] When the second silica is utilized, the selection of the second silica source can have an impact when the material is added to the aforementioned slurry. When using acidic colloidal silica, the silica may be added at any step prior to the pH adjustment step. However, when the second silica source is sodium-stabilized polysilicic acid or sodium-free polysilicic acid, the silica should be added immediately prior to the pH adjustment step after the zeolite addition. Furthermore, due to the sodium content of the polysilicic acid, it may be necessary to wash the final catalyst to remove excess sodium. It may further be necessary or desirable to calcine the final catalyst.

[0026] A particular feature of the present invention is that due to the nature of the binding properties of the above components, clay is not required for this catalyst. Thus, no clay is added to the slurry, and the resulting catalyst essentially does not contain the added clay. Even if there are clay impurity levels without adding any clay to the slurry.

[0027] In the next step, a monovalent acid is added to the suspension to cause digestion. Both organic monovalent acids 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 less than 7, more preferably between 1 and 4.

[0028] In the next step, one or more zeolites are added. The zeolites used in the method according to the present invention preferably have a low sodium content (less than 1.5 wt% Na2O) or do not contain sodium. Suitable zeolites for being present in the slurry of step a) include zeolites such as zeolite Y - HY, USY, dealuminated Y, RE - Y, and RE - USY - containing zeolite beta, 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 1 to about 50 wt% of one or more zeolites based on the final catalyst.

[0029] Next, the slurry is passed through a high-shear mixer to destabilize it by increasing its pH. Then, the pH of the slurry is adjusted to a value greater than 3, more preferably greater than 3.5, and even more preferably greater than 4. The pH of the slurry is preferably 7 or less, as slurries with a higher pH can become difficult to handle. The pH can be adjusted by adding a base (e.g., NaOH or NH4OH) to the slurry. The time 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 solid content of the slurry is preferably about 10 to about 45 wt%, more preferably about 15 to about 40 wt%, and most preferably about 25 to about 35 wt%.

[0030] Next, the slurry is formed. Suitable forming methods include spray drying, pulse drying, pelletizing, extrusion (sometimes combined with kneading), beading, or any other conventional forming method used in the field of catalysts and absorbents, or a combination thereof. A preferred forming method is spray drying. When the catalyst is formed by spray drying, the inlet temperature of the spray dryer is preferably in the range of 300 to 600°C, and the outlet temperature is preferably in the range of 105 to 200°C.

[0031] The resulting catalyst The catalyst thus obtained has exceptionally good wear resistance and accessibility. Therefore, the present invention also relates to a catalyst obtained by the method according to the present invention. The catalyst is generally a particulate FCC catalyst composition with improved iron resistance, comprising one or more zeolites, at least one alumina component, and at least one silica component, and essentially clay-free. Furthermore, the catalyst may generally contain about 1 to about 50% of one or more zeolites, about 1 to about 45 wt% of quasicrystalline boehmite, about 1 to about 45 wt% of microcrystalline boehmite, about 0 to more than 40 wt% of non-collapsible alumina including gamma, alpha, or kai phase alumina or gibbsite, about 1 wt% to about 20 wt% of sodium-stabilized silica, and about 0 to 20 wt% of low sodium or acid or ammonia-stabilized colloidal silica or polysilicic acid, and essentially clay-free.

[0032] These catalysts can be used as FCC catalysts or FCC additives in hydrogenation catalysts, alkylation catalysts, reforming catalysts, gas-liquid conversion catalysts, coal conversion catalysts, hydrogen production catalysts, and automotive catalysts. Accordingly, the present invention also relates to the use of these catalysts, which can be obtained by the methods of the present invention, as catalysts or additives in fluid catalytic cracking, hydrogenation, alkylation, reforming, gas-liquid conversion, coal conversion, and hydrogen production, as well as as automotive catalysts.

[0033] The method of the present invention is particularly applicable to fluid catalytic cracking (FCC). In the FCC process, the details of which are generally known, the catalyst is generally more than 90 wt% and about 5 to about 30 The catalyst exists as fine particles, including particles with a diameter in the range of 0 microns. In the reactor section, the aforementioned hydrocarbon-containing feedstock is vaporized and guided upward through the reaction zone, resulting in the particulate catalyst being entrained with the hydrocarbon feedstock flow and fluidized. The high-temperature catalyst coming from the regenerator reacts with the hydrocarbon feed, which is vaporized and decomposed by the catalyst. Typically, the temperature in the reactor is 400-650°C, and the pressure can be reduced pressure, atmospheric pressure, or hyperatmospheric pressure, usually around atmospheric pressure to about 5 atmospheres. The catalytic process can be a fixed bed, moving bed, or fluidized bed, and the hydrocarbon flow can be either parallel or counterflowing to the catalyst flow. The method of the present invention is also suitable for TCC (Thermofor catalytic cracking), DCC (Deep Catalytic Cracking), or HSFCC. Furthermore, hydrocarbon raw materials include vegetable oils (soybeans, canola, corn, palm, rapeseed, etc.), waste oil, animal fat, biowaste and / or other oils obtained by thermal or other treatment of biomass, or plastics, sewage, municipal waste, agricultural waste, or other suitable organic mass waste and combinations thereof (e.g., Fischer It may include a mixture with Tropsch solution. A unique feature of the present invention is that the catalyst is essentially clay-free and contains three or more alumina sources. [Examples]

[0034] The abrasion resistance of the catalysts was measured using a method based on the ASTM 5757 Standard Test Method for Determination of Attrition and Abrasion of Powdered Catalysts by Air Jets. The results showed that catalysts with higher abrasion resistance had lower resulting abrasion resistance index values ​​when the material was tested using the above method.

[0035] The accessibility of the catalysts prepared according to the following examples was measured by adding 1 g of the catalyst to a stirring vessel containing 50 ml of vacuum-reduced diesel fuel diluted with toluene. The solution was circulated between the vessel and a spectrophotometer, and the VGO concentration was continuously measured during this process.

[0036] Prior to any laboratory testing, catalysts must be deactivated to mimic those in a purification unit, which is typically done using vapor and metal contaminants. These catalysts were deactivated with Fe, Ni, V, and Ca contaminants in a modified periodic deactivation mode with lower vapor partial pressure and temperature, as described in previous literature (Applied Catalysis A: General 249 (2003) 69-80) (incorporated herein by reference). Similar to periodic deactivation, the catalysts are subjected to a decomposition and regeneration cycle with a feed containing metal contaminants. Mimicking Fe deactivation on a laboratory scale is an industrially recognized deactivation procedure.

[0037] Example 1 As shown in Table 1 below, Example 1 compares the substitution of clay with additional non-collapsible microcrystalline boehmite and alumina that is partly in the kai phase. An example, Experiment-1, was carried out according to the present invention and the methods disclosed herein. In addition to three alumina, sodium-stabilized colloidal silica and acid-stabilized colloidal silica were used for binding. The resulting catalyst exhibited comparable wear to the reference catalyst containing clay and had improved accessibility. The Fe resistance of this catalyst was verified by subjecting it to laboratory-scale deactivation using Fe, Ca, Ni, and V metals as described in the literature (Applied Catalysis A: General 249 (2003) 69-80). The essentially clay-free catalyst showed higher accessibility than the reference catalyst after Fe deactivation, indicating better Fe resistance. The better Fe resistance of the essentially clay-free catalyst was evident in better sediment improvement in ACE performance evaluation. The improved sediment was converted into high-value gasoline and LCO fractions, and all other important components were converted with the reference catalyst. It was equivalent or better. [Table 1]

[0038] Example 2: In the following examples, clay was replaced with gibbsite or alpha-alumina. Experiments 2 and 3 were conducted according to the methods disclosed herein and herein. The experimental catalysts consist of three different aluminas (quasicrystalline boehmite, microcrystalline boehmite, and gibbsite or alpha-alumina) and two different colloidal silicas. The iron tolerance of these essentially clay-free catalysts is shown to be higher than that of the reference catalyst after laboratory-scale deactivation with Fe, Ca, Ni, and V metals. In this case as well, the advantage of higher accessibility in the essentially clay-free catalysts is confirmed by better sediment improvement in ACE performance evaluation. [Table 2]

[0039] Example 3: In the following embodiments, clay was replaced with amorphous alumina containing kai phase and gibbsite. Sodium-stabilized colloidal silica and sodium-stabilized polysilicic acid were used. Experiments 4 and 5 were conducted according to the present invention and the methods disclosed herein. The experimental catalysts consisted of three different aluminas (quasicrystalline boehmite, microcrystalline boehmite, and gibbsite or kai alumina) and two different colloidal silicas (sodium-stabilized colloidal silica and sodium-containing polysilicic acid). The iron tolerance of these essentially clay-free catalysts is shown to be higher than that of the reference catalyst after laboratory-scale deactivation with Fe, Ca, Ni, and V metals. The advantage of maintaining higher accessibility in essentially clay-free catalysts is confirmed by better sediment improvement in ACE performance evaluation. [Table 3]

Claims

1. A particulate FCC catalyst composition comprising one or more zeolites, at least one alumina component, and at least one silica component, without the addition of clay, having improved contaminant resistance indicated by higher accessibility retention after inactivation with iron.

2. The particulate FCC catalyst composition according to claim 1, wherein the at least one alumina component comprises a non-collectible alumina selected from quasicrystalline boehmite, microcrystalline boehmite, gamma, alpha, or kai phase alumina or gibbsite, or a mixture thereof.

3. The particulate FCC catalyst composition according to Claim 2, comprising 1 to 50% of one or more zeolites based on the final catalyst, 15 to 35 wt% of non-collapsible quasicrystalline boehmite based on the final catalyst, 1 to 35 wt% of microcrystalline boehmite based on the final catalyst, 40 wt% or less of non-collapsible alumina selected from gamma, alpha, or kai phase alumina or gibbsite based on the final catalyst, 1 to 20 wt% of colloidal silica based on the final catalyst, and 5 to 20 wt% of low-sodium or sodium-free colloidal silica or ammonia-stabilized colloidal silica or polysilicic acid based on the final catalyst, without the addition of clay.

4. A method for decomposing a raw material, comprising: a) A step of providing the particulate FCC catalyst composition according to any one of claims 1 to 3; b) The method comprising the step of contacting the FCC catalyst with the raw material at a temperature in the range of 400 to 650°C for a residence time in the range of 0.5 to 12 seconds.

5. The method according to claim 4, wherein the raw material is a hydrocarbon raw material.

6. The raw materials include hydrocarbons and vegetable oils (soybeans, canola, corn, palm, rapeseed, etc.), waste oil, animal fat, biowaste and / or pyrolysis, or other oils obtained by any thermal or other treatment of biomass, plastics, sewage, municipal waste, agricultural waste, or other suitable organic mass waste and combinations thereof (e.g., Fischer The method according to claim 4 or 5, wherein the mixture is Tropsch solution.

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