FCC catalysts with ultrastable zeolites and transition aluminas and their uses.

Abstract

A catalyst comprising the preparation of a catalyst and the use of chi or gamma or gibbsite alumina.Accordingly, in one embodiment, the present invention provides an ultra-stable Y zeolite (USY zeolite) having a total Lewis acidity retention of at least 15% as the adsorption temperature increases from 200 to 400°C as measured by pyridine adsorption FT-IR and a total acidity retention of at least 35% as the desorption temperature increases from 300 to 400°C as measured by ammonia TPD, and at least two different types of alumina, at least one of which is a dispersively bound alumina sol and the other alumina is a dispersively bound alumina sol having a total acidity of about 37.6(311)°C. and at least two different types of alumina, either of a transition alumina phase having XRD peaks at 2θ of 45.8 (400) and 67 (440) (referred to herein as gamma alumina), or an alumina comprising a metastable phase having characteristic XRD peaks at 2θ values ​​of 37, 43 and 67° (referred to herein as chi alumina), or a non-peptizing gibbsite alumina having characteristic XRD peaks at 2θ values ​​of 18, 20.3 and 38° (referred to herein as gibbsite alumina). Further, the total amount of chi or gamma or gibbsite alumina is from greater than 0% to about 20-30% by weight.

Description

FIELD OF THEINVENTION

[0001] The present invention relates to a catalyst composition and its use in a process for cracking or converting a feed containing hydrocarbons, such as those obtained from the processing of a feedstock, such that the process exhibits increased bottoms conversion and increased coke selectivity, resulting in less coke production. [Background technology]

[0002] A general challenge in the design and preparation of heterogeneous catalysts is to find a good compromise between the availability and / or accessibility of the active sites and the effectiveness of the immobilization matrix in providing the catalyst particles with sufficient physical strength, i.e., resistance to attrition.

[0003] The preparation of attrition-resistant catalysts has been disclosed in several prior art documents. US 4,086,187 discloses a process for preparing attrition-resistant catalysts by spray drying an aqueous slurry prepared by mixing (i) faujasite-type zeolite with a sodium content of less than 5% by weight, (ii) kaolin, (iii) peptided pseudoboehmite, and (iv) ammonium polysilicate. The attrition-resistant catalysts described in US 4,206,085 are prepared by spray drying a slurry prepared by mixing two types of acidified pseudoboehmite, zeolite, alumina, clay, and either ammonium polysilicate or silica sol.

[0004] GB1315553 discloses the preparation of an attrition-resistant hydrocarbon conversion catalyst comprising zeolite, clay and an alumina binder. The catalyst is prepared by first dry mixing the zeolite and clay, and then adding the alumina sol. The resulting mixture is then mixed to a plastic consistency, which requires about 20 minutes of mixing time. The plastic consistency is pelletized or extruded to form shaped particles, or mixed with water and then spray dried. The alumina sol disclosed in this British patent specification comprises aluminum hydroxide and aluminum trichloride in a molar ratio of 4.5 to 7.0 (also called aluminum chlorohydrol).

[0005] US 4,458,023 relates to a similar preparation method, followed by calcination of the spray-dried particles. The aluminum chlorohydrol component is converted to an alumina binder during calcination. WO 96 / 09890 discloses a process for preparing an attrition-resistant fluid catalytic cracking catalyst, in which an aluminum sulfate / silica sol, a clay slurry, a zeolite slurry, and an alumina slurry are mixed and then spray-dried. In this case, an acid- or alkali-stable surfactant is added to the silica sol, the clay slurry, the zeolite slurry, the alumina slurry, and / or the spray-dried slurry. CN 1247885 also relates to the preparation of a spray-dried cracking catalyst, in which a slurry containing an alumina sol, pseudoboehmite, a molecular sieve, a clay, and an inorganic acid is used. In this process, the alumina sol is added to the slurry before the addition of the clay and the inorganic acid, and the molecular sieve slurry is added after the addition of the inorganic acid. According to one embodiment, the aluminum sol is first mixed with the pseudoboehmite, followed by the addition of the inorganic acid. After acidification, the molecular sieve is added, followed by the addition of the kaolin.

[0006] WO02 / 098563 discloses a process for preparing an FCC catalyst that combines high attrition resistance with high accessibility. The catalyst is prepared by slurrying zeolite, clay and boehmite, feeding the slurry into a forming device and forming the mixture to form particles, characterized in that the mixture is destabilized just before the forming step. Destabilization is achieved, for example, by increasing the temperature, increasing the pH, decreasing the pH, or by the addition of gel-inducing agents, such as salts, phosphates, sulfates, (partially) gelled silica, etc. Prior to destabilization, all peptidizable compounds present in the slurry must be fully peptidized.

[0007] WO06 / 067154 describes FCC catalysts, their preparation and their use. It discloses a process for preparing an FCC catalyst that combines high attrition resistance with high accessibility. The catalyst is prepared by slurrying clay, zeolite, a sodium-free silica source, semi-crystalline boehmite and microcrystalline boehmite, where the slurry does not contain peptized semi-crystalline boehmite, b) adding a monovalent acid to the slurry, c) adjusting the pH of the slurry to a value greater than 3, and d) forming the slurry to form particles. Summary of the Invention

[0008] The present invention relates to an FCC catalyst intended to be employed in a process for cracking a hydrocarbon or hydrocarbon blend feed over a specific catalyst composition to produce products containing lower molecular weight conversion product hydrocarbon compounds than the feed hydrocarbon, e.g., high gasoline fractions. A unique feature of the present invention is the use of aluminas including gamma alumina and / or chi-phase or gibbsite phase alumina, and / or combinations thereof, in addition to other aluminas.

[0009] Thus, in one embodiment, an ultra-stable Y zeolite (USY zeolite) having a total Lewis acidity retention of at least greater than 15% as the adsorption temperature is increased from 200 to 400° C. as measured by pyridine adsorption FT-IR and a total acidity retention of at least greater than 35% as the desorption temperature is increased from 300 to 400° C. as measured by ammonia temperature programmed desorption (TPD) measurements, and at least two different types of alumina, at least one of which is a dispersively bound alumina sol and the other alumina is a dispersively bound alumina sol having a total acidity of about 37.6(311)° C. and at least two different types of alumina, either of a transition alumina phase having XRD peaks at 2θ of 45.8 (400) and 67 (440) (referred to herein as gamma alumina), or including a metastable phase having characteristic XRD peaks at 2θ values ​​of 37, 43 and 67° (referred to herein as alumina having a chi phase), or non-peptizing gibbsite alumina having characteristic XRD peaks at 2θ values ​​of 18, 20.3 and 38° (referred to herein as gibbsite alumina). Further, the total amount of alumina that is chi or gamma or gibbsite phase is from greater than 0% to about 30% by weight.

[0010] The resulting catalysts exhibit improved advantages over catalysts known in the art, for example, the improved catalysts exhibit improved bottoms conversion.

[0011] In a further embodiment, a process for cracking a petroleum distillate feed is provided, the process comprising the steps of: a) a USY zeolite having a total Lewis acidity retention of at least greater than 15% as the adsorption temperature is increased from 200 to 400°C as measured by pyridine adsorption FT-IR and a total acidity retention of at least greater than 35% as the desorption temperature is increased from 300 to 400°C as measured by ammonia TPD; and at least two different types of alumina, at least one of which is a dispersively bound alumina sol and the other alumina is of a transition alumina phase having XRD peaks at 2θ of about 37.6 (311), 45.8 (400), and 67 (440), or an alumina containing a metastable phase having characteristic XRD peaks at 2θ values ​​of 37, 43, and 67°, or a non-peptized gibbsite alumina having characteristic XRD peaks at 2θ values ​​of 18, 20.3, and 38°. providing an FCC catalyst composition comprising: b) contacting the FCC catalyst with the petroleum fraction feedstock or blends of greater than 0 wt. % vegetable oil (soybean, canola, corn, palm, rapeseed, etc.), waste oil, tallow, and / or pyrolysis oil obtained by any thermal treatment of biomass or plastics, and combinations thereof, at a temperature in the range of 400-650° C. and for a residence time in the range of 0.5-12 seconds.

[0012] These and still other embodiments, advantages and features of the present invention will become more apparent from the following detailed description, including the appended claims.

[0013] Unless otherwise indicated, weight percent (1-10% by weight) used herein is the dry basis weight percent of a particular form of a substance based on the total dry basis weight of the product of which the particular substance or form of a substance is a component or ingredient. Furthermore, when steps or ingredients or elements that are preferred in any aspect are described herein, they are preferred as of the first date of this disclosure, and it should be understood that such preferred aspect(s) may, of course, change depending on the given circumstances or future developments in the art.

[0014] General Procedure Typically, the first step in the process of making the improved catalyst is to mix a clay source, silica, and one or more alumina (boehmite) sources, including gamma alumina. The clay, zeolite, quasicrystalline boehmite (QCB), microcrystalline boehmite (MCB), gamma alumina, chialumina, gibbsite alumina, and silica, as well as any other components, such as rare earth components, can be slurried by adding them as dry solids to water. Alternatively, slurries containing the individual materials are mixed together as appropriate to form a slurry. It is also possible to add some of the materials as slurries and others as dry solids. Optionally, other components may be added, such as aluminum chlorohydrol, aluminum nitrate, Al2O3, Al(OH)3, anionic clays (e.g., hydrotalcite), smectites, sepiolites, barium titanate, calcium titanate, calcium silicate, magnesium silicate, magnesium titanate, mixed metal oxides, layered hydroxide salts, additional zeolites, magnesium oxides, bases or salts, and / or metal additives such as compounds containing alkaline earth metals (e.g., Mg, Ca, 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), or mixtures thereof. These compounds may be added in any order. It is also possible to combine all of these compounds at the same time.

[0015] The term "boehmite" is used in the art to describe alumina hydrates that exhibit X-ray diffraction (XRD) patterns that are close to aluminum oxide-hydroxide [AlO(OH)]. Furthermore, the term boehmite is generally used to describe a wide range of alumina hydrates that contain different amounts of water of hydration, have different surface areas, pore volumes, specific densities, and exhibit different thermal properties upon heat treatment. However, their XRD patterns, although they do exhibit the characteristic boehmite [AlO(OH)] peak, usually vary in width and may shift in position. The sharpness of the XRD peak and its position have been used to indicate the degree of crystallinity, crystal size, and amount of defects.

[0016] Broadly speaking, there are two categories of boehmite alumina: quasicrystalline boehmite (QCB) and microcrystalline boehmite (MCB). In the state of the art, quasicrystalline boehmite is called pseudo-boehmite. These QCBs are also called boehmite or gelled boehmite. These QCBs typically have a larger surface area, larger pores and pore volume, and a lower specific density than MCBs. They disperse easily in water and acid, have smaller crystal sizes, and have a higher number of hydration water molecules than MCBs. The degree of hydration of QCBs can vary over a wide range, e.g., from about 1.4 to about 2 moles of water per mole of Al, usually regularly or otherwise intercalated between the octahedral layers. Representative commercially available QCBs include the Pural®, Catapal®, and Versal® product families.

[0017] Microcrystalline boehmite is distinguished from QCB by its high degree of crystallinity, relatively large crystal size, very small surface area, and high density. In contrast to QCB, MCB shows XRD patterns with higher peak intensities and very narrow half-widths. This is due to the relatively small number of intercalated water molecules, the large crystal size, the high crystallinity of the bulk material, and the low number of crystal defects. Typically, the number of intercalated water molecules can vary from about 1 to about 1.4 per mole of Al. A representative MCB available commercially is P-200® from Condea.

[0018] MCB and QCB are characterized by powder X-ray reflections. The ICDD has an entry on boehmite and confirms that there will be reflections corresponding to the (020), (021) and (041) planes. For copper radiation, such reflections will appear at 14, 28 and 38 degrees 2θ. The exact location of the reflections depends on the degree of crystallinity and the amount of interstitial water. With increasing amounts of interstitial water, the (020) reflection will shift to lower values, which correspond to larger d-spacings. However, lines close to the above positions will indicate the presence of one or more boehmite phases. For the purposes of this specification, quasicrystalline boehmite is defined as a (020) reflection with a full width at half maximum (FWHH) of 1.5 degrees 2θ or greater. A (020) reflection with a full width at half maximum (FWHH) of less than 1.5 degrees 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 non-peptidized 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, of MCB based on the final catalyst.

[0019] A unique aspect of the present application is the combination of an FCC catalyst with a third alumina source. The third alumina of the present invention is a non-peptizing alumina containing gamma phase, or a non-peptizing alumina containing chi phase, or a non-peptizing gibbsite phase alumina, and / or a combination thereof. The present invention contains about 1 to about 30 weight percent of the non-peptizing alumina containing gamma phase or chi phase or gibbsite phase alumina.

[0020] Gamma alumina is understood to be a transition phase of alumina. Boehmite or pseudo-boehmite can be converted to gamma alumina by heat treatment. Typically, boehmite or pseudo-boehmite 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). For the purposes of the present invention, it is preferred to utilize gamma alumina with small crystallite size. Specifically, it is preferred to utilize gamma alumina with crystallite size of less than about 20 nm. It is more preferred to utilize gamma alumina with crystallite size of less than about 10 nm. Furthermore, since gamma alumina is non-bonding, it is preferred to utilize gamma alumina with small particle size. The small particle size (<5.0 microns) ensures that the benefits of gamma alumina are utilized while minimizing the impact on the physical properties of the catalyst. The total amount of gamma alumina is from greater than 0% to about 30% by weight based on the final catalyst.

[0021] The chi phase is a metastable phase of alumina and is non-peptizable. It has characteristic XRD peaks at 2θ values ​​of 37, 43, and 67°. It is a gibbsite alumina that is melted at moderate temperatures (3 The kaya phase is introduced into the slurry as an alumina-containing kaya phase component. Typically, the kaya phase-containing alumina component contains about 1 to 25% kaya phase alumina.

[0022] Gibbsite is an important ore of aluminum in that it is one of the mineral forms of aluminum hydroxide and one of the three major phases that make up the rock bauxite. The basic structure forms stacked sheets of interlocking octahedra. Each octahedron consists of an aluminum ion bound to six hydroxide groups, with each hydroxide group shared by two aluminum octahedra. Non-peptized gibbsitic alumina has characteristic XRD peaks at 2θ values ​​of 18, 20.3, and 38°. The total amount of gibbsitic alumina ranges from greater than 0% to about 30% by weight based on the final catalyst.

[0023] The total amount of silica added is from greater than 0% to about 25% by weight. The silica source is typically a low sodium silica source, acidic or ammonia stabilized silica, 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, ammonium 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-OCO-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 or acid or ammonia stabilized colloidal silica.

[0024] Also, the clay preferably has a low sodium content or is sodium-free. Suitable clays include anionic clays such as kaolin, bentonite, saponite, sepiolite, attapulgite, laponite, halloysite, hectorite, English clay, hydrotalcite, and heat-treated or chemically treated clays such as metakaolin. The slurry preferably contains about 5 to about 70% by weight, more preferably about 10 to about 60% by weight, and most preferably about 10 to about 50% by weight of clay.

[0025] In the next step, a monovalent acid is added to the suspension to allow digestion to occur. Both organic and inorganic monovalent acids, or mixtures thereof, can be used. Examples of suitable monovalent acids are formic acid, acetic acid, propionic acid, methylsulfonic acid, nitric acid, and hydrochloric acid. The acid is added to the slurry in an amount sufficient to obtain a pH below 7, more preferably a pH between 1 and 4.

[0026] One or more zeolites may be added at any time, but preferably after the addition of the monovalent acid. The zeolites used in the process according to the invention preferably have a low sodium content (less than 1.5 wt.% Na2O) or are sodium-free. Suitable zeolites to be present in the slurry of step a) include zeolites such as HY, USY, dealuminated Y, RE-Y and RE-USY, 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 20-60 wt.% of one or more zeolites based on the final catalyst.

[0027] Additionally, optionally, a rare earth component is added to the mixture in the form of a salt or solution in an amount of about 0.1 to about 10% by weight based on the oxide form. Examples of suitable rare earth elements include, but are not limited to, lanthanum, yttrium, and cerium. Rare earths are typically present as hydroxides, chlorides, oxides, nitrates, sulfates, oxychlorides, acetates, or carbonates. Preferably, lanthanum nitrate and / or yttrium nitrate are added in the form of a salt or solution in an amount of about 0.1 to about 10% by weight based on the oxide form. The rare earth component can be added before or after the peptization (or digestion) of the alumina described above.

[0028] Another unique aspect of the present invention is the presence of ultra-stabilized Y zeolite. In particular, USY zeolite has a total Lewis acidity retention of at least 15% when the adsorption temperature is increased from 200 to 400°C in pyridine adsorption FT-IR and at least 35% when the desorption temperature is increased from 300 to 400°C in ammonia TPD measurements. USY is characterized by improved / enhanced mesoporosity and controlled acidity and acid site density compared to non-USY zeolites. The increased mesoporosity in USY improves the diffusivity of heavier hydrocarbon molecules into the zeolite pores and enhances their interaction with the acid sites within the zeolite structure. The controlled acid site density of USY also helps in selective cracking of these heavier molecules, resulting in less coke deposition in the pores and improved stability of the zeolite compared to microporous non-USY zeolites in FCC catalysts. There are various ways to increase the mesoporosity and modify the acidity of Y zeolites. The more classical method for forming mesopores in Y zeolites is steam calcination at high temperatures, which removes Al from the lattice to form vacancies (dealuminization) and stabilises the zeolite framework by migrating silicon species into the vacancies, forming mesopores. The migration of silicon increases the SiO2 / Al2O3 ratio of the framework, which results in a reduction in acid site density compared to non-USY zeolites. The extent of mesopore formation and reduction in acid site density can be controlled by the degree of steam calcination / dealuminization.

[0029] The above slurry is then passed through a high shear mixer where it is destabilized by increasing the pH. The pH of the slurry is then adjusted to a value above 3, more preferably above 3.5, and even more preferably above 4. The pH of the slurry is preferably not higher than 7, since slurries with higher pH can be difficult to handle. The pH can be adjusted by adding a base (e.g., NaOH or NH4OH) to the slurry. The time from pH adjustment to the forming step d) 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 20 to about 35% by weight.

[0030] The slurry is then shaped. Suitable shaping methods include spray drying, pulse drying, pelletizing, extrusion (optionally combined with kneading), beading, or other conventional shaping methods used in the field of catalysts and absorbents, or combinations thereof. A preferred shaping method is spray drying. When the catalyst is shaped by spray drying, the inlet temperature of the spray dryer is preferably in the range of 300-600°C, and the outlet temperature is preferably in the range of 105-200°C.

[0031] Resulting catalyst The catalyst thus obtained has very good attrition resistance and accessibility. The present invention therefore also relates to a catalyst obtained by the process according to the invention, which generally comprises a USY zeolite having a total Lewis acidity retention of at least 15% when the adsorption temperature is increased from 200 to 400° C. in pyridine adsorption FT-IR and a total acidity retention of at least 35% when the desorption temperature is increased from 300 to 400° C. in ammonia TPD measurement, and at least two different types of alumina, at least one of which is a dispersively bound alumina sol and the other alumina is of a transition alumina phase having XRD peaks at 2θ of about 37.6 (311), 45.8 (400) and 67 (440) and / or of a metastable phase having characteristic XRD peaks at 2θ values ​​of 37, 43 and 67°, or a gibbsite alumina having characteristic XRD peaks at 2θ values ​​of 18, 20.3 and 38°. CC catalyst composition. Additionally, the resulting catalyst may comprise about 20 to about 60 weight percent of one or more zeolites, about 15 to about 35 weight percent of paracrystalline boehmite as dispersed bound alumina, about 0 to about 35 weight percent of microcrystalline boehmite, greater than 0 weight percent to about 25 weight percent of silica, optionally rare earth components, and the balance clay.

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

[0033] The process of the invention is particularly applicable to fluid catalytic cracking (FCC). In FCC processes, the details of which are generally known, the catalyst is generally present as particulates with more than 90% by weight of the particles having diameters in the range of about 5 to about 300 microns. In the reactor section, the hydrocarbon feedstock is gasified and directed upwards through a reaction zone, where the particulate catalyst is entrained and fluidized in the hydrocarbon feedstock stream. The hot catalyst provided from the regenerator reacts with the hydrocarbon feed, which is vaporized and cracked by the catalyst. Typically, the temperature in the reactor is between 400 and 650° C., and the pressure may be subatmospheric, atmospheric, or superatmospheric, but is usually from about atmospheric to about 5 atm. The catalytic process may be fixed bed, moving bed, or fluidized bed, and the hydrocarbon flow may be cocurrent or countercurrent to the catalyst flow. The process of the invention is also suitable for TCC (thermal catalytic cracking) or DCC (deep catalytic cracking). Additionally, the hydrocarbon feedstock may comprise blends of greater than 0% by weight of vegetable oils (soybean, canola, corn, palm, rapeseed, etc.), waste oils, tallow, and / or pyrolysis oils obtained by any thermal treatment of biomass or plastics, and combinations thereof. EXAMPLES

[0034] Prior to laboratory testing, the catalyst must be deactivated to simulate the catalyst in the refinery, typically with steam. The samples were deactivated by circulation deactivation with Ni / V with decomposition in the presence of steam, stripping, and regeneration steps, or by 100% steam deactivation at high temperature. These are industrially accepted methods for deactivating FCC catalysts. The deactivation step is known in the art and is necessary for catalytic activity. In a commercial FCC environment, deactivation is performed immediately after catalyst introduction and does not need to be performed as a separate step.

[0035] Accessibility measures: The accessibility of the catalysts 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 with toluene. The solution was circulated between the vessel and a spectrophotometer, with the VGO concentration being measured continuously during the process.

[0036] Temperature Programmed Desorption of Ammonia (NH3-TPD): The total acidity and strength of acid sites of any catalytic material can be measured by the temperature programmed desorption method using ammonia as the probe molecule. The amount of ammonia desorbed indicates the total acidity, and the desorption temperature indicates the strength of the acid sites. This procedure is very close to the ASTM D4824 method for acidity measurement. This procedure is a gravimetric temperature programmed desorption method, whereas ASTM D4824 is a volumetric method. This method determines the acidity on the surface and in the pores of the sample by measuring the amount of ammonia that desorbs during the temperature increase. The experiment is carried out using a thermogravimetric analyzer (Mettler Toledo TGA). The sample is pre-calcined at 600 °C in air for at least 1 hour. About 50 mg to 100 mg of the sample is reprocessed in the TGA instrument by heating in nitrogen at 600 °C for about 30 minutes and then reducing the temperature to 100 °C. Subsequently, a stream of ammonia accompanied by a stream of nitrogen is directed over the sample for 30 to 60 minutes to allow adsorption on the acid sites. The physically adsorbed ammonia molecules are then transported to nitrogen at 100°C. The ammonia was removed by a flash step in nitrogen for 30-60 min. The actual temperature programmed desorption is then performed. The temperature is increased to 600 °C and the weight change during desorption is monitored. The amount of desorbed ammonia is recorded as the weight change. The amount of acid sites is expressed as the amount of desorbed ammonia (mmol) per gram of dry sample using the weight change during desorption.

[0037] FTIR spectroscopy of pyridine adsorption (pyridine FT-IR): Total acidity and type of acid sites (Lewis or Bronsted) can be quantified by FTIR spectroscopy using pyridine as a probe molecule. Measurements are performed by an FTIR instrument (Thermo Fisher) equipped with a high-temperature transmission cell (Specac). Zeolite powder samples are pressed into self-supporting wafers (approximately 15-30 mg, 13 mm diameter) and the wafers are calcined at 600 °C in air for approximately 1 h. The sample wafers are then transferred to the IR cell and reprocessed at 500 °C-600 °C in nitrogen for approximately 15 min. After lowering the temperature to 200 °C, pyridine is passed through the IR cell with a nitrogen flow for 1 h and then vacuum processed at the same temperature for approximately 60 min. The spectrum of desorption at 200 °C is then recorded in the region of 400-3800 cm-1 with a spectral resolution of 2 cm-1. This spectrum is usually measured at approximately 100 °C to obtain a better baseline. For desorption at higher temperatures, the IR cell temperature is increased to a set temperature and the IR cell is held at that temperature for 1 h under nitrogen flow. The desorption spectrum at that temperature is recorded after cooling the cell to 100 °C. The characteristic absorption bands of Lewis and Brønsted acid sites (1450 cm-1 and 1545 cm-1, respectively) are integrated. For quantification of Lewis and Brønsted acid sites, the apparent integrated absorption coefficients of 2.22 (for Lewis acid sites) and 1.67 (for Brønsted acid sites) are adopted for the integration of the absorption bands at 1450 cm-1 and 1545 cm-1.

[0038] As explained in the previous section, the Bronsted acidity and Lewis acidity of USY and normal Y zeolite were measured by pyridine adsorption FT-IR spectroscopy. The profiles are shown in the figure below. -1 The peak at 1455 cm indicates the Brønsted acid site. -1 The peaks indicate Lewis acid sites. The area under each peak is considered to be the amount of acid sites. Although normal RE-Y and RE-USY, which have different UCS, both showed similar FT-IR profiles, their total acidity was significantly different. [Table 1]

[0039] Both Bronsted and Lewis acid sites were quantified at 200 and 400 °C. The values ​​are shown in the table below. It is noteworthy that all USY zeolites have a higher retention of Lewis acid sites when the desorption temperature is increased from 200 to 400 °C compared with normal RE-Y zeolites. USY zeolites have a higher retention of Lewis acid sites when the desorption temperature is increased from 200 to 400 °C, whereas normal Y zeolites have a lower retention of Lewis acid sites than 15%. USY zeolites have a higher framework SiO2 / Al2O3 ratio due to possible silicon intercalation, which leads to the formation of stronger Lewis acid sites. Such strong Lewis acid sites may have a favorable effect on the hydrocarbon cracking reaction, especially the cracking of heavier molecules. [Table 2]

[0040] Similarly, the acidity profiles of these zeolites were measured by the temperature programmed desorption method using ammonia as a probe molecule as described in the previous section. In general, desorption below 300°C is considered to be ammonia desorbed from weak and medium acid sites, and desorption above 300°C is considered to be ammonia desorbed from strong acid sites. [Table 3]

[0041] The following table shows the results of the comparison of USY zeolite and non-USY zeolite in both the low and high temperature ranges. The acidity data for the USY zeolites show that the USY zeolites have at least 40% retention at 400° C. compared to 300° C. The acidity retention of non-USY zeolites is lower, indicating that the strong acid sites of USY zeolites may have some effect on the hydrocarbon cracking reactions. [Table 4]

[0042] Example 1 Example 1 below describes a comparison of an FCC catalyst prepared with only RE-Y zeolite (non-USY) as a reference catalyst with catalysts prepared with USY with UCS of 24.52 Å and two different levels of transition phase (gamma) alumina. All other active components, including total RE2O3, were kept equal in this comparison. The catalysts were deactivated with Ni and V using the commercially practical recycle deactivation method and their performance was evaluated in an ACE with a resid feed oil. As shown in the table below, the catalysts prepared with USY and gamma alumina showed improved bottoms upgrading compared to the reference catalyst prepared with only RE-Y zeolite. [Table 5]

[0043] Example 2 In Example 2 below, USY with UCS of 24.57 Å and alumina containing approximately 7% chi phase were compared to a reference catalyst prepared containing only RE-Y zeolite. As in the previous examples, these catalysts were deactivated and tested in an ACE with a resid feed oil. Again, the catalyst containing USY and alumina containing chi phase showed improved bottom cracking compared to the reference catalyst. [Table 6]

[0044] Example 3 In the examples below, a catalyst prepared with RE-USY and transition alumina (gamma phase) with UCS of 24.57 Å was compared to a catalyst prepared with RE-Y. Again, the performance advantage of the catalyst using USY and gamma alumina is clearly shown, especially in the ability to upgrade the bottom portion. [Table 7]

Claims

1. a USY zeolite having a total Lewis acidity retention of at least 15% when the adsorption temperature is increased from 200 to 400°C in pyridine adsorption FT-IR and a total acidity retention of at least 35% when the desorption temperature is increased from 300 to 400°C in ammonia TPD measurement; at least one dispersible bonded alumina; a second alumina which is a non-peptizing gamma alumina having XRD peaks at 2θ of 37.6 (311), 45.8 (400), and 67 (440), and / or a non-peptizing chi-phase alumina having characteristic XRD peaks at 2θ values ​​of 37, 43, and 67°, and / or a non-peptizing gibbsite alumina having characteristic XRD peaks at 2θ values ​​of 18, 20.3, and 38°; Including, the dispersible bound alumina is semi-crystalline boehmite in an amount of 15 to 35 wt. %, and further comprises 20 to 60 wt. % of one or more USY zeolites and optionally one or more other zeolites, greater than 0 wt. % to 35 wt. % of microcrystalline boehmite, greater than 0 wt. % to 25 wt. % of silica, and the balance being clay; FCC catalyst composition.

2. 10. The FCC catalyst composition of claim 1 comprising at least one dispersible bound alumina and at least one non-peptizing gamma alumina having XRD peaks at 2θ of 37.6 (311), 45.8 (400), and 67 (440).

3. 10. The FCC catalyst composition of claim 1, comprising at least one dispersible bound alumina and at least one non-peptizing chi-phase alumina having characteristic XRD peaks at 2θ values ​​of 37, 43 and 67°.

4. 3. The FCC catalyst composition of claim 2, wherein the gamma alumina has a crystallite size of less than 20 nm.

5. 5. The FCC catalyst composition of claim 4, wherein the gamma alumina has a crystallite size of less than 10 nm.

6. The FCC catalyst composition of claim 3, wherein the amount of non-peptizing chiral alumina is greater than 0% to 10% by weight.

7. The FCC catalyst composition of claim 2, wherein the amount of non-peptizing gamma alumina is greater than 0% by weight to 30% by weight.

8. An FCC catalyst composition described in any one of claims 1 to 3, wherein the total amount of alumina is more than 35 wt%.

9. 1. A method for producing more liquid components from a feedstock, comprising: a) providing the FCC catalyst composition of claim 1; b) contacting the FCC catalyst composition with a feedstock at one or more temperatures ranging from 400 to 650°C and for a residence time ranging from 0.5 to 12 seconds; The method comprises the steps of:

10. The method of claim 9 wherein the feedstock is a hydrocarbon feedstock.

11. 10. The method of claim 9, wherein the feedstock is a hydrocarbon and vegetable oil, waste oil obtained by any thermal treatment of biomass or plastics, tallow oil or pyrolysis oil, and any combination thereof.

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