Zeolite, its production and its use for upgrading heavy oil

Abstract

According to one or more embodiments, the nano-sized mesoporous zeolite particles may include a microporous framework including a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type. The nano-sized mesoporous zeolite particles may also include a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. The zeolite particles may be integrated into a hydrocracking catalyst and used for heavy oil cracking during pretreatment.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Patent Application No. 15 / 790,361, filed on October 23, 2017, and U.S. Provisional Patent Application No. 62 / 507,515, filed on May 17, 2017, and entitled ZEOLITE BETA CATALYSTS, THE PRODUCTION THEREOF, AND THEIR USES FOR UPGRADING HEAVY OILS, the entire contents of which are incorporated by reference. Technical Field

[0003] The present disclosure relates to zeolites, and more particularly to zeolites that may be suitable for use in treating heavy oils, including crude oil, using catalytic pretreatment processes. Background Art

[0004] Ethylene, propylene, butylene, butadiene and aromatic compounds such as benzene, toluene and xylene are basic intermediates for most petrochemical industries. They are mainly obtained by thermal cracking (sometimes referred to as "steam cracking" or "steam cracking") of petroleum gas and distillates such as naphtha, kerosene or even gas oil. These intermediate compounds can also be produced by refining fluid catalytic cracking (FCC) processes, in which heavy feedstocks such as gas oil or residual oil are converted. For example, an important source of propylene production is refined propylene from FCC units. However, distillate feedstocks such as gas oil or residual oil are usually limited and are produced in refineries by several high-cost and energy-intensive processing steps.

[0005] However, as the demand for these essential intermediate compounds increases, other sources of production must be considered in addition to the traditional thermal cracking process using petroleum gas and distillates as feedstocks. Summary of the invention

[0006] Therefore, in view of the growing demand for these intermediate petrochemical products such as butenes, there is a need for methods of producing these intermediate compounds from other types of feedstocks that can be obtained in large quantities at relatively low cost. The present disclosure relates to zeolites that can be used in some embodiments to produce these intermediate compounds (sometimes referred to as "system products" in the present disclosure) by directly converting heavy oil feedstocks such as crude oil. In producing these intermediate compounds, conversion from crude oil as a feedstock can be beneficial compared to other feedstocks because it can generally be cheaper, more commonly available, or both compared to other feedstock materials.

[0007] According to one or more embodiments, heavy oil can be cracked by steam cracking to form system products such as light olefins (such as butenes). However, steam cracking of heavy oil may cause coking to increase, which may require stopping refining operations to remove coke. In addition, a relatively large amount of aromatics in heavy oil may cause heavy oil steam cracking to form undesirable products and low light olefin content. In some cases, polyaromatics present in heavy oil feedstock may not be converted by steam cracking. It has been found that pre-treatment of heavy oil feedstock to reduce or remove other undesirable species such as one or more of aromatics and metals, sulfur and nitrogen can increase the production of light olefins and reduce coking. According to one or more embodiments, such pre-treatment may include one or more of hydrodemetallization, hydrodenitrogenation, hydrodesulfurization and aromatic hydrocracking.

[0008] Conventional hydrotreating catalysts may not be able to effectively convert polyaromatics and saturated polycyclic species due, at least in part, to their relatively weak acidity. Hydrocracking catalysts with zeolites as the primary cracking component (e.g., hydrocracking catalysts used in steam cracking) can have a higher degree of acidity than conventional hydrotreating catalysts and can greatly enhance the conversion of aromatics. However, the pore openings of conventional zeolite catalysts, such as zeolite Y and zeolite beta, may be too small to allow the macromolecules of the heavy oil feedstock to diffuse into the active sites located within the zeolite. In addition, the relatively large particle size of these conventional zeolite catalysts may limit the access of the heavy oil to the active catalytic sites on the catalyst.

[0009] It has been found that two approaches to address this problem (i.e., the problem of increasing aromatic conversion for relatively large molecules present in heavy oil streams) are to increase the zeolite pore size and to reduce the zeolite particle size. It has been found that nano-sized zeolites can greatly increase the surface area and shorten the molecular diffusion paths, and that the addition of mesopores in the zeolite can make additional active sites available for catalytic activity. In one or more embodiments, as described herein, pore size increase can be achieved by incorporating mesopores into the zeolite. According to one or more embodiments, particle size reduction can be achieved by specific zeolite manufacturing techniques described herein.

[0010] According to the embodiments disclosed herein, zeolite beta can be produced and used as a hydrocracking catalyst having a relatively small particle size (e.g., less than or equal to 100 nm) and containing mesopores. In some embodiments, as described herein, with the zeolite beta described in the present invention as a bottom-bed hydrocracking catalyst, the 540°C+ fraction in the hydrotreated Arabian light crude oil can be completely converted into a light fraction with a high percentage of paraffin content.

[0011] According to one or more embodiments, the nano-sized mesoporous zeolite particles may include a plurality of micropores having a diameter less than or equal to 2 nm and a microporous framework of the BEA framework type. The nano-sized mesoporous zeolite particles may also include a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. The particle size of the nano-sized mesoporous zeolite particles may be less than or equal to 100 nm.

[0012] According to another embodiment, nanometer-sized mesoporous zeolite particles can be synthesized by a method that can include combining a first mixture with one or more of an alkali or hexadecyltrimethylammonium bromide to form a second mixture. The first mixture can include one or more nanometer-sized zeolite particles with a particle size less than or equal to 100nm. The method can further include heating the second mixture to a high temperature for a heating time to form mesopores in the nanometer-sized zeolite particles. In some embodiments, the method can further include forming the first mixture by a method including: combining at least one quaternary ammonium salt, a silica source material, an alumina source material, and water to form a precursor mixture, and high-pressure treating the precursor mixture to form nanometer-sized zeolite particles consisting of the first mixture.

[0013] According to another embodiment, the catalyst may include one or more nanometer-sized mesoporous zeolite particles, a metal oxide support material, and one or more metal catalyst materials. Each of the nanometer-sized mesoporous zeolite particles may include a microporous framework including a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type. Each of the nanometer-sized mesoporous zeolite particles may also include a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. The particle size of the nanometer-sized mesoporous zeolite particles may be less than or equal to 100 nm.

[0014] According to another embodiment, heavy oil can be upgraded by a method that can include the following: reducing the aromatic content in the heavy oil by contacting the heavy oil with a hydrocracking catalyst comprising one or more nano-sized mesoporous zeolite particles. Each nano-sized mesoporous zeolite particle can include a microporous framework including a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type. Each of the nano-sized mesoporous zeolite particles can also include a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. The particle size of the nano-sized mesoporous zeolite particles can be less than or equal to 100 nm.

[0015] According to another embodiment, the hydroprocessing system may include one or more of a hydrodemetallization catalyst, a transition catalyst, or a hydrodenitrogenation catalyst, and may further include a hydrocracking catalyst located downstream of one or more of the hydrodemetallization catalyst, the transition catalyst, or the hydrodenitrogenation catalyst. The hydrocracking catalyst may include nano-sized mesoporous zeolite particles, wherein each nano-sized mesoporous zeolite particle may include a microporous framework including a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type. Each nano-sized mesoporous zeolite particle may also include a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm. The particle size of the nano-sized mesoporous zeolite particles may be less than or equal to 100 nm.

[0016] Additional features and advantages of the techniques described in the present disclosure will be set forth in the detailed description that follows, and in part will be apparent to those skilled in the art based on this description, or will be recognized by practicing the techniques as described in the present disclosure (including the detailed description that follows, the claims, and the accompanying drawings). BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The following detailed description of specific embodiments of the present disclosure may be best understood when read in conjunction with the following drawings, in which like structures are indicated by like figure reference numerals and in which:

[0018] Figure 1 is a comprehensive diagram of a chemical pretreatment system according to one or more embodiments described in the present disclosure, the chemical pretreatment system including a pretreatment reactor including a hydrodemetallization (HDM) catalyst, a transition catalyst, a hydrodesulfurization (HDS) / hydrodenitrogenation (HDN) catalyst, and a hydrocracking catalyst; and

[0019] Figure 2 According to one or more embodiments described in the present disclosure Figure 1 A comprehensive diagram of a chemical treatment system utilized after a chemical pretreatment system, the chemical treatment system including a hydrocracking unit.

[0020] Out of Figure 1 and 2 For purposes of simplified schematic illustration and description, numerous valves, temperature sensors, electronic controllers, etc. that may be employed and are well known to those of ordinary skill in the art of certain chemical processing operations are not included. In addition, accompanying components that are often included in conventional chemical processing operations such as refineries, such as air supplies, catalyst hoppers, and flue gas processors, are not depicted. It should be understood that these components are within the spirit and scope of the disclosed embodiments of the invention. However, operating components such as those described in the present disclosure may be added to the embodiments described in the present disclosure.

[0021] It should be further noted that the arrows in the diagram refer to process streams. However, arrows can equally refer to transmission lines that can be used to transfer process streams between two or more system components. In addition, arrows connected to system components define inlets or outlets in each given system component. The direction of the arrows generally corresponds to the main direction of movement of the material of the material flow contained in the physical transmission line represented by the arrows. In addition, arrows that do not connect two or more system components represent product flows leaving the depicted system or system inlet flows entering the depicted system. The product flow can be further processed in a companion chemical treatment system or can be commercialized as a final product. The system inlet flow can be a material flow transferred from a companion chemical treatment system or can be an untreated feedstock flow.

[0022] Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. Wherever possible, the same figure reference numerals are used throughout the drawings to refer to the same or like parts. DETAILED DESCRIPTION

[0023] Embodiments of zeolites such as BEA framework type zeolites (e.g., zeolite beta) that can be incorporated into hydroprocessing catalysts are generally described in the present disclosure. In some embodiments, the hydroprocessing catalyst can be used to crack aromatics in heavy oils during pretreatment that can be performed before steam cracking or other subsequent processing. The present disclosure also relates to methods for producing the zeolites and the properties and structures of the produced zeolites. According to one or more embodiments, the zeolite composition can contain relatively small particle sizes and can include mesopores. Throughout the present disclosure, the zeolite material can be referred to as "nano-sized mesoporous zeolites". "Zeolite" as used throughout the present disclosure refers to a microporous inorganic material having regular internal crystalline cavities and channels of molecular size. The microporous structure of the zeolite (e.g., 0.3nm to 1nm pore size) can provide a large surface area and a desired size / shape selectivity, which may be beneficial for catalysis. The described mesoporous zeolite may include, for example, aluminosilicates, titanosilicates, or pure silicates. In one or more embodiments, the described zeolite may include micropores (present in the microstructure of the zeolite) and additionally include mesopores. As used throughout this disclosure, micropores refer to pores in the zeolite structure having a diameter less than or equal to 2 nm and greater than or equal to 0.1 nm, and mesopores refer to pores in the zeolite structure having a diameter greater than 2 nm and less than or equal to 50 nm. The zeolites described herein can be characterized as beta (i.e., having an aluminosilicate BEA framework type).

[0024] As used in the present disclosure, "reactor" refers to a container in which one or more chemical reactions can occur between one or more reactants, optionally in the presence of one or more catalysts. For example, a reactor can include a tank or tubular reactor configured to operate as a batch reactor, a continuous stirred tank reactor (CSTR), or a plug flow reactor. Exemplary reactors include packed bed reactors such as fixed bed reactors and fluidized bed reactors. One or more "reaction zones" can be disposed in a reactor. As used in the present disclosure, "reaction zone" refers to an area in a reactor where a specific reaction occurs. For example, a packed bed reactor with multiple catalyst beds can have multiple reaction zones, wherein each reaction zone is defined by the area of ​​each catalyst bed.

[0025] As used in the present disclosure, "separation unit" refers to any separation device that at least partially separates one or more chemical substances that are mixed with each other in a process flow. For example, a separation unit can selectively separate different chemical species from each other to form one or more chemical fractions. Examples of separation units include, but are not limited to, distillation towers, flash tanks, separation tanks, separation pots, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, and the like. It should be understood that the separation method described in the present disclosure may not completely separate all of one chemical substance from all of another chemical component. It should be understood that the separation method described in the present disclosure "at least partially" separates different chemical components from each other, and even if it is not explicitly stated, it should be understood that separation may only include partial separation. One or more chemical components as used in the present disclosure can be "separated" from a process flow to form a new process flow. In general, a process flow can enter a separation unit and be divided or separated into two or more process flows with a desired composition. In addition, in some separation methods, a "light fraction" and a "heavy fraction" can leave a separation unit, wherein in general, the light fraction stream has a lower boiling point than the heavy fraction stream.

[0026] It should be understood that "reaction effluent" generally refers to the stream that leaves a separation unit, reactor or reaction zone after a particular reaction or separation and generally has a different composition than the stream that entered the separation unit, reactor or reaction zone.

[0027] As used in this disclosure, "catalyst" refers to any substance that increases the rate of a specific chemical reaction. The catalysts described in this disclosure can be used to promote various reactions such as, but not limited to, hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, aromatic cracking, or combinations thereof. As used in this disclosure, "cracking" generally refers to a chemical reaction in which a molecule having carbon-carbon bonds is split into more than one molecule by breaking one or more of the carbon-carbon bonds, or a compound including a cyclic portion such as an aromatic is converted into a compound that does not include the cyclic portion or is more saturated than before the reaction.

[0028] It should be understood that when two or more pipelines are Figure 1 and 2 Two or more process streams are "mixed" or "combined" when they intersect in a schematic flow diagram of FIG. Mixing or combining can also include mixing by introducing two streams directly into similar reactors, separation devices, or other system components.

[0029] It should be understood that the reactions performed by the catalysts as described in the present disclosure can remove chemical components, such as only a portion of the chemical components, from the process stream. For example, a hydrodemetallization (HDM) catalyst can remove a portion of one or more metals from the process stream, a hydrodenitrification (HDN) catalyst can remove a portion of the nitrogen present in the process stream, and a hydrodesulfurization (HDS) catalyst can remove a portion of the sulfur present in the process stream. In addition, a hydrocracking catalyst, such as a hydrocracking catalyst having a dearomatization (HDA) function, can reduce the amount of aromatic portions in the process stream by cracking those aromatic portions. It should be understood that throughout the present disclosure, when a particular catalyst is referred to as having a particular function, it is not necessarily functionally limited to the removal or cracking of a particular chemical component or portion. For example, a catalyst identified as a HDN catalyst in the present disclosure may additionally provide a hydrocracking function, an HDA function, an HDS function, or a combination thereof.

[0030] It should be further understood that a material stream can be named based on its component, and the named component of the material stream can be the major component of the material stream (e.g., accounting for 50wt.%, 70wt.%, 90wt.%, 95wt.% or even 95wt.% to 100wt.% of the material stream content).

[0031] According to one or more embodiments, nano-sized mesoporous zeolites can be characterized as mesoporous by having an average pore size of 2nm to 50nm. By comparison, conventional zeolites that can be used for hydrocracking catalysts contain microporous zeolites, which means that their average pore size is less than 2nm, but may not include mesopores. According to one or more embodiments, the average pore size of the nano-sized mesoporous zeolite beta disclosed in the present invention can be 2nm to 25nm, 4nm to 20nm, 5nm to 15nm, 5nm to 10nm or 10nm to 15nm. It should be understood that, unless otherwise stated, the pore size as used throughout this disclosure is related to the average pore size. The average pore size can be determined by nitrogen physical adsorption analysis. In addition, the average pore size can be confirmed by transmission electron microscopy (TEM) characterization.

[0032] In additional embodiments, the pore volume of the nano-sized mesoporous zeolites described herein can be 0.5 mL / g to 1.0 mL / g. For example, the pore volume of the embodiments of nano-sized mesoporous zeolite beta can be 0.5 mL / g to 0.6 mL / g, 0.5 mL / g to 0.7 mL / g, 0.5 mL / g to 0.8 mL / g, 0.5 mL / g to 0.9 mL / g, 0.6 mL / g to 1.0 mL / g, 0.7 mL / g to 1.0 mL / g, 0.8 mL / g to 1.0 mL / g, or 0.9 mL / g to 1.0 mL / g. "Pore volume" as used in the present disclosure refers to the total pore volume measured.

[0033] In additional embodiments, the surface area of ​​the nano-sized mesoporous zeolites described herein may be 500 m 2 / g to 700m 2 / g. For example, the surface area of ​​an embodiment of nano-sized mesoporous zeolite beta may be 500 m 2 / g to 550m 2 / g、500m 2 / g to 600m 2 / g、500m 2 / g to 650m 2 / g, 550m 2 / g to 700m 2 / g、600m 2 / g to 700m 2 / g or 650m 2 / g to 700m 2 / g.

[0034] Without being bound by its theory, it is believed that the relatively large pore size (i.e., mesopore) of the nano-sized mesoporous zeolite and the hydrocracking catalyst comprising the nano-sized mesoporous zeolite described in the present invention allows larger molecules to diffuse inside the zeolite, and it is believed that this situation enhances the reactivity and selectivity of the catalyst. As the pore size increases, the molecules containing aromatics can be more easily diffused into the catalyst, and the aromatic cracking can be increased. For example, in some conventional embodiments, the raw material converted by the hydrotreating catalyst can be vacuum gas oil, light cycle oil from, for example, a fluidized catalytic cracking reactor, or coker gas oil from, for example, a coking unit. The molecular size in these oils is relatively small compared to the molecular size of heavy oils such as crude and atmospheric residues, which can be the raw material of the method and system described in the present invention. Heavy oil generally cannot diffuse inside conventional zeolites to convert on active sites located inside the zeolite. Therefore, zeolites (i.e., mesoporous zeolites) with larger pore sizes can enable larger molecules of heavy oil to overcome diffusion limitations, and can enable the reaction and conversion of larger molecules of heavy oil to be possible.

[0035] In addition to containing mesopores, the particle size of the zeolite described in the present invention can be less than or equal to 100nm (i.e., nano-sized). As described herein, "nano-sized" zeolites or particles refer to zeolites or particles with a particle size less than or equal to 100nm. The nano-sized mesoporous zeolite beta described herein can be shaped as particles that can generally be spherical or irregularly spherical (i.e., non-spherical). In an embodiment, the particles have a "particle size" measured as the maximum distance between two points located on a single zeolite particle. For example, the particle size of a spherical particle is equal to its diameter. In other shapes, the particle size is measured as the distance between the two farthest points of the same particle, where these points may be located on the outer surface of the particle. The particle size of the particles can be 10nm to 100nm, 20nm to 100nm, 30nm to 100nm, 40nm to 100nm, 50nm to 100nm, 60nm to 100nm, 70nm to 100nm, 80nm to 100nm, 90nm to 100nm, 10nm to 80nm, 10nm to 70nm, 10nm to 60nm, 10nm to 50nm, 10nm to 40nm, 10nm to 30nm or 10nm to 20nm. Without being bound by theory, it is believed that the relatively small particle size allows molecules in the heavy oil to more easily enter the active sites on the zeolite. For example, the increased external surface area may be caused by the small particle size, which may increase the catalytic activity.

[0036] It should be understood that a catalyst containing nano-sized mesoporous zeolite particles may also include zeolites that are non-nano-sized (i.e., greater than 100 nm), do not contain mesopores, or both. Thus, it should be understood that "nano-sized mesoporous zeolite particles" refer to zeolites that have a particle size of less than or equal to 100 nm and contain mesopores, and do not include other zeolites that do not have these characteristics. For example, when it is said that the particle size of nano-sized mesoporous zeolite particles is less than or equal to 100 nm, this statement refers only to nano-sized zeolites with a particle size of less than or equal to 100 nm, and does not describe other zeolites that may exist with a particle size greater than 100 nm.

[0037] The nanosized, mesoporous zeolite materials described herein can be produced by a method comprising several manufacturing steps, which may include one or more of the following: forming or otherwise providing nanosized zeolite beta in a colloidal mixture, treating the nanosized zeolite particles with a base, such as an alkaline aqueous solution comprising, for example, NaOH or ammonia, and / or treating the nanosized zeolite particles with cetyltrimethylammonium bromide ("CTAB") to form mesopores, and subsequently isolating the nanosized, mesoporous zeolite beta particles by methods such as washing, drying, calcining, etc.

[0038] In one or more embodiments, the synthesis method for forming nano-sized mesoporous zeolites can start with the step of providing nano-sized zeolite crystalline particles. The nano-sized zeolite crystals can be in a colloidal mixture. The step of providing a colloidal mixture containing nano-sized zeolite particles can include, for example, but not limited to, the process of manufacturing nano-sized zeolite particles in the colloidal mixture or directly obtaining such a colloidal mixture containing nano-sized zeolite particles. It should be understood that a variety of methods can be used to manufacture a colloidal mixture containing nano-sized zeolite particles, and the method for manufacturing a colloidal mixture containing nano-sized zeolite particles is not explicitly described in the present disclosure. As used in the present disclosure, "colloidal mixture" refers to a mixture of at least two materials, wherein the mixture has a subdivided state so that the molecules or multi-molecular particles dispersed in the medium have at least one size between about 1 nanometer and 1 micron (μm).

[0039] According to one or more embodiments for providing a colloidal mixture containing nano-sized zeolite particles, the colloidal mixture containing nano-sized zeolite particles can be produced by mixing at least a quaternary ammonium salt, a silica source material, an alumina source material and water, and high pressure treatment containing at least a quaternary ammonium salt, a silica source material, an alumina source material and water to form nano-sized zeolite crystals in the colloidal mixture. In one embodiment, the quaternary ammonium salt can be tetraethylammonium hydroxide (TEAOH). According to one or more embodiments, the mixture containing at least a quaternary ammonium salt, a silica source material, an alumina source material and water can have a certain molar ratio of these contents, i.e. 1 mole of alumina source material, 15 moles to 40 moles (e.g. 15 moles to 30 moles or 30 moles to 40 moles) of quaternary ammonium salt, 20 moles to 500 moles (e.g. 20 moles to 250 moles or 250 moles to 500 moles) of silica source material and 500 moles to 1000 moles (e.g. 500 moles to 750 moles or 750 moles to 100 moles) of water. According to one embodiment, a mixture containing at least a quaternary ammonium salt, a silica source material, an alumina source material, and water as previously described in the present disclosure may be autoclaved at 100 degrees Celsius (° C.) to 150° C. (e.g., 130° C. to 150° C. or 140° C.) at, for example, 40 revolutions per minute (rpm) to 80 rpm (e.g., 60 rpm) for 1 to 7 days to form nano-sized zeolite crystals. Prior to autoclaving, the mixture containing at least a quaternary ammonium salt, a silica source material, an alumina source material, and water may be aged, for example, by stirring at room temperature for 4 hours. It should be understood that the autoclaving and aging steps described may be modified to some extent, depending on the exact composition of the autoclaved mixture and the desired zeolite crystal structure to be formed.

[0040] In one or more embodiments, a mixture containing nano-sized zeolite crystals is combined with one or more of a base such as an alkaline aqueous solution (e.g., containing NaOH or ammonia) and hexadecyltrimethylammonium bromide to form a second mixture. For example, a base aqueous solution (e.g., NaOH or ammonia in water) can be added to a mixture containing nano-sized zeolite crystals, and then hexadecyltrimethylammonium bromide can be subsequently added. In one or more embodiments, the alkaline aqueous solution concentration can be 0.05M to 2M of the base, and the weight ratio of hexadecyltrimethylammonium bromide to zeolite can be 0.1 to 1.5. This second mixture can then be heated to an elevated temperature for a heating period to form mesopores in the nano-sized zeolite crystals. For example, the elevated temperature can be 100°C to 150°C, and the heating period can be 1 day to 5 days. Then, the nano-sized zeolite crystals can be separated from the other contents of the second mixture to produce pure or nearly pure nano-sized mesoporous zeolite beta particles suitable for making a catalyst. According to one or more embodiments, separation may include solid / liquid separation techniques (e.g., centrifugation, filtration, etc.), followed by washing with water, drying at, for example, 100° C. for a period of several hours, and then calcining by exposure to a temperature of at least 400° C. (e.g., 500° C. to 600° C.) for several hours (e.g., 3 hours to 6 hours).

[0041] According to one or more embodiments described herein, CTAB, alkali, or both may be added directly to the first mixture. Thus, the methods disclosed herein may not separate, wash, dry, and calcine the produced zeolite particles, as is required in some conventional zeolite manufacturing methods. This aspect may reduce synthesis costs. In additional embodiments, the methods disclosed herein may not utilize pH adjusting materials such as acetic acid in the mesopore production step, as is sometimes required in the manufacture of mesopores by conventional techniques.

[0042] According to one or more embodiments, the nano-sized mesoporous zeolite beta disclosed in the present invention can be incorporated into a catalyst. As described in detail later, the catalyst can be used as a hydrocracking catalyst in heavy oil pretreatment. As such, a catalyst comprising nano-sized mesoporous zeolite beta may be referred to herein as a "hydrocracking catalyst". However, it should be understood that although the hydrocracking catalyst is described in the context of pretreatment (e.g., hydroprocessing) of heavy oil, the hydrocracking catalyst described herein may be used for other catalytic reactions for producing other petrochemical products.

[0043] In one or more embodiments, the hydrocracking catalyst may comprise nano-sized mesoporous zeolite particles described herein, one or more metal oxide support materials, and one or more metal catalysts. The hydrocracking catalyst described herein may have a material composition comprising 10 wt.% to 80 wt.% of one or more metal oxide support materials (e.g., alumina), 18 wt.% to 32 wt.% of metal catalyst materials, and 10 wt.% to 60 wt.% of nano-sized mesoporous zeolite particles.

[0044] The metal catalyst material may comprise one or more metals from IUPAC Group 5, 6, 8, 9 or 10 of the periodic table. For example, the hydrocracking catalyst may comprise one or more metals from IUPAC Group 5 or 6 and one or more metals from IUPAC Group 8, 9 or 10 of the periodic table. For example, the hydrocracking catalyst may comprise molybdenum or tungsten from IUPAC Group 6 and nickel or cobalt from IUPAC Group 8, 9 or 10. In one embodiment, the hydrocracking catalyst may comprise tungsten and nickel metal catalysts. In another embodiment, the hydrocracking catalyst may comprise molybdenum and nickel metal catalysts. For example, in one embodiment, the hydrocracking catalyst may comprise 20 wt.% to 26 wt.% tungsten sulfide or oxide, 4 wt.% to 6 wt.% nickel oxide or sulfide, 10 wt.% to 70 wt.% metal oxide support material such as alumina, and 10 wt.% to 60 wt.% nano-sized medium-pore zeolite beta. In another embodiment, the hydrocracking catalyst may comprise 14 wt.% to 16 wt.% molybdenum oxide or sulfide, 4 wt.% to 6 wt.% nickel oxide or sulfide, 20 wt.% to 80 wt.% metal oxide support material such as alumina, and 10 wt.% to 60 wt.% nano-sized medium pore zeolite beta.

[0045] The described hydrocracking catalyst can be manufactured by providing nano-sized mesoporous zeolite particles and impregnating the nano-sized mesoporous zeolite particles with one or more catalytic metals or by blending the mesoporous zeolite with other components. In one embodiment, the mesoporous zeolite, activated alumina (e.g., boehmitealumina) and a binder (e.g., acid peptized alumina) can be mixed. An appropriate amount of water can be added to form a sticky mass that can be extruded using an extruder. The extrudate can be dried at 80°C to 120°C for 4 to 10 hours and then calcined at 500°C to 600°C for 4 to 6 hours. Then, a metal catalyst material such as an oxide or sulfide of Mo, Ni, W or Ni can be added to this alumina support material including the nano-sized mesoporous zeolite. For example, in one embodiment, the support material can be impregnated with one or more metals to form a hydrocracking catalyst. According to the described embodiment, the impregnation of the support material can include contacting the support material with a solution containing one or more metal catalyst precursors. For example, the support material can be immersed in a solution containing one or more metal catalyst precursors, and the impregnation method is sometimes referred to as saturation impregnation. In an embodiment of saturation impregnation, the support can be immersed in a certain amount of solution containing metal catalyst precursors, the amount of which is 2 to 4 times the solution absorbed by the support, and the remaining solution is then removed. According to another embodiment, the impregnation can be performed by initial wetness impregnation, which is sometimes referred to as capillary impregnation or dry impregnation. In an embodiment of initial wetness impregnation, a solution containing a metal catalyst precursor is contacted with the support, wherein the amount of solution is approximately equal to the pore volume of the support, and the capillary action can draw the solution into the pores. After contacting the support material with the solution, the support material can be calcined at a temperature of at least 500°C (e.g., 500°C to 600°C) for a time of at least 3 hours (e.g., 3 hours to 6 hours). For example, calcination can be at a temperature of 500°C for 4 hours. In general, the impregnation process will allow the metal catalyst to attach to the support material (i.e., zeolite and metal oxide support). The metal catalyst precursor may include one or more of Ni, W, Mo, Co, and after impregnation, is present on the catalyst support in the form of a compound comprising Ni, W, Mo, Co, or a combination thereof. When two metal catalysts are required, two or more metal catalyst precursors may be utilized. However, some embodiments may only include one of Ni, W, Mo, or Co. For example, if a W-Ni catalyst is required, the catalyst support material may be composed of nickel nitrate hexahydrate (i.e., Ni(NO3)2·6H2O) and ammonium metatungstate (i.e., (NH4)6H2W 12 O 40) mixture. Although it should be understood that the scope of the present disclosure should not be limited by the selected metal catalyst precursor, other suitable metal catalyst precursors may include cobalt nitrate hexahydrate (Co(NO3)2·6H2O), ammonium heptamolybdate ((NH4)6Mo7O 24 4H2O) or ammonium molybdate ((NH4)2MoO4). After impregnation, the impregnated metal catalyst may be in the form of metal oxides such as WO3, MoO3, NiO, and CoO, and is referred to as "metal catalyst material" in this disclosure. Although these metal catalyst materials may include metal oxides, it should be understood that the metal catalyst material is different from the metal oxide support material of the catalyst, which in some embodiments may be alumina.

[0046] As described herein, nano-sized medium-pore zeolite beta can be used as a hydrocracking catalyst in upgrading heavy oils such as crude oil. The upgrading process can be a pretreatment step before other petrochemical processes, such as a refining operation performed using one or more of, for example, steam cracking, hydrocracking, thermal cracking, or fluid catalytic cracking. In general, the upgrading process can remove one or more of nitrogen, sulfur, and at least a portion of one or more metals from the heavy oil, and can additionally split the aromatic portion of the heavy oil. According to one or more embodiments, the heavy oil can be treated with a hydrodemetallization catalyst (sometimes referred to as a "HDM catalyst" in this disclosure), a transition catalyst, a hydrodenitrogenation catalyst (sometimes referred to as a "HDN" catalyst in this disclosure), and a hydrocracking catalyst. The HDM catalyst, the transition catalyst, the HDN catalyst, and the hydrocracking catalyst can be positioned in series, or contained in a single reactor such as a packed bed reactor having multiple beds, or contained in two or more reactors arranged in series.

[0047] Reference now Figure 1, schematically depicts a pretreatment system including one or more of a HDM reaction zone 106, a transition reaction zone 108, a HDN reaction zone 110, and a hydrocracking reaction zone 120. According to an embodiment of the present disclosure, a heavy oil feed stream 101 may be mixed with a hydrogen stream 104. The hydrogen stream 104 may include unspent hydrogen from a recycled process gas component stream 113, supplemental hydrogen from a hydrogen feed stream 114, or both, to form a pretreatment catalyst input stream 105. In one or more embodiments, the pretreatment catalyst input stream 105 may be heated to a treatment temperature of 350 degrees Celsius (° C.) to 450° C. The pretreatment catalyst input stream 105 may enter and pass through a series of reaction zones, including a HDM reaction zone 106, a transition reaction zone 108, a HDN reaction zone 110, and a hydrocracking reaction zone 120. The HDM reaction zone 106 contains a HDM catalyst, the transition reaction zone 108 contains a transition catalyst, the HDN reaction zone 110 contains a HDN catalyst, and the hydrocracking reaction zone 120 contains a hydrocracking catalyst comprising a nano-sized medium pore zeolite.

[0048] The described systems and methods are applicable to a wide variety of heavy oil feeds (in the heavy oil feed stream 101), including crude oil, vacuum residue, tar sands, asphalt, and vacuum gas oil using a catalytic hydrotreating pretreatment process. For example, when the heavy oil feed is crude oil, its American Petroleum Institute (API) gravity can be greater than or equal to 25 degrees, such as 25 degrees to 50 degrees, 25 degrees to 30 degrees, 30 degrees to 35 degrees, 35 degrees to 40 degrees, 40 degrees to 45 degrees, 45 degrees to 50 degrees, or any combination of these ranges. For example, the heavy oil feed used can be Arab heavy crude oil or Arab light crude oil. For example, typical properties of Arab heavy crude oil are shown in Table 1.

[0049] Table 1 - Arab heavy export raw materials

[0050]

[0051] Still reference Figure 1 , depicts a pretreatment system that is an example of a system in which the nano-sized mesoporous zeolites described herein may be utilized. Figure 1In an embodiment of the present invention, the pretreatment catalyst input stream 105 can be introduced into the pretreatment reactor 130. According to one or more embodiments, the pretreatment reactor 130 can include a plurality of reaction zones (e.g., a HDM reaction zone 106, a transition reaction zone 108, a HDN reaction zone 110, and a hydrocracking reaction zone 120) arranged in series, and each of these reaction zones can include a catalyst bed. In such embodiments, the pretreatment reactor 130 includes a HDM catalyst bed including a HDM catalyst in the HDM reaction zone 106, a transition catalyst bed including a transition catalyst in the transition reaction zone 108, a HDN catalyst bed including a HDN catalyst in the HDN reaction zone 110, and a hydrocracking catalyst bed including a hydrocracking catalyst in the hydrocracking reaction zone 120.

[0052] According to one or more embodiments, a pretreated catalyst input stream 105 comprising heavy oil is introduced into the HDM reaction zone 106 and contacts the HDM catalyst. The contact of the HDM catalyst with the pretreated catalyst input stream 105 can remove at least a portion of the metals present in the pretreated catalyst input stream 105. After contacting with the HDM catalyst, the pretreated catalyst input stream 105 can be converted into a HDM reaction effluent. The HDM reaction effluent can have a reduced metal content compared to the content of the pretreated catalyst input stream 105. For example, the HDM reaction effluent can have at least 70 wt.%, at least 80 wt.%, or even at least 90 wt.% less metal than the pretreated catalyst input stream 105.

[0053] According to one or more embodiments, the weighted average bed temperature of the HDM reaction zone 106 may be 350° C. to 450° C., such as 370° C. to 415° C., and the pressure may be 30 bar to 200 bar, such as 90 bar to 110 bar. The HDM reaction zone 106 contains a HDM catalyst, and the HDM catalyst may fill the entire HDM reaction zone 106.

[0054] The HDM catalyst may comprise one or more metals from the International Union of Pure and Applied Chemistry (IUPAC) Groups 5, 6, or 8-10 of the periodic table. For example, the HDM catalyst may comprise platinum. The HDM catalyst may further comprise a support material, and the metal may be disposed on the support material. In one embodiment, the HDM catalyst may comprise a platinum metal catalyst on an alumina support (sometimes referred to as a "Mo / Al2O3 catalyst"). It should be understood throughout this disclosure that the metals contained in any of the disclosed catalysts may be present in the form of sulfides or oxides or even other compounds.

[0055] In one embodiment, the HDM catalyst may include a metal sulfide on a support material, wherein the metal is selected from the group consisting of IUPAC Groups 5, 6, and 8-10 elements of the periodic table and combinations thereof. The support material may be gamma-alumina or silica / alumina extrudates, spheres, cylinders, beads, pellets, and combinations thereof.

[0056] In one embodiment, the HDM catalyst may comprise a gamma-alumina support having a surface area of ​​100 m 2 / g to 160m 2 / g (e.g. 100m 2 / g to 130m 2 / g or 130m 2 / g to 160m 2 / g). HDM catalysts can be best described as having relatively large pore volumes, e.g., at least 0.8 cm 3 / g (e.g. at least 0.9 cm 3 / g or even at least 1.0cm 3 / g). The pore size of the HDM catalyst can be primarily macroporous (i.e., pore size greater than 50 nm). This can provide a large capacity for capturing metals and optional dopants on the surface of the HDM catalyst. In one embodiment, the dopant can be selected from the group consisting of boron, silicon, halogens, phosphorus, and combinations thereof.

[0057] In one or more embodiments, the HDM catalyst may contain 0.5 wt.% to 12 wt.% molybdenum oxide or sulfide (e.g., 2 wt.% to 10 wt.% or 3 wt.% to 7 wt.% molybdenum oxide or sulfide) and 88 wt.% to 99.5 wt.% alumina (e.g., 90 wt.% to 98 wt.% or 93 wt.% to 97 wt.% alumina).

[0058] Without being bound by theory, in some embodiments, it is believed that during the reaction in HDM reaction zone 106, the porphyrin compounds present in the heavy oil are first hydrogenated to produce intermediates using hydrogen through a catalyst. After this primary hydrogenation, the nickel or vanadium present in the center of the porphyrin molecule is reduced with hydrogen, and then further reduced to the corresponding sulfide with hydrogen sulfide (H2S). The final metal sulfide is deposited on the catalyst, thereby removing the metal sulfide from the original crude oil. Sulfur is also removed from sulfur-containing organic compounds. This is performed by parallel pathways. The rates of these parallel reactions can depend on the sulfur species considered. In general, hydrogen is used to extract sulfur, which is converted into H2S in the process. The remaining sulfur-free hydrocarbon fragments are retained in the liquid hydrocarbon stream.

[0059] The HDM reaction effluent can be transferred from the HDM reaction zone 106 to the transition reaction zone 108 where it contacts the transition catalyst. The contact of the transition catalyst with the HDM reaction effluent can remove at least a portion of the metal present in the HDM reaction effluent stream, and can remove at least a portion of the nitrogen present in the HDM reaction effluent stream. After contacting with the transition catalyst, the HDM reaction effluent is converted into a transition reaction effluent. Compared with the HDM reaction effluent, the transition reaction effluent can have a reduced metal content and nitrogen content. For example, the transition reaction effluent can have a metal content of at least 1wt.%, at least 3wt.%, or even at least 5wt.% less than the HDM reaction effluent. In addition, the transition reaction effluent can have nitrogen of at least 10wt.%, at least 15wt.%, or even at least 20wt.% less than the HDM reaction effluent.

[0060] According to an embodiment, the weighted average bed temperature of the transition reaction zone 108 is about 370° C. to 440° C. The transition reaction zone 108 includes a transition catalyst, and the transition catalyst may fill the entire transition reaction zone 108 .

[0061] In one embodiment, the transition reaction zone 108 is operable to remove an amount of metal components and an amount of sulfur components from the HDM reaction effluent stream.The transition catalyst may comprise an alumina-based support in the form of an extrudate.

[0062] In one embodiment, the transition catalyst comprises a metal from IUPAC Group 6 and a metal from IUPAC Groups 8-10. Example IUPAC Group 6 metals include molybdenum and tungsten. Example IUPAC Group 8-10 metals include nickel and cobalt. For example, the transition catalyst may comprise Mo and Ni on a titanium dioxide support (sometimes referred to as a "Mo-Ni / Al2O3 catalyst"). The transition catalyst may also contain a dopant selected from the group consisting of boron, phosphorus, halogens, silicon, and combinations thereof. The surface area of ​​the transition catalyst may be 140 m 2 / g to 200m 2 / g (e.g. 140m 2 / g to 170m 2 / g or 170m 2 / g to 200m 2 / g). The mesopore volume of the transition catalyst may be 0.5 cm 3 / g to 0.7cm 3 / g (e.g. 0.6cm 3 / g). Transition catalysts can generally contain a mesoporous structure with pore sizes ranging from 12nm to 50nm. These features provide balanced activity in HDM and HDS.

[0063] In one or more embodiments, the transition catalyst may contain 10wt.% to 18wt.% molybdenum oxide or sulfide (e.g., 11wt.% to 17wt.% or 12wt.% to 16wt.% molybdenum oxide or sulfide), 1wt.% to 7wt.% nickel oxide or sulfide (e.g., 2wt.% to 6wt.% or 3wt.% to 5wt.% nickel oxide or sulfide), and 75wt.% to 89wt.% alumina (e.g., 77wt.% to 87wt.% or 79wt.% to 85wt.% alumina).

[0064] The transition reaction effluent can be transferred from the transition reaction zone 108 to the HDN reaction zone 110 where it contacts the HDN catalyst. The contact of the HDN catalyst with the transition reaction effluent can remove at least a portion of the nitrogen present in the transition reaction effluent stream. After contacting with the HDN catalyst, the transition reaction effluent can be converted into the HDN reaction effluent. Compared with the transition reaction effluent, the HDN reaction effluent can have a reduced metal content and nitrogen content. For example, the HDN reaction effluent can have at least 80wt.%, at least 85wt.%, or even at least 90wt.% nitrogen content reduction relative to the transition reaction effluent. In another embodiment, the HDN reaction effluent can have at least 80wt.%, at least 90wt.%, or even at least 95wt.% sulfur content reduction relative to the transition reaction effluent. In another embodiment, the HDN reaction effluent can have at least 25wt.%, at least 30wt.%, or even at least 40wt.% aromatic content reduction relative to the transition reaction effluent.

[0065] According to an embodiment, the weighted average bed temperature of the HDN reaction zone 110 may be 370° C. to 440° C. The HDN reaction zone 110 may include a HDN catalyst, and the HDN catalyst may fill the entire HDN reaction zone 110 .

[0066] In one embodiment, the HDN catalyst may include a metal oxide or sulfide on a support material, wherein the metal is selected from the group consisting of IUPAC Groups 5, 6, and 8-10 of the periodic table and combinations thereof. The support material may include gamma-alumina, mesoporous alumina, silica, or both in the form of extrudates, spheres, cylinders, and pellets.

[0067] According to one or more embodiments, the HDN catalyst may have a surface area of ​​180 m 2 / g to 240m 2 / g (e.g. 180m 2 / g to 210m 2 / g or 210m 2 / g to 240m 2 / g) of gamma alumina-based support. This relatively large surface area of ​​the HDN catalyst can allow for a smaller pore volume (e.g., less than 1.0 cm 3 / g, less than 0.95cm 3 / g or even less than 0.9cm 3 / g). In one embodiment, the HDN catalyst contains at least one metal from IUPAC Group 6 (e.g., molybdenum) and at least one metal from IUPAC Groups 8-10 (e.g., nickel). The HDN catalyst may also include at least one dopant selected from the group consisting of boron, phosphorus, silicon, halogens, and combinations thereof. In one or more embodiments, cobalt may be used to increase the desulfurization of the HDN catalyst. In one or more embodiments, the HDN catalyst has a higher metal loading for the active phase than the HDM catalyst. This increased metal loading may result in increased catalytic activity. In one or more embodiments, the HDN catalyst comprises nickel and molybdenum and has a molar ratio of nickel to molybdenum (Ni / (Ni+Mo)) of 0.1 to 0.3 (e.g., 0.1 to 0.2 or 0.2 to 0.3). In embodiments including cobalt, the molar ratio of (Co+Ni) / Mo may range from 0.25 to 0.85 (e.g., 0.25 to 0.5 or 0.5 to 0.85).

[0068] According to embodiments described herein, a HDN catalyst may be produced by mixing a support material, such as alumina, with a binder, such as acid-peptized alumina. Water or another solvent may be added to the mixture of the support material and the binder to form an extrudable phase, which is then extruded into a desired shape. The extrudate may be dried at an elevated temperature (e.g., greater than 100° C., such as 110° C.), and then calcined at a suitable temperature (e.g., at a temperature of at least 400° C., at least 500° C., such as 550° C.). The calcined extrudate may be impregnated with an aqueous solution containing a catalyst precursor material, such as a precursor material including Mo, Ni, or a combination thereof. For example, the aqueous solution may contain ammonium heptamolybdate, nickel nitrate, and phosphoric acid to form a HDN catalyst containing compounds comprising molybdenum, nickel, and phosphorus.

[0069] According to one or more embodiments, the HDN catalyst may contain 10 wt.% to 18 wt.% molybdenum oxide or sulfide (e.g., 13 wt.% to 17 wt.% or 14 wt.% to 16 wt.% molybdenum oxide or sulfide), 2 wt.% to 8 wt.% nickel oxide or sulfide (e.g., 3 wt.% to 7 wt.% or 4 wt.% to 6 wt.% nickel oxide or sulfide), and 74 wt.% to 88 wt.% alumina (e.g., 76 wt.% to 84 wt.% or 78 wt.% to 82 wt.% alumina).

[0070] In a similar manner to the HDM catalyst and again without intending to be bound by any theory, it is believed that hydrodenitrogenation and hydrodearomatization can work through related reaction mechanisms. Both involve a certain degree of hydrogenation. For hydrodenitrogenation, the organic nitrogen compound is generally in the form of a heterocyclic structure with the heteroatom being nitrogen. These heterocyclic structures may be saturated before the nitrogen heteroatom is removed. Similarly, hydrodearomatization involves aromatic ring saturation. Each of these reactions can occur to different amounts on each of the catalyst types because the catalyst selectively favors one type of transfer over other catalysts and because the transfer is competitive.

[0071] Still reference Figure 1 , the HDN reaction effluent can be transferred from the HDN reaction zone 110 to the hydrocracking reaction zone 120 where it contacts the hydrocracking catalyst described above. Contact of the hydrocracking catalyst with the HDN reaction effluent can reduce the content of aromatics present in the HDN reaction effluent. After contacting with the hydrocracking catalyst, the HDN reaction effluent is converted into a pretreated catalyst reaction effluent stream 109. The pretreated catalyst reaction effluent stream 109 can have a reduced aromatic content compared to the HDN reaction effluent. For example, the pretreated catalyst reaction effluent stream 109 can have at least 50 wt.%, at least 60 wt.%, or even at least 80 wt.% less aromatic content than the HDN reaction effluent.

[0072] According to one or more embodiments described, the volume ratio of HDM catalyst: transition catalyst: HDN catalyst: hydrocracking catalyst can be 5-20:5-30:30-70:5-30 (e.g., 5-15:5-15:50-60:15-20 or about 10:10:60:20). The ratio of the catalysts can depend at least in part on the metal content in the processed oil feedstock.

[0073] Still reference Figure 1, the pretreatment catalyst reaction effluent stream 109 can enter the separation unit 112 and can be separated into a recycled process gas component stream 113 and an intermediate liquid product stream 115. In one embodiment, the pretreatment catalyst reaction effluent stream 109 can also be purified to remove hydrogen sulfide and other process gases to increase the purity of the hydrogen to be recycled in the recycled process gas component stream 113. The hydrogen consumed in the process can be compensated by adding fresh hydrogen from the hydrogen feed stream 114, which can be derived from a steam or naphtha reformer or other source. The recycled process gas component stream 113 and the fresh make-up hydrogen feed stream 114 can be combined to form the hydrogen gas stream 104. In one embodiment, the intermediate liquid product stream 115 from the process can be flashed in a flash vessel 116 to separate a light hydrocarbon fraction stream 117 and a pretreatment final liquid product stream 118; however, it should be understood that this flashing step is optional. In one embodiment, light hydrocarbon fraction stream 117 acts as a recycle and is mixed with fresh light hydrocarbon dilution stream 102 to produce light hydrocarbon dilution stream 103. Fresh light hydrocarbon dilution stream 102 can be used to provide supplemental dilution to the process as needed to help further reduce deactivation of one or more of the catalysts in pretreatment reactor 130.

[0074] In one or more embodiments, one or more of the pretreated catalyst reaction effluent stream 109, the intermediate liquid product stream 115, and the pretreated final liquid product stream 118 can have a reduced aromatics content compared to the heavy oil feed stream 101. Additionally, in embodiments, one or more of the pretreated catalyst reaction effluent stream 109, the intermediate liquid product stream 115, and the pretreated final liquid product stream 118 can have greatly reduced sulfur, metals, asphaltenes, Conradson carbon, nitrogen content, or a combination thereof, as well as increased API and increased naphtha, middle and vacuum distillate yields compared to the heavy oil feed stream 101.

[0075] According to one or more embodiments, the pretreated catalyst reaction effluent stream 109 may have at least an 80 wt.% nitrogen reduction, at least a 90 wt.% nitrogen reduction, or even at least a 95 wt.% nitrogen reduction relative to the heavy oil feed stream 101. According to another embodiment, the pretreated catalyst reaction effluent stream 109 may have at least an 85 wt.% sulfur reduction, at least a 90 wt.% sulfur reduction, or even at least a 99 wt.% sulfur reduction relative to the heavy oil feed stream 101. According to another embodiment, the pretreated catalyst reaction effluent stream 109 may have at least a 70 wt.% aromatic content reduction, at least an 80 wt.% aromatic content reduction, or even at least an 85 wt.% aromatic content reduction relative to the heavy oil feed stream 101. According to another embodiment, the pretreated catalyst reaction effluent stream 109 may have at least an 80 wt.% metal reduction, at least a 90 wt.% metal reduction, or even at least a 99 wt.% metal reduction relative to the heavy oil feed stream 101.

[0076] Still reference Figure 1 In various embodiments, one or more of the pretreated catalyst reaction effluent stream 109, the intermediate liquid product stream 115, and the pretreated final liquid product stream 118 may be suitable for use as, for example, Figure 2 , as described later in this disclosure. As used in this disclosure, one or more of the pretreated catalyst reaction effluent stream 109, the intermediate liquid product stream 115, and the pretreated final liquid product stream 118 may be referred to as "upgraded fuel," as described in reference to Figure 2 As described, it can be processed downstream by refining.

[0077] Reference now Figure 2, depicting a steam cracking and separation system. The upgraded fuel stream 203 may be passed to a steam cracker unit 248. The steam cracker unit 248 may include a convection zone 250 and a cracking zone 251. The lower boiling fuel grade split stream 203 may be passed to the convection zone 250 along with steam 205. In the convection zone 250, the upgraded fuel stream 203 may be preheated to a desired temperature of, for example, 400° C. to 650° C. The contents of the upgraded fuel stream 203 present in the convection zone 250 may then be passed to the cracking zone 251 where steam cracking is performed. The steam cracking effluent stream 207 may leave the steam cracker unit 248 and pass through a heat exchanger 208 where a treatment fluid 209, such as water or cracked fuel oil, cools the steam cracking effluent stream 207 to form a cooled steam cracking effluent stream 210. The steam cracking effluent stream 207 and the cooled steam cracking effluent stream 210 may include a mixture of cracked hydrocarbon materials that may be separated into one or more petrochemical products included in one or more system product streams. For example, the steam cracking effluent stream 207 and the cooled steam cracking effluent stream 210 may include one or more of fuel oil, gasoline, mixed butenes, butadiene, propylene, ethylene, methane, and hydrogen, each of which may be further mixed with water from steam cracking.

[0078] According to one or more embodiments, the cracking zone 251 may operate at a temperature of 700° C. to 900° C. The cracking zone 251 may operate with a residence time of 0.05 seconds to 2 seconds. The mass ratio of steam 205 to upgraded fuel stream 203 may be 0.3:1 to 2:1.

[0079] The cooled steam cracking effluent stream 210 may be separated into system product streams by a separation unit 211. For example, the separation unit 211 may be a distillation column that separates the contents of the cooled steam cracking effluent stream 210 into one or more of a fuel oil stream 212, a gasoline stream 213, a mixed butene stream 214, a butadiene stream 215, a propylene stream 216, an ethylene stream 217, a methane stream 218, and a hydrogen stream 219. As used in the present disclosure, system product streams (e.g., the fuel oil stream 212, the gasoline stream 213, the mixed butene stream 214, the butadiene stream 215, the propylene stream 216, the ethylene stream 217, and the methane stream 218) may be referred to as system products and are sometimes used as feeds in subsequent chemical processing.

[0080] According to one or more embodiments, at least 5 wt.%, 10 wt.%, or even 15 wt.% of the upgraded fuel stream 203 may have a boiling point of 540°C or higher. In conventional systems, such as conventional systems that do not include a hydrocracking catalyst comprising the nano-sized, medium-pore zeolite beta described herein, it may be necessary to remove the nano-sized, medium-pore zeolite beta from the upgraded fuel stream 203 due to excessive coke formation and non-stationary steam cracking operation. Figure 2 The steam cracking process depicted in the present invention discharges this 540°C+ fraction. However, in the case of using the hydrocracking catalyst described in the present invention comprising the nano-sized mesoporous zeolite beta described in the present invention, this 540°C+ fraction can be reduced by wt.% in the upgraded fuel stream 203. Since the 540°C+ fraction is reduced, the steam cracking efficiency is higher. Without being bound by theory, it is believed that the relatively small particle size and the presence of mesopores in the zeolite beta described in the present invention and included in the hydrocracking catalyst can facilitate better conversion (e.g., aromatic reduction) of the 540°C+ fraction in the heavy oil feed stream 101, because these relatively large molecules (e.g., 540°C+ residues) can enter the active site and thus be converted into light fractions, which are more easily converted by steam cracking, thereby producing more light olefins.

[0081] Examples

[0082] Various embodiments of methods for producing nano-sized, mesoporous zeolite beta are further illustrated by the following examples. The examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0083] Example 1 - Synthesis of nano-sized mesoporous zeolite beta disclosed in the present invention

[0084] In order to form nano-sized zeolite β, fumed silica ( 200, available from Evonic Industries), aluminum powder and tetraethylammonium hydroxide (TEAOH) (35wt.% aqueous solution, available from Aldrich) as silica source, aluminum source and template. The precursor gel has an oxide molar combination ratio of 15-40TEAOH:20-500SiO2:Al2O3:500-1000H2O. The metallic aluminum is dissolved in a portion of the TEAOH aqueous solution to form a clear solution, and then added to the slurry made of fumed silica and another portion of the TEAOH aqueous solution. The formed aluminosilicate fluid gel is stirred in a beaker at ambient temperature for 4 hours, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene (PTFE). Crystallization is performed at 100°C to 150°C for 1-7 hours in an oven at a static state or in a rotary oven at 60 rpm in a rotating state.

[0085] Next, the resulting nano-sized zeolite beta is treated with an aqueous alkali solution (NaOH or ammonia) by combining the nano-sized zeolite beta with a 0.05-2M NaOH or ammonia solution at room temperature under stirring for 4 to 24 hours. Then, cetyltrimethylammonium bromide is added to the mixture, wherein the weight ratio of cetyltrimethylammonium bromide to zeolite is 0.1 to 1.5, and the mixture is stirred at room temperature for 4 to 24 hours. Next, this mixture is subjected to high pressure treatment at 100° C. to 150° C. for 1 to 5 days to form mesopores in the nano-sized zeolite beta. Then, the mixture is separated and washed three times with purified water, and then dried at 100° C. overnight, followed by calcination at 500° C. to 600° C. for 3-6 hours.

[0086] Example 2 - Characterization of the Nanosized Mesoporous Zeolite Beta Disclosed in the Present Invention

[0087] The effects of synthesis conditions on the main properties of nanosized zeolite beta and nanosized mesoporous zeolite beta were synthesized as described in Example 1 and studied in the laboratory. The main properties of nanosized zeolite and nanosized mesoporous zeolite beta were characterized by BET, XRD, TEM, NMR, etc., and the results are summarized in Tables 2A, 2B and 3, respectively.

[0088] Table 2A

[0089] Sample No. 1 2 3 4 Synthesis conditions Static Spin at 60 rpm Static Spin at 60 rpm Starting gel composition <![CDATA[Molar ratio of SiO2 / Al2O3]]> 41.6 50 50 50 TEAOH / Si molar ratio 0.2 0.6 0.2 0.4 <![CDATA[H2O / Al2O3 molar ratio]]> 800 1000 700 1000 Synthesis conditions Temperature, °C 140 140 140 140 Time, day 6 6 8 8 Main properties of the product XRD β β β β According to the average particle size of TEM, nm 450 35 550 120

[0090] Table 2B

[0091]

[0092] Table 3

[0093] Sample No. 9 10 11 12 13 Starting nano zeolite sample number 1 5 2 4 7 Composition of initial gel of nano-mesoporous zeolite SDA / zeolite weight ratio 1 1 1 1 1 <![CDATA[H2O / Zeolite weight ratio]]> 30 30 30 30 30 NaOH / zeolite weight ratio 0.1 0.1 0.05 0.05 0.1 NaOH, concentration (M) 0.1 0.1 0.05 0.05 0.1 Processing conditions in autoclave Temperature, °C 120 120 120 120 120 Time, day 7 7 7 7 7 The main properties of the final product According to the particle size of TEM, nm 470 70 43 100 25 XRD Zeolite Zeolite Zeolite Zeolite Zeolite <![CDATA[Surface area (m 2 / g)]]> 430 510 500 580 510 Pore ​​volume (ml / g) 0.4 0.92 0.53 0.9 0.95 Pore ​​size (nm) 3.7 7.2 4.2 6.2 7.5

[0094] It should be noted that one or more of the appended claims utilize the term "wherein" as a transitional phrase. For purposes of defining the present inventive technology, it should be noted that this term is introduced in the claims as an open transitional phrase that is used to introduce a recitation of a series of features of a structure and should be interpreted in the same manner as the more commonly used open introductory term "comprising."

[0095] It will be understood that any two quantitative values ​​assigned to a property may form a range for that property, and that all combinations of ranges formed by all specified quantitative values ​​for a given property are contemplated herein.

[0096] It should be apparent to those skilled in the art that various modifications may be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Therefore, it is intended that this specification covers modifications and changes to the various described embodiments, provided that the modifications and changes are within the scope of the appended claims and their equivalents.

[0097] The subject matter described herein may include one or more aspects, which should not be considered as limiting the teachings of the present disclosure. A first aspect may include nanometer-sized mesoporous zeolite particles, comprising: a microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nanometer-sized mesoporous zeolite particles is less than or equal to 100 nm.

[0098] A second aspect may include a method for synthesizing nanosized mesoporous zeolite particles, the method comprising: combining a first mixture with one or more of a base or hexadecyltrimethylammonium bromide to form a second mixture, wherein the first mixture comprises one or more nanosized zeolite particles having a particle size less than or equal to 100 nm; and heating the second mixture to an elevated temperature for a heating time to form mesopores in the nanosized zeolite particles.

[0099] The third aspect may include a catalyst comprising: one or more nanosized mesoporous zeolite particles, each of which comprises: a plurality of micropores having a diameter less than or equal to 2 nm and a microporous framework of the BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nanosized mesoporous zeolite particles is less than or equal to 100 nm; a metal oxide support material; and one or more metal catalyst materials.

[0100] A fourth aspect may include a method for upgrading heavy oil, the method comprising: reducing the aromatics content in the heavy oil by contacting the heavy oil with a hydrocracking catalyst comprising one or more nanosized mesoporous zeolite particles, wherein each of the one or more nanosized mesoporous zeolite particles comprises: a microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nanosized mesoporous zeolite particles is less than or equal to 100 nm.

[0101] The fifth aspect may include a hydroprocessing system comprising: one or more of a hydrodemetallization catalyst, a transition catalyst, or a hydrodenitrogenation catalyst; and a hydrocracking catalyst located downstream of one or more of the hydrodemetallization catalyst, the transition catalyst, or the hydrodenitrogenation catalyst, the hydrocracking catalyst comprising nanosized mesoporous zeolite particles, wherein each nanosized mesoporous zeolite particle comprises: a microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nanosized mesoporous zeolite particles is less than or equal to 100 nm.

[0102] Another aspect includes any of the preceding aspects, wherein the nano-sized mesoporous zeolite particles have a pore volume of 0.5 mL / g to 1.0 mL / g.

[0103] Another aspect includes any of the preceding aspects, wherein the surface area of ​​the nano-sized mesoporous zeolite particles is 500 m 2 / g to 700m 2 / g.

[0104] Another aspect includes any of the preceding aspects, wherein the nano-sized mesoporous zeolite particles have an average pore size of 5 nm to 15 nm.

[0105] Another aspect includes any of the preceding aspects, further comprising forming a first mixture by a method comprising: combining at least a quaternary ammonium salt, a silica source material, an alumina source material, and water to form a precursor mixture; and high pressure treating the precursor mixture to form nano-sized zeolite particles comprised of the first mixture.

[0106] Another aspect includes any of the preceding aspects, wherein the first mixture is in a colloidal mixture.

[0107] Another aspect includes any of the preceding aspects, further comprising separating the nano-sized zeolite particles from other contents of the second mixture.

[0108] Another aspect includes any of the preceding aspects, wherein separating comprises one or more of washing, drying, or calcining the nano-sized zeolite particles.

[0109] Another aspect includes any of the preceding aspects, wherein the elevated temperature is 100° C. to 150° C., and the heating period is 1 day to 5 days.

[0110] Another aspect includes any of the preceding aspects, wherein the base comprises an aqueous solution comprising one or more of NaOH or ammonia.

[0111] Another aspect includes any of the preceding aspects, wherein cetyltrimethylammonium bromide is combined with the first mixture after combining the base with the first mixture.

[0112] Another aspect includes any of the preceding aspects, wherein the nanosized zeolite particles comprising mesopores comprise: a microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm.

[0113] Another aspect includes any of the preceding aspects, wherein the metal oxide support material comprises alumina.

[0114] Another aspect includes any of the preceding aspects, wherein one or more of the metal catalyst materials comprises an oxide or sulfide of W, Mo, Ni, or Co.

[0115] Another aspect includes any of the preceding aspects, wherein the catalyst comprises an oxide or sulfide of W and an oxide or sulfide of Ni.

[0116] Another aspect includes any of the preceding aspects, wherein the catalyst comprises an oxide or sulfide of Mo and an oxide or sulfide of Ni.

[0117] Another aspect includes any of the preceding aspects, wherein the catalyst comprises: 20 wt.% to 26 wt.% W oxide or sulfide; 4 wt.% to 6 wt.% Ni oxide or sulfide; 10 wt.% to 60 wt.% nano-sized mesoporous zeolite particles; and 10 wt.% to 70 wt.% alumina.

[0118] Another aspect includes any of the preceding aspects, wherein the catalyst comprises: 14 wt.% to 16 wt.% Mo oxide or sulfide; 4 wt.% to 6 wt.% Ni oxide or sulfide; 10 wt.% to 60 wt.% nano-sized mesoporous zeolite particles; and 20 wt.% to 80 wt.% alumina.

[0119] Another aspect includes any of the preceding aspects, further comprising removing at least a portion of one or more of metals, nitrogen, or sulfur from the heavy oil by contacting the heavy oil with one or more additional hydroprocessing catalysts.

[0120] Another aspect includes any of the preceding aspects, wherein the one or more additional hydroprocessing catalysts comprise one or more of a hydrodemetallization catalyst comprising molybdenum, a transition catalyst comprising molybdenum and nickel, or a hydrodenitrogenation catalyst comprising molybdenum and nickel.

[0121] Another aspect includes any of the preceding aspects, wherein the heavy oil comprises crude oil.

[0122] Another aspect includes any of the preceding aspects, wherein the heavy oil has an American Petroleum Institute (API) gravity of at least 25 degrees.

[0123] Another aspect includes any of the preceding aspects, wherein the hydroprocessing system comprises a hydrodemetallization catalyst, a transition catalyst, and a hydrodenitrogenation catalyst.

[0124] Another aspect includes any of the preceding aspects, wherein the hydrodemetallization catalyst, transition catalyst, hydrodenitrogenation catalyst are in a packed bed reactor.

[0125] Another aspect includes any of the preceding aspects, wherein the hydrocracking catalyst is in a packed bed reactor.

[0126] Another aspect includes any of the preceding aspects, wherein the hydrocracking catalyst further comprises a metal oxide support material and one or more metal catalyst materials.

[0127] The subject matter of the present disclosure has been described in detail and with reference to specific embodiments of the present disclosure, it should be noted that even in the case where specific elements are illustrated in each of the drawings accompanying the description of the present invention, the various details disclosed herein should not be considered to imply that these details relate to elements that are essential components of the various embodiments described herein. In fact, the claims attached hereto should be considered as a separate representation of the breadth of the present disclosure and the corresponding scope of the various embodiments described herein. In addition, it is apparent that modifications and changes are possible without departing from the scope of the attached claims.

Claims

1. A nano-sized mesoporous zeolite particle comprising: A microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nano-sized mesoporous zeolite particles is between 10 nm and 100 nm; and the particle size is measured as the distance between the two farthest points on the outer surface of the particles; wherein the average pore size of the nano-sized mesoporous zeolite particles is 5 nm to 15 nm; and and The nano-sized mesoporous zeolite particles are synthesized by a method for synthesizing nano-sized mesoporous zeolite particles comprising the following steps: combining the first mixture with a base, which is then combined with cetyltrimethylammonium bromide to form a second mixture, wherein: The first mixture comprises one or more nano-sized zeolite particles having a particle size of 10 nm to 100 nm, and the particle size is measured as the distance between two farthest points of the outer surface of the particle; the base comprises NaOH or ammonia; and the second mixture has a base concentration of 0.05 M to 2 M; and The second mixture is autoclaved at a temperature of 100° C. to 150° C. for a heating period to form mesopores in the nano-sized zeolite particles.

2. The nano-sized mesoporous zeolite particles according to claim 1, wherein the nano-sized mesoporous zeolite particles have a pore volume of 0.5 mL / g to 1.0 mL / g or 500 m 2 / g to 700m 2 / g of surface area or a combination thereof.

3. A method for synthesizing nano-sized mesoporous zeolite particles, wherein the nano-sized mesoporous zeolite particles comprise: A microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nano-sized mesoporous zeolite particles is between 10 nm and 100 nm; and the particle size is measured as the distance between the two farthest points on the outer surface of the particles; wherein the average pore size of the nano-sized mesoporous zeolite particles is 5 nm to 15 nm; and The method comprises: combining the first mixture with a base, which is then combined with cetyltrimethylammonium bromide to form a second mixture, wherein: The first mixture comprises one or more nano-sized zeolite particles having a particle size of 10 nm to 100 nm, and the particle size is measured as the distance between two farthest points of the outer surface of the particle; the base comprises NaOH or ammonia; and the second mixture has a base concentration of 0.05 M to 2 M; and The second mixture is autoclaved at a temperature of 100° C. to 150° C. for a heating period to form mesopores in the nano-sized zeolite particles.

4. The method of claim 3, further comprising forming the first mixture by a method comprising: combining at least a quaternary ammonium salt, a silica source material, an alumina source material, and water to form a precursor mixture; and The precursor mixture is high pressure treated to form the nano-sized zeolite particles composed of the first mixture.

5. The method of claim 3 or 4, wherein the first mixture is in a colloidal mixture.

6. A catalyst comprising: One or more nanometer-sized mesoporous zeolite particles, each comprising: A microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nano-sized mesoporous zeolite particles is between 10 nm and 100 nm, and the particle size is measured as the distance between the two farthest points on the outer surface of the particles; metal oxide support material; and one or more metal catalyst materials, wherein the average pore size of the nano-sized mesoporous zeolite particles is 5 nm to 15 nm; and The nano-sized mesoporous zeolite particles are synthesized by a method for synthesizing nano-sized mesoporous zeolite particles comprising the following steps: combining the first mixture with a base, which is then combined with cetyltrimethylammonium bromide to form a second mixture, wherein: The first mixture comprises one or more nano-sized zeolite particles having a particle size of 10 nm to 100 nm, and the particle size is measured as the distance between two farthest points of the outer surface of the particle; the base comprises NaOH or ammonia; and the second mixture has a base concentration of 0.05 M to 2 M; and The second mixture is autoclaved at a temperature of 100° C. to 150° C. for a heating period to form mesopores in the nano-sized zeolite particles.

7. The catalyst of claim 6, wherein the metal oxide support material comprises alumina.

8. The catalyst according to claim 6 or 7, wherein one or more of the metal catalyst materials comprises an oxide or sulfide of W, Mo, Ni or Co.

9. A method for upgrading heavy oil, the method comprising: The aromatics content of the heavy oil is reduced by contacting the heavy oil with a hydrocracking catalyst comprising one or more nano-sized mesoporous zeolite particles, each of the one or more nano-sized mesoporous zeolite particles comprising: A microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nano-sized mesoporous zeolite particles is between 10 nm and 100 nm, and the particle size is measured as the distance between the two farthest points on the outer surface of the particles; wherein the average pore size of the nano-sized mesoporous zeolite particles is 5 nm to 15 nm; and The nano-sized mesoporous zeolite particles are synthesized by a method for synthesizing nano-sized mesoporous zeolite particles comprising the following steps: combining the first mixture with a base, which is then combined with cetyltrimethylammonium bromide to form a second mixture, wherein: The first mixture comprises one or more nano-sized zeolite particles having a particle size of 10 nm to 100 nm, and the particle size is measured as the distance between two farthest points of the outer surface of the particle; the base comprises NaOH or ammonia; and the second mixture has a base concentration of 0.05 M to 2 M; and The second mixture is autoclaved at a temperature of 100° C. to 150° C. for a heating period to form mesopores in the nano-sized zeolite particles.

10. The method of claim 9, further comprising removing at least a portion of one or more of metals, nitrogen, or sulfur from the heavy oil by contacting the heavy oil with one or more additional hydroprocessing catalysts.

11. The process of claim 10, wherein the one or more additional hydrotreating catalysts comprise one or more of: a hydrodemetallization catalyst comprising molybdenum, a transition catalyst comprising molybdenum and nickel, or a hydrodenitrogenation catalyst comprising molybdenum and nickel.

12. A hydroprocessing system comprising: one or more of a hydrodemetallization catalyst, a transition catalyst, or a hydrodenitrogenation catalyst; and a hydrocracking catalyst located downstream of one or more of the hydrodemetallization catalyst, the transition catalyst, or the hydrodenitrogenation catalyst, the hydrocracking catalyst comprising nano-sized mesoporous zeolite particles, wherein each nano-sized mesoporous zeolite particle comprises: A microporous framework comprising a plurality of micropores having a diameter less than or equal to 2 nm and a BEA framework type; and a plurality of mesopores having a diameter greater than 2 nm and less than or equal to 50 nm; wherein the particle size of the nano-sized mesoporous zeolite particles is between 10 nm and 100 nm, and the particle size is measured as the distance between the two farthest points on the outer surface of the particles; wherein the average pore size of the nano-sized mesoporous zeolite particles is 5 nm to 15 nm; and The nano-sized mesoporous zeolite particles are synthesized by a method for synthesizing nano-sized mesoporous zeolite particles comprising the following steps: combining the first mixture with a base, which is then combined with cetyltrimethylammonium bromide to form a second mixture, wherein: The first mixture comprises one or more nano-sized zeolite particles having a particle size of 10 nm to 100 nm, and the particle size is measured as the distance between two farthest points of the outer surface of the particle; the base comprises NaOH or ammonia; and the second mixture has a base concentration of 0.05 M to 2 M; and The second mixture is autoclaved at a temperature of 100° C. to 150° C. for a heating period to form mesopores in the nano-sized zeolite particles.

13. The hydroprocessing system of claim 12, wherein the hydroprocessing system comprises the hydrodemetallization catalyst, the transition catalyst, and the hydrodenitrogenation catalyst.

14. The hydroprocessing system of claim 12 or 13, wherein the hydrodemetallization catalyst, the transition catalyst, and the hydrodenitrogenation catalyst are in a packed bed reactor.

15. The nano-sized mesoporous zeolite particle according to claim 1, wherein the particle size of the nano-sized mesoporous zeolite particle is less than or equal to 75 nm.

16. The method for synthesizing nano-sized mesoporous zeolite particles according to claim 3, wherein the particle size of the nano-sized mesoporous zeolite particles is less than or equal to 75 nm.

17. The catalyst of claim 6, wherein the nano-sized mesoporous zeolite particles have a particle size less than or equal to 75 nm.

18. The method for upgrading heavy oil according to claim 9, wherein the particle size of the nano-sized medium-pore zeolite particles is less than or equal to 75 nm.

19. The hydroprocessing system of claim 12, wherein the nano-sized mesoporous zeolite particles have a particle size less than or equal to 75 nm.

20. The method for synthesizing nano-sized mesoporous zeolite particles according to claim 3, wherein: The first mixture includes water.

21. The catalyst of claim 6, wherein the catalyst comprises: 20 wt.% to 26 wt.% tungsten sulfide or oxide, 4 wt.% to 6 wt.% nickel oxide or sulfide, 10 wt.% to 60 wt.% nano-sized mesoporous zeolite beta, and 10 wt.% to 70 wt.% alumina; or 14 wt.% to 16 wt.% of molybdenum oxide or sulfide, 4 wt.% to 6 wt.% of nickel oxide or sulfide, 10 wt.% to 60 wt.% of nano-sized medium-pore zeolite beta, and 20 wt.% to 80 wt.% of alumina.

22. The process of claim 9, wherein the hydrocracking catalyst comprises: 20 wt.% to 26 wt.% tungsten oxide or sulfide, 4 wt.% to 6 wt.% nickel oxide or sulfide, 10 wt.% to 60 wt.% nano-sized mesoporous zeolite particles, and 10 wt.% to 70 wt.% alumina; or 14 wt.% to 16 wt.% of molybdenum oxide or sulfide, 4 wt.% to 6 wt.% of nickel oxide or sulfide, 10 wt.% to 60 wt.% of nano-sized mesoporous zeolite particles and 20 wt.% to 80 wt.% of alumina.

23. The method of claim 3, wherein the base is NaOH.

24. The method of claim 3, wherein the heating period is 1 day to 5 days.

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