Method for producing mesoporous beta zeolite

Abstract

A method of producing a mesoporous beta zeolite includes mixing a crystalline beta zeolite with one or more solvents, cetyltrimethylammonium bromide, and a metal hydroxide to produce a solution; heating the solution at a temperature of 50 DEG C to 150 DEG C to convert the crystalline beta zeolite to an amorphous material having a reduced silica content relative to the crystalline beta zeolite; cooling the solution to a temperature of 25 DEG C to 40 DEG C; adjusting the pH of the solution from 8 to 10 by adding an acid; and aging the solution at a temperature of 50 DEG C to 150 DEG C for a time sufficient to crystallize the amorphous material to produce beta zeolite particles.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. patent application serial number 17 / 964,155, filed on October 12, 2022, entitled “Method for Producing Mesoporous Beta Zeolite,” the entire contents of which are incorporated by reference into this disclosure. Technical Field

[0003] The present disclosure relates generally to zeolites and, more particularly, to methods of producing zeolites. Background Art

[0004] Ethylene, propylene, butylenes, butadiene, as well as aromatic compounds such as benzene, toluene and xylenes are basic intermediates for most of the petrochemical industry. They are usually obtained by thermal cracking (or steam pyrolysis) of petroleum gas and distillates such as naphtha, kerosene or even gas oil. These compounds are also produced by the refinery fluid catalytic cracking (FCC) process, in which classic heavy feedstocks such as gas oil or residual oil are converted. Typical FCC feedstocks range from hydrocracking bottoms to heavy feedstock fractions such as vacuum gas oil and atmospheric residue; however, these feedstocks are limited. Currently, the second most important source of propylene production is refinery propylene from FCC units. With the continuous growth in demand, FCC unit owners are increasingly looking to the petrochemical market to increase their revenues by taking advantage of the economic opportunities that arise in the propylene market.

[0005] The increasing global demand for light olefins remains a major challenge for many integrated refineries. In particular, the production of some valuable light olefins such as ethylene, propylene and butenes has attracted increasing attention as pure olefin streams are considered as building blocks for polymer synthesis. The production of light olefins depends on several process variables such as feed type, operating conditions and catalyst type.

[0006] Despite the availability of options for producing higher yields of propylene and other light olefins, intensive research activities are ongoing in this area. These options include developing more selective catalysts for the process and enhancing the process configuration to obtain more favorable reaction conditions and yields. In particular, zeolites are of great significance in industrial catalysis in petrochemical and chemical conversion processes due to their excellent stability, strong acidity and regular pore size. Summary of the invention

[0007] Therefore, there is a continuing need for methods for producing mesoporous beta zeolites suitable for chemical treatment. As described herein, embodiments of the present disclosure meet this need by producing mesoporous beta zeolites. The method now described produces mesoporous beta zeolites by a method comprising the steps of mixing crystalline beta zeolite with one or more solvents, hexadecyltrimethylammonium bromide (CTAB) and a metal hydroxide to produce a solution, and adjusting the pH of the solution from 8 to 10 by adding an acid. In some embodiments, the mesoporous beta zeolite produced by the method now described may have mesopores and micropores; and the mesopores and micropores may be more uniform compared to conventional mesoporous beta zeolites. This mesoporous beta zeolite prepared by the method disclosed herein can be particularly useful in steam enhanced catalytic cracking systems and can directly convert crude oil into light olefins, and the yield of light olefins (such as at least one of ethylene, propylene and butene) is increased. The mesoporous beta zeolite prepared by the method disclosed herein can withstand high hydrothermal conditions while retaining its activity and selectivity.

[0008] According to one or more aspects of the present disclosure, a method for producing mesoporous β zeolite may include: mixing crystalline β zeolite with one or more solvents, cetyltrimethylammonium bromide (CTAB), and a metal hydroxide to produce a solution; heating the solution at a temperature of 50°C to 150°C to convert the crystalline β zeolite into a non-crystalline material having a reduced silica content relative to the crystalline β zeolite; cooling the solution to a temperature of 25°C to 40°C; adjusting the pH of the solution from 8 to 10 by adding an acid; and aging the solution at a temperature of 50°C to 150°C for a period of time sufficient to crystallize the non-crystalline material to produce β zeolite particles.

[0009] Additional features and advantages of the technology described in this disclosure will be described in subsequent specific embodiments, and for those skilled in the art, some of the additional features and advantages will be apparent from the description or will be recognized by practicing the technology described in this disclosure (including the following specific embodiments, claims and drawings).

[0010] BRIEF DESCRIPTION OF THE DRAWINGS

[0011] 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 represented by like reference numerals and in which:

[0012] Figure 1 depicts a flow chart of a method of producing mesoporous beta zeolite according to one or more embodiments shown and described in the present disclosure;

[0013] Figure 2 is a general schematic diagram of a fixed bed reaction system according to one or more embodiments described in the present disclosure; and

[0014] Figure 3 The yield analysis for Example 4 is depicted.

[0015] To describe Figure 2 The simplified schematic diagram and description do not include many valves, temperature sensors, electronic controllers, etc. that are available and well known to those of ordinary skill in the art of certain chemical processing operations. In addition, accompanying components that are typically included in chemical processing operations, such as gas sources, heat exchangers, buffer tanks, catalyst hoppers, or other related systems, are not depicted. It should be understood that these components are within the spirit and scope of the disclosed embodiments. However, operating components such as those described in the present disclosure can be added to the embodiments described in the present disclosure.

[0016] It should also be noted that the arrows in the accompanying drawings refer to process streams. However, arrows can equally refer to a transmission line that can be used to transmit process steam between two or more system components. In addition, the arrows connected to the system components define the inlet or outlet in each given system component. The direction of the arrows generally corresponds to the main direction of movement of the material contained in the physical transmission line represented by the arrow. In addition, the arrows that do not connect two or more system components represent the product stream of the system leaving the depicted system or the system feed stream entering the depicted system. The product stream can be further processed in the accompanying chemical treatment system, or it can be commercialized as a final product. The system feed stream can be a stream transferred from the accompanying chemical treatment system, or it can be an untreated raw material stream. Some arrows can represent a recycle stream, which is an outflow stream of the system components that is recycled back to the system. However, it should be understood that in some embodiments, any recycle stream represented can be replaced by a system feed stream of the same material, and a part of the recycle stream can leave the system as a system product.

[0017] In addition, arrows in the figures may schematically depict process steps that convey streams from one system component to another system component. For example, an arrow pointing from one system component to another system component may represent "transferring" a system component effluent to another system component, which may include "leaving" or "removing" the contents of a process stream from one system component, and "introducing" the contents of that product stream to another system component.

[0018] It should be understood that when two or more lines are Figure 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 the two streams directly into a similar reactor, separation device, or other system component. For example, it should be understood that when two streams are depicted as being combined directly before entering a separator or reactor, in some embodiments, the streams may be equivalent to being introduced into a separator or reactor and mixed in the reactor.

[0019] Reference will now be made in more detail to various embodiments of the present disclosure, some of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts. DETAILED DESCRIPTION

[0020] Disclosed herein is a method for forming mesoporous beta zeolite, which in some embodiments can be used in steam enhanced fluid catalytic cracking reactions of hydrocarbons. The method generally may include mixing crystalline beta zeolite with hexadecyltrimethylammonium bromide (CTAB) and a metal hydroxide, converting the crystalline beta zeolite to a non-crystalline material with reduced silica content, cooling the solution, adjusting the pH of the solution, and aging the solution to produce beta zeolite particles. Specific non-limiting embodiments of this method are disclosed herein.

[0021] As used in this disclosure, the term "catalyst" may refer to any substance that increases the rate of a particular chemical reaction.

[0022] As used in this disclosure, the term "cracking" may refer to a chemical reaction in which a molecule having a carbon-carbon bond is broken into more than one molecule by breaking one or more of the carbon-carbon bonds; in which a compound including a cyclic portion, such as an aromatic compound, is converted to a compound that does not include a cyclic portion; or in which a molecule having a carbon-carbon double bond is reduced to a carbon-carbon single bond. Some catalysts may have multiple forms of catalytic activity, and calling a catalyst by one particular function does not render the catalyst inactive for other functions.

[0023] As used in the present disclosure, the term "particle size" of a crystalline beta zeolite or mesoporous beta zeolite may refer to the maximum distance between two points located on the crystalline beta zeolite or mesoporous beta zeolite. For example, the particle size of a spherical particle is 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 can be determined by scanning electron microscopy (SEM).

[0024] As used in this disclosure, the term "crystal size" of crystalline beta zeolite or mesoporous beta zeolite may refer to the length of the coherent scattering domain in a direction orthogonal to the set of lattice planes causing the reflection. The crystal size may be calculated by XRD.

[0025] As used in the present disclosure, the term "pore size" of crystalline beta zeolite or mesoporous beta zeolite may refer to the pore size determined by mercury intrusion porosimetry.

[0026] As used in the present disclosure, the term "microporous" may refer to a material having pores with an average pore size of 0.1 nanometers (nm) to 2 nm, such as beta zeolite.

[0027] As used in the present disclosure, the term "mesoporous" may refer to a material having pores with an average pore diameter of 2 nm to 50 nm, such as beta zeolite.

[0028] As used in this disclosure, the term "crude oil" may refer to a mixture of petroleum liquids and gases, including impurities, such as sulfur-containing compounds, nitrogen-containing compounds, and metallic compounds, which is extracted directly from an underground formation or received from a desalter without separating any fractions, such as naphtha, by distillation.

[0029] As used in this disclosure, the term "reactor" may refer to one or a series of vessels in which one or more chemical reactions may occur between one or more reactants in the presence of one or more catalysts. For example, a reactor may include a tank reactor or a tubular reactor configured as a batch reactor, a continuous stirred tank reactor (CSTR), or a plug flow reactor. Example reactors include packed bed reactors, such as fixed bed reactors and fluidized bed reactors.

[0030]

[0013] Embodiments of the present disclosure are directed to methods of producing mesoporous beta zeolite. Figure 1 Depicted is a flow chart of a method of producing mesoporous beta zeolite according to one or more embodiments shown and described in the present disclosure. Figure 1 The method described herein may also include other steps, and the method described herein should not be understood as being limited to only Figure 1 Steps shown.

[0031] refer to Figure 1 In step 110, the crystalline beta zeolite is mixed with one or more solvents, hexadecyltrimethylammonium bromide (CTAB), and a metal hydroxide to produce a solution. In some embodiments, the mixing step includes mixing the crystalline beta zeolite with the metal hydroxide and then adding the CTAB to the mixture of the crystalline beta zeolite and the metal hydroxide. Without being limited by any particular theory, it is believed that the mixing step can evenly disperse the crystalline beta zeolite, CTAB, and the metal hydroxide. Mixing can include one or more of stirring, swirling, vortexing, shaking, sonication, homogenization, fusion, etc.

[0032] The crystalline beta zeolite may have an average particle size of 0.01 micrometers (μm) to 5.0 μm, 0.01 μm to 3.0 μm, 0.01 μm to 2.0 μm, 0.01 μm to 1.5 μm, or 0.01 μm to 1.4 μm. The particle size may be calculated by XRD. The particles of the crystalline beta zeolite may comprise one or more crystals. The crystals may comprise one or more unit cells.

[0033] The crystalline beta zeolite may have an average crystal size of 0.05 μm to 5.0 μm, 0.05 μm to 3.0 μm, 0.05 μm to 2.0 μm, 0.05 μm to 1.5 μm, 0.05 μm to 1.4 μm, 0.1 μm to 5.0 μm, 0.1 μm to 3.0 μm, 0.1 μm to 2.0 μm, 0.1 μm to 1.5 μm, or 0.1 μm to 1.4 μm. The crystal size may be calculated by XRD.

[0034] The crystalline beta zeolite can have an average pore size of 0.5 nanometers (nm) to 3.0 nm, 0.5 nm to 2.0 nm, 0.5 nm to 1.0 nm, 0.5 nm to 0.75 nm, 0.5 nm to 0.74 nm, 0.56 nm to 3.0 nm, 0.56 nm to 2.0 nm, 0.56 nm to 1.0 nm, 0.56 nm to 0.75 nm, or 0.56 nm to 0.74 nm. The pore size can be determined using mercury intrusion porosimetry.

[0035] The crystalline beta zeolite may have a silicon dioxide (SiO 2 ) and aluminum oxide (Al 2 O 3 The crystalline beta zeolite may have a SiO content of less than or equal to 400. 2 With Al 2 O 3 The crystalline beta zeolite may have a SiO molar ratio of 10 to 400, 10 to 350, 10 to 300, 20 to 400, 20 to 350, 20 to 300, 30 to 400, 30 to 350, 30 to 300, 10 to 70, 20 to 60, 30 to 50, 250 to 400, 280 to 350, or 300 to 320. 2 With Al 2 O 3 molar ratio.

[0036] The metal hydroxide may include a single metal hydroxide species or a combination of two or more metal hydroxide chemical species. In an embodiment, the metal hydroxide includes at least one alkaline metal hydroxide, at least one alkaline earth metal hydroxide, or a combination thereof. The metal hydroxide may include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), Strontium hydroxide (Sr(OH) 2 ), barium hydroxide (Ba(OH) 2 ), or a combination thereof.

[0037] In one or more embodiments, the metal hydroxide can be in solution. The metal hydroxide solution can have a metal hydroxide concentration of 0.01 moles / liter (M) to 10M, such as 0.01M to 5M, 0.01M to 3M, 0.01M to 1M, 0.05M to 1M, 0.05M to 0.8M, 0.05M to 0.5M, or 0.1M to 0.4M.

[0038] Still reference Figure 1 In step 110, the crystalline beta zeolite and the metal hydroxide may be mixed with cetyltrimethylammonium bromide (CTAB). CTAB is a surfactant. In particular, when the solution contains crystalline beta zeolite, metal hydroxide, and CTAB, the CTAB is heated to produce a non-crystalline material, and the CTAB may reduce the silica content of the crystalline beta zeolite. Therefore, the non-crystalline material may have a lower silica content than the crystalline beta zeolite.

[0039] CTAB can be included in the CTAB solution. The CTAB solution can have CTAB greater than or equal to 1wt.%, greater than or equal to 2wt.%, or greater than or equal to 3wt.%. The CTAB solution can have CTAB less than or equal to 10wt.%, less than or equal to 8wt.%, less than or equal to 7wt.%, or less than or equal to 6wt.%. The CTAB solution can have 1wt.% to 10wt.%, 1wt.% to 8wt.%, 1wt.% to 7wt.%, 1wt.% to 6wt.%, 2wt.% to 10wt.%, 2wt.% to 8wt.%, 2wt.% to 7wt.%, 2wt.% to 6wt.%, 3wt.% to 10wt.%, 3wt.% to 8wt.%, 3wt.% to 7wt.%, or 3wt.% to 6wt.% CTAB.

[0040] Still reference Figure 1 In step 120, the solution may be heated at a temperature of 50°C to 150°C to convert the crystalline zeolite beta into a non-crystalline material having a reduced silica content relative to the crystalline zeolite beta. During the heating step, the crystalline zeolite beta may be decomposed. The term "decomposed" may refer to the breaking of siloxane bonds (silicate groups) of the crystalline zeolite beta.

[0041] The solution may be heated at a temperature of 50° C. or more, 60° C. or more, 70° C. or more, or 80° C. or more. The solution may be heated at a temperature of 150° C. or less, 140° C. or less, 130° C. or less, or 120° C. or less. The solution may be heated at a temperature of 50° C. to 150° C., 50° C. to 140° C., 50° C. to 130° C., 50° C. to 120° C., 60° C. to 150° C., 60° C. to 140° C., 60° C. to 130° C., 60° C. to 120° C., 70° C. to 150° C., 70° C. to 140° C., 70° C. to 130° C., 70° C. to 120° C., 80° C. to 150° C., 80° C. to 140° C., 80° C. to 130° C., or 80° C. to 120° C.

[0042] Still reference Figure 1 In step 130, the heated solution may be cooled to a temperature of 25°C to 40°C. The solution may be cooled to a temperature greater than or equal to 0°C, greater than or equal to 10°C, greater than or equal to 20°C, or greater than or equal to 25°C. The solution may be cooled to a temperature less than or equal to 50°C, less than or equal to 45°C, less than or equal to 40°C, or less than or equal to 30°C. The solution may be cooled to a temperature of 0°C to 50°C, 0°C to 45°C, 0°C to 40°C, 0°C to 30°C, 10°C to 50°C, 10°C to 45°C, 10°C to 40°C, 10°C to 30°C, 20°C to 50°C, 20°C to 45°C, 20°C to 40°C, 20°C to 30°C, 25°C to 50°C, 25°C to 45°C, or 25°C to 40°C.

[0043] Still reference Figure 1 In step 140, the pH of the solution may be adjusted from 8 to 10 by adding an acid. In the step of adjusting the pH of the solution, the CTAB already present in the solution adopts a round micelle morphology.

[0044] The acid may include dilute sulfuric acid, nitric acid, acetic acid, citric acid, oxalic acid, or a combination thereof. In some embodiments, the acid may have a normality (N) of 0.1 to 5N, 0.1 to 4N, 0.1 to 3N, 0.5 to 5N, 0.5 to 4N, 0.5 to 3N, 1 to 5N, 1 to 4N, or 1 to 3N.

[0045] In some embodiments, the pH of the solution can be greater than or equal to 13. The pH of the solution can be adjusted to greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9. The pH of the solution can be adjusted to less than or equal to 12, less than or equal to 11, or less than or equal to 10. The pH of the solution can be adjusted to 7 to 12, 7 to 11, 7 to 10, 8 to 12, 8 to 11, 8 to 10, 9 to 12, 9 to 11, or 9 to 10.

[0046] In some embodiments, the method of producing mesoporous beta zeolite of the present disclosure comprises stirring the solution for 10 hours to 48 hours ( Figure 1 The solution can be stirred for a time period of 10 hours to 48 hours, 10 hours to 40 hours, 10 hours to 35 hours, 10 hours to 30 hours, 13 hours to 48 hours, 13 hours to 40 hours, 13 hours to 35 hours, 13 hours to 30 hours, 17 hours to 48 hours, 17 hours to 40 hours, 17 hours to 35 hours, 17 hours to 30 hours, 20 hours to 48 hours, 20 hours to 40 hours, 20 hours to 35 hours or 20 hours to 30 hours.

[0047] Still reference Figure 1 In step 150, the solution can be aged at a temperature of 50°C to 150°C for a period of time sufficient to crystallize the non-crystalline material to produce beta zeolite particles. When the non-crystalline material crystallizes, the silica removed (broken) from the crystalline beta zeolite helps to produce beta zeolite with uniform mesopores and micropores. In particular, a surfactant, CTAB, can act as a structure directing agent. Recrystallization of beta zeolite in the presence of CTAB can prevent dissolution of crystals and almost completely recover the zeolite. After calcination, the surfactant portion can be removed, and the resulting voids constitute the mesopores of the mesoporous zeolite. Since the mesoporous quality covering size, distribution and connectivity helps to improve stability against coke deactivation, it is highly desirable to achieve uniform mesopores. Conventional microporous beta zeolite may inhibit larger molecules from entering the catalytically active sites on the beta zeolite, which may have a molecular size equal to or greater than the average pore size of the microporous beta zeolite. The mesoporous beta zeolite produced by the currently described method can be a hierarchical mesoporous beta zeolite with uniform mesopores and micropores. Through these uniform mesopores and micropores, mesoporous zeolite beta can increase the entry of large molecules, thereby being suitable for hydrocarbon feedstocks including larger hydrocarbon molecules, such as crude oil. In addition, mesoporous zeolite beta may exhibit stability at high temperatures (such as temperatures above 500°C), and the acid sites of mesoporous zeolite beta are compatible with hydrocracking reactions, which helps to decompose hydrocarbon feeds or hydrocarbon fractions into smaller molecules. Therefore, mesoporous zeolite beta can promote the transport of larger hydrocarbon molecules in crude oil to catalytic sites and reduce the diffusion limitations of these catalysts.

[0048] The solution can be aged at a temperature greater than or equal to 50 °C, greater than or equal to 60 °C, greater than or equal to 70 °C, or greater than or equal to 80 °C. The solution can be aged at a temperature less than or equal to 150 °C, less than or equal to 140 °C, less than or equal to 130 °C, or less than or equal to 120 °C. The solution can be aged at a temperature from 50 °C to 150 °C, 50 °C to 140 °C, 50 °C to 130 °C, 50 °C to 120 °C, 60 °C to 150 °C, 60 °C to 140 °C, 60 °C to 130 °C, 60 °C to 120 °C, 70 °C to 150 °C, 70 °C to 140 °C, 70 °C to 130 °C, 70 °C to 120 °C, 80 °C to 150 °C, 80 °C to 140 °C, 80 °C to 130 °C, or 80 °C to 120 °C. The solution can be aged for a period of time greater than or equal to 10 hours, greater than or equal to 13 hours, greater than or equal to 17 hours, or greater than or equal to 20 hours. The solution can be aged for a period of time less than or equal to 48 hours, less than or equal to 40 hours, less than or equal to 35 hours, or less than or equal to 30 hours. The solution can be aged for a period of time from 10 hours to 48 hours, 10 hours to 40 hours, 10 hours to 35 hours, 10 hours to 30 hours, 13 hours to 48 hours, 13 hours to 40 hours, 13 hours to 35 hours, 13 hours to 30 hours, 17 hours to 48 hours, 17 hours to 40 hours, 17 hours to 35 hours, 17 hours to 30 hours, 20 hours to 48 hours, 20 hours to 40 hours, 20 hours to 35 hours, or 20 hours to 30 hours.

[0049] In some embodiments, the method for producing mesoporous beta zeolite of the present disclosure includes filtering beta zeolite particles from a solution ( Figure 1 not shown in

[0050] In some embodiments, the method for producing mesoporous beta zeolite of the present disclosure includes washing beta zeolite particles with distilled water ( Figure 1 not shown in

[0051] The beta zeolite particles can be washed with distilled water to remove excess metal hydroxide and CTAB from the beta zeolite particles. Figure 1 In some embodiments, the method for producing mesoporous beta zeolite of the present disclosure includes drying the beta zeolite particles at a temperature from 50 °C to 150 °C ( Figure 1β zeolite particles may be dried at a temperature of greater than or equal to 50° C., greater than or equal to 60° C., or greater than or equal to 70° C. The β zeolite particles may be dried at a temperature of less than 200° C., less than 150° C., or less than 100° C. The β zeolite particles may be dried at a temperature of 50° C. to 200° C., 50° C. to 150° C., 50° C. to 100° C., 60° C. to 200° C., 60° C. to 150° C., 60° C. to 100° C., 70° C. to 200° C., 70° C. to 150° C., or 70° C. to 100° C. The solution may be dried for a period of greater than or equal to 2 hours, greater than or equal to 4 hours, greater than or equal to 6 hours, or greater than or equal to 8 hours. The solution may be dried for a period of less than 24 hours, less than 20 hours, less than 15 hours, or less than 12 hours. The solution can be dried for a time period of 2 hours to 24 hours, 2 hours to 20 hours, 2 hours to 15 hours, 2 hours to 12 hours, 4 hours to 24 hours, 4 hours to 20 hours, 4 hours to 15 hours, 4 hours to 12 hours, 6 hours to 24 hours, 6 hours to 20 hours, 6 hours to 15 hours, 6 hours to 12 hours, 8 hours to 24 hours, 8 hours to 20 hours, 8 hours to 15 hours or 8 hours to 12 hours.

[0052] In some embodiments, the method of producing mesoporous zeolite beta of the present disclosure comprises calcining zeolite beta particles at a temperature of 400° C. to 800° C. for 1 to 12 hours to remove surfactants such as CTAB ( Figure 1 β zeolite particles may be calcined at a temperature of 400°C or more, 450°C or more, or 500°C or more. β zeolite particles may be calcined at a temperature of 800°C or less, 700°C or less, or 600°C or less. β zeolite particles may be calcined at a temperature of 400°C to 800°C, 400°C to 700°C, 400°C to 600°C, 450°C to 800°C, 450°C to 700°C, 450°C to 600°C, 500°C to 800°C, 500°C to 700°C, or 500°C to 600°C. The solution may be calcined for a period of time of 1 hour or more, 3 hours or more, or 5 hours or more. The solution may be calcined for a period of time of 15 hours or less, 12 hours or less, 10 hours or less, or 8 hours or less. The solution may be calcined for a period of 1 hour to 15 hours, 1 hour to 12 hours, 1 hour to 10 hours, 1 hour to 8 hours, 3 hours to 15 hours, 3 hours to 12 hours, 3 hours to 10 hours, 3 hours to 8 hours, 5 hours to 15 hours, 5 hours to 12 hours, 5 hours to 10 hours, or 5 hours to 8 hours.

[0053] Still reference Figure 1In some embodiments, the method of producing mesoporous beta zeolite of the present disclosure comprises treating beta zeolite particles with an ammonium salt at a temperature of 70° C. to 90° C. for 1 to 12 hours ( Figure 1 β zeolite particles may be treated with an ammonium salt at a temperature of 40°C or more, 50°C or more, or 60°C or more. β zeolite particles may be treated with an ammonium salt at a temperature of 200°C or less, 150°C or less, or 100°C or less. β zeolite particles may be treated with an ammonium salt at a temperature of 40°C to 200°C, 40°C to 150°C, 40°C to 100°C, 50°C to 200°C, 50°C to 150°C, 50°C to 100°C, 60°C to 200°C, 60°C to 150°C, or 60°C to 100°C. The solution may be treated with an ammonium salt for a period of time of 1 hour or more, 2 hours or more, or 3 hours or more. The solution may be treated with the ammonium salt for a period of time of less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, or less than or equal to 8 hours. The solution may be treated with the ammonium salt for a period of time of 1 hour to 12 hours, 1 hour to 10 hours, 1 hour to 9 hours, 1 hour to 8 hours, 2 hours to 12 hours, 2 hours to 10 hours, 2 hours to 9 hours, 2 hours to 8 hours, 3 hours to 12 hours, 3 hours to 10 hours, 3 hours to 9 hours, or 3 hours to 8 hours.

[0054] In some embodiments, the treating step may include: first, treating the zeolite beta particles with an ammonium salt at a temperature of 70° C. to 90° C. for 1 to 12 hours, and second, treating the zeolite beta particles with an ammonium salt at a temperature of 70° C. to 90° C. for 1 to 12 hours to produce mesoporous zeolite beta ( Figure 1β zeolite particles may be first treated with an ammonium salt at a temperature of greater than or equal to 40° C., greater than or equal to 50° C., or greater than or equal to 60° C. The β zeolite particles may be first treated with an ammonium salt at a temperature of less than or equal to 200° C., less than or equal to 150° C., or less than or equal to 100° C. The β zeolite particles may be first treated with an ammonium salt at a temperature of 40° C. to 200° C., 40° C. to 150° C., 40° C. to 100° C., 50° C. to 200° C., 50° C. to 150° C., 50° C. to 100° C., 60° C. to 200° C., 60° C. to 150° C., or 60° C. to 100° C. The solution may be first treated with an ammonium salt for a period of greater than or equal to 1 hour, greater than or equal to 2 hours, or greater than or equal to 3 hours. The solution may be first treated with an ammonium salt for a period of less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, or less than or equal to 8 hours. The solution may be first treated with the ammonium salt for a period of 1 hour to 12 hours, 1 hour to 10 hours, 1 hour to 9 hours, 1 hour to 8 hours, 2 hours to 12 hours, 2 hours to 10 hours, 2 hours to 9 hours, 2 hours to 8 hours, 3 hours to 12 hours, 3 hours to 10 hours, 3 hours to 9 hours, or 3 hours to 8 hours. The beta zeolite particles may be secondarily treated with the ammonium salt at a temperature greater than or equal to 40° C., greater than or equal to 50° C., or greater than or equal to 60° C. The beta zeolite particles may be secondarily treated with the ammonium salt at a temperature less than or equal to 200° C., less than or equal to 150° C., or less than or equal to 100° C. The zeolite beta particles may be secondarily treated with an ammonium salt at a temperature of 40° C. to 200° C., 40° C. to 150° C., 40° C. to 100° C., 50° C. to 200° C., 50° C. to 150° C., 50° C. to 100° C., 60° C. to 200° C., 60° C. to 150° C., or 60° C. to 100° C. The solution may be secondarily treated with the ammonium salt for a period of time greater than or equal to 1 hour, greater than or equal to 2 hours, or greater than or equal to 3 hours. The solution may be secondarily treated with the ammonium salt for a period of time less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, or less than or equal to 8 hours. The solution may be secondarily treated with an ammonium salt for a period of 1 hour to 12 hours, 1 hour to 10 hours, 1 hour to 9 hours, 1 hour to 8 hours, 2 hours to 12 hours, 2 hours to 10 hours, 2 hours to 9 hours, 2 hours to 8 hours, 3 hours to 12 hours, 3 hours to 10 hours, 3 hours to 9 hours, or 3 hours to 8 hours.

[0055] The ammonium salt may include a salt containing an ammonium cation and at least one anion, such as, but not limited to, a nitrate, a chloride, a carbonate, a sulfate, or a combination thereof. In some embodiments, the ammonium salt may include ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, or a combination thereof.

[0056] The ammonium salt may be included in an ammonium salt solution. The ammonium salt solution may have an ammonium salt concentration of 0.05 mol / L (M) to 0.5M, such as 0.05M to 0.4M, 0.05M to 0.3M, 0.1M to 0.5M, 0.1M to 0.4M, 0.1M to 0.3M, 0.2M to 0.5M, 0.2M to 0.4M or 0.2M to 0.3M.

[0057] In step 150, mesoporous beta zeolite particles are produced. The mesoporous beta zeolite particles may have an average particle size of 0.1 μm to 3.0 μm, 0.1 μm to 2.0 μm, 0.1 μm to 1.1 μm, 0.2 μm to 3.0 μm, 0.2 μm to 2.0 μm, 0.2 μm to 1.1 μm, 0.4 μm to 3.0 μm, 0.4 μm to 2.0 μm, or 0.4 μm to 1.1 μm. The particle size may be calculated by XRD.

[0058] The crystalline beta zeolite may have an average crystal size of 0.1 μm to 2.0 μm, 0.1 μm to 1.5 μm, 0.1 μm to 1.4 μm, 0.1 μm to 1.2 μm, 0.5 μm to 2.0 μm, 0.5 μm to 1.5 μm, 0.5 μm to 1.4 μm, 0.5 μm to 1.2 μm, 0.6 μm to 2.0 μm, 0.6 μm to 1.5 μm, 0.6 μm to 1.4 μm, or 0.6 μm to 1.2 μm. The crystal size may be calculated by XRD.

[0059] The mesoporous beta zeolite produced according to the aforementioned method may have both mesopores and micropores. In some embodiments, the average mesopore size of the mesoporous beta zeolite may be 2nm to 20nm, 2nm to 15nm, 2nm to 10nm, 2nm to 5nm, 2nm to 4.5nm, 3nm to 20nm, 3nm to 15nm, 3nm to 10nm, 3nm to 5nm or 3nm to 4.5nm. In some embodiments, the average micropore size of the mesoporous beta zeolite may be 0.01nm to 3nm, 0.01nm to 2.5nm, 0.01nm to 2.0nm, 0.05nm to 3nm, 0.05nm to 2.5nm, 0.05nm to 2.0nm, 0.1nm to 3nm, 0.1nm to 2.5nm, 0.1nm to 2.0nm, 0.5nm to 3nm, 0.5nm to 2.5nm or 0.5nm to 2.0nm.

[0060] In some embodiments, the mesoporous beta zeolite may have a diameter of 0.1 cm 3 / g to 1.0cm 3 / g, 0.1cm 3 / g to 0.85cm 3 / g, 0.1cm 3 / g to 0.8cm 3 / g, 0.5cm 3 / g to 1.0cm 3 / g, 0.5cm 3 / g to 0.85cm 3 / g or 0.5cm 3 / g to 0.8cm 3 The total pore volume of the mesoporous zeolite beta is the total pore volume of the mesoporous zeolite beta, which is determined by Brunauer-Emmett-Teller (BET) analysis. The total pore volume of the mesoporous zeolite beta may represent the total volume of micropores and mesopores in the mesoporous zeolite beta.

[0061] Mesoporous zeolite beta may have a surface area of ​​400 m2 / g (m 2 / g) to 800m 2 / g, 400m 2 / g to 750m 2 / g, 400m 2 / g to 700m 2 / g, 450m 2 / g to 800m 2 / g, 450m 2 / g to 750m 2 / g, 450m 2 / g to 700m 2 / g、500m 2 / g to 800m 2 / g、500m 2 / g to 750m 2 / g or 500m 2 / g to 700m 2 / g Brunauer-Emmett-Teller (BET) surface area.

[0062] Mesoporous zeolite beta can have a diameter of 300 cm 3 / g to 500cm 3 / g、300cm 3 / g to 450cm 3 / g、300cm 3 / g to 400cm 3 / g, 350cm 3 / g to 500cm 3 / g, 350cm 3 / g to 450cm 3 / g or 350cm 3 / g to 400cm 3 / g of mesopore volume.

[0063] In some embodiments, the mesoporous beta zeolite produced by the aforementioned method can be used as a catalyst in a fluidized catalytic cracking (FCC) reactor. The reactor can be a fluidized bed reactor. In the reactor, a catalyst comprising a mesoporous beta zeolite can be contacted with crude oil in the presence of steam to produce light olefins. In some embodiments, the catalyst is composed of mesoporous beta zeolite. Examples of suitable methods for catalytic cracking of crude oil in the presence of steam are disclosed in the following patent applications: U.S. Patent Application No. 17 / 009,008, U.S. Patent Application No. 17 / 009,012, U.S. Patent Application No. 17 / 009,020, U.S. Patent Application No. 17 / 009,022, U.S. Patent Application No. 17 / 009,039, U.S. Patent Application No. 17 / 009,048, and U.S. Patent Application No. 17 / 009,073, all of which are incorporated by reference as a whole.

[0064] In some embodiments, the crude oil may have a relatively large API gravity, such as at least 30 degrees, typically greater than 50 degrees. In some embodiments, the crude oil may have an API gravity of at least about 30 degrees, at least 35 degrees, at least 40 degrees, at least 45 degrees, at least 50 degrees, at least 55 degrees, or even at least 60 degrees.

[0065] In some embodiments, the crude oil may have a boiling point curve described as a 5wt.% boiling point temperature, a 25wt.% boiling point temperature, a 50wt.% boiling point temperature, a 75wt.% boiling point temperature, and a 95wt.% boiling point temperature. These respective boiling point temperatures correspond to the temperatures at which a given weight percentage of the hydrocarbon feed stream boils. In some embodiments, the crude oil may have a 5wt.% boiling point temperature below 150°C, a 25wt.% boiling point temperature below 225°C, a 50wt.% boiling point temperature below 300°C, a 75wt.% boiling point temperature below 400°C, and a 95wt.% boiling point temperature below 600°C. One or more. In some embodiments, the crude oil may have one or more of a 5 wt. % boiling point temperature of 0°C to 100°C, a 25 wt. % boiling point temperature of 75°C to 175°C, a 50 wt. % boiling point temperature of 150°C to 250°C, a 75 wt. % boiling point temperature of 250°C to 350°C, and a 95 wt. % boiling point temperature of 450°C to 550°C.

[0066] In some embodiments, the reactor may be operated at a temperature of at least about 500° C. In some embodiments, the reactor may be operated at a temperature of 500° C. to 800° C., 550° C. to 800° C., 600° C. to 800° C., 650° C. to 800° C., 500° C. to 750° C., 550° C. to 750° C., 600° C. to 750° C., 650° C. to 750° C., 500° C. to 700° C., 550° C. to 700° C., 600° C. to 700° C., or 650° C. to 700° C.

[0067] In some embodiments, steam can be injected into the reactor. Crude oil can be catalytically cracked in the presence of steam and mesoporous beta zeolite. Steam can act as a diluent to reduce the partial pressure of hydrocarbons in crude oil. The mass ratio of steam to crude oil can be 0.2 to 1.0, 0.3 to 1.0, 0.4 to 1.0, 0.5 to 1.0, 0.2 to 0.8, 0.3 to 0.8, 0.4 to 0.8, 0.5 to 0.8, 0.2 to 0.7, 0.3 to 0.7, 0.4 to 0.7, 0.5 to 0.7, 0.2 to 0.6, 0.3 to 0.6, 0.4 to 0.6 or 0.5 to 0.6. Steam can refer to all H in steam. 2 O.

[0068] In some embodiments, the residence time of the crude oil and steam can be from 1 second to 20 seconds, from 2 seconds to 20 seconds, from 5 seconds to 20 seconds, from 8 seconds to 20 seconds, from 1 second to 18 seconds, from 2 seconds to 18 seconds, from 5 seconds to 18 seconds, from 8 seconds to 18 seconds, from 1 second to 16 seconds, from 2 seconds to 16 seconds, from 5 seconds to 16 seconds, from 8 seconds to 16 seconds, from 1 second to 14 seconds, from 2 seconds to 14 seconds, from 5 seconds to 14 seconds, from 8 seconds to 14 seconds, from 1 second to 12 seconds, from 2 seconds to 12 seconds, from 5 seconds to 12 seconds, or from 8 seconds to 12 seconds.

[0069] In some embodiments, the weight ratio of mesoporous beta zeolite to crude oil can be 7 to 50, 7.5 to 50, 8 to 50, 7 to 45, 7.5 to 45, 8 to 45, 7 to 40, 7.5 to 40, or 8 to 40.

[0070] In some embodiments, crude oil is contacted with mesoporous beta zeolite in the presence of steam to produce a product stream, which may include at least 30wt.% of light olefins selected from ethylene, propylene and butene. For example, in embodiments, the product stream may include at least 35wt.% of light olefins, at least 38wt.% of light olefins or at least 40wt.% of light olefins. In some embodiments, the product stream may include at least 10wt.% of ethylene, at least 12wt.% of ethylene, at least 15wt.% of ethylene or even at least 16wt.% of ethylene, at least 10wt.% of propylene, at least 12wt.% of propylene, at least 13wt.% of propylene or even at least 14wt.% of propylene, at least 5wt.% of butene, at least 6wt.% of butene, at least 7wt.% of butene or even at least 8wt.% of butene.

[0071] Example

[0072] Various embodiments of the process for producing hierarchical mesoporous beta zeolite will be 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.

[0073] Example 1: Production of mesoporous zeolite beta

[0074] In a glass reactor, 7 grams of crystalline beta zeolite (CP-814C) having a silicon to aluminum molar ratio of 38 was mixed with a 0.40M sodium hydroxide (NaOH) solution. 4.45 wt.% of hexadecyltrimethylammonium bromide (CTAB) was also mixed with the crystalline beta zeolite and the NaOH solution to produce a solution. The solution was heated at 100°C with stirring for 24 hours to convert the crystalline beta zeolite into a non-crystalline material with a reduced silica content. The heated solution was cooled to a temperature of 25°C to 40°C. The pH of the cooled solution was adjusted to 9.0 by adding dilute sulfuric acid (2N). The solution was stirred for 24 hours, and then aged at 100°C for 24 hours to crystallize the non-crystalline material to produce beta zeolite particles. The beta zeolite particles were filtered, washed thoroughly with distilled water, and then dried at 80°C overnight. The dried beta zeolite particles were calcined at 570°C for 6 hours to remove CTAB. The 0.25N ammonium nitrate (NH 4 NO 3 ) solution was treated twice for 5 hours to produce mesoporous zeolite beta.

[0075] Example 2: Production of mesoporous zeolite beta

[0076] In a glass reactor, 7 grams of crystalline beta zeolite (HSZ-940NHA) having a silicon to aluminum molar ratio of 40 was mixed with a 0.40M sodium hydroxide (NaOH) solution. 4.45 wt.% of hexadecyltrimethylammonium bromide (CTAB) was also mixed with the crystalline beta zeolite and the NaOH solution to produce a solution. The solution was heated at 100°C with stirring for 24 hours to convert the crystalline beta zeolite into a non-crystalline material with a reduced silica content. The heated solution was cooled to a temperature of 25°C to 40°C. The pH of the cooled solution was adjusted to 9.0 by adding dilute sulfuric acid (2N). The solution was stirred for 24 hours, and then aged at 100°C for 24 hours to crystallize the non-crystalline material to produce beta zeolite particles. The beta zeolite particles were filtered, washed thoroughly with distilled water, and then dried at 80°C overnight. The dried beta zeolite particles were calcined at 570°C for 6 hours to remove CTAB. The 0.25N ammonium nitrate (NH 4 NO 3 ) solution was treated twice for 5 hours to produce mesoporous zeolite beta.

[0077] Example 3: Production of mesoporous zeolite beta

[0078] In a glass reactor, 7 grams of crystalline beta zeolite (CP-811C) having a silicon to aluminum molar ratio of 300 was mixed with a 0.40M sodium hydroxide (NaOH) solution. 4.45 wt.% of hexadecyltrimethylammonium bromide (CTAB) was also mixed with the crystalline beta zeolite and the NaOH solution to produce a solution. The solution was heated at 100°C with stirring for 24 hours to convert the crystalline beta zeolite into a non-crystalline material with a reduced silica content. The heated solution was cooled to a temperature of 25°C to 40°C. The pH of the cooled solution was adjusted to 9.0 by adding dilute sulfuric acid (2N). The solution was stirred for 24 hours, and then aged at 100°C for 24 hours to crystallize the non-crystalline material to produce beta zeolite particles. The beta zeolite particles were filtered, washed thoroughly with distilled water, and then dried at 80°C overnight. The dried beta zeolite particles were calcined at 570°C for 6 hours to remove CTAB. The 0.25N ammonium nitrate (NH 4 NO 3 ) solution was treated twice for 5 hours to produce mesoporous zeolite beta.

[0079] Comparative Example 1

[0080] A catalyst comprising 75 wt.% of an equilibrium catalyst (ECAT) and 25 wt.% of ZSM-5 (commercially available, such as from WR Grace and Company) was prepared. ) (referred to as "UMIX75").

[0081] Example 4: Steam Enhanced Fluid Catalytic Cracking Test

[0082] Example 4 provides data related to cracking crude oil in the presence of steam using Examples 1 to 3 and Comparative Example 1. Experiments were conducted in a fixed bed reactor (FBR) system with Arabian Extra Light (AXL) crude oil as feed at atmospheric pressure in the presence and absence of steam. Figure 2, AXL crude oil 301 is fed into a fixed bed reactor 30 using a metering pump 311. A constant feed rate of 2 g / h of AXL crude oil 301 is adopted. Water 302 is fed into the reactor 30 using a metering pump 312. Water 302 is preheated using a preheater 321. A constant feed rate of 1 g / h of water 302 is adopted. Nitrogen 303 is used as a carrier gas, 65 mL / min. Nitrogen 303 is fed into the reactor 30 using a mass flow controller (MFC) 313. Nitrogen 303 is preheated using a preheater 322. Water 302 and nitrogen 303 are mixed using a mixer 330, and the mixture is introduced into the reactor 30. Before entering the reactor tube, the oil, water and nitrogen are preheated to up to 250°C in a preheating zone 342. The preheating zone 342 is preheated using a pipeline heating furnace 331. Crude oil 301 is introduced from the top of the reactor 30 through an injector 341 and mixed with steam inside the upper two-thirds of the reactor tube 340 before reaching the catalyst bed 344. The mass ratio of steam to crude oil is 0.5. The crude oil is cracked at a cracking temperature of 675°C, and the weight ratio of catalyst to oil is 1:2. The residence time of crude oil and steam in the reactor is 10 seconds. Examples 1 to 3 and Comparative Example 1 are used as cracking catalysts, respectively. 1 g of cracking catalyst with a mesh size of 30-40 is placed in the center of the reactor tube 340 and supported by quartz wool 343, 346 and a reactor insert 345. Quartz wool 343, 346 is placed at the bottom and top of the catalyst bed 344 to hold it in place. The height of the catalyst bed 344 is 1-2 cm. The reaction is allowed to proceed for 45-60 minutes until a steady state is reached. The reaction conditions of the fixed bed flow reactor 30 are listed in Table 1. The cracking reaction product stream is introduced into the gas-liquid separator 351. A wet gas flow meter 352 was placed downstream of the gas-liquid separator 351. The cracked gaseous products 361 and liquid products 362 were characterized by off-line gas chromatography (GC) analysis using simulated distillation and naphtha analysis techniques. The reaction product stream from the cracking reaction was analyzed for the yields of ethylene, propylene, and butene. The yield analysis of Example 4 is as follows: Figure 3 shown.

[0083] Table 1

[0084] condition Feed used AXL All Crude Oil Specific gravity of raw materials 0.829 API 39.3 Reaction device Fixed bed reactor Weight Hourly Space Speed 3 Reaction temperature, °C 675 Reaction temperature range, ℃ 600-700

[0085] like Figure 3As shown, the ethylene yield of Example 3 (17.9 wt.%) is greater than that of Comparative Example 1 (17.0 wt.%). In addition, the ethylene and propylene yield of Example 3 (33.8 wt.%) is greater than that of Comparative Example 1 (33.3 wt.%). These results show that, compared with Comparative Example 1, the catalyst of Example 3 has much higher selectivity for ethylene and for ethylene and propylene. In addition, the butene yields of Example 1 (11.7 wt.%) and Example 2 (11.2 wt.%) are higher than that of Comparative Example 1 (9.9 wt.%), while maintaining selectivity for ethylene, propylene, or ethylene and propylene. In addition, the catalysts in Examples 1 to 3 show the ability to withstand high hydrothermal conditions while maintaining their activity and selectivity.

[0086] A first aspect of the present disclosure may relate to a method for producing mesoporous β-zeolite, comprising: mixing crystalline β-zeolite with one or more solvents, cetyltrimethylammonium bromide (CTAB), and a metal hydroxide to produce a solution; heating the solution at a temperature of 50°C to 150°C to convert the crystalline β-zeolite into an amorphous material, the amorphous material having a reduced silica content relative to the crystalline β-zeolite; cooling the solution to a temperature of 25°C to 40°C; adjusting the pH of the solution from 8 to 10 by adding an acid; and aging the solution at a temperature of 50°C to 150°C for a period of time sufficient for the amorphous material to crystallize to produce β-zeolite particles.

[0087] A second aspect of the present disclosure may include the first aspect, and further include filtering the β-zeolite particles from the solution.

[0088] A third aspect of the present disclosure may include any one of the first aspect or the second aspect, and further include washing the β-zeolite particles with distilled water.

[0089] A fourth aspect of the present disclosure may include any one of the first aspect to the third aspect, and further include drying the β-zeolite particles at a temperature of 50°C to 150°C.

[0090] A fifth aspect of the present disclosure may include any one of the first aspect to the fourth aspect, and further include calcining the β-zeolite particles at a temperature of 500°C to 600°C for 1 hour to 12 hours to remove CTAB.

[0091] A sixth aspect of the present disclosure may include any one of the first aspect to the fifth aspect, and further include treating the β-zeolite particles with an ammonium salt at a temperature of 70°C to 90°C for 1 hour to 12 hours.

[0092] The seventh aspect of the present disclosure may include any one of the first to sixth aspects, wherein the treatment step includes: in a first step, treating the β zeolite particles with an ammonium salt at a temperature of 70°C to 90°C for 1 hour to 12 hours; and in a second step after the first step, treating the β zeolite particles with an ammonium salt at a temperature of 70°C to 90°C for 1 hour to 12 hours to produce mesoporous β zeolite.

[0093] An eighth aspect of the present disclosure may include any one of the first to seventh aspects, wherein the ammonium salt includes ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, or a combination thereof.

[0094] A ninth aspect of the present disclosure may include any one of the first to eighth aspects, wherein the ammonium salt is in solution and comprises a concentration of 0.05M to 0.5M.

[0095] A tenth aspect of the present disclosure may include any one of the first to ninth aspects, wherein the crystalline beta zeolite comprises an average crystal size of 0.1 micrometers (μm) to 1.4 μm.

[0096] An eleventh aspect of the present disclosure may include any one of the first to tenth aspects, wherein the crystalline beta zeolite includes a molar ratio of silica to alumina of 30 to 350.

[0097] A twelfth aspect of the present disclosure may include any one of the first to eleventh aspects, wherein the metal hydroxide is in solution and includes a concentration of 0.01 mole / liter (M) to 5M.

[0098] The thirteenth aspect of the present disclosure may include any one of the first to twelfth aspects, wherein the metal hydroxide comprises lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), Strontium hydroxide (Sr(OH) 2 ), barium hydroxide (Ba(OH) 2 ), or a combination thereof.

[0099] A fourteenth aspect of the present disclosure may include any one of the first to thirteenth aspects, wherein the mesoporous beta zeolite includes an average particle size of 0.4 μm to 1.1 μm.

[0100] A fifteenth aspect of the present disclosure may include any one of the first to fourteenth aspects, wherein the mesoporous beta zeolite comprises 0.5 cubic centimeters per gram (cm 3 / g) to 0.8cm 3 / g total pore volume.

[0101] A sixteenth aspect of the present disclosure may include any one of the first to fifteenth aspects, wherein the mesoporous beta zeolite comprises 450 m2 / g (m 2 / g) to 700m 2 / g Brunauer-Emmett-Teller (BET) surface area.

[0102] A seventeenth aspect of the present disclosure may include any one of the first to sixteenth aspects, wherein the mesoporous beta zeolite includes an average mesopore size of 3 nm to 20 nm and an average micropore size of 0.5 nm to 2.0 nm.

[0103] An eighteenth aspect of the present disclosure may relate to a method for cracking crude oil, the method comprising contacting the crude oil with a mesoporous beta zeolite in a fluidized bed reactor, wherein the mesoporous beta zeolite is produced by the method described in any one of the first to seventeenth aspects.

[0104] A nineteenth aspect of the present disclosure may include any one of the first to eighteenth aspects, further comprising injecting steam into the reactor, wherein a mass ratio of steam to crude oil is 0.2 to 1.0.

[0105] A twentieth aspect of the present disclosure may include any one of the first to nineteenth aspects, wherein a weight ratio of the mesoporous beta zeolite to the crude oil is 7 to 40.

[0106] It should be noted that one or more of the following claims utilize the term “wherein” as a transition phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transition phrase to introduce a recitation of a list of features of a structure and should be interpreted in a manner similar to the more commonly used open preamble term “comprising.” For purposes of defining the present technology, the transition phrase “consisting of” may be introduced in the claims as a closed preamble term to limit the scope of the claim to the recited components or steps and any naturally occurring impurities. For purposes of defining the present technology, the transition phrase “consisting essentially of” may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps, and any unrecited elements, components, materials, or method steps that do not materially affect the novel features of the claimed subject matter. The transitional phrases "consisting of" and "consisting essentially of" may be interpreted as subsets of open transitional phrases such as "comprising" and "including", and thus any description using an open phrase to introduce a list of elements, components, materials, or steps should be interpreted as also disclosing the description of the list of elements, components, materials, or steps using the closed terms "consisting of" and "consisting essentially of". For example, a description of a composition "comprising" components A, B, and C should be interpreted as also disclosing a composition "consisting of" components A, B, and C, as well as a composition "consisting essentially of" components A, B, and C. Any quantitative value expressed in this application may be considered to include open embodiments consistent with the transitional phrases "comprising" or "including", as well as closed or partially closed embodiments consistent with the transitional phrases "consisting of" and "consisting essentially of".

[0107] As used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural meanings unless the context clearly indicates otherwise. The verb "comprise" and its conjugated forms should be interpreted as referring to elements, components or steps in a non-exclusive manner. The referenced elements, components or steps may be present, used or combined with other elements, components or steps not explicitly referenced.

[0108] It should be understood that any two quantitative values ​​assigned to a property may constitute the range of that property, and all combinations of ranges formed by all said quantitative values ​​of a given property are contemplated in the present disclosure. The subject matter of the present disclosure has been described in detail with reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily mean that the component or feature is essential to a particular embodiment or any other embodiment. In addition, it should be understood by those skilled in the art that various modifications and variations may be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

1. A method for producing mesoporous beta zeolite, the method comprising: include: mixing crystalline beta zeolite with one or more solvents, cetyltrimethylammonium bromide (CTAB), and a metal hydroxide to produce a solution; heating the solution at a temperature of 50° C. to 150° C. to convert the crystalline zeolite beta into a non-crystalline material having a reduced silica content relative to the crystalline zeolite beta; Cooling the solution to a temperature of 25°C to 40°C; The pH of the solution was adjusted from 8 to 10 by adding acid; as well as The solution is aged at a temperature of 50°C to 150°C for a period of time sufficient to crystallize the amorphous material to produce zeolite beta particles. 2 . The method of claim 1 , further comprising filtering the zeolite beta particles from the solution.

3. The method according to any one of claims 1 or 2, further comprising washing the zeolite beta particles by distilled water.

4. The method according to any one of the preceding claims, further comprising drying the zeolite beta particles at a temperature of 50°C to 150°C.

5. The method of any one of the preceding claims, further comprising calcining the zeolite beta particles at a temperature of 500 to 600°C for 1 to 12 hours to remove CTAB.

6. The method according to any one of the preceding claims, further comprising treating the zeolite beta particles with an ammonium salt at a temperature of 70°C to 90°C for 1 hour to 12 hours.

7. A method according to any one of the preceding claims, wherein the processing step include: In the first step, the beta zeolite particles are treated with the ammonium salt at a temperature of 70° C. to 90° C. for 1 to 12 hours; as well as In a second step following the first step, the β zeolite particles are treated with the ammonium salt at a temperature of 70° C. to 90° C. for 1 to 12 hours to produce the mesoporous β zeolite.

8. The method of any one of the preceding claims, wherein the ammonium salt comprises ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, or a combination thereof.

9. The method according to any one of the preceding claims, wherein the ammonium salt is in solution and comprises a concentration of 0.05M to 0.5M.

10. The method of any one of the preceding claims, wherein the crystalline beta zeolite comprises an average crystal size of 0.1 micrometers (μm) to 1.4 μm.

11. The process according to any one of the preceding claims, wherein the crystalline beta zeolite comprises a silica to alumina molar ratio of 30 to 350.

12. The method according to any one of the preceding claims, wherein the metal hydroxide is in solution and comprises a concentration of 0.01 mole / liter (M) to 5M.

13. The method according to any one of the preceding claims, wherein the metal hydroxide comprises lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), Strontium hydroxide (Sr(OH) 2 ), barium hydroxide (Ba(OH) 2 ) or a combination thereof.

14. The method of claim 1, wherein one or more of the following: The mesoporous beta zeolite comprises an average particle size of 0.4 μm to 1.1 μm; The total pore volume is from 0.5 cubic centimeters per gram (cm 3 / g) to 0.8 cm 3 / g; Brunauer-Emmett-Teller (BET) surface area is 450 m2 / g (m 2 / g) to 700m 2 / g; or The average mesopore size is 3 nm to 20 nm, and the average micropore size is 0.5 nm to 2.0 nm.

15. A method of cracking crude oil, the method comprising contacting the crude oil with a mesoporous beta zeolite in a fluidized bed reactor, wherein the mesoporous beta zeolite is produced by a method according to any one of the preceding claims.

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