Catalyst production method

Abstract

A catalyst production method includes forming mesoporous beta zeolite particles, impregnating the mesoporous beta zeolite particles with a metal and phosphorus to produce a metal and phosphorus impregnated zeolite, and combining the metal and phosphorus impregnated zeolite with clay and alumina to produce a catalyst. The forming step includes converting the crystalline beta zeolite into a non-crystalline material having a reduced silica content relative to the crystalline beta zeolite, and crystallizing the non-crystalline material to produce mesoporous beta zeolite particles.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Patent Application Serial No. 17 / 964,156, filed on October 12, 2022, entitled "Method for Producing Catalysts", the entire content of which is incorporated herein by reference. Technical Field

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

[0004] Ethylene, propylene, butene, butadiene, and aromatic compounds such as benzene, toluene, and xylene are basic intermediates in most of the petrochemical industry. They are typically obtained by thermal cracking (or steam pyrolysis) of petroleum gas and distillate oils such as naphtha, kerosene, or even gas oil. These compounds are also produced by the fluid catalytic cracking (FCC) process in refineries, in which classical heavy feedstocks such as gas oil or residue are converted. The range of typical FCC feedstocks extends 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. As demand continues to grow, FCC unit owners are increasingly focused on the petrochemical market to increase their revenues by taking advantage of economic opportunities presented 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 butene has attracted increasing attention because pure olefin streams are considered 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 options available for producing higher yields of propylene and other light olefins, intensive research activities are still ongoing in this field. These options include developing more selective catalysts for the process and enhancing process configurations 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] Accordingly, there remains a need for a method of producing a catalyst suitable for chemical treatment. As described herein, embodiments of the present disclosure meet this need by producing a catalyst. The method now described produces a catalyst by the steps of: forming mesoporous beta zeolite particles, impregnating the mesoporous beta zeolite particles with metal and phosphorus to produce a metal- and phosphorus-impregnated zeolite, and combining the metal- and phosphorus-impregnated zeolite with clay and alumina to produce a catalyst. In some embodiments, the catalyst produced by the method now described may have micropores, mesopores, and macropores; and the mesopores and micropores may be more uniform compared to conventional catalysts. Such a catalyst prepared by the method disclosed herein may be particularly useful in a steam enhanced catalytic cracking system and is capable of directly converting crude oil into light olefins, such as at least one of ethylene and propylene, with increased yields. The catalyst prepared by the method disclosed herein may be tolerant to high hydrothermal conditions while retaining its activity and selectivity.

[0008] According to one or more embodiments of the present disclosure, a method of producing a fluid catalytic cracking catalyst includes: forming mesoporous beta zeolite particles, impregnating the mesoporous beta zeolite particles with metal and phosphorus to produce a metal- and phosphorus-impregnated zeolite, and combining the metal- and phosphorus-impregnated zeolite with clay and alumina to produce a catalyst. The forming step includes: converting crystalline beta zeolite into an amorphous material having a reduced silica content relative to the crystalline beta zeolite, and crystallizing the amorphous material to produce mesoporous beta zeolite particles.

[0009] Additional features and advantages of the techniques described in this disclosure will be set forth in the detailed description that follows, and in part will be obvious to those skilled in the art from the description, or can be learned by practice of the techniques described in this disclosure, including the detailed description, the claims, and the drawings that follow.

[0010] Brief Description of the Drawings

[0011] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structures are denoted with like reference numerals and where:

[0012] Figure 1A A flowchart depicting a method of producing a catalyst according to one or more embodiments shown and described in the present disclosure;

[0013] Figure 1B A flowchart depicting a method of forming mesoporous beta zeolite according to one or more embodiments shown and described in the present disclosure;

[0014] 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

[0015] Figure 3 Depicts the yield analysis for Example 2.

[0016] For the purpose of describing the simplified schematic diagram and Figure 2 For the purpose of description, many valves, temperature sensors, electronic controllers, etc. that are used and well-known to those of ordinary skill in the art in some fields of chemical processing operations are not included. In addition, the accompanying components that are usually included in chemical processing operations are not depicted, such as, for example, a gas source, a heat exchanger, a buffer tank, a catalyst hopper, or other related systems. It should be understood that these components are within the spirit and scope of the disclosed embodiments herein. However, operating components such as those described in the present disclosure can be added to the embodiments described in the present disclosure.

[0017] It should also be noted that the arrows in the drawings refer to process flows. However, the arrows can equivalently refer to transfer pipelines that can be used to convey process steam between two or more system components. In addition, the arrows connected to system components define the inlets or outlets in each given system component. The arrow direction generally corresponds to the main movement direction of the material contained in the flow within the physical transfer pipeline represented by the arrow. In addition, arrows that do not connect two or more system components represent product streams leaving the depicted system or system inlet streams entering the depicted system. The product stream can be further processed in an accompanying chemical processing system or can be commercialized as a final product. The system inlet stream can be a stream transferred from an accompanying chemical processing system or can be an unprocessed feed stream. Some arrows can represent recycle streams, which are outlet streams that are recycled back to system components within the system. However, it should be understood that in some embodiments, any represented recycle stream can be replaced by a system inlet stream of the same material, and a portion of the recycle stream can leave the system as a system product.

[0018] In addition, the arrows in the drawings can schematically depict the process steps of conveying a flow from one system component to another system component. For example, an arrow pointing from one system component to another system component can represent "transferring" the system component effluent to another system component, which can include the contents of the process flow "leaving" or "being removed" from one system component, and "introducing" the contents of the product stream into another system component.

[0019] It should be understood that when two or more lines intersect in a Figure 3 schematic flow chart, two or more process flows are "mixed" or "combined". Mixing or combining can also include mixing by directly introducing two flows into a similar reactor, separation device, or other system component. For example, it should be understood that when two flows are depicted as being directly combined before entering a separator or reactor, in some embodiments, the flows may be equivalent to being introduced into the separator or reactor and mixed in the reactor.

[0020] 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

[0021] Disclosed herein are methods for forming catalysts, which in some embodiments can be used in steam enhanced fluid catalytic cracking reactions of hydrocarbons. The methods generally can include forming mesoporous beta zeolite, impregnating mesoporous beta zeolite particles, and combining with clay and alumina. Particular non-limiting embodiments of such methods are disclosed herein.

[0022] As used in the present disclosure, the term "catalyst" can refer to any substance that increases the rate of a specific chemical reaction.

[0023] As used in the present disclosure, the term "cracking" can refer to a chemical reaction in which a molecule having a carbon-carbon bond is broken into more than one molecule by the breaking of one or more of the bonds in the carbon-carbon bond; in which a compound including a ring portion, such as an aromatic compound, is converted into a compound not including a ring portion; or in which a molecule having a carbon-carbon double bond is reduced to a carbon-carbon single bond. Some catalysts can have multiple forms of catalytic activity, and naming a catalyst with one specific function does not render the catalyst non-catalytically active for other functions.

[0024] As used in the present disclosure, the "particle size" of crystalline beta zeolite or mesoporous beta zeolite can refer to the maximum distance between two points on the crystalline beta zeolite or mesoporous beta zeolite. For example, the particle size of a spherical particle would be 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 on the outer surface of the particle. The particle size can be determined by scanning electron microscopy (SEM).

[0025] As used in the present disclosure, the "crystal size" of crystalline beta zeolite or mesoporous beta zeolite can refer to the length of the coherent scattering domain in a direction orthogonal to the set of lattice planes that give rise to the reflection. The crystal size can be calculated by XRD.

[0026] As used in the present disclosure, the "pore diameter" of crystalline beta zeolite or mesoporous beta zeolite can refer to the pore diameter determined by Barrett-Joyner-Halenda (BJH) analysis. BJH analysis measures the amount of gas (argon) desorbed from a material such as mesoporous beta zeolite over a certain pressure range at 87 Kelvin. Using the Kelvin equation, the amount of argon adsorbate removed from the pores of the material and the relative pressure of the system can be used to calculate the pore diameter of the material.

[0027] As used in the present disclosure, the term "microporous" can refer to a material having pores with an average pore diameter of 0.1 nanometers (nm) to 2 nm, such as beta zeolite.

[0028] As used herein, 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.

[0029] As used herein, the term "macroporous" may refer to a material having pores with an average pore diameter greater than 50 nm, such as a catalyst.

[0030] As used herein, 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 metal compounds, which mixture is directly extracted from a subterranean formation or received from a desalting unit without any fractions being separated by distillation, such as naphtha.

[0031] As used herein, 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.

[0032] Embodiments of the present disclosure relate to methods for producing catalysts. Figure 1A A flowchart depicting a method for producing a catalyst according to one or more embodiments shown and described herein is presented. Figure 1B A flowchart depicting a method for forming mesoporous beta zeolite according to one or more embodiments shown and described herein is presented.

[0033] Reference Figure 1A and 1B , in step 110, mesoporous beta zeolite particles are formed. Step 110 includes converting crystalline beta zeolite into an amorphous material, which amorphous material has a reduced silica content relative to the crystalline beta zeolite. In one or more embodiments, step 110 includes steps 111 and 112 ( Figure 1B ).

[0034] In step 111, the crystalline beta zeolite is converted into an amorphous material. The crystalline beta zeolite may have an average crystal 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 crystalline beta zeolite may comprise one or more crystals. The crystals may comprise one or more unit cells.

[0035] The crystalline beta zeolite may have an average crystal size of from 0.05 μm to 5.0 μm, from 0.05 μm to 3.0 μm, from 0.05 μm to 2.0 μm, from 0.05 μm to 1.5 μm, from 0.05 μm to 1.4 μm, from 0.1 μm to 5.0 μm, from 0.1 μm to 3.0 μm, from 0.1 μm to 2.0 μm, from 0.1 μm to 1.5 μm, or from 0.1 μm to 1.4 μm. The crystal size can be calculated by XRD.

[0036] The crystalline beta zeolite may have an average pore diameter of from 0.5 nanometers (nm) to 3.0 nm, from 0.5 nm to 2.0 nm, from 0.5 nm to 1.0 nm, from 0.5 nm to 0.75 nm, from 0.5 nm to 0.74 nm, from 0.56 nm to 3.0 nm, from 0.56 nm to 2.0 nm, from 0.56 nm to 1.0 nm, from 0.56 nm to 0.75 nm, or from 0.56 nm to 0.74 nm. The pore diameter can be determined using mercury intrusion porosimetry.

[0037] The crystalline beta zeolite may have a molar ratio of silicon dioxide (SiO 2 ) to aluminum oxide (Al 2 O 3 ) of greater than or equal to 10, greater than or equal to 20, or even greater than or equal to 30. The crystalline beta zeolite may have a molar ratio of SiO 2 to Al 2 O 3 of less than or equal to 400, such as less than or equal to 350 or even less than or equal to 300. The crystalline beta zeolite may have a molar ratio of SiO 2 to Al 2 O 3 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.

[0038] In step 111, the crystalline beta zeolite can be mixed with one or more solvents, cetyltrimethylammonium 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 bound by any particular theory, it is believed that this mixing step can uniformly disperse the crystalline beta zeolite, CTAB, and the metal hydroxide. The mixing can include one or more of stirring, swirling, vortexing, shaking, sonication, homogenization, fusion, etc.

[0039] The metal hydroxide may include a monometallic hydroxide species or a combination of two or more metal hydroxide chemical species. In an embodiment, the metal hydroxide includes at least one alkali 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.

[0040] In one or more embodiments, the metal hydroxide may be in solution. The metal hydroxide solution may have a metal hydroxide concentration of 0.01 moles per liter (M) to 10 M, such as 0.01 M to 5 M, 0.01 M to 3 M, 0.01 M to 1 M, 0.05 M to 1 M, 0.05 M to 0.8 M, 0.05 M to 0.5 M, or 0.1 M to 0.4 M.

[0041] Still referring to Figure 1A and 1B , as described above, in step 111, the crystalline β-zeolite and the metal hydroxide may be mixed with cetyltrimethylammonium bromide (CTAB). CTAB is a surfactant. In particular, when the solution contains crystalline β-zeolite, metal hydroxide, and CTAB, heating CTAB to produce an amorphous material, CTAB can reduce the silica content of the crystalline β-zeolite. Thus, the amorphous material may have a lower silica content than the crystalline β-zeolite.

[0042] CTAB may be included in a CTAB solution. The CTAB solution may have a CTAB of greater than or equal to 1 wt.%, greater than or equal to 2 wt.%, or greater than or equal to 3 wt.%. The CTAB solution may have a CTAB of less than or equal to 10 wt.%, less than or equal to 8 wt.%, less than or equal to 7 wt.%, or less than or equal to 6 wt.%. The CTAB solution may have a CTAB of 1 wt.% to 10 wt.%, 1 wt.% to 8 wt.%, 1 wt.% to 7 wt.%, 1 wt.% to 6 wt.%, 2 wt.% to 10 wt.%, 2 wt.% to 8 wt.%, 2 wt.% to 7 wt.%, 2 wt.% to 6 wt.%, 3 wt.% to 10 wt.%, 3 wt.% to 8 wt.%, 3 wt.% to 7 wt.%, or 3 wt.% to 6 wt.%.

[0043] Still referring to Figure 1A and 1B, in step 111, the solution can be heated at a temperature of 50 °C to 150 °C to convert crystalline beta zeolite into an amorphous material, which has a reduced silica content relative to the crystalline beta zeolite. During the heating step, the crystalline beta zeolite can be decomposed. The term "decomposed" can refer to the breaking of the siloxane bonds (silicate groups) of the crystalline beta zeolite.

[0044] The solution can be heated 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 heated 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 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.

[0045] Still referring to Figure 1A and 1B , in step 111, the heated solution can be cooled to a temperature of 25 °C to 40 °C. The solution can 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 can 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 can 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.

[0046] Still referring to Figure 1A and 1B , step 110, forming mesoporous beta zeolite, includes step 112, crystallizing the amorphous material to produce mesoporous beta zeolite particles. In some embodiments, in step 112, the pH of the solution can be adjusted from 8 to 10 by adding an acid. During the step of adjusting the pH of the solution, the CTAB already present in the solution adopts a spherical micelle morphology.

[0047] 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 from 0.1 to 5N, from 0.1N to 4N, from 0.1N to 3N, from 0.5N to 5N, from 0.5N to 4N, from 0.5N to 3N, from 1N to 5N, from 1N to 4N, or from 1N to 3N.

[0048] In some embodiments, the pH of the solution may be greater than or equal to 13. The pH of the solution may be adjusted to be greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9. The pH of the solution may be adjusted to be less than or equal to 12, less than or equal to 11, or less than or equal to 10. The pH of the solution may be adjusted to be from 7 to 12, from 7 to 11, from 7 to 10, from 8 to 12, from 8 to 11, from 8 to 10, from 9 to 12, from 9 to 11, or from 9 to 10.

[0049] In some embodiments, the method for producing the catalyst of the present disclosure includes stirring the solution for 10 hours to 48 hours ( Figure 1A and 1B not shown in). The solution may be stirred 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 may be stirred 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 may be stirred for a period of time from 10 hours to 48 hours, from 10 hours to 40 hours, from 10 hours to 35 hours, from 10 hours to 30 hours, from 13 hours to 48 hours, from 13 hours to 40 hours, from 13 hours to 35 hours, from 13 hours to 30 hours, from 17 hours to 48 hours, from 17 hours to 40 hours, from 17 hours to 35 hours, from 17 hours to 30 hours, from 20 hours to 48 hours, from 20 hours to 40 hours, from 20 hours to 35 hours, or from 20 hours to 30 hours.

[0050] Still referring to Figure 1A and 1B, in step 112, the solution is aged at a temperature of 50 °C to 150 °C for a period of time sufficient for the non-crystalline material to crystallize to produce β-zeolite particles. When the non-crystalline material crystallizes, the silica removed (broken) from the crystalline β-zeolite contributes to the production of mesoporous β-zeolite with uniform mesopores and micropores. In particular, a surfactant CTAB can act as a structure-directing agent. The recrystallization of β-zeolite in the presence of CTAB can prevent the dissolution of the crystals and almost completely recover the zeolite. After calcination, the surfactant moiety can be removed, and the resulting voids constitute the mesopores of the mesoporous zeolite. Since the mesopore quality, which encompasses size, distribution, and connectivity, helps improve the stability against coke deactivation, it is highly desirable to achieve uniform mesopores. Conventional microporous β-zeolite may inhibit the entry of larger molecules into the catalytic active sites on the β-zeolite, and these larger molecules can have a molecular size equal to or greater than the average pore diameter of the microporous β-zeolite. The mesoporous β-zeolite produced by the currently described method can be a hierarchical mesoporous β-zeolite with uniform mesopores and micropores. Through these uniform mesopores and micropores, the mesoporous β-zeolite can increase the entry of larger molecules, thus being suitable for hydrocarbon feeds including larger hydrocarbon molecules such as crude oil. In addition, the mesoporous β-zeolite may exhibit stability at high temperatures (such as temperatures above 500 °C), and the acidic sites of the mesoporous β-zeolite can be compatible with hydrocracking reactions, which helps decompose the hydrocarbon feed or hydrocarbon fraction into smaller molecules. Therefore, the mesoporous β-zeolite can facilitate the transport of larger hydrocarbon molecules in crude oil to the catalytic sites and reduce the diffusion limitations of these catalysts.

[0051] 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 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. 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 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.

[0052] In some embodiments, the catalyst production method of the present disclosure includes filtering β-zeolite particles from a solution ( Figure 1A and 1B not shown in

[0053] In some embodiments, the catalyst production method of the present disclosure includes washing the β-zeolite particles with distilled water ( Figure 1A and 1B not shown in

[0054] The β-zeolite particles can be washed with distilled water to remove excess metal hydroxide and CTAB from the β-zeolite particles. Figure 1A and 1B(not shown in []) The β-zeolite particles can 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 can be dried 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 can 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 can 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 can be dried for a period of less than or equal to 24 hours, less than or equal to 20 hours, less than or equal to 15 hours, or less than or equal to 12 hours. The solution can be dried for a 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.

[0055] In some embodiments, the catalyst production method of the present disclosure includes calcining the β-zeolite particles at a temperature of 400 °C to 800 °C for 1 hour to 12 hours to remove surfactants such as CTAB ( Figure 1A and 1B (not shown in []) The β-zeolite particles can be calcined at a temperature of greater than or equal to 400 °C, greater than or equal to 450 °C, or greater than or equal to 500 °C. The β-zeolite particles can be calcined at a temperature of less than or equal to 800 °C, less than or equal to 700 °C, or less than or equal to 600 °C. The β-zeolite particles can 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 can be calcined for a period of greater than or equal to 1 hour, greater than or equal to 3 hours, or greater than or equal to 5 hours. The solution can be calcined for a period of less than or equal to 15 hours, less than or equal to 12 hours, less than or equal to 10 hours, or less than or equal to 8 hours. The solution can 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.

[0056] Still referring to Figure 1A and 1B , in some embodiments, the catalyst production method of the present disclosure includes treating β-zeolite particles with an ammonium salt at a temperature of 70 °C to 90 °C for 1 hour to 12 hours( Figure 1A and 1B not shown in). Treating the β-zeolite particles with an ammonium salt can allow sufficient ion exchange between sodium ions and ammonium ions present in the ammonium salt to produce mesoporous β-zeolite. The β-zeolite particles can be treated with an 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 β-zeolite particles can be treated with an 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 β-zeolite particles can 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 β-zeolite particles can be treated with an ammonium salt solution 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 β-zeolite particles can be treated with an ammonium salt solution 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 β-zeolite particles can be treated with an ammonium salt solution 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.

[0057] In some embodiments, the treatment step may include: first, 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 second, 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( Figure 1A and 1B(not shown in the figure). The β-zeolite particles can be treated with an ammonium salt first 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 β-zeolite particles can be treated with an ammonium salt first 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 β-zeolite particles can be treated with an ammonium salt first at a temperature in the range 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,

[0058] 60 °C to 150 °C, or 60 °C to 100 °C. The β-zeolite particles can be treated with an ammonium salt solution for a period greater than or equal to 1 hour, greater than or equal to 2 hours, or greater than or equal to 3 hours. The β-zeolite particles can be treated with an ammonium salt solution for a period 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 β-zeolite particles can be treated with an ammonium salt solution for a period in the range 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.

[0059] The ammonium salt can include a salt containing an ammonium cation and at least one anion, such as but not limited to nitrates, chlorides, carbonates, sulfates, or combinations thereof. In some embodiments, the ammonium salt can include ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, or combinations thereof.

[0060] The ammonium salt can be included in an ammonium salt solution. The ammonium salt solution can have an ammonium salt concentration of 0.05 moles per liter (M) to 0.5 M, such as 0.05 M to 0.4 M, 0.05 M to 0.3 M, 0.1 M to 0.5 M, 0.1 M to 0.4 M, 0.1 M to 0.3 M, 0.2 M to 0.5 M, 0.2 M to 0.4 M, or 0.2 M to 0.3 M.

[0061] In step 120, mesoporous β-zeolite particles are produced. The mesoporous β-zeolite particles can 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 can be calculated by XRD.

[0062] The mesoporous β-zeolite produced according to the foregoing method can have both mesopores and micropores. In some embodiments, the average mesopore size of the mesoporous β-zeolite can be 2 nm to 20 nm, 2 nm to 15 nm, 2 nm to 10 nm, 2 nm to 5 nm, 2 nm to 4.5 nm, 3 nm to 20 nm, 3 nm to 15 nm, 3 nm to 10 nm, 3 nm to 5 nm, or 3 nm to 4.5 nm. In some embodiments, the average micropore size of the mesoporous β-zeolite can be 0.01 nm to 3 nm, 0.01 nm to 2.5 nm, 0.01 nm to 2.0 nm, 0.05 nm to 3 nm, 0.05 nm to 2.5 nm, 0.05 nm to 2.0 nm, 0.1 nm to 3 nm, 0.1 nm to 2.5 nm, 0.1 nm to 2.0 nm, 0.5 nm to 3 nm, 0.5 nm to 2.5 nm, or 0.5 nm to 2.0 nm.

[0063] In some embodiments, the mesoporous β-zeolite can have 0.1 cm 3 / g to 1.0 cm 3 / g, 0.1 cm 3 / g to 0.85 cm 3 / g, 0.1 cm 3 / g to 0.8 cm 3 / g, 0.5 cm 3 / g to 1.0 cm 3 / g, 0.5 cm 3 / g to 0.85 cm 3 / g or 0.5 cm 3 / g to 0.8 cm 3The total pore volume per gram (g), which is determined by Brunauer-Emmett-Teller (BET) analysis. The total pore volume of the mesoporous β-zeolite can represent the sum of the volumes of the micropores and mesopores in the mesoporous β-zeolite.

[0064] The mesoporous β-zeolite can have a Brunauer-Emmett-Teller (BET) surface area of 400 square meters per gram (m 2 / g) to 800 m 2 / g, 400 m 2 / g to 750 m 2 / g, 400 m 2 / g to 700 m 2 / g, 450 m 2 / g to 800 m 2 / g, 450 m 2 / g to 750 m 2 / g, 450 m 2 / g to 700 m 2 / g, 500 m 2 / g to 800 m 2 / g, 500 m 2 / g to 750 m 2 / g or 500 m 2 / g to 700 m 2 / g.

[0065] The mesoporous β-zeolite can have a mesopore volume of 300 cm 3 / g to 500 cm 3 / g, 300 cm 3 / g to 450 cm 3 / g, 300 cm 3 / g to 400 cm 3 / g, 350 cm 3 / g to 500 cm 3 / g, 350 cm 3 / g to 450 cm 3 / g or 350 cm 3 / g to 400 cm 3 / g.

[0066] Still referring to Figure 1A and 1B , in step 120, the mesoporous β-zeolite particles are impregnated with a metal and phosphorus to produce a metal- and phosphorus-impregnated zeolite. For the impregnation method, the mesoporous β-zeolite particles can be mixed with water to form a mass that can be extruded using an extruder. The extrudate can be impregnated with an aqueous solution containing the metal and phosphorus.

[0067] In some embodiments, the metal includes Ce, La, Fe, or a combination thereof. In some embodiments, the metal and phosphorus-impregnated zeolite includes from 0.1 wt.% to 10 wt.%, 0.1 wt.% to 8 wt.%, 0.1 wt.% to 5 wt.%, 0.5 wt.% to 10 wt.%, 0.5 wt.% to 8 wt.%, 0.5 wt.% to 5 wt.%, 1 wt.% to 10 wt.%, 1 wt.% to 8 wt.%, 1 wt.% to 5 wt.%, or any combination of these ranges of metal, based on the total weight of the metal and phosphorus-impregnated zeolite.

[0068] In some embodiments, the metal and phosphorus-impregnated zeolite includes Ce, La, and Fe. In some embodiments, the metal and phosphorus-impregnated zeolite includes from 0.1 wt.% to 5 wt.%, 0.1 wt.% to 3 wt.%, 0.1 wt.% to 2 wt.%, 0.5 wt.% to 5 wt.%, 0.5 wt.% to 3 wt.%, or 0.5 wt.% to 2 wt.% of Ce, based on the total weight of the metal and phosphorus-impregnated zeolite; from 0.1 wt.% to 5 wt.%, 0.1 wt.% to 3 wt.%, 0.1 wt.% to 2 wt.%, 0.5 wt.% to 5 wt.%, 0.5 wt.% to 3 wt.%, or 0.5 wt.% to 2 wt.% of La, based on the total weight of the metal and phosphorus-impregnated zeolite; and from 0.1 wt.% to 5 wt.%, 0.1 wt.% to 3 wt.%, 0.1 wt.% to 2 wt.%, 0.5 wt.% to 5 wt.%, 0.5 wt.% to 3 wt.%, or 0.5 wt.% to 2 wt.% of Fe, based on the total weight of the metal and phosphorus-impregnated zeolite.

[0069] In some embodiments, the metal and phosphorus-impregnated zeolite includes phosphorus. In some embodiments, the metal and phosphorus-impregnated zeolite includes P 2 O 5 . In some embodiments, the metal and phosphorus-impregnated zeolite includes from 1 wt.% to 10 wt.%, 1 wt.% to 8 wt.%, 1 wt.% to 5 wt.%, 2 wt.% to 10 wt.%, 2 wt.% to 8 wt.%, 2 wt.% to 5 wt.%, 3 wt.% to 10 wt.%, 3 wt.% to 8 wt.%, 3 wt.% to 5 wt.%, or any combination of these ranges of P 2 O 5 .

[0070] In some embodiments, the metal and phosphorus impregnated zeolite includes 0.1 wt.% to 5 wt.% Ce based on the total weight of the metal and phosphorus impregnated zeolite; 0.1 wt.% to 5 wt.% La based on the total weight of the metal and phosphorus impregnated zeolite; 0.1 wt.% to 5 wt.% Fe based on the total weight of the metal and phosphorus impregnated zeolite; and 2 wt.% to 10 wt.% P based on the total weight of the metal and phosphorus impregnated zeolite. 2 O 5 .

[0071] Still reference Figure 1A and 1B , in step 130, the metal and phosphorus impregnated zeolite is combined with clay and alumina to produce a catalyst.

[0072] In some embodiments, the catalyst may include metals and phosphorus impregnated zeolites in an amount of 25 wt.% to 60 wt.%, based on the total weight of the catalyst. For example, the catalyst may include metals and phosphorus impregnated zeolites in an amount of 25 wt.% to 55 wt.%, 25 wt.% to 50 wt.%, 30 wt.% to 60 wt.%, 30 wt.% to 55 wt.%, 30 wt.% to 50 wt.%, 35 wt.% to 60 wt.%, 35 wt.% to 55 wt.%, 35 wt.% to 50 wt.%, or any combination of these ranges, based on the total weight of the catalyst.

[0073] Clay can serve as a matrix material. Without being bound by theory, it is believed that the matrix material of the catalyst has both physical and catalytic functions. Physical functions include providing particle integrity and wear resistance, serving as a heat transfer medium, and providing a porous structure to allow hydrocarbons to diffuse into or out of the catalyst microspheres. The matrix material can also affect catalyst selectivity, product quality, and poison resistance. For those reactions that directly involve relatively large molecules, the matrix material may tend to have its strongest impact on the overall catalytic performance.

[0074] In some embodiments, the clay may include kaolin. As used in the present disclosure, the term "kaolin" may refer to a clay material having a relatively large amount (e.g., at least about 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or even at least 95 wt.%) of kaolinite, which can be represented by the chemical formula Al 2 Si 2 O 5 (OH) 4 Express.

[0075] In some embodiments, the catalyst may comprise from 25 wt.% to 60 wt.% of clay, based on the total weight of the catalyst. For example, the catalyst may comprise from 25 wt.% to 55 wt.%, from 25 wt.% to 50 wt.%, from 30 wt.% to 60 wt.%, from 30 wt.% to 55 wt.%, from 30 wt.% to 50 wt.%, from 35 wt.% to 60 wt.%, from 35 wt.% to 55 wt.%, from 35 wt.% to 50 wt.% of clay, or any combination of these ranges.

[0076] Alumina can act as a binder. As used herein, the term "binder" can refer to a material that can be used to "glue" or otherwise fix zeolite and matrix together in microspheres. It can improve the abrasion resistance of the catalyst.

[0077] In some embodiments, the catalyst may comprise from 10 wt.% to 40 wt.% of alumina, based on the total weight of the catalyst. For example, the catalyst may comprise from 10 wt.% to 35 wt.%, from 10 wt.% to 30 wt.%, from 12 wt.% to 40 wt.%, from 12 wt.% to 35 wt.%, from 12 wt.% to 30 wt.%, from 15 wt.% to 40 wt.%, from 15 wt.% to 35 wt.%, from 15 wt.% to 30 wt.% of alumina, or any combination of these ranges.

[0078] The catalyst can be formed by a variety of methods. In some embodiments, the clay can be mixed with a fluid such as water to form a slurry, and the mesoporous beta zeolite can be separately mixed with a fluid such as water to form a slurry. The clay slurry and the mesoporous beta zeolite slurry can be combined under stirring. Additionally, by combining alumina with a fluid such as water, another slurry can be formed. Then, the alumina slurry can be combined with the slurry containing mesoporous beta zeolite and clay to form a full-composition slurry. The full-composition slurry can be, for example, spray-dried and then calcined to produce the catalyst.

[0079] In step 130, a catalyst is produced. The catalyst can include mesopores, micropores, and macropores. The mesoporous beta zeolite in the catalyst can provide mesopores and micropores. As described above, compared with conventional zeolites, mesoporous beta zeolites have uniform mesopores and micropores. Through these uniform mesopores and micropores, mesoporous beta zeolites can have a longer catalytic cracking activity and increase the entry of large molecules, thus being applicable to hydrocarbon feeds including larger hydrocarbon molecules such as crude oil. In addition, mesoporous beta zeolites may exhibit improved hydrothermal stability at high temperatures (such as temperatures above 500 °C), and the acidic sites of mesoporous beta zeolites are compatible with hydrocracking reactions, which helps to decompose hydrocarbon feeds or hydrocarbon fractions into smaller molecules. Therefore, mesoporous beta zeolites can facilitate the transport of larger hydrocarbon molecules in crude oil to catalytic sites and reduce the diffusion limitations of these catalysts. In addition, the alumina and clay contained in the catalyst can provide macropores in the catalyst. The macropores in the catalyst can decompose large molecules in crude oil, making them more easily diffuse into the mesopores and micropores of mesoporous beta zeolites. In addition, these macropores in the catalyst can trap contaminant metals. Through these mesopores, micropores, and macropores, the catalyst produced by the currently described method may be able to increase the light olefin yield of steam-enhanced fluid catalytic cracking of crude oil while having very good hydrothermal stability and a longer catalytic cracking activity.

[0080] The catalyst produced by the foregoing method can be used as a catalyst in a fluid catalytic cracking (FCC) process. The catalyst can be contacted with crude oil in the presence of steam to produce light olefins in a reactor, such as a fluid catalytic cracking (FCC) reactor. As used in this disclosure, a "fluid catalytic cracking (FCC) reactor" refers to a reactor operable to contact a fluidized reactant with a solid material such as a catalyst (usually in particulate form). The reactor can be a fluidized bed reactor. As described in this disclosure, a fluidized bed reactor that cracks a reaction stream with a fluidized solid catalyst can be referred to as a fluid catalytic FCC reactor. Examples of suitable processes for catalytically cracking 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 the above patent applications are incorporated herein by reference in their entirety.

[0081] Before being used in a reactor to convert crude oil, the catalyst can be deactivated by contacting it with steam. The purpose of the steam treatment is to accelerate hydrothermal aging, which occurs in a normally operating FCC regenerator to obtain equilibrium catalyst. The steam treatment may cause the removal of aluminum from the framework, thereby reducing the number of sites where framework hydrolysis can occur under hydrothermal and thermal conditions. This removal of aluminum increases the thermal and hydrothermal stability of dealuminated mesoporous beta zeolite. Dealumination can cause the unit cell size to decrease because smaller SiO 4 tetrahedra replace larger AlO 4 tetrahedra. By removing framework aluminum and forming additional framework aluminum species, the acidity of mesoporous beta zeolite may also be affected by dealumination. Dealumination may affect the acidity of mesoporous beta zeolite by reducing the total acidity and increasing the acid strength of the mesoporous beta zeolite. The total acidity may decrease due to the removal of framework aluminum that acts as Bronsted acid sites. The acid strength of the mesoporous beta zeolite may increase due to the removal of paired acid sites or the removal of second-coordinated next-nearest-neighbor aluminum. The increase in acid strength may be caused by the highest charge density on the proton of the OH group when there is no framework aluminum in the second coordination sphere.

[0082] In some embodiments, the crude oil may have a relatively high API gravity, such as at least 30 degrees, and 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.

[0083] In some embodiments, the crude oil may have a boiling point curve as described by the 5 wt.%, 25 wt.%, 50 wt.%, 75 wt.%, and 95 wt.% boiling point temperatures. 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 one or more of a 5 wt.% boiling point temperature below 150 °C, a 25 wt.% boiling point temperature below 225 °C, a 50 wt.% boiling point temperature below 300 °C, a 75 wt.% boiling point temperature below 400 °C, and a 95 wt.% boiling point temperature below 600 °C. In some embodiments, the crude oil may have one or more of a 5 wt.% boiling point temperature from 0 °C to 100 °C, a 25 wt.% boiling point temperature from 75 °C to 175 °C, a 50 wt.% boiling point temperature from 150 °C to 250 °C, a 75 wt.% boiling point temperature from 250 °C to 350 °C, and a 95 wt.% boiling point temperature from 450 °C to 550 °C.

[0084] In some embodiments, the reactor can be operated at a temperature of at least about 500 °C. In some embodiments, the reactor can 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.

[0085] In some embodiments, steam can be injected into the reactor. The crude oil can be catalytically cracked in the presence of steam and a catalyst. The steam can act as a diluent to reduce the partial pressure of the hydrocarbons in the 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. The steam can refer to all H 2 O in the steam.

[0086] In some embodiments, the residence time of the crude oil and steam can be 1 second to 20 seconds, 2 seconds to 20 seconds, 5 seconds to 20 seconds, 8 seconds to 20 seconds, 1 second to 18 seconds, 2 seconds to 18 seconds, 5 seconds to 18 seconds, 8 seconds to 18 seconds, 1 second to 16 seconds, 2 seconds to 16 seconds, 5 seconds to 16 seconds, 8 seconds to 16 seconds, 1 second to 14 seconds, 2 seconds to 14 seconds, 5 seconds to 14 seconds, 8 seconds to 14 seconds, 1 second to 12 seconds, 2 seconds to 12 seconds, 5 seconds to 12 seconds, or 8 seconds to 12 seconds.

[0087] In some embodiments, the weight ratio of the catalyst to the 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.

[0088] In some embodiments, crude oil is contacted with a catalyst in the presence of steam to produce a product stream that can include at least 30 wt.% of light olefins selected from ethylene, propylene, and butene. For example, in an embodiment, the product stream can include at least 35 wt.% of light olefins, at least 38 wt.% of light olefins, or at least 40 wt.% of light olefins. In some embodiments, the product stream can include at least 12 wt.% of ethylene, at least 15 wt.% of ethylene, at least 18 wt.% of ethylene, or even at least 20 wt.% of ethylene, at least 12 wt.% of propylene, at least 14 wt.% of propylene, or even at least 15 wt.% of propylene, at least 4 wt.% of butene, at least 5 wt.% of butene, or even at least 6 wt.% of butene.

[0089] Examples

[0090] Various embodiments of the method for producing hierarchical mesoporous β-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.

[0091] Example 1: Production of Catalyst

[0092] In a glass reactor, 7 grams of crystalline β-zeolite (HSZ-940NHA) with a silicon-to-aluminum molar ratio of 40 was mixed with a 0.40 M sodium hydroxide (NaOH) solution. 4.45 wt.% of cetyltrimethylammonium bromide (CTAB) was also mixed with the crystalline β-zeolite and the NaOH solution to produce a solution. The solution was heated with stirring at 100 °C for 24 hours to convert the crystalline β-zeolite into an amorphous 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 amorphous material to produce β-zeolite particles. The β-zeolite particles were filtered, thoroughly washed with distilled water, and then dried overnight at 80 °C. The dried β-zeolite particles were calcined at 570 °C for 6 hours to remove CTAB. The calcined β-zeolite particles were treated with a 0.25 N ammonium nitrate (NH 4 NO 3 ) solution twice for 5 hours to produce mesoporous β-zeolite.

[0093] First, the mesoporous β-zeolite was impregnated with phosphorus and a metal, in which the target phosphorus content was 3.5 wt.% of P 2 O 5Meanwhile, the metal content (Ce, La, and Fe) is 1 wt.%, both weight percentages being based on the total zeolite weight. Then the metal- and phosphorus-impregnated zeolite is used to form a catalyst by spray drying. The formed catalyst is prepared by making a kaolin slurry by mixing 200 g (dry basis) of kaolin powder with 431.92 g of deionized water (DI water). In a separate step, 200 g (dry basis) of the metal- and phosphorus-impregnated mesoporous beta zeolite is made into a slurry with 462.59 g of DI water and stirred for 10 minutes. The zeolite slurry is added to the kaolin slurry and stirred for 5 minutes. Separately, a slurry of Catapal B alumina is prepared by mixing 100.0 g (dry basis) of kaolin powder with 194.92 g of distilled water, and the slurry is peptized by adding 7.22 g of concentrated formic acid (70 wt.%) and stirring for 30 minutes. The resulting peptized Catapal B slurry is added to the zeolite-kaolin slurry and mixed for 10 minutes, resulting in a slurry with high viscosity where each particle remains suspended. The resulting slurry consisting of 30 wt.% solids is spray dried to produce particles of 20 - 100 microns, and then calcined at 550 °C for 6 hours to produce the catalyst. The resulting catalyst is deactivated with steam and tested for catalytic cracking in a fixed bed reactor.

[0094] Comparative Example 1

[0095] Prepare a mixture (referred to as "UMIX75") comprising 75 wt.% of an equilibrium catalyst (ECAT) and 25 wt.% of ZSM-5 (commercially available, e.g., from W.R. Grace and Company ).

[0096] Example 2: Steam-Enhanced Fluid Catalytic Cracking Test

[0097] Example 2 provides data related to cracking crude oil in the presence of steam using Example 1 and Comparative Example 1. Experiments are conducted at atmospheric pressure in a fixed bed reactor (FBR) system with Arab Extra Light (AXL) crude oil as the feed, both in the presence and absence of steam. Refer to Figure 3, a metering pump 311 is used to feed AXL crude oil 301 into a fixed-bed reactor 30. A constant feed rate of 2 g / h of AXL crude oil 301 is adopted. A metering pump 312 is used to feed water 302 into the reactor 30. A preheater 321 is used to preheat water 302. A constant feed rate of 1 g / h of water 302 is adopted. Nitrogen 303 is used as a carrier gas at 65 mL / min. A mass flow controller (MFC) 313 is used to feed nitrogen 303 into the reactor 30. A preheater 322 is used to preheat nitrogen 303. A mixer 330 is used to mix water 302 and nitrogen 303 and introduce the mixture 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. A pipeline heating furnace 331 is used to preheat this preheating zone 342. The crude oil 301 is introduced from the top of the reactor 30 through a syringe 341 and mixed with steam inside the upper two-thirds of the reactor tube 340, and then reaches 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 the crude oil and steam in the reactor is 10 seconds. Example 1 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. The 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 cracked reaction product stream is introduced into a gas-liquid separator 351. A wet gas flowmeter 352 is placed downstream of the gas-liquid separator 351. Using simulated distillation and naphtha analysis techniques, the cracked gaseous products 361 and liquid products 362 are characterized by off-line gas chromatography (GC) analysis. The ethylene, propylene, and butene yields of the reaction product stream from the cracking reaction are analyzed. The yield analysis of Example 2 is as Figure 3 shown.

[0098] Table 1

[0099] Conditions Feedstock Used AXL Whole Crude Oil Specific Gravity of Feedstock 0.829 API 39.3 Reactor Fixed-Bed Reactor Weight Hourly Space Velocity 3 Reaction Temperature, °C 675 Reaction Temperature Range, °C 600-700

[0100] As Figure 3 shown, the ethylene yield of Example 1 (20.7 wt.%) is greater than that of Comparative Example 1 (16.3 wt.%). In addition, the ethylene and propylene yields of Example 1 (37.0 wt.%) are greater than those of Comparative Example 1 (33.3 wt.%). These results show that the catalyst of Example 1 has much higher selectivity for ethylene and for ethylene and propylene compared to Comparative Example 1. In addition, the catalyst of Example 1 shows the ability to withstand high hydrothermal conditions while maintaining its activity and selectivity.

[0101] In addition, the light olefin yield of Example 1 (43.3 wt.%) is greater than that of Comparative Example 1 (43.2 wt.%).

[0102] The first aspect of the present disclosure may relate to a method for producing a catalyst, the method comprising: forming mesoporous β-zeolite particles, the forming step comprising: converting crystalline β-zeolite into an amorphous material, the amorphous material having a reduced silica content relative to the crystalline β-zeolite; and crystallizing the amorphous material to produce mesoporous β-zeolite particles; impregnating the mesoporous β-zeolite particles with a metal and phosphorus to produce a metal- and phosphorus-impregnated zeolite; and combining the metal- and phosphorus-impregnated zeolite with clay and alumina to produce a catalyst.

[0103] The second aspect of the present disclosure may include the first aspect, wherein the metal comprises Ce, La, Fe, or a combination thereof.

[0104] The third aspect of the present disclosure may include any one of the first aspect or the second aspect, wherein the metal- and phosphorus-impregnated zeolite comprises 0.1 wt.% to 5 wt.% of Ce based on the total weight of the metal- and phosphorus-impregnated zeolite; 0.1 wt.% to 5 wt.% of La based on the total weight of the metal- and phosphorus-impregnated zeolite; 0.1 wt.% to 5 wt.% of Fe based on the total weight of the metal- and phosphorus-impregnated zeolite; and 2 wt.% to 10 wt.% of P based on the total weight of the metal- and phosphorus-impregnated zeolite 2 O 5 .

[0105] The fourth aspect of the present disclosure may include any one of the first aspect to the third aspect, wherein the clay comprises kaolin.

[0106] The fifth aspect of the present disclosure may include any one of the first aspect to the fourth aspect, wherein the mass ratio of the metal- and phosphorus-impregnated zeolite to the clay is 0.5 to 2.

[0107] The sixth aspect of the present disclosure may include any one of the first aspect to the fifth aspect, wherein the conversion step comprises: mixing the crystalline β-zeolite with one or more solvents, cetyltrimethylammonium bromide (CTAB), and a metal hydroxide to form a solution; and 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.

[0108] The seventh aspect of the present disclosure may include any one of the first aspect to the sixth aspect, wherein the forming step further comprises cooling the solution to a temperature of -25°C to 50°C.

[0109] The eighth aspect of the present disclosure may include any one of the first aspect to the seventh aspect, wherein the crystallization step includes: 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.

[0110] The ninth aspect of the present disclosure may include any one of the first aspect to the eighth aspect, wherein the forming step further includes treating the β-zeolite particles with an ammonium salt at a temperature of 70°C to 90°C for 1 hour to 12 hours.

[0111] The tenth aspect of the present disclosure may include any one of the first aspect to the ninth aspect, wherein the crystalline β-zeolite has an average crystal size of 0.1 micrometer (μm) to 1.4 μm.

[0112] The eleventh aspect of the present disclosure may include any one of the first aspect to the tenth aspect, wherein the crystalline β-zeolite has a molar ratio of silica to alumina of 30 to 350.

[0113] The twelfth aspect of the present disclosure may include any one of the first aspect to the eleventh aspect, wherein the metal hydroxide is in solution and has a concentration of 0.01 mole per liter (M) to 5 M.

[0114] The thirteenth aspect of the present disclosure may include any one of the first aspect to the twelfth aspect, wherein the metal hydroxide includes 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.

[0115] The fourteenth aspect of the present disclosure may include any one of the first aspect to the thirteenth aspect, wherein the mesoporous β-zeolite has an average particle size of 0.4 μm to 1.1 μm.

[0116] The fifteenth aspect of the present disclosure may include any one of the first aspect to the fourteenth aspect, wherein the mesoporous β-zeolite has a total pore volume of 0.5 cubic centimeter per gram (cm 3 / g) to 0.8 cm 3 / g.

[0117] The sixteenth aspect of the present disclosure may include any one of the first aspect to the fifteenth aspect, wherein the mesoporous β-zeolite has a specific surface area of 450 square meters per gram (m 2 / g) to 700 m 2The Brunauer-Emmett-Teller (BET) surface area per gram.

[0118] The seventeenth aspect of the present disclosure may include any one of the first aspect to the sixteenth aspect, wherein the mesoporous β-zeolite has an average mesopore size of 2 nm to 5 nm and an average micropore size of 0.5 nm to 2.0 nm.

[0119] The eighteenth aspect of the present disclosure may relate to a method for cracking crude oil, the method comprising contacting the crude oil with a catalyst in a fluidized bed reactor, wherein the catalyst is produced by the method according to any one of the first aspect to the seventeenth aspect.

[0120] The nineteenth aspect of the present disclosure may include any one of the first aspect to the eighteenth aspect, further comprising injecting steam into the reactor, wherein the mass ratio of the steam to the crude oil is 0.2 to 1.0.

[0121] The twentieth aspect of the present disclosure may include any one of the first aspect to the nineteenth aspect, wherein the weight ratio of the catalyst to the crude oil is 7 to 40.

[0122] It should be noted that one or more of the following claims use the term "wherein" as a transitional phrase. To define the present technology, it should be noted that this term is introduced in the claim as an open transitional phrase for introducing a recitation of a series of characteristics of a structure, and should be interpreted in a manner similar to the more commonly used open preamble term "comprising". To define the present technology, the transitional phrase "consisting of" may be introduced in the claim as a closed preamble term to limit the scope of the claim to the recited components or steps and any naturally occurring impurities. To define the present technology, the transitional phrase "consisting essentially of" may be introduced in the claim 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 characteristics of the claimed subject matter. The transitional phrases "consisting of" and "consisting essentially of" may be interpreted as subsets of the open transitional phrases (such as "comprising" and "including"), and thus, any recitation using an open phrase to introduce a series of elements, components, materials, or steps should be interpreted as also disclosing a recitation of the series of elements, components, materials, or steps using the closed terms "consisting of" and "consisting essentially of". For example, a recitation of a composition "comprising" components A, B, and C should be interpreted as also disclosing a composition "consisting of" components A, B, and C, and a composition "consisting essentially of" components A, B, and C. Any quantitative value expressed in this application can be considered to include open embodiments consistent with the transitional phrase "comprising" or "including", as well as closed or partially closed embodiments consistent with the transitional phrases "consisting of" and "consisting essentially of".

[0123] As used in the specification and the appended claims, unless the context clearly dictates otherwise, the singular forms "a", "an", and "the" include plural referents. The verb "comprise" and its conjugations should be interpreted to refer to elements, components, or steps in a non-exclusive manner. The recited elements, components, or steps may be present, be used, or be combined with other elements, components, or steps not expressly recited.

[0124] It should be understood that any two quantitative values assigned to a property can constitute a range of that property, and all combinations of ranges formed by all the recited 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. Furthermore, those skilled in the art should understand that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

1. A method for producing a catalyst, the method comprising: forming mesoporous β-zeolite particles, the forming step comprising: converting crystalline β-zeolite into an amorphous material, the amorphous material having a reduced silica content relative to the crystalline β-zeolite; and crystallizing the amorphous material to produce mesoporous β-zeolite particles; impregnating the mesoporous β-zeolite particles with metal and phosphorus to produce a metal- and phosphorus-impregnated zeolite; and combining the metal- and phosphorus-impregnated zeolite with clay and alumina to produce the catalyst.

2. The method according to claim 1, wherein the metal comprises Ce, La, Fe, or a combination thereof.

3. The method according to any one of the preceding claims, wherein the metal- and phosphorus-impregnated zeolite comprises: 0.1 wt.% to 5 wt.% of Ce based on the total weight of the metal- and phosphorus-impregnated zeolite; 0.1 wt.% to 5 wt.% of La based on the total weight of the metal- and phosphorus-impregnated zeolite; 0.1 wt.% to 5 wt.% of Fe based on the total weight of the metal- and phosphorus-impregnated zeolite; and P in an amount of 2 wt.% to 10 wt.% based on the total weight of the metal- and phosphorus-impregnated zeolite 2 O 5 .

4. The method according to any one of the preceding claims, wherein the clay comprises kaolin.

5. The method according to any one of the preceding claims, wherein the mass ratio of the metal- and phosphorus-impregnated zeolite to the clay is 0.5 to 2.

6. The method according to any one of the preceding claims, wherein the conversion step comprises: mixing the crystalline β-zeolite with one or more solvents, cetyltrimethylammonium bromide (CTAB), and a metal hydroxide to form a solution; and heating the solution at a temperature of 50°C to 150°C to convert the crystalline β-zeolite into the amorphous material, the amorphous material having a reduced silica content relative to the crystalline β-zeolite.

7. The method according to claim 6, wherein the forming step further comprises cooling the solution to a temperature of -25°C to 50°C.

8. The method according to claim 6, wherein the crystallization step comprises: 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 amorphous material to produce the β-zeolite particles.

9. The method according to any one of the preceding claims, wherein the forming step further comprises treating the β-zeolite particles with an ammonium salt at a temperature of 70°C to 90°C for 1 hour to 12 hours.

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

11. The method according to any one of the preceding claims, wherein the crystalline β-zeolite has 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 has a concentration of 0.01 moles per liter (M) to 5 M.

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 according to any one of the preceding claims, wherein the mesoporous β-zeolite comprises one or more of the following: The average particle size is from 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; The Brunauer-Emmett-Teller (BET) surface area is from 450 square meters per gram (m 2 / g) to 700 m 2 / g; or The average mesopore size is from 2 nm to 5 nm, and the average micropore size is from 0.5 nm to 2.0 nm.

15. A process for cracking crude oil, the process comprising contacting the crude oil with a catalyst in a fluidized bed reactor, wherein the catalyst is produced by the process according to any one of the preceding claims.

16. The process according to claim 13, further comprising injecting steam into the reactor, wherein the mass ratio of the steam to the crude oil is from 0.2 to 1.

0.

17. The process according to claim 13, wherein the weight ratio of the catalyst to the crude oil is from 7 to 40.

Images