Catalysts containing phosphorus-stabilized MSE framework zeolite, their preparation and use in fluid contact applications

Abstract

Disclosed herein are catalyst components suitable for petroleum refining applications (e.g., fluid catalytic cracking and hydrocracking) comprising an MSE zeolite structure (e.g., MCM-68) and a non-zeolitic matrix. The first component can be combined with additional components to form a catalyst composition. Also disclosed herein are methods for preparing the catalyst component and / or catalyst composition, and methods for using the catalyst component and / or catalyst composition.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 109,414, filed on November 4, 2020, the disclosure of which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to petroleum refining catalysts and compositions thereof. In particular, this disclosure relates to the use of MSE zeolite structures for fluid catalytic cracking (FCC) applications, methods for preparing them, and methods for using them. [Background technology]

[0003] FCCs are the primary source of butylene production worldwide. Nearly half of butylene production comes from FCC units, with over 40% consumed to produce high-octane blend components via alkylation units. Due to increasing demand for improved fuel efficiency, more refineries are finding it beneficial to increase butylene production in these units. However, conventional olefin maximization additives based solely on ZSM-5 are insufficient to achieve this goal. ZSM-5 additives are designed to produce propylene, and therefore, they produce more propylene than butylene. If a unit is limited to a wet gas compressor, the use of ZSM-5 increases propylene production over butylene, leading to the liquefied petroleum gas (LPG) limit being reached before the required butylene yield is achieved. In such cases, the unit requires a catalyst (or additive) solution that contributes to an increased butylene / propylene (C4= / C3=) ratio compared to ZSM-5. Identifying materials with controlled and intentionally tuned selectivity for specific small olefins (e.g., butylene) is of interest in petroleum refining applications (e.g., fluid catalytic cracking, hydrocracking). [Overview of the Initiative] [Means for solving the problem]

[0004] In certain embodiments, the disclosure provides a catalyst component comprising a zeolite (e.g., MCM-68 zeolite) having a phosphorus-stabilized MSE zeolite structure with about 0.5% to about 10% by weight of phosphorus based on the total weight of the zeolite, and a non-zeolite matrix.

[0005] In certain embodiments, the phosphorus content in the catalyst component is in the range of about 1% to about 5% by weight or about 2% to about 4% by weight, based on the total weight of the zeolite.

[0006] In certain embodiments, the non-zeolite matrix includes one or more of the following: clay, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, or mixtures thereof.

[0007] In certain embodiments, a phosphorus-stabilized zeolite having an MSE structure (e.g., MCM-68) is present in the catalyst component in an amount of about 1% to about 90% by weight, about 2% to about 80% by weight, or about 5% to about 60% by weight, based on the total weight of the catalyst component.

[0008] In certain embodiments, the catalyst component has a total acidity of about 0.5 mmol / (g catalyst component).

[0009] In certain embodiments, phosphorus-stabilized zeolites having an MSE structure (e.g., MCM-68) have silicon-to-aluminum ratios (SARs) in the range of about 5 to about 60, about 7 to about 30, or about 9 to about 15.

[0010] In a particular embodiment, the total BET surface area of ​​the catalyst component is approximately 150 m². 2 / g ~ approx. 750m 2 / g, approx. 175m 2 / g ~ approx. 675m2 / g or about 200 m 2 / g to about 600 m 2 / g.

[0011] In certain embodiments, the t-plot micropore volume of the catalyst component ranges from about 0.05 cc / g to about 0.3 cc / g, from about 0.06 cc / g to about 0.23 cc / g, or from about 0.07 cc / g to about 0.16 cc / g.

[0012] In certain embodiments, the phosphorus-stabilized zeolite has an MSE structure comprising a porous crystalline material comprising at least one channel system wherein each channel is defined by a 12-membered ring of tetrahedrally coordinated atoms, and at least two additional independent channel systems wherein each channel is defined by a 10-membered ring of tetrahedrally coordinated atoms, and the number of unique 10-membered ring channels is twice the number of 12-membered ring channels.

[0013] In certain embodiments, a phosphorus-stabilized zeolite having an MSE structure (e.g., phosphorus-stabilized MCM-68) has a first X-ray diffraction (XRD) pattern that is substantially similar in peak position and relative intensity to a second XRD pattern of the zeolite without phosphorus stabilization (e.g., phosphorus-free MCM-68 zeolite).

[0014] In certain embodiments, the present disclosure provides a catalyst composition for petroleum refining applications (such as fluid catalytic cracking (FCC) and / or hydrocracking) comprising a first component and a second component.

[0015] The first component comprises a zeolite having a phosphoric acid-stabilized MSE zeolite structure (e.g., MCM-68 zeolite) with from about 0.5 wt% to about 10 wt% phosphorus, based on the total weight of the zeolite in the first component, and a non-zeolitic matrix. The first component can also be any catalyst component described herein comprising a zeolite having an MSE zeolite structure.

[0016] The second component is compositionally different from the first component. In certain embodiments, the second component comprises a second non-zeolite matrix and one or more zeolites (e.g., ZSM-5, zeolite Y, beta-zeolite, etc.). In certain embodiments, the catalyst composition may include at least one additional catalyst component (e.g., ZSM-5, zeolite Y, beta-zeolite, etc.) that is compositionally different from the first and second components.

[0017] In certain embodiments, the first catalyst component is present in the catalyst composition in an amount ranging from about 1% to about 25% by weight, about 1.5% to about 15% by weight, or about 2% to about 10% by weight, based on the total weight of the catalyst composition.

[0018] In certain embodiments, the second catalyst component and any additional catalyst components, if included, are present in the catalyst composition in amounts ranging from about 75% to about 99% by weight, about 85% to about 98.5% by weight, or about 90% to about 98% by weight (cumulative), based on the total weight of the catalyst composition.

[0019] In certain embodiments, the disclosure relates to a process for preparing any of the catalyst components described herein, including a phosphate-stabilized zeolite having an MSE zeolite structure. In certain embodiments, the process includes stabilizing (e.g., modifying by impregnation) a zeolite having an MSE zeolite structure (e.g., MCM-68) with a phosphorus-containing compound, but not limited to phosphoric acid, diammonium phosphate, or a combination thereof. In certain embodiments, the process may further include calcining the phosphorus-stabilized zeolite having an MSE zeolite structure (e.g., phosphorus-stabilized MCM-68).

[0020] In certain embodiments, the disclosure relates to a process for preparing any catalyst composition described herein by combining any catalyst component described herein (referred to as the first catalyst component), which includes a phosphorus-stabilized zeolite having an MSE zeolite structure, with a second catalyst component that is compositionally different from the first catalyst component and optionally at least one additional catalyst component.

[0021] The catalyst compositions described herein include multiple zeolite skeletons that provide excellent butylene activity, butylene yield, and butylene selectivity while maintaining constant or low yields and selectivity of less desirable products such as hydrogen, coke, higher hydrocarbons (such as C6 and C7), and lower hydrocarbons (such as C3). The catalyst components described herein, including phosphorus-stabilized zeolites having an MSE zeolite structure, also provide similar excellent performance.

[0022] In certain embodiments, the disclosure relates to a process of catalytic cracking of a hydrocarbon feedstock by contacting the feedstock with any of the catalyst components described herein, comprising a phosphorus-stabilized zeolite having an MSE zeolite structure (e.g., phosphorus-stabilized MCM-68) and a non-zeolite matrix. In certain embodiments, the contact occurs with a catalyst component that is part of any of the catalyst compositions described herein.

[0023] In certain embodiments, a first butylene-to-propylene selectivity ratio achieved by contacting the feedstock with any of the catalyst components described herein, including a phosphorus-stabilized zeolite having an MSE zeolite structure (e.g., phosphorus-stabilized MCM-68), and a non-zeolite matrix is ​​greater than a second butylene-to-propylene selectivity ratio achieved by contacting the feedstock with a catalyst component including a beta-zeolite and / or ZSM-5 zeolite (e.g., un-phosphorus-stabilized MCM-68), without the phosphorus-stabilized zeolite having an MSE zeolite structure.

[0024] In certain embodiments, the zeolite structure and activity may be demonstrated by one or more of the following properties: zeolite surface area (ZSA), total surface area (TSA), steamed zeolite surface area (sZSA), total acidity, pore volume, TC4=(total butylene) yield, and butylene-to-propylene selectivity ratio. These values ​​are achievable targets and should be considered not specific to the catalyst components or catalyst compositions described herein.

[0025] The above and other features of this disclosure, their properties, and various advantages will become more apparent from the following detailed description, which will be considered in conjunction with the accompanying drawings. [Brief explanation of the drawing]

[0026] [Figure 1A] This shows the X-ray diffraction (XRD) pattern of the catalyst component containing MCM-68 zeolite. [Figure 1B] Figure 1A shows the XRD pattern after steaming of the same catalyst component. [Figure 2] Figure 2A shows the performance (in terms of conversion and selectivity) of the catalyst component containing MCM-68 zeolite before steaming and without phosphorus modification. Figure 2B shows the performance (in terms of conversion and selectivity) of the catalyst component containing MCM-68 zeolite after steaming and without phosphorus modification. Figure 2C shows the performance (in terms of conversion and selectivity) of the catalyst component containing MCM-68 zeolite after phosphorus modification with 2 wt% phosphorus and steaming. Figure 2D shows the performance (in terms of conversion and selectivity) of the catalyst component containing MCM-68 zeolite after phosphorus modification with 4 wt% phosphorus and steaming. Figure 2E shows the performance (in terms of conversion and selectivity) of the catalyst component containing MCM-68 zeolite and the comparative base catalyst component containing ZSM-5 zeolite. [Modes for carrying out the invention]

[0027] definition As used herein, the singular forms “a,” “an,” and “it” include multiple references unless the context explicitly indicates otherwise. For example, a reference to “component” includes a single component and mixtures of two or more similar or different components.

[0028] As used herein, the term “about” in relation to a measured quantity refers to the normal variation in that measured quantity that can be expected by a person skilled in the art who performs the measurement and exercises a level of care commensurate with the purpose of the measurement and the precision of the measuring instrument. In certain embodiments, the term “about” includes the number mentioned ± 10%, for example, “about 10” would include 9 to 11.

[0029] As used herein, the terms “catalyst,” “catalytic composition,” or “catalytic material” refer to a material that facilitates a reaction. As used herein, the term “composition,” when referring to a catalytic composition or additive composition, means a blend or mixture of two or more distinct components, such as a first component mixed or blended with a second component. In certain embodiments, the components in a composition are chemically bound and cannot be separated by physical means (e.g., filtration). In other embodiments, the components in a composition are not chemically bound and can be separated by physical means (e.g., filtration).

[0030] As used herein, the terms “fluid catalytic cracking” or “FCC” refer to a conversion process in a petroleum refinery that converts high-boiling-point, high-molecular-weight hydrocarbon fractions of crude petroleum into more valuable products such as gasoline, olefinic gases, and other products.

[0031] "Decomposition conditions" or "FCC conditions" refer to typical FCC process conditions. A typical FCC process is carried out at a reaction temperature of 450°C to 650°C and a catalyst regeneration temperature of 600°C to 850°C. A high-temperature regenerating catalyst is added to the hydrocarbon feed at the bottom of the rise reactor. Fluidization of the solid catalyst particles can be facilitated by a lift gas. The catalyst vaporizes and superheats the feed to the desired decomposition temperature. As the catalyst and feed rise, the feed decomposes and coke deposits on the catalyst. The coked catalyst and decomposition products exit the riser and enter a solid-gas separation system, such as a series of cyclones, at the top of the reaction vessel. The decomposed products are fractionated into a range of products including gas, gasoline, light gas oil, and heavy cycle gas oil. Some heavier hydrocarbons can be recycled back into the reactor.

[0032] As used herein, the terms “feed” or “supply material” refer to portions of crude oil having high boiling points and high molecular weight. In the FCC process, hydrocarbon feed material is injected into the riser section of the FCC unit, where it is broken down into lighter, more valuable products upon contact with a high-temperature catalyst that is circulated from the catalyst regenerator to the riser-reactor.

[0033] As used herein, “particles” may be in the form of microspheres that can be obtained by spray drying. As understood by the parties, the microspheres do not necessarily have to be perfectly spherical.

[0034] As used herein, the terms “non-zeolite component,” “matrix,” or “non-zeolite matrix” refer to components of an FCC catalyst that are not zeolites or molecular sieves. As used herein, non-zeolite components may include binders and fillers.

[0035] As used herein, the term "zeolite" refers to a crystalline aluminosilicate having a framework based on a broad three-dimensional network of silicon, aluminum, and oxygen ions, and having a substantially uniform pore distribution.

[0036] The enumeration of value ranges herein is intended solely as a simplification for referring individually to each individual value within the range unless otherwise indicated herein, and each individual value is incorporated herein in the same way as it is individually enumerated herein. All methods described herein may be carried out in any preferred order unless otherwise indicated herein or unless otherwise clearly contradicted by the context. The use of any and all examples or exemplary language provided herein (e.g., "etc.") is intended merely to illustrate specific materials and methods and does not raise any limitation on scope. Nothing in this specification should be construed as indicating that any unclaimed element is essential for carrying out the disclosed materials and methods.

[0037] This disclosure relates, in certain embodiments, to a catalyst component comprising a phosphorus-stabilized zeolite having an MSE zeolite structure such as phosphorus-stabilized MCM-68, a method for preparing the same, and a method for using the same. In certain embodiments, this disclosure relates to a catalyst composition comprising the catalyst component, a method for preparing the same, and a method for using the same.

[0038] In this specification, the above-mentioned catalyst component, referred to as the first catalyst component, and a method for preparing the same are described, followed by a description of catalyst compositions and a method for preparing the same, and further, a method for using any of the first catalyst components and / or any of the catalyst compositions considered in this disclosure is described.

[0039] First catalytic component In certain embodiments, the first catalyst component comprises a zeolite having an MSE zeolite structure, such as phosphorus-stabilized MCM-68, and a first non-zeolite matrix. The MSE zeolite structure refers to a porous crystalline material comprising at least one channel system in which each channel is defined by a 12-membered ring of tetrahedral coordinating atoms, and at least two further independent channel systems, each of which comprises at least two further independent channel systems in which each channel is defined by a 10-membered ring of tetrahedral coordinating atoms, wherein the number of intrinsic 10-membered ring channels is twice the number of 12-membered ring channels.

[0040] In certain embodiments, the dimensions of the 12-membered ring channels in the MSE zeolite structure are approximately 0.64 × 0.68 nm, the dimensions of one of the 10-membered ring channels in the MSE zeolite structure are approximately 0.52 × 0.58 nm, and the dimensions of another of the 10-membered ring channels in the MSE zeolite structure are approximately 0.52 × 0.52 nm. An exemplary X-ray diffraction (XRD) pattern of the MSE zeolite structure is shown in Figure 1 (see MCM-68 curve).

[0041] In certain embodiments, a phosphorus-stabilized MSE structured zeolite (e.g., phosphorus-stabilized MCM-68) has a first XRD pattern that is substantially similar in terms of peak position and intensity to a second XRD pattern of the same zeolite without phosphorus stabilization.

[0042] In certain embodiments, the silicon-to-aluminum ratio (SAR) of the phosphorus-stabilized MSE structure zeolite (e.g., phosphorus-stabilized MCM-68) is in the range of about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13 or about 14 to about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55 or about 60, or any sub-range thereof or a single SAR value. In one embodiment, the SAR of the phosphorus-stabilized MSE structure zeolite (e.g., phosphorus-stabilized MCM-68) in the first catalyst component is in the range of about 5 to about 60. In one embodiment, the SAR of the phosphorus-stabilized MSE structure zeolite (e.g., phosphorus-stabilized MCM-68) in the first catalyst component is in the range of about 7 to about 30. In one embodiment, the SAR of the phosphorus-stabilized MSE structure zeolite (e.g., phosphorus-stabilized MCM-68) in the first catalyst component is in the range of about 9 to about 15. While not to be interpreted restrictively, SAR is considered to be an important parameter affecting the stability and activity of the zeolite. The SAR value should be balanced between maintaining the stability of the zeolite structure and its butylene activity.

[0043] The phosphorus content in the first catalyst component is in the range of about 0.5% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 2.5% by weight, about 3% by weight, or about 3.5% by weight, based on the total weight of the zeolite in the first catalyst component, to about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, or about 10% by weight, or any partial range thereof, or a single phosphorus concentration value. In one embodiment, the phosphorus content is in the range of about 0.5% by weight to about 10% by weight, based on the total weight of the zeolite in the first catalyst component. In one embodiment, the phosphorus content is in the range of about 1% by weight to about 5% by weight, based on the total weight of the zeolite in the first catalyst component. In one embodiment, the phosphorus content is in the range of about 2% by weight to about 4% by weight, based on the total weight of the zeolite in the first catalyst component.

[0044] The first catalyst component may include phosphorus-stabilized MSE structured zeolite (e.g., phosphorus-stabilized MCM-68) in amounts ranging from about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, or about 35% by weight, to about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, about 80% by weight, about 85% by weight, or about 90% by weight, or any sub-range or single concentration value thereof. The remainder may be the first non-zeolite matrix and / or one or more additional zeolites.

[0045] The first non-zeolite matrix may include one or more of the following: clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titanium, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, rare earth-doped alumina (e.g., selected from one or more of ytterbium-doped alumina, gadolinium-doped alumina, cerium-doped alumina, or lanthanum-doped alumina), silica-doped alumina, gamma-alumina, α-alumina, χ-alumina, δ-alumina, θ-alumina, κ-alumina, or mixtures thereof.

[0046] The one or more additional zeolites may comprise zeolites having a structure selected from the group consisting of BEA (e.g., beta zeolite), MSE, -SVR, FAU (e.g., zeolite Y), MOR, CON, SOF, MFI (e.g., ZSM-5), IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, TUN, YFI, and combinations thereof. In certain embodiments, the one or more additional zeolites include, but are not limited to, (1) large pore zeolites (e.g., those having a pore opening larger than about 7 angstroms), such as USY, REY, silicoaluminophosphate SAPO-5, SAPO-37, SAPO-40, MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5, or mesoporous crystalline material MCM-41; REUSY, zeolite X, zeolite Y, dealuminated zeolite Y, silica-enhanced dealuminated zeolite Y, zeolite beta, ZSM-3, ZSM-4, ZSM-18, and ZSM-20, (2) medium pore zeolites (e.g., those having a pore opening from about 4 angstroms to about 7 angstroms), such as ZSM-5, MCM-68, ZSM-11, ZSM-11 intermediate, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, silicoaluminophosphate SAPO-31, and (3) small pore zeolites (e.g., those having a pore opening of less than about 4 angstroms), such as erionite and ZSM-34. In certain embodiments, the one or more additional zeolites may include, but are not limited to, zeolite A, zeolite B, zeolite F, zeolite H, zeolite K~G, zeolite L, zeolite M, zeolite Q, zeolite R, zeolite T, mordenite, erionite, offretite, ferrierite, chabazite, clinoptilolite, gmelinite, phillipsite, and faujasite.

[0047] In certain embodiments, the BET total surface area (TSA) of the first catalyst component before steaming and / or after steaming is about 150 m 2 / g, about 175 m 2 / g, about 200 m 2 / g, about 225 m2 / g, approx. 250m 2 / g, approx. 275m 2 / g, approx. 300m 2 / g, approx. 325m 2 / g, approx. 350m 2 / g, approx. 375m 2 / g or approximately 400m 2 Approximately 425m from any of / g 2 / g, approx. 450m 2 / g, approx. 475m 2 / g, approx. 500m 2 / g, approx. 525m 2 / g, approx. 550m 2 / g, approx. 575m 2 / g, approx. 600m 2 / g, approx. 625m 2 / g, approx. 650m 2 / g, approx. 675m 2 / g, approx. 700m 2 / g, approx. 725m 2 / g or approximately 750m 2 The range is any of the values ​​up to / g, or any partial range or single area value. In one embodiment, the total BET surface area of ​​the first catalyst component before and / or after steaming is approximately 150 m². 2 / g ~ approx. 750m 2 The range is / g. In one embodiment, the total BET surface area of ​​the first catalyst component before and / or after steaming is approximately 175 m². 2 / g ~ approx. 675m 2 The range is / g. In one embodiment, the total BET surface area of ​​the first catalyst component before and / or after steaming is approximately 200m². 2 / g~about 600m 2 The range is / g. Although not to be interpreted restrictively, butylene activity (quantified as the amount of butylene per dose of the first catalytic component produced when at least the first catalytic component is brought into contact with a hydrocarbon feed) is thought to increase with increasing zeolite surface area (ZSA) (or TSA) and / or steamed zeolite surface area (SZSA) (or steamed TSA).

[0048] In a particular embodiment, the first catalyst component is present in an amount of approximately 0.16cc / g, approximately 0.17cc / g, from approximately 0.05cc / g, approximately 0.06cc / g, approximately 0.07cc / g, approximately 0.08cc / g, approximately 0.09cc / g, approximately 0.10cc / g, approximately 0.11cc / g, approximately 0.12cc / g, approximately 0.13cc / g, approximately 0.14cc / g, or approximately 0.15cc / g, before and / or after steaming. The t-plot micropore volume is in the range of approximately 0.18 cc / g, approximately 0.19 cc / g, approximately 0.20 cc / g, approximately 0.21 cc / g, approximately 0.22 cc / g, approximately 0.23 cc / g, approximately 0.24 cc / g, approximately 0.25 cc / g, approximately 0.26 cc / g, approximately 0.27 cc / g, approximately 0.28 cc / g, approximately 0.29 cc / g, or approximately 0.30 cc / g, or any sub-range thereof, or a single micropore volume value. In one embodiment, the first catalyst component has a t-plot micropore volume in the range of approximately 0.05 cc / g to approximately 0.30 cc / g before and / or after steaming. In one embodiment, the first catalyst component has a t-plot micropore volume in the range of approximately 0.06 cc / g to approximately 0.23 cc / g before and / or after steaming. In one embodiment, the first catalyst component has a t-plot micropore volume in the range of about 0.07 cc / g to about 0.16 cc / g before and / or after steaming. Without being interpreted restrictively, the micropore volume of the first catalyst component is considered to make a significant contribution to the butylene-related activity of the first catalyst component.

[0049] In certain embodiments, the first catalyst component has an acidity in the range of approximately 0.3 mmol / (g catalyst) to approximately 0.7 mmol / (g catalyst), approximately 0.3 mmol / (g catalyst) to approximately 0.6 mmol / (g catalyst), or approximately 0.3 mmol / (g catalyst) to approximately 0.5 mmol / (g catalyst), or any sub-range thereof, or a single total acidity value, before and / or after steaming. Without being interpreted restrictively, the total acidity of the first catalyst component may reflect the butylene-related activity of the first catalyst component. The total acidity, which provides information on the total number of acidic sites in the catalyst component tested, is measured by NH3 temperature-controlled desorption.

[0050] Preparation of a first catalyst component according to one embodiment of the present disclosure is initiated by combining a silicon source (e.g., colloidal SiO2), an aluminum source (e.g., Al(OH)3), a base (e.g., KOH), and water, and stirring the mixture over a first period of time. The initial stirring may be carried out at room temperature for about 10 to about 60 minutes, about 15 to about 45 minutes, or about 20 to about 40 minutes. The amounts of silicon and aluminum sources added may be adjusted to achieve a target SAR. The types of silicon, aluminum, or base should not be interpreted restrictively. Other suitable silicon, aluminum, or bases that can be easily identified by those skilled in the art may be used.

[0051] Subsequently, a structural indicator (SDA), such as an SDA having the chemical structure shown below, may be added to the mixture, and the SDA and the mixture may then be stirred over a second period. [ka] The SDA and mixture may be stirred at room temperature for approximately 1 to 10 hours, 2 to 7 hours, or 3 to 5 hours.

[0052] Subsequently, the SDA and the stirred mixture may undergo hydrothermal synthesis at a high temperature over a third period. Hydrothermal synthesis can be carried out at temperatures ranging from about 100°C to about 250°C, about 120°C to about 200°C, or about 140°C to about 180°C. The third period of hydrothermal synthesis may range from about 1 day to about 30 days, about 5 days to about 25 days, or about 10 days to about 20 days.

[0053] In certain embodiments, once the hydrothermal synthesis and crystallization process of the MSE structured zeolite (e.g., MCM-68) is complete, the slurry may be filtered to separate the MSE structured zeolite from a substantial portion of its mother liquor. The microspheres may be washed, for example, by contact with water either during or after filtration. The purpose of the washing step is to remove any mother liquor remaining in the microspheres. The microspheres may then be dried. Drying may be carried out at temperatures in the range of about 40°C to about 120°C, about 60°C to about 100°C, or about 70°C to about 90°C. The drying period may range from about 2 hours to about 72 hours, about 5 hours to about 24 hours, or about 8 hours to about 15 hours.

[0054] The process for preparing the first catalyst component may further include modifying or stabilizing a synthesized MSE structured zeolite (e.g., synthesized MCM-68) with phosphorus. In certain embodiments, modification or stabilization may include impregnating the synthesized MSE structured zeolite (e.g., synthesized MCM-68) with phosphorus. Impregnation may be through induce wet impregnation with a phosphorus source. Suitable phosphorus sources may include, but are not limited to, phosphoric acid, diammonium phosphate, or a combination thereof. In certain embodiments, other methods may be utilized for modifying or stabilizing the MSE structured zeolite (e.g., MCM-68) with phosphorus. The amount of phosphorus source utilized may be adjusted to achieve a target phosphorus content in the first catalyst component.

[0055] Phosphorus-stabilized MSE structured zeolite (e.g., phosphorus-stabilized MCM-68) may be dried (in addition to or instead of the previously described drying step, before phosphorus denaturation / stabilization). In certain embodiments, drying of phosphorus-stabilized MSE zeolite may occur at temperatures in the range of about 40°C to about 250°C, about 80°C to about 200°C, or about 100°C to about 140°C. The drying time for phosphorus-stabilized MSE zeolite may be in the range of about 2 hours to about 72 hours, about 5 hours to about 24 hours, or about 8 hours to about 15 hours.

[0056] The process for preparing the first catalyst component may further include calcining a phosphorus-stabilized MSE structured zeolite (e.g., phosphorus-stabilized MCM-68) in, for example, a muffle furnace. The calcination period may range from about 30 minutes to about 10 hours, about 1 hour to about 8 hours, or about 2 hours to about 4 hours. The calcination temperature may range from about 400°C to about 800°C, about 500°C to about 750°C, or about 600°C to about 700°C. The calcination temperature and period should not be interpreted restrictively. Other calcination periods and temperatures may be used under various circumstances.

[0057] The processes described herein for preparing the first catalyst component should not be interpreted restrictively. In particular embodiments, one or more drying steps may be carried out in various parts of the process, one or more calcination steps may be carried out in various parts of the process, one or more phosphorus stabilization / modification steps may be carried out in various parts of the process, and so on. Similarly, the order of the steps should not be interpreted restrictively, and it should be understood that phosphorus stabilization / modification, and / or drying, and / or calcination (and optionally other steps) may be introduced in process steps different from those described herein. In particular embodiments, a single entity may carry out all of the above process steps, while in other embodiments, two or more entities may carry out the above process steps.

[0058] While not to be interpreted restrictively, the inclusion of phosphorus in the first catalyst component is thought to stabilize the first catalyst component against steam treatment, which contributes to improved performance in fluid catalytic cracking and / or hydrocracking applications. Different zeolite structures exhibit different behaviors under harsh conditions such as steam treatment, and therefore each zeolite will benefit from customized stabilization techniques as needed. In certain zeolite structures, such as zeolite Y, rare earth cations may be used for structural stabilization. A stabilization technique that may be effective for one zeolite structure may not be effective for a different zeolite structure. Notwithstanding the foregoing, surprisingly, it has been confirmed herein that phosphorus may be used for structural stabilization of MSE structure zeolites such as MCM-68 under steam treatment conditions.

[0059] Catalyst composition In certain embodiments, the disclosure relates to a catalyst composition comprising any of the first catalyst components described herein, together with a second catalyst component and optionally at least one additional component. The second catalyst composition is compositionally different from the first catalyst component. Any additional components that may be present may also be compositionally different from the first and second catalyst components.

[0060] The second catalyst component may include a second zeolite and a second non-zeolite matrix. Each of the at least one additional component may include each of the one additional non-zeolite matrix. In certain embodiments, the at least one additional component includes at least one additional zeolite.

[0061] The second zeolite and / or at least one additional zeolite may be independently selected from zeolites having the structures BEA (e.g., beta zeolite), MSE, -SVR, FAU (e.g., zeolite Y), MOR, CON, SOF, MFI (e.g., ZSM-5), IMF, FER, MWW, MTT, TON, EUO, MRE, NAT, CHA, TUN, YFI, or combinations thereof. In certain embodiments, the second zeolite and / or at least one additional zeolite is, but is not limited to, (1) a large-pore zeolite (e.g., having a pore opening larger than about 7 angstroms), e.g., USY, REY, silicoaluminophosphate SAPO-5, SAPO-37, SAPO-40, MCM-9, metalloaluminophosphate MAPO-36, aluminophosphate VPI-5 or mesoporous crystalline material MCM-41; REUSY, zeolite X, zeolite Y, dealuminized zeolite Y, silica-reinforced dealuminized zeolite Y, zeolite (2) Medium-pore zeolites (e.g., those having pore openings of about 4 angstroms to about 7 angstroms), such as ZSM-5, MCM-68, ZSM-11, ZSM-11 intermediate, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-57 silicoaluminophosphate SAPO-31, and (3) Small-pore zeolites (e.g., those having pore openings of less than about 4 angstroms), such as erionite and ZSM-34, can be independently selected. In certain embodiments, the second zeolite and / or at least one additional zeolite may be independently selected from, but are not limited to, zeolite A, zeolite B, zeolite F, zeolite H, zeolite K-G, zeolite L, zeolite M, zeolite Q, zeolite R, zeolite T, mordenite, erionite, offret, ferrielite, chabasite, clinoptilolite, gmelin, philipsite, faujasite and combinations thereof.

[0062] Many of the hydrothermal and / or chemically modified forms of the above-mentioned zeolites can also be appropriately used as a second catalyst component and / or at least one additional component (if any) in the catalyst compositions considered herein.

[0063] In one embodiment, the second zeolite in the second component and / or at least one additional zeolite in at least one additional component (if present) includes a large-pore molecular sieve zeolite having a pore diameter greater than 7 angstroms. In one embodiment, the second zeolite in the second component and / or at least one additional zeolite in at least one additional component (if present) includes zeolite Y. In one embodiment, the second zeolite in the second component and / or at least one additional zeolite in at least one additional component (if present) includes ZSM-5, beta-zeolite, or a combination thereof. In one embodiment, the second zeolite in the second component is Y zeolite, and at least one additional zeolite in at least one additional component (if present) is ZSM-5, beta-zeolite, or a combination thereof. In one embodiment, the second zeolite in the second component is a combination of Y zeolite and at least one of ZSM-5 and beta-zeolite.

[0064] The second non-zeolite matrix in at least one additional component and / or at least one additional non-zeolite matrix (if present) is independently clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, It may include one or more of the following: silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, rare earth-doped alumina (e.g., one or more selected from ytterbium-doped alumina, gadolinium-doped alumina, cerium-doped alumina, or lanthanum-doped alumina), silica-doped alumina, gamma-alumina, α-alumina, χ-alumina, δ-alumina, θ-alumina, κ-alumina, or mixtures thereof.

[0065] Any of the first catalyst components described herein may be present in amounts of about 1% by weight, about 1.5% by weight, about 2.0% by weight, about 2.5% by weight, about 3.0% by weight, about 3.5% by weight, about 4.0% by weight, about 4.5% by weight, about 5.0% by weight, about 5.5% by weight, about 6.0% by weight, about 6.5% by weight, about 7.0% by weight, about 7.5% by weight, about 8.0% by weight, about 8.5% by weight, about 9.0% by weight, or about 9.5% by weight, based on the total weight of the catalyst composition. Any of the following may be present in any catalyst composition considered herein in amounts ranging from about 10% by weight, about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, about 15% by weight, about 16% by weight, about 17% by weight, about 18% by weight, about 19% by weight, about 20% by weight, about 21% by weight, about 22% by weight, about 23% by weight, about 24% by weight, or about 25% by weight, or in any partial range or single concentration value thereof. In one embodiment, the first catalyst composition is present in the catalyst composition in an amount ranging from about 1% by weight to about 25% by weight based on the total weight of the catalyst composition. In one embodiment, the first catalyst composition is present in the catalyst composition in an amount ranging from about 1.5% by weight to about 15% by weight based on the total weight of the catalyst composition. In one embodiment, the first catalyst composition is present in the catalyst composition in an amount ranging from about 2% by weight to about 10% by weight based on the total weight of the catalyst composition.

[0066] The second catalyst component and / or any additional components are present in the catalyst composition in an amount that cumulatively adds up to 100% by weight, together with the concentration of the first catalyst component.

[0067] In certain embodiments, the second catalyst component includes a large-pore molecular sieve zeolite having a pore diameter greater than 7 angstroms (for example, but not limited to zeolite Y, dealuminized zeolite Y, silica-reinforced dealuminized zeolite Y, REY, USY, CREY, REUSY, etc.) present in the catalyst composition in amounts ranging from about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, about 60% by weight, about 65% by weight, about 70% by weight, about 75% by weight, or about 80% by weight, to about 85% by weight, about 91% by weight, about 92% by weight, about 93% by weight, about 94% by weight, about 95% by weight, or about 96% by weight, or any partial range or single value thereof.

[0068] In certain embodiments, at least one additional component is present in the catalyst composition in an amount ranging from about 0.5% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 2.5% by weight, or about 3% by weight, to about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, or about 15% by weight, or any partial range or single value thereof.

[0069] In certain embodiments, the amount of the first catalyst component in the catalyst composition is lower than the amount of the second catalyst component. For example, the weight-to-weight ratio of the first catalyst component to the second catalyst component in the FCC catalyst composition may be about 1:1.5 to about 1:20, about 1:3 to about 1:15, or about 1:5 to about 1:13, or any sub-range or single ratio value thereof.

[0070] In certain embodiments, the Disclosure relates to a method for preparing any catalyst composition described herein by combining any first catalyst component described herein with a second catalyst component and, if present, optionally at least one additional component. This process may further include preparing each component in the catalyst composition, for example, preparing the first catalyst component and / or preparing the second catalyst component and / or preparing any additional components that may be present in the composition.

[0071] In certain embodiments, various components may be formulated as separate, distinct particles. In this embodiment, the first catalyst component may be added to the FCC catalyst composition as needed to provide a customized catalyst solution with customized performance. The catalyst composition may be designed to exhibit improved performance, such as improved total butylene yield, improved butylene-to-propylene selectivity ratio, and improved catalyst stability (e.g., stability of the catalyst component and / or zeolite structure in the catalyst composition).

[0072] How to use MSE-structured zeolites have been used in specific reactions such as methanol to olefin (MTO), methanol to propylene (MTP), isomerization, alkylation, and dimethoxyethane to light olefins, but these zeolites have not attracted much attention in the realm of fluid catalytic cracking (FCC). The reaction pathways of the above reactions and the reactions considered herein are different. Furthermore, the problems arising from vapor deactivation of catalyst components and the need for zeolite structure stabilization are not apparent in the above reactions.

[0073] Accordingly, in certain embodiments, this disclosure relates to the use of any first catalyst component described herein and / or the use of any catalyst composition described herein in petroleum refining applications such as fluid catalytic cracking and / or hydrocracking.

[0074] Fluid catalytic cracking (FCC) is one of the most widely used catalytic cracking processes. This process typically utilizes a powdered catalyst with particles suspended in an upward flow of feed hydrocarbons that form a fluidized bed. Zeolite-based catalysts are commonly used, as are composite catalysts containing zeolite, silica-alumina, alumina, and other binders. In a typical process, cracking is carried out in a riser, which is a pipe inclined vertically or upwards.

[0075] A preheated feed (e.g., vacuum gas oil) can be sprayed through a feed nozzle to the base of a riser, where it comes into contact with a thermal fluidizing catalyst at a temperature of approximately 400°C to 800°C. The feed vaporizes upon contact with the catalyst, decomposition occurs, and the high molecular weight oil is converted into lighter components, including liquefied petroleum gas (LPG), gasoline, and distillates. The catalyst-feed mixture flows upward through the riser for a short time (a few seconds) before being separated by a cyclone. The hydrocarbons thus separated from the catalyst are then introduced into a fractionator for separation into LPG, gasoline, diesel, kerosene, jet fuel, and other possible fractions.

[0076] As the catalyst passes through the riser, this process involves the formation of deposit coke on the catalyst particles, thus inactivating the decomposition catalyst. The thus contaminated catalyst is separated from the decomposed hydrocarbon vapor and further treated with the vapor to remove any hydrocarbons remaining in the catalyst pores. The catalyst is then introduced into a regenerator, where its activity is restored by burning the coke from the surface of the catalyst particles, supplying the heat necessary for the next reaction cycle. The decomposition process is endothermic. The regenerated catalyst is then used in a new cycle. Therefore, new catalysts for catalytic cracking processes such as FCC should be regenerative. MCM-68 zeolite and the first catalyst component are stable with respect to regeneration in one embodiment.

[0077] The catalytic cracking process may be carried out using the first catalyst components and / or catalyst compositions described herein, with feedstocks such as gas oil, heavy naphtha, cycle oil, detrecced crude oil residue, Fischer-Tropsch wax, slack wax, the aforementioned hydrogenation products, and combinations thereof, with gasoline being a typically desired product. Suitable temperature conditions are about 400°C to about 800°C, pressure conditions are about 0 to about 688 kPa·g (about 0 to 100 psig), and contact times are about 0.1 seconds to about 1 hour. Temperature conditions are about 450°C to about 700°C, pressure conditions are about 0 to about 344 kPa·g (about 0 to 50 psig), and contact times are often preferred, are about 0.1 seconds to about several minutes. Preferred conditions are determined based on the hydrocarbon feedstocks to be cracked and the desired cracking products.

[0078] The naphtha cracking process may be carried out using the first catalyst component and / or catalyst composition described herein, using naphtha feedstock such as straight-run naphtha, coker naphtha, bisbreaker naphtha, FCC naphtha, and catalytically polymerized naphtha (Cat Poly naphtha), which are catalytically cracked into light olefins such as ethylene and propylene, but are not limited to these. The naphtha is in contact with the first catalyst component in, for example, a fluid catalytic cracking (FCC) type reactor. The reactor selection can be any type of reactor that closely mixes the naphtha feed stream with the catalyst. This type of reactor is well known to those skilled in the art.

[0079] Alternatively, the hydrocarbon feed and the first catalyst component can be brought into contact using a type of reactor such as a moving-bed reactor with continuous catalyst regeneration or a fixed-bed reactor with periodic catalyst regeneration by pressure swing or temperature swing. Therefore, new catalysts for catalytic cracking processes such as naphtha cracking should be regenerative. In one embodiment, the MCM-68 zeolite and the first catalyst component are stable with respect to regeneration.

[0080] The naphtha decomposition reaction can be carried out at temperatures of approximately 400°C to approximately 700°C. The decomposition process can be carried out using pressure conditions of approximately 0 to approximately 688 kPa·g (approximately 0 to 100 psig) and contact times of approximately 0.1 seconds to approximately 1 hour, preferably approximately 0.1 seconds to approximately 0.1 hours. Assuming all other process variables are equal, longer contact times are used at lower temperatures, while shorter contact times are used at higher temperatures.

[0081] The olefin decomposition process is preferably C4 or C5-C 10 The process is carried out using a feedstock such as a mixed olefin stream containing olefins, with a first catalyst component and / or catalyst composition, where ethylene, propylene, and butylene are the main desired products. The olefin decomposition reactor is operated at a temperature of 400°C to 650°C, preferably 500°C to 600°C. The pressure of the olefin decomposition reactor during operation is 0 kPa to 344 kPa, and the preferred operating pressure for the olefin partial pressure is 10 kPa to 200 kPa. The contact time for the olefin decomposition process is about 0.1 seconds to about 1 hour.

[0082] C4 or C5~C 10 Olefin feedstock is passed over a first catalyst component and / or catalyst composition to break down the olefin into smaller molecules. The decomposition process generates some coking on the catalyst component and / or catalyst composition, and over time the catalyst pores become clogged with coke, reducing catalytic activity. The catalyst component and / or catalyst composition can be regenerated by oxidizing the coke and removing it as a gas mainly containing N2, H2O, CO, and CO2. Catalysts in reactors can be regenerated periodically, and thus processes can be frequently moved between multiple reactors. Alternatively, types of reactors such as transfer or fluidized bed reactors with continuous catalyst regeneration can be used to bring hydrocarbon feed into contact with the first catalyst component and / or catalyst composition. Therefore, new catalysts for catalytic decomposition processes such as olefin decomposition should be regenerative. The first catalyst component and / or catalyst composition described herein is stable with respect to regeneration in one embodiment.

[0083] In certain embodiments, the Disclosure comprises a process for catalytic and / or hydrocracking of a hydrocarbon feedstock by contacting the feedstock with any first catalyst component or any catalyst composition described herein. In one embodiment, the Disclosure relates to a process for catalytic and / or hydrocracking of a hydrocarbon feedstock by contacting the feedstock with a first catalyst component comprising a phosphorus-stabilized MSE structured zeolite (such as phosphorus-stabilized MCM-68) and a first non-zeolite matrix. The first catalyst component may have any of the properties described herein above with respect to phosphorus content, porous crystal structure, total acidity, SAR, micropore volume, surface area, or a combination thereof. In one embodiment, the Disclosure relates to a process for catalytic and / or hydrocracking of a hydrocarbon feedstock by contacting the feedstock with any catalyst composition described herein (including any first catalyst component, a second catalyst component, and optionally at least one additional component described herein). The catalyst composition and its components may, but are not limited, have any of the characteristics described herein with respect to the concentrations of various components, the compositions of various components, or combinations thereof.

[0084] In certain embodiments, the first catalyst component and / or catalyst composition described herein have higher selectivity for butylene and a higher total butylene yield compared to, for example, ZSM-5, a zeolite commonly used for decomposition to small olefins.

[0085] In one embodiment, when the first catalyst component and / or catalyst composition described herein is brought into contact with a hydrocarbon feedstock under FCC conditions, it exhibits a first butylene selectivity ratio to propylene. When the same hydrocarbon feedstock is brought into contact with a catalyst component containing ZSM-5 and phosphorus-free stabilized MCM-68 under the same FCC conditions, it exhibits a propylene selectivity to a second butylene that is lower than the first butylene selectivity ratio to propylene.

[0086] In certain embodiments, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 0.7, greater than about 0.8, greater than about 0.85, greater than about 0.9, greater than about 0.95, or greater than about 1. In one embodiment, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 0.7. In one embodiment, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 0.8. In one embodiment, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 0.85. In one embodiment, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 0.9. In one embodiment, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 0.95. In one embodiment, the method for decomposing a hydrocarbon feed described herein yields an average butylene-to-propylene selectivity ratio greater than about 1.

[0087] In one embodiment, when the first catalyst component and / or catalyst composition described herein is brought into contact with a hydrocarbon feedstock under FCC conditions, a first total butylene yield is observed (at a predetermined conversion value). When the same hydrocarbon feedstock is brought into contact with a catalyst component containing ZSM-5 and phosphorus-unstabilized MCM-68 under the same FCC conditions, a second total butylene yield is observed (at the same conversion value) that is substantially similar to or lower than the first total butylene yield.

[0088] In certain embodiments, the first catalyst component and / or catalyst composition described herein exhibits improved performance with respect to favorable products such as butylene, but with reduced selectivity for less desirable products such as benzene, toluene, xylene (BTX), methane, C6, and C7.

[0089] In certain embodiments, this disclosure relates to a process for stabilizing the catalytic activity (after steaming) of a catalyst component containing an MSE structured zeolite (such as MCM-68) by modifying the MSE structured zeolite (such as MCM-68) with a phosphorus-containing compound. Maintenance of catalytic activity after steaming can be evaluated by comparing pre- and post-steaming values ​​for parameters such as total butylene yield, butylene-to-propylene selectivity ratio, SAR, zeolite surface area, micropore volume, total acidity, or combinations thereof at specific conversion values, but not limited to these. In certain embodiments, any of the above parameters remain substantially the same before and after steaming for the first catalyst component and / or catalyst composition described herein. Furthermore, in certain embodiments, any of the above parameters remain substantially the same for the first catalyst component described herein (whether before or after steaming) compared to the first catalyst component before steaming without phosphorus stabilization / modification. Exemplary steaming conditions include steaming at 816°C for approximately 4 hours at a flow rate of 1 ml / min. In some embodiments, steaming is performed for approximately 1 to 24 hours. The steaming temperature and duration should not be interpreted restrictively. Other steaming durations and temperatures may be used under various circumstances.

[0090] As used herein, the term “substantially similar” means that a particular value is within approximately 5%, 10%, or 15% of the value being compared. [Examples]

[0091] The following examples are provided to facilitate understanding of this disclosure and should not be construed as particularly limiting the invention described herein and claimed herein. Such variations of the invention, including substitution of all currently known or subsequently developed equivalents, which would fall within the scope of those skilled in the art, and modifications in formulation or minor modifications in experimental design are considered to fall within the scope of the invention as incorporated herein.

[0092] Example 1: Hydrothermal synthesis of MCM-68 A mixture of 100 mmol of SiO2, 10 mmol of Al(OH)3, 3000 mmol of water, and 37.5 mmol of KOH was mixed at room temperature for approximately 30 minutes. Approximately 10 mmol of a structural indicator (SDA) having the following chemical structure was added to the mixture, and the mixture was then stirred at room temperature for approximately 4 hours. [ka]

[0093] The mixture with SDA was subjected to hydrothermal synthesis at approximately 160°C for approximately 16 days, followed by filtration, washing, and drying overnight at approximately 80°C to form "as-manufactured [Al]-MCM-68". The as-manufactured [Al]-MCM-68 was calcined at 650°C for approximately 10 hours to form "[Al]-MCM-68(X)". Here, X represents the silica-to-alumina ratio (SAR) estimated by inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0094] Example 2: Effect of phosphorus denaturation on the MSE structure of MCM-68 The X-ray diffraction patterns of MCM-68 synthesized in Example 1 were measured before steaming (see Figure 1A) and after steaming (see Figure 1B).

[0095] Figure 1A shows the X-ray diffraction (XRD) patterns of catalyst components including MCM-68 zeolite before steaming and without phosphorus modification ("H-MCM-68"), MCM-68 zeolite before steaming but after phosphorus modification with 2 wt% phosphorus ("H-MCM-68_P 2wt%"), MCM-68 zeolite before steaming but after phosphorus modification with 4 wt% phosphorus ("H-MCM-68_P 4wt%"), and MCM-68 zeolite before steaming but after phosphorus modification with 6 wt% phosphorus ("H-MCM-68_P 6wt%").

[0096] Figure 1B shows the XRD patterns of the same catalyst components as in Figure 1A after steaming. Specifically, these are the catalyst component after steaming and without phosphorus modification ("H-MCM-68-ST"), the catalyst component after phosphorus modification with 2 wt% phosphorus and steaming ("H-MCM-68_P 2wt%-ST"), the catalyst component after phosphorus modification with 4 wt% phosphorus and steaming ("H-MCM-68_P wt%-ST"), and the catalyst component after phosphorus modification with 6 wt% phosphorus and steaming ("H-MCM-68_P 6wt%-ST").

[0097] Phosphorus modification was achieved by taking approximately 0.6 g of the MCM-68 zeolite-containing catalyst component and performing induce wet impregnation with an appropriate amount of diammonium phosphate. This phosphorus-impregnated catalyst component was dried at 120°C for 12 hours, and then calcined in a muffle furnace at 650°C for approximately 3 hours. The steaming conditions for the steamed phosphate-modified catalyst component were 816°C for 4 hours with a water flow rate of 1 ml / min.

[0098] As can be seen in Figures 1A and 1B, the MSE structure of MCM-68 is retained even after phosphorus denaturation and / or steaming.

[0099] Example 3: Performance of MCM-68 zeolite (with and without P modification) in 1-octene degradation reaction In the decomposition reaction of 1-octene, the performance of MCM-68 zeolite-containing catalyst components (with and without phosphorus modification) before and after steaming was compared with the performance of the base catalyst. The reaction conditions were as follows: the catalyst component was 2.5 mg, and P 1-オクテン The pressure was 33 kPa, the temperature was 600°C, and the argon flow rate was 30 ml / min. The pretreatment conditions were 1 hour at 600°C with an air flow rate of 21.4 ml / min. The steaming conditions were 4 hours at 816°C with a water flow rate of 1 ml / min.

[0100] Five catalyst components were evaluated: A) a catalyst component containing MCM-68 zeolite (Figure 2A, "MCM-68"), B) a catalyst component containing MCM-68 after steaming under the above steaming conditions (Figure 2B, "MCM-68_ST"), C) a catalyst component containing MCM-68 modified with 2 wt% phosphorus after steaming under the above steaming conditions (Figure 2C, "2wt%P / MCM-68_ST"), D) a catalyst component containing MCM-68 modified with 4 wt% phosphorus after steaming under the above steaming conditions (Figure 2D, "4wt%P / MCM-68_ST"), and E) a catalyst component containing ZSM-5 as the base catalyst (B) after steaming under the above steaming conditions (Figure 2E, "B_ST").

[0101] As seen in Figure 2A, the conversion rate of 1-octene to butylene in the catalyst component containing MCM-68 before P modification or steaming is close to 80%. This conversion rate is higher than that of the base catalyst, which is about 60%, as seen in Figure 2E. However, after steaming the catalyst component containing MCM-68 without performing P modification, the conversion decreases to 40%, as seen in Figure 2B. Surprisingly, phosphorus modification of MCM-68 provides a catalyst component that maintains a conversion value equivalent to or higher than that of the base catalyst even after steaming, as seen in Figures 2C (about 60% conversion) and 2D (about 70% conversion).

[0102] Figures 2A to 2D clearly show that catalyst components containing MCM-68 zeolite (whether phosphorus-modified or not) produce far more butylene (C4 = total) than propylene (C3), especially in the early stages (e.g., up to about 4 hours). In contrast, during the first 4 hours of the 1-octene decomposition reaction, the base catalyst shown in Figure 2E produces almost equal amounts of butylene and propylene. This indicates that catalyst components containing MCM-68 zeolite exhibit greater selectivity for butylene than for propylene compared to catalyst components containing ZSM-5 zeolite.

[0103] Example 4: Activity-related properties of MCM-68 zeolite at various levels of phosphorus denaturation Catalyst components with varying levels of phosphorus were prepared as described in Example 2, and their acidity, total surface area, and micropore volume were characterized. These characteristics are considered to indicate the performance of the catalyst components. The results are summarized in Table 1 below.

[0104] [Table 1]

[0105] The results in Table 1 suggest that adding phosphorus to the MCM-68 zeolite-containing catalyst component does not appear to improve the amount of surface area and / or pore volume retained after steam deactivation, but it does help retain more acidic sites (until a certain amount of phosphorus is added). Higher total acidity is thought to reflect higher activity or improved catalytic performance. The results in Table 1 also suggest that there may be a preferred range of phosphorus content that provides improved catalytic performance.

[0106] For the sake of simplicity, embodiments of the methods of this disclosure are depicted and described as a series of actions. However, actions according to this disclosure can be performed in various orders and / or simultaneously, and in conjunction with other actions not presented and described herein. Furthermore, not all illustrated actions are necessarily required to carry out a method according to the subject matter disclosed. In addition, those skilled in the art will understand and recognize that the method may alternatively be represented as a series of interrelated states via a state diagram or events.

[0107] The preceding description includes numerous specific details, such as specific materials, dimensions, and process parameters, in order to provide a complete understanding of the invention. Specific features, structures, materials, or properties may be combined in any suitable manner in one or more embodiments. The terms “example” or “exemplary” are used herein to mean that they serve as examples, illustrations, or descriptive. Any embodiment or design described herein as “example” or “exemplary” is not necessarily to be construed as being preferable or advantageous to other embodiments or designs. Rather, the use of the terms “example” or “exemplary” is intended to present a concept in a specific manner. As used in this application, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or.” That is, unless otherwise specified or evident from the context, “X includes A or B” is intended to mean any of the natural inclusive permutations. That is, if X includes A, X includes B, or X includes both A and B, then “X includes A or B” is satisfied in any of the examples above. Throughout this specification, any reference to “embodiment,” “specific embodiment,” or “one embodiment” means that a particular feature, structure, or characteristic described in relation to an embodiment is included in at least one embodiment. Therefore, although the expressions “embodiment,” “specific embodiment,” or “one embodiment” appear in various places throughout this specification, they do not necessarily all refer to the same embodiment.

[0108] This disclosure has been described with reference to certain exemplary embodiments. Therefore, this specification and the drawings are to be considered illustrative rather than restrictive. In addition to what is shown and described herein, various modifications of this disclosure will be apparent to those skilled in the art and are intended to fall within the scope of the appended claims. The present invention includes the following embodiments. [Section 1] A catalytic cracking process for a hydrocarbon feedstock, comprising contacting the feedstock with a first catalyst component comprising phosphorus-stabilized MCM-68 zeolite and a first non-zeolite matrix. [Section 2] The process according to item 1, wherein the first catalyst component contains phosphorus in an amount of about 0.5% to about 10% by weight, about 1% to about 5% by weight, or about 2% to about 4% by weight, based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the first catalyst component. [Section 3] The aforementioned phosphorus-stabilized MCM-68 zeolite is A channel system in which each channel is defined by a 12-membered ring of a tetrahedral coordination atom, At least two further independent channel systems, in each of which each channel is defined by a 10-membered ring of a tetrahedral coordination atom, and The process according to item 1 or 2, having a porous crystalline MSE zeolite structure containing, wherein the number of intrinsic 10-membered ring channels is twice the number of 12-membered ring channels. [Section 4] The process according to any one of claims 1 to 3, wherein the first catalyst component has a total acidity of about 0.3 mmol / (g catalyst) to about 0.5 mmol / (g catalyst). [Section 5] The process according to any one of items 1 to 4, wherein the silicon-to-aluminum ratio of the phosphorus-stabilized MCM-68 zeolite is in the range of about 5 to about 60, about 7 to about 30, or about 9 to about 15. [Section 6] The process according to any one of claims 1 to 5, wherein a first butylene-to-propylene selectivity ratio achieved by contacting the feedstock with the first catalyst component is greater than a second butylene-to-propylene selectivity ratio achieved by contacting the feedstock with a catalyst component containing beta-zeolite and / or ZSM-5 zeolite, without phosphorus-stabilized MCM-68 zeolite. [Section 7] The process according to any one of claims 1 to 6, wherein the first catalyst is part of a catalyst composition, and the first catalyst component is present in the catalyst composition in an amount ranging from about 1% to about 25% by weight, about 1.5% to about 15% by weight, or about 2% to about 10% by weight, based on the total weight of the catalyst composition. [Section 8] The process according to claim 7, wherein the catalyst composition further comprises a second catalyst component. [Section 9] The process according to claim 8, wherein the second catalyst component comprises at least one large-pore molecular sieve zeolite having a pore diameter greater than 7 angstroms. [Section 10] The process according to item 8 or 9, wherein the at least one large-pore molecular sieve zeolite is zeolite Y. [Section 11] The process according to any one of claims 7 to 10, wherein the catalyst composition further comprises at least one additional component that is compositionally different from the second catalyst component and the first catalyst component. [Section 12] The process according to claim 11, wherein the at least one additional component comprises a beta-zeolite and / or ZSM-5 zeolite and at least one additional non-zeolite matrix. [Section 13] Catalytic cracking is a process according to any one of items 1 to 12, including fluid catalytic cracking or hydrocracking. [Section 14] A catalytic component, A phosphorus-stabilized MCM-68 zeolite having about 0.5% to about 10% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the catalyst component; and Non-zeolite matrix A catalytic component containing the above. [Section 15] The catalyst component according to claim 14, comprising about 1% to about 5% by weight or about 2% to about 4% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the catalyst component. [Section 16] The catalyst component according to claim 14 or 15, wherein the matrix comprises one or more of the following: clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titanium, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, rare earth-doped alumina (e.g., one or more selected from ytterbium-doped alumina, gadolinium-doped alumina, cerium-doped alumina, or lanthanum-doped alumina), silica-doped alumina, gamma-alumina, α-alumina, χ-alumina, δ-alumina, θ-alumina, κ-alumina, or mixtures thereof. [Section 17] The catalyst component according to any one of claims 14 to 16, wherein the phosphorus-stabilized MCM-68 zeolite is present in the catalyst component in an amount of about 1% to about 90% by weight, about 2% to about 80% by weight, or about 5% to about 60% by weight, based on the total weight of the catalyst component. [Section 18] A catalyst component according to any one of items 14 to 17, having a total acidity of approximately 0.3 mmol / (g catalyst) to approximately 0.5 mmol / (g catalyst). [Section 19] The catalyst component according to any one of claims 14 to 18, wherein the silicon-to-aluminum ratio of the phosphorus-stabilized MCM-68 zeolite is in the range of about 5 to about 60, about 7 to about 30, or about 9 to about 15. [Section 20] Approximately 150m 2 / g ~ approx. 750m 2 / g, approx. 175m 2 / g ~ approx. 675m 2 / g or approximately 200m 2 / g~about 600m 2 A catalyst component according to any one of items 14 to 19, having a total surface area (TSA) of BET of 1 / g. [Section 21] A catalyst component according to any one of claims 14 to 20, having a t-plot micropore volume of approximately 0.05 cc / g to approximately 0.3 cc / g, approximately 0.06 cc / g to approximately 0.23 cc / g, or approximately 0.07 cc / g to approximately 0.16 cc / g. [Section 22] The aforementioned phosphorus-stabilized MCM-68 zeolite is A channel system in which each channel is defined by a 12-membered ring of a tetrahedral coordination atom, At least two further independent channel systems, in each of which each channel is defined by a 10-membered ring of a tetrahedral coordination atom, and The catalyst component according to item 14 or 15, having a porous crystalline MSE structure containing, wherein the number of intrinsic 10-membered ring channels is twice the number of 12-membered ring channels. [Section 23] The catalyst component according to any one of claims 14 to 22, wherein the first XRD peak pattern of the catalyst component is substantially similar to the second XRD peak pattern of the catalyst component without phosphorus with respect to peak position and relative intensity. [Section 24] A catalyst composition, The first catalyst component is A phosphorus-stabilized MCM-68 zeolite comprising a phosphorus-stabilized MCM-68 zeolite having about 0.5% to about 10% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the first catalyst component; The first non-zeolite matrix and A first catalytic component containing; and A second catalytic component comprising a second zeolite and a second non-zeolite matrix. A catalyst composition containing the following: [Section 25] The catalyst composition according to claim 24, wherein the first catalyst component is present in the catalyst composition in an amount ranging from about 1% to about 25% by weight, about 1.5% to about 15% by weight, or about 2% to about 10% by weight, based on the total weight of the catalyst composition. [Section 26] The catalyst composition according to claim 24 or 25, wherein the second zeolite comprises a large-pore molecular sieve zeolite having a pore diameter greater than 7 angstroms. [Section 27] The catalyst composition according to any one of claims 24 to 26, wherein the second zeolite is zeolite Y. [Section 28] The catalyst composition according to any one of claims 24 to 27, further comprising the second catalyst component and at least one additional component that is compositionally different from the first catalyst component. [Section 29] The catalyst composition according to claim 28, wherein the at least one additional component comprises at least one additional zeolite selected from beta-zeolite, ZSM-5 zeolite, or a combination thereof. [Section 30] A process for preparing a catalyst component as described in any one of items 14 to 23, comprising modifying MCM-68 zeolite with a phosphorus-containing compound. [Section 31] The process according to claim 30, wherein the phosphorus-containing compound comprises phosphoric acid, diammonium phosphate, or a combination thereof. [Section 32] The denaturation process according to claim 30 or 31 comprises impregnating the MCM-68 zeolite with a phosphorus-containing compound. [Section 33] The process according to claim 32, further comprising calcining the phosphorus-modified MCM-68 zeolite. [Section 34] A process for preparing a catalyst composition according to any one of items 24 to 29, comprising combining the first catalyst component with the second catalyst component and optionally at least one additional component.

Claims

1. A fluid catalytic cracking (FCC) process for hydrocarbon feedstock, comprising contacting feedstock containing at least a hydrocarbon fraction of crude petroleum with a first catalyst component containing phosphorus-stabilized MCM-68 zeolite and a first non-zeolite matrix to produce a product containing at least gasoline and an olefin gas.

2. The process according to claim 1, wherein the first catalyst component contains 0.5% to 10% by weight, 1% to 5% by weight, or 2% to 4% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the first catalyst component.

3. The phosphorus-stabilized MCM-68 zeolite is A channel system in which each channel is defined by a 12-membered ring of a tetrahedral coordination atom, At least two further independent channel systems, in each of which each channel is defined by a 10-membered ring of a tetrahedral coordination atom, and The process according to claim 1 or 2, having a porous crystalline MSE zeolite structure containing, wherein the number of intrinsic 10-membered ring channels is twice the number of 12-membered ring channels.

4. The process according to any one of claims 1 to 3, wherein the first catalyst component has a total acidity of 0.3 mmol / (g catalyst) to 0.5 mmol / (g catalyst).

5. The process according to any one of claims 1 to 4, wherein the silicon-to-aluminum ratio of the phosphorus-stabilized MCM-68 zeolite is in the range of 5 to 60, 7 to 30, or 9 to 15.

6. The process according to any one of claims 1 to 5, wherein the first catalyst is part of a catalyst composition, and the first catalyst component is present in the catalyst composition in an amount ranging from 1% to 25% by weight, 1.5% to 15% by weight, or 2% to 10% by weight, based on the total weight of the catalyst composition.

7. The process according to claim 6, wherein the catalyst composition further comprises a second catalyst component.

8. The process according to claim 7, wherein the second catalyst component comprises at least one large-pore molecular sieve zeolite having a pore diameter greater than 7 angstroms.

9. The process according to claim 7 or 8, wherein the at least one large-pore molecular sieve zeolite is zeolite Y.

10. The process according to any one of claims 6 to 9, wherein the catalyst composition further comprises at least one additional component that is compositionally different from the second catalyst component and the first catalyst component.

11. The process according to claim 10, wherein the at least one additional component comprises beta-zeolite and / or ZSM-5 zeolite and at least one additional non-zeolite matrix.

12. A catalytic component for catalytic cracking of hydrocarbon feedstocks, including at least the hydrocarbon fraction of crude petroleum, The catalyst components are, A phosphorus-stabilized MCM-68 zeolite having 0.5% to 10% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the catalyst component; and A non-zeolite matrix containing one or more of the following: clay, spinel, mullite, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-tria, silica-beryllia, and silica-aluminatoria. Contains microspheres containing The phosphorus-stabilized MCM-68 zeolite is a catalyst component present in the catalyst component at an amount of 1% to 90% by weight.

13. The catalyst component according to claim 12, wherein the catalyst component contains 1% to 5% by weight or 2% to 4% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the catalyst component.

14. The catalyst component according to claim 12 or 13, wherein the matrix comprises one or more of the following: clay, spinel, mullite, boehmite, alumina, silica, titania, zirconia, magnesia, kaolin, metakaolin, halloysite, kaolinite, dickite, nacrite, anauxite, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titanium, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, rare earth-doped alumina (for example, selected from one or more of ytterbium-doped alumina, gadolinium-doped alumina, cerium-doped alumina, or lanthanum-doped alumina), silica-doped alumina, gamma-alumina, α-alumina, χ-alumina, δ-alumina, θ-alumina, κ-alumina, or mixtures thereof.

15. The catalyst according to claim 12 or 13, wherein the phosphorus-stabilized MCM-68 zeolite is present in the catalyst component in an amount of 2% to 80% by weight or 5% to 60% by weight based on the total weight of the catalyst component.

16. The catalyst component according to claim 12 or 13, having a total acidity of 0.3 mmol / (g catalyst) to 0.5 mmol / (g catalyst).

17. The catalyst component according to claim 12 or 13, wherein the silicon-to-aluminum ratio of the phosphorus-stabilized MCM-68 zeolite is in the range of 5 to 60, 7 to 30, or 9 to 15.

18. 150m ２ / g ~ 750m ２ / g, 175m ２ / g ~ 675m ２ / g or 200m ２ / g ~ 600m ２ The catalyst component according to claim 12 or 13, having a total surface area (TSA) of BET of 1 / g.

19. The catalyst component according to claim 12 or 13, having a t-plot micropore volume of 0.05 cc / g to 0.3 cc / g, 0.06 cc / g to 0.23 cc / g, or 0.07 cc / g to 0.16 cc / g.

20. The phosphorus-stabilized MCM-68 zeolite is A channel system in which each channel is defined by a 12-membered ring of a tetrahedral coordination atom, At least two further independent channel systems, in each of which each channel is defined by a 10-membered ring of a tetrahedral coordination atom, and The catalyst component according to claim 12 or 13, having a porous crystalline MSE structure containing, wherein the number of unique 10-membered ring channels is twice the number of 12-membered ring channels.

21. The catalyst component according to claim 12 or 13, wherein the first XRD peak pattern of the catalyst component is substantially similar to the second XRD peak pattern of the catalyst component without phosphorus with respect to peak position and relative intensity.

22. A catalyst composition for catalytic cracking of hydrocarbon feedstocks containing at least the hydrocarbon fraction of crude petroleum, The first catalyst component is a microsphere, A phosphorus-stabilized MCM-68 zeolite comprising a phosphorus-stabilized MCM-68 zeolite having 0.5% to 10% by weight of phosphorus based on the total weight of the phosphorus-stabilized MCM-68 zeolite in the first catalyst component; The first non-zeolite matrix and Microspheres of a first catalytic component containing; and It comprises microspheres of a second catalytic component, which includes a second zeolite having a pore diameter larger than 7 angstroms and a second non-zeolite matrix, A catalyst composition wherein the microspheres of the first catalyst component are present in the catalyst composition in an amount ranging from 1% to 25% by weight based on the total weight of the catalyst composition.

23. The catalyst composition according to claim 22, wherein the microspheres of the first catalyst component are present in the catalyst composition in an amount ranging from 1.5% to 15% by weight or 2% to 10% by weight based on the total weight of the catalyst composition.

24. The catalyst composition according to claim 22 or 23, wherein the second zeolite is zeolite Y.

25. The catalyst composition according to claim 22 or 23, further comprising at least one additional component that is compositionally different from the second catalyst component and the first catalyst component.

26. The catalyst composition according to claim 25, wherein the at least one additional component comprises at least one additional zeolite selected from beta-zeolite, ZSM-5 zeolite, or a combination thereof.

27. A process for preparing the catalyst component according to claim 12 or 13, comprising modifying MCM-68 zeolite with a phosphorus-containing compound.

28. The process according to claim 27, wherein the phosphorus-containing compound comprises phosphoric acid, diammonium phosphate, or a combination thereof.

29. The process according to claim 27 or 28, wherein the modification includes impregnating the MCM-68 zeolite with a phosphorus-containing compound.

30. The process according to claim 29, further comprising calcining the phosphorus-modified MCM-68 zeolite.

31. A process for preparing the catalyst composition according to claim 22 or 23, comprising combining the first catalyst component with the second catalyst component and optionally at least one additional component.

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