Molecular sieve SSZ-91 with hierarchical porosity, method for preparation, and use thereof

Abstract

Disclosed are crystalline mesoporous molecular sieves based on the SSZ-91 molecular sieve, methods for making the mesoporous SSZ-91, and the use of the mesoporous SSZ-91 in hydroconversion applications. The SSZ-91 mesoporous molecular sieve is characterized by a low level of defects, a low aspect ratio that inhibits hydrocracking compared to conventional ZSM-48 materials having aspect ratios greater than 8, being substantially phase pure, and having a total pore volume in the mesopore diameter range (measured at a P / P of 0.95) of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is related to and claims the benefit of priority to U.S. Provisional Application No. 63 / 394,286, filed August 1, 2022, which is incorporated herein in its entirety.

[0002] Described herein are crystalline molecular sieves having hierarchical porosity designated SSZ-91, which belong to the ZSM-48 family of molecular sieves, methods for preparing such SSZ-91 molecular sieves, and their uses. [Background technology]

[0003] Crystalline molecular sieves and molecular sieves are particularly useful in applications such as hydrocarbon conversion, gas drying and separation due to their unique sieving properties and their catalytic properties. Although many different crystalline molecular sieves have been disclosed, there is a continuing need for new molecular sieves with desirable properties for gas separation and drying, hydrocarbon and chemical conversion, and other applications. New molecular sieves contain novel internal pore structures that may result in improved selectivity in these processes.

[0004] Molecular sieves have characteristic crystalline structures, revealed by characteristic X-ray diffraction patterns, which define cavities and pores characteristic of different species.

[0005] Molecular sieves are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature, which assigns three-letter codes to framework-type zeolites and other crystalline microporous molecular sieves whose structures have been established and are listed in the "Atlas of Zeolite Framework Types," Sixth Revised Edition, Elsevier (2007) and in the Database of Molecular Sieve Structures on the website of the International Zeolite Association (http: / / www.iza-online.org).

[0006] Molecular sieve structures can be ordered or disordered. Molecular sieves with ordered structures have periodic building blocks (PerBUs) arranged periodically in all three dimensions. Structurally disordered structures exhibit periodic order in less than three dimensions (i.e., two, one, or zero dimensions). Disorder occurs when PerBUs connect in different ways or when two or more PerBUs intergrow within the same crystal. Crystal structures constructed from PerBUs are called end-member structures when periodic order is achieved in all three dimensions.

[0007] In disordered materials, planar stacking faults arise when the material contains order in two dimensions. Planar defects disrupt the channels formed by the material's pore system. Planar defects located near the surface restrict the diffusion paths otherwise required for feedstock components to access the catalytically active portions of the pore system. Therefore, as the degree of defects increases, the catalytic activity of the material typically decreases.

[0008] For crystals with planar defects, interpretation of X-ray diffraction patterns requires the ability to simulate the effects of stacking disorder. DIFFaX is a computer program based on a mathematical model for calculating intensities from crystals containing planar defects (see M.M.J. Treacy et al., Proceedings of the Royal Chemical Society, London, A (1991), Vol. 433, pp. 499-520). DIFFaX is the simulation program selected and available by the International Zeolite Association for simulating XRD powder patterns of intergrown phases of molecular sieves (see "Collection of Simulated XRD Powder Patterns for Zeolites," 2001, Fourth Edition, by M.M.J. Treacy and J.B. Higgins, published by the Structure Commission of the International Zeolite Association). DIFFaX has also been used to theoretically study the intergrown phases of AEI, CHA, and KFI molecular sieves, as reported by KP Lillerud et al. in "Studies in Surface Science and Catalysis," 1994, Vol. 84, pp. 543-550. DIFFaX is a well-known and established method for characterizing disordered crystalline materials with planar defects (e.g., intergrown molecular sieves).

[0009] The designation ZSM-48 refers to a family of disordered materials characterized by one-dimensional, ten-ring tubular pore systems. The pores are formed by the rolling up of honeycomb-like sheets of fused tetrahedral six-ring structures, with the pore openings containing ten tetrahedral atoms. Zeolites EU-2, ZSM-30, and EU-11 are classified as part of the ZSM-48 family of zeolites. The ZSM-48 family of molecular sieves consists of nine polytypes. These materials have very similar, but not identical, X-ray diffraction patterns. Polytypes can be distinguished, at least in part, according to their morphological differences. For example, polytype 6 consists of needle-like crystals approximately 20 nm in diameter and approximately 0.5 μm in length. Another polytype, described as defective polytype 6, consists of elongated crystals approximately 0.5 μm wide and 4-8 μm long.

[0010] Kirschhock and coworkers claim to have successfully synthesized pure-phase polytype 6 (see Chem. Mater. 2009, 21, 371-380). In their paper, Kirschhock and coworkers explain that their pure-phase polytype 6 material, which they call COK-8, has a morphology consisting of long, needle-like crystals (15-80 nm wide, 0.5-4 μm long) with a very large length / width ratio, growing along the direction of interconnecting pores.

[0011] As shown in Kirschhock's paper, molecular sieves of the ZSM-48 family consist of a 10-ring, one-dimensional pore structure, with the channels formed by interconnected pores running perpendicular to the long axis of the needles. Therefore, the channel openings are located at the short ends of the needles. As the length:diameter ratio (also known as the aspect ratio) of these needles increases, the diffusion path for the hydrocarbon feed also increases. As the diffusion path increases, so does the residence time of the feed within the channels. Longer residence times result in increased undesired hydrocracking of the feed and a concomitant decrease in selectivity.

[0012] There is a continuing need for molecular sieves of the ZSM-48 family that provide a lower degree of hydrocracking and offer other improvements over known ZSM-48 molecular sieves. There is also a continuing need for molecular sieves that are phase pure or substantially phase pure and have a low degree of disorder (low degree of defects) in their structure. Summary of the Invention

[0013] Disclosed herein is a family of crystalline molecular sieves with unique properties, referred to herein as "molecular sieve SSZ-91" or simply "SSZ-91." Molecular sieve SSZ-91 is structurally similar to sieves in the ZSM-48 family of zeolites and is characterized by (1) a low level of defects, (2) a low aspect ratio that inhibits hydrocracking compared to conventional ZSM-48 materials with aspect ratios greater than 8, and (3) being substantially phase pure. Also described herein are SSZ-91s that have been further modified to improve pore size and pore size distribution characteristics.

[0014] In contrast to conventional ZSM-48 materials, ZSM-48 materials lacking any one of the three unique combinations of properties of SSZ-91 (low aspect ratio, low EU-1 content, high polytype 6 composition) exhibit poor catalytic performance. SSZ-91, as well as SSZ-91 modified as further described herein, exhibit improved catalytic performance, particularly in hydroprocessing applications.

[0015] In one embodiment, the molecular sieve has a silicon oxide to aluminum oxide molar ratio of 40 to 220 and is described herein as SSZ-91. In its pure form, the X-ray diffraction lines in Table 2 herein represent SSZ-91. The SSZ-91 material is characterized as having at least 70% of the total ZSM-48-type material present in the product composed of polytype 6, as determined by DIFFaX simulations and described in Lobo and Koningsveld, J. Am. Chem. Soc. 2012, 124, 13222-13230, where failure was adjusted for three different failure probabilities. Note that the phrase "at least 70%" includes the case where no other ZSM-48 polytypes are present in the structure, i.e., the material is 100% phase-pure polytype 6.

[0016] In another embodiment, the SSZ-91 is substantially phase pure. The SSZ-91 contains an additional EUO-type molecular sieve phase in an amount of 0 to 3.5 wt. % (inclusive) of the total product.

[0017] The molecular sieve SSZ-91 has a morphology characterized as polycrystalline aggregates, each of which is collectively composed of crystallites having an average aspect ratio of 1 to 8 (inclusive). SSZ-91 exhibits a lower degree of hydrocracking than ZSM-48 materials, which have higher aspect ratios. An aspect ratio of 1 is the ideal minimum, where the length and width are equal.

[0018] In further embodiments, the SSZ-91 can include modified pore size and distribution characteristics, including, for example, a total pore volume (measured at a P / P of 0.95) in the mesopore diameter range (2-50 nm) of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g.

[0019] In another aspect, there is provided a method for preparing a mesoporous crystalline SSZ-91 material by contacting, under crystallization conditions, (1) at least one source of silicon oxide, (2) at least one source of aluminum oxide, (3) at least one source of an element selected from Groups 1 and 2 of the periodic table, (4) hydroxide ion, and (5) hexamethonium cation under conditions that result in the formation of SSZ-91, followed by subjecting the SSZ-91 to calcination conditions; contacting the calcined SSZ-91 molecular sieve with an organic base, a quaternary ammonium salt, a quaternary ammonium base, an inorganic base, ammonium fluoride, or a combination thereof under solution conditions effective to desilicate the molecular sieve; and contacting the desilicate molecular sieve with an ammonium salt under solution conditions effective to form an ammonium-exchanged mesoporous molecular sieve. The mesoporous SSZ-91 according to the foregoing can be characterized by having defined pore characteristics, for example, a total pore volume in the mesopore diameter range (measured at a P / P of 0.95) of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g.

[0020] In another aspect, a hydroconversion process useful for hydroisomerizing a hydrocarbon feed is provided, the process comprising contacting the hydrocarbon feed under hydroisomerization conditions with a hydroisomerization catalyst to produce a product, the hydroisomerization catalyst comprising a mesoporous molecular sieve belonging to the ZSM-48 family of zeolites, the molecular sieve having a total pore volume in the mesopore diameter range (measured at a P / P of 0.95) of at least about 0.2 cc / g and The molecular sieve has a pore volume of at least 0.05 cc / g, a silicon oxide to aluminum oxide molar ratio of 40 to 220, and comprises at least 70% polytype 6 of the total ZSM-48 type material present in the molecular sieve, and an additional EUO type molecular sieve phase in an amount of 0 to 3.5 wt.% of the total product, the molecular sieve having a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of about 1 to 8. [Brief explanation of the drawings]

[0021] [Figure 1] 1 shows the nitrogen isotherm described in Example 1.

[0022] [Figure 2] 1 shows the pore size distribution (PSD) calculated from the nitrogen isotherm described in Example 1.

[0023] [Figure 3] 1 shows the nitrogen isotherm described in Example 5.

[0024] [Figure 4] 1 shows the pore size distribution (PSD) calculated from the nitrogen isotherm described in Example 5.

[0025] [Figure 5] 1 shows the nitrogen isotherm described in Example 11.

[0026] [Figure 6] 1 shows the pore size distribution (PSD) calculated from the nitrogen isotherm described in Example 11.

[0027] [Figure 7] 1 shows the nitrogen isotherm described in Example 17.

[0028] [Figure 8] 1 shows the pore size distribution (PSD) calculated from the nitrogen isotherm described in Example 17.

[0029] [Figure 9] 1 shows the nitrogen isotherm described in Example 20.

[0030] [Figure 10] 1 shows the pore size distribution (PSD) calculated from the nitrogen isotherm described in Example 20. DETAILED DESCRIPTION OF THE INVENTION

[0031] While exemplary embodiments of one or more aspects are provided herein, the disclosed processes may be implemented using any number of technologies. The present disclosure is not limited to the exemplary or specific embodiments, any drawings, and any technologies illustrated herein, including any exemplary designs and embodiments shown and described herein, but may be modified within the scope of the appended claims, along with the full range of equivalents thereof.

[0032] The following description of the embodiments provides non-limiting representative examples, with reference to numerical values to further describe the features and teachings of various aspects of the present invention. It should be recognized that the described embodiments can be implemented separately or in combination with other embodiments from the description of the embodiments. Those skilled in the art can learn and understand other described aspects of the present invention by reviewing the description of the embodiments. The description of the embodiments should facilitate understanding of the present invention, so that other practical embodiments that are not specifically covered but are within the ability of those skilled in the art upon reading the description of the embodiments are understood to be consistent with the application of the present invention.

[0033] Unless otherwise indicated, the following terms have the meanings as defined herein below.

[0034] The term "hydroconversion" refers to processes or steps carried out in the presence of hydrogen for the hydrocracking, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodechlorination, hydrodecarboxylation, hydrodecarbonylation, and / or hydrodearomatization (e.g., of impurities) of hydrocarbon or biomass feedstocks, and / or for the hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrocracking and reaction conditions, the products of a hydrocracking process may have, for example, improved aromatics content, oxygen content, viscosity, viscosity index, saturated fat content, low temperature properties, volatility, and depolarization.

[0035] The term "hydrotreating" refers to a process or step carried out in the presence of hydrogen for the hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, and / or hydrodearomatization of components (e.g., impurities) of a diesel feedstock and / or the hydrogenation of unsaturated compounds in the feedstock.

[0036] The term "active source" means a reagent or precursor material capable of providing at least one element in a form that can react and be incorporated into the molecular sieve structure. The terms "source" and "active source" may be used interchangeably herein.

[0037] The terms "molecular sieve" and "zeolite" are synonymous and include (a) intermediate, (b) final or target molecular sieve, and molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary modification). Secondary synthesis techniques allow for the synthesis of target materials from intermediate materials by heteroatom lattice substitution or other techniques. For example, aluminosilicates can be synthesized from intermediate borosilicates by post-crystallization heteroatom lattice substitution of Al for B. Such techniques are known and are described, for example, in U.S. Patent No. 6,790,433, issued September 14, 2004, to C.Y. Chen and Stacey Zones.

[0038] The terms "MRE-type molecular sieve" and "EUO-type molecular sieve" include all molecular sieves and their isotypes assigned to the International Zeolite Association framework as set forth in Atlas of Zeolite Framework Types, eds. Ch. Baerlocher, L.B. McCusker and D.H. Olson, Elsevier, 6th revised edition, 2007, and in the Database of Zeolite Structures on the International Zeolite Association website (http: / / www.iza-online.org).

[0039] "Periodic Table" refers to the IUPAC Periodic Table of the Elements dated June 22, 2007, and the notation for group numbers in the periodic table is as described in Chem. Eng. News, 63(5), 26-27 (1985).

[0040] For purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values used in the specification and claims, should be understood to be modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations and may vary depending upon the desired properties sought to be obtained. It should be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and clearly limited to one referent. As used herein, the term "comprising" and its grammatical variations are intended to be open-ended, such that the recitation of items in a list does not exclude other similar items that may be substituted for or added to the listed items. As used herein, the term "comprising" means including the elements or steps identified following the term, but does not exhaustively list any such elements or steps, and an embodiment may include other elements or steps.

[0041] Unless otherwise specified, the recitation of a genus of elements, materials, or other components from which individual components or mixtures of components may be selected is intended to include all possible subgeneric combinations of the listed components and mixtures thereof. Furthermore, all numerical ranges set forth herein are inclusive of their upper and lower limits.

[0042] The patentable scope is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they contain equivalent structural elements that do not have substantial differences from the literal language of the claims. To the extent not inconsistent herewith, all citations referred to herein are incorporated by reference.

[0043] In the preparation of SSZ-91, at least one organic compound selective for the synthesis of molecular sieves from the ZSM-48 family of zeolites is used as a structure directing agent ("SDA"), also known as a crystallization template. The SDA useful for producing SSZ-91 is represented by the following structure (1): [ka]

[0044] The SDA cation is typically associated with an anion, which can be any anion that is not detrimental to the formation of the molecular sieve. Representative examples of anions include hydroxide, acetate, sulfate, carboxylate, and halogens such as fluoride, chloride, bromide, and iodide. In one embodiment, the anion is bromide.

[0045] Generally, SSZ-91 is prepared by (a) preparing a reaction mixture containing (1) at least one source of silicon oxide, (2) at least one source of aluminum oxide, (3) at least one source of an element selected from Groups 1 and 2 of the Periodic Table, (4) hydroxide ions, (5) hexamethonium cations, and (6) water, and (b) maintaining the reaction mixture under crystallization conditions sufficient to form molecular sieve crystals.

[0046] The composition of the reaction mixture from which the molecular sieve is formed is shown in Table 1 below in molar ratios. [Table 1]

[0047] Silicon sources useful herein include fumed silica, precipitated silica, silica hydrogel, silicic acid, colloidal silica, tetraalkyl orthosilicate (eg, tetraethyl orthosilicate), and silica hydroxide.

[0048] Aluminum sources useful herein include aluminates, alumina, and aluminum compounds such as AlCl, Al(SO), Al(OH), kaolin clay, and other zeolites. An example of an aluminum oxide source is LZ-210 zeolite (a type of Y zeolite).

[0049] As noted hereinabove, for each embodiment described herein, the reaction mixture can be formed containing at least one source of an element selected from Groups 1 and 2 of the Periodic Table (referred to herein as M). In one subembodiment, the reaction mixture is formed using a source of an element from Group 1 of the Periodic Table. In another subembodiment, the reaction mixture is formed using a source of sodium (Na). Any M-containing compound that does not adversely affect the crystallization process is suitable. Such sources of Group 1 and Group 2 elements include their oxides, hydroxides, nitrates, sulfates, halides, oxalates, citrates, and acetates.

[0050] For each embodiment described herein, the molecular sieve reaction mixture can be supplied by multiple sources, and two or more reactants can be provided by a single source.

[0051] The reaction mixture can be prepared batchwise or continuously. The crystal size, morphology, and crystallization time of the molecular sieves described herein can vary depending on the nature of the reaction mixture and the crystallization conditions.

[0052] The reaction mixture is maintained at an elevated temperature until molecular sieve crystals are formed. Generally, zeolite hydrothermal crystallization is usually carried out under pressure, usually in an autoclave, so that the reaction mixture is subjected to autogenous pressure, optionally stirred at a temperature of 125°C to 200°C for 1 to 18 hours or more.

[0053] As described hereinabove, SSZ-91 is a substantially phase-pure material. As used herein, the term "substantially phase-pure material" means that the material is completely free of zeolitic phases other than those belonging to the ZSM-48 family of zeolites, or that these phases are present in amounts that do not measurably affect the selectivity of the material, or that are present in amounts so small that they impose a material detrimental effect on the selectivity of the material. Two common phases that cocrystallize with SSZ-91 are EUO-type molecular sieves, e.g., EU-1, as well as magadiite and Kenyaite. These additional phases can exist as separate phases or intergrow with the SSZ-91 phase. As shown in the examples below, the presence of large amounts of EU-1 in the product is detrimental to selectivity for hydroisomerization with SSZ-91.

[0054] In one embodiment, the SSZ-91 product contains an additional EUO-type molecular sieve phase in an amount of 0 to 3.5 wt%. In a subembodiment, the SSZ-91 contains 0.1 to 2 wt% EU-1. In another subembodiment, the SSZ-91 contains 0.1 to 1 wt% EU-1.

[0055] The ratio of powder XRD peak intensities is known to vary linearly as a function of the weight fraction of any two phases in a mixture: (Iα / Iβ) = (RIRα / RIRβ) * (xα / xβ), where the RIR (reference intensity ratio) parameter can be found in The International Centre for Diffraction Data's Powder Diffraction File (PDF) database (http: / / www.icdd.com / products / ). Therefore, the weight percent of the EUO phase can be calculated by measuring the ratio between the peak intensity of the EUO phase and the peak intensity of the SSZ-91 phase.

[0056] The amount of EUO phase formation is controlled by selecting the optimal hydrogel composition, temperature, and crystallization time to minimize EUO phase formation while maximizing the yield of the SSZ-91 product. The following examples provide guidance on how varying these process variables can minimize EU-1 formation. One skilled in the art would be able to readily select the process variables necessary to minimize EU-1 formation, as these variables depend on the scale of the manufacturing process, the capabilities of the available equipment, the desired target yield, and the acceptable level of EU-1 material in the product.

[0057] During the hydrothermal crystallization step, molecular sieve crystals can spontaneously nucleate from the reaction mixture. Using molecular sieve crystals as seed material can be advantageous in shortening the time required for complete crystallization to occur. Furthermore, seeding can increase the purity of the resulting product by promoting nucleation and / or molecular sieve formation in preference to any undesired phases. However, when using seeding, it has been found that the seeds must be highly phase-pure SSZ-91 to avoid the formation of large amounts of EUO phase. When used as seeds, seed crystals are added in amounts between 0.5% and 5% of the weight of the silicon source used in the reaction mixture.

[0058] Since magadiite and kenyaite are layered sodium silicate compositions, optimizing the hexamethonium bromide / SiO ratio, controlling the hydroxide concentration, and minimizing the sodium concentration minimizes the production of magadiite and kenyaite.

[0059] Once the molecular sieve crystals are formed, the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration. The crystals are washed with deionized water and then dried to obtain the as-synthesized molecular sieve crystals. The drying step can be carried out at atmospheric pressure or under vacuum.

[0060] Molecular sieves can be used as synthesized, but are typically thermally treated (calcined). The term "as-synthesized" refers to the molecular sieve in its form after crystallization and prior to removal of the SDA cations. SDA can be removed by thermal treatment (e.g., calcination), preferably in an oxidizing atmosphere (e.g., air, a gas with an oxygen partial pressure greater than 0 kPa) at a temperature readily determinable by one skilled in the art sufficient to remove SDA from the molecular sieve. SDA can also be removed by ozonation and photolysis techniques (e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation having wavelengths shorter than visible light under conditions sufficient to selectively remove organic compounds from the molecular sieve), as described in U.S. Pat. No. 6,960,327.

[0061] The molecular sieve may then be calcined in steam, air, or an inert gas at a temperature of 200°C to 800°C for a period of 1 to 48 hours or more. Typically, the extraframework cations (e.g., Na) are removed by ion exchange. + ) and replace it with hydrogen, ammonium, or any desired metal ion.

[0062] If the formed molecular sieve is an intermediate molecular sieve, the target molecular sieve can be achieved using post-synthesis techniques such as heteroatom lattice replacement techniques. The target molecular sieve (e.g., silicate SSZ-91) can also be achieved by removing heteroatoms from the lattice by known techniques such as acid leaching.

[0063] The molecular sieves produced from the processes disclosed herein can be formed into a wide variety of physical shapes. Generally, the molecular sieves can be in the form of powders, granules, or shaped products such as extrudates having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen. When the catalyst is shaped, such as by extrusion with an organic binder, the molecular sieve may be extruded before, after, or partially dried.

[0064] Molecular sieves can be composited with other materials that can withstand the temperatures and other conditions used in organic conversion processes. Such matrix materials include active and inactive materials, synthetic or natural molecular sieves, and inorganic materials such as clays, silica, and metal oxides. Examples of such materials and methods for their use are disclosed in U.S. Patent Nos. 4,910,006 and 5,316,753.

[0065] The extrudates or particles can then be further loaded with one or more active metals selected from the group consisting of metals from Groups 8-10 of the periodic table using techniques such as impregnation or ion exchange to enhance hydrogenation functionality. It may be desirable to simultaneously co-impregnate the modifier metal and one or more Group 8-10 metals, as taught in U.S. Pat. No. 4,094,821. In one embodiment, the at least one active metal is selected from the group consisting of nickel, platinum, palladium, and combinations thereof. After loading the metals, the metal-loaded extrudates or particles can be calcined in air or an inert gas at a temperature of 200°C to 500°C. In one embodiment, the metal-loaded extrudates are calcined in air or an inert gas at a temperature of 390°C to 482°C.

[0066] SSZ-91 is useful in a variety of hydrocarbon conversion reactions, such as hydrocracking, dewaxing, olefin isomerization, alkylation, and isomerization of aromatics, etc. SSZ-91 is also useful as an adsorbent for general separations.

[0067] The SSZ-91 molecular sieve produced by the process disclosed herein has a SiO / AlO molar ratio (SAR) of 40 to 200. The SAR is determined by inductively coupled plasma (ICP) elemental analysis. In one subembodiment, the SSZ-91 has a SAR of 70 to 160. In another subembodiment, the SSZ-91 has a SAR of 80 to 140.

[0068] The SSZ-91 material is comprised of at least 70% polytype 6 of the total ZSM-48-type material present in the product, as determined by DIFFaX simulations and described in Lobo and Koningsveld, J. Am. Chem. Soc. 2012, 124, 13222-13230, where failure was adjusted for three different failure probabilities. Note that the phrase "at least X%" includes the case where no other ZSM-48 polytypes are present in the structure, i.e., the material is 100% polytype 6. The structure of polytype 6 is described by Lobo and Koningsveld (see J. Am. Chem. Soc. 2002, 124, 13222-13230). In one embodiment, the SSZ-91 material is comprised of at least 80% polytype 6 of the total ZSM-48-type material present in the product. In another embodiment, the SSZ-91 material is composed of at least 90% of the total ZSM-48 type material present in the product as polytype 6. The polytype 6 structure has been given the framework code *MRE by the Structure Commission of the International Zeolite Association.

[0069] The molecular sieve SSZ-91 has a morphology characterized by polycrystalline aggregates having diameters of approximately 100 nm to 1.5 μm, each of which contains a collection of crystallites collectively having an average aspect ratio of 1 to 8. As used herein, the term diameter refers to the shortest dimension of each crystallite examined. SSZ-91 exhibits a lower degree of hydrocracking than ZSM-48 materials, which have higher aspect ratios. In one subembodiment, the average aspect ratio is 1 to 5. In another subembodiment, the average aspect ratio is 1 to 4. In yet another subembodiment, the average aspect ratio is 1 to 3.

[0070] Molecular sieves synthesized by the process disclosed herein can be characterized by their XRD patterns. The powder XRD lines in Table 2 represent as-synthesized SSZ-91 prepared according to the method described in U.S. Pat. No. 9,802,830. Slight variations in the diffraction pattern may be due to variations in the molar ratio of framework species in a particular sample due to changes in lattice constants. Furthermore, sufficiently small crystals affect peak shape and intensity, leading to significant peak broadening. Slight variations in the diffraction pattern may also be due to variations in the organic compounds used in preparation or variations in the Si / Al molar ratio from sample to sample. Calcination may also cause slight shifts in the XRD pattern. Despite these small perturbations, the basic crystal lattice structure remains unchanged. [Table 2]

[0071] The X-ray diffraction pattern lines in Table 3 represent calcined SSZ-91 made according to the methods described herein. [Table 3]

[0072] The powder X-ray diffraction patterns presented herein were collected by standard techniques. α The height and position of the peaks as a function of 2θ (θ is the Bragg angle) can be read from the relative intensity of the peaks (adjusted for background) and the interplanar spacing d corresponding to the recorded lines can be calculated.

[0073] SSZ-91 can be further modified to introduce mesoporosity, particularly to provide mesoporosity that enhances the performance of catalysts made from mesoporous SSZ-91. As is commonly known in the art, creating mesopores in zeolite crystals increases the accessible surface area of the catalyst, allowing for more rapid diffusion of both reactants and products. These mesopores, often referred to as hierarchical porosity, can generally be created by two methods: 1) a "top-down" strategy, in which hierarchical porosity is formed in the zeolite crystal after synthesis, or 2) a "bottom-up" strategy, in which hierarchical porosity is formed in the zeolite crystal during synthesis. While such methods have commonly been used with other zeolites, achieving economically viable catalytic performance improvements presents challenges due to unpredictable behavior.

[0074] Nevertheless, certain methods have been found to be effective in introducing mesoporosity into SSZ-91 and preparing catalysts therefrom with enhanced catalytic performance. According to the present invention, mesoporous molecular sieves, such as mesoporous SSZ-91, belonging to the ZSM-48 family of zeolites and having a total pore volume (measured at a P / P of 0.95) of at least about 0.2 cc / g in the mesopore diameter range (2-50 nm) and a micropore volume of at least 0.05 cc / g, can be prepared by preparing a reaction mixture containing at least one source of silicon, at least one source of aluminum, at least one source of an element selected from Groups 1 and 2 of the Periodic Table, hydroxide ions, hexamethonium cations, and water; and, by dissolving the reaction mixture in a solution containing the hydroxyl group of the molecular sieve. The molecular sieve may be prepared by a process comprising: subjecting the molecular sieve to crystallization conditions sufficient to form crystals; subjecting the molecular sieve to calcination conditions sufficient to form a calcined molecular sieve; contacting the calcined molecular sieve with an organic base, a quaternary ammonium salt, a quaternary ammonium base, an inorganic base, ammonium fluoride, or a combination thereof under solution conditions effective to desilicate the molecular sieve; and contacting the desilicate molecular sieve with an ammonium salt under solution conditions effective to form an ammonium-exchanged mesoporous molecular sieve.

[0075] Generally, suitable calcination conditions include heating the molecular sieve to a temperature in the range of 80-140°C for 60-200 minutes, and either or a combination of: a) heating the molecular sieve to a temperature in the range of 450-550°C for 60-300 minutes, or b) heating the molecular sieve to a temperature in the range of 560-600°C for 60-300 minutes. The calcination conditions may include one or all of the foregoing conditions, for example, heating the molecular sieve to a temperature in the range of 80-140°C for 60-200 minutes, heating the molecular sieve to a temperature in the range of 450-550°C for 60-300 minutes, and heating the molecular sieve to a temperature in the range of 560-600°C for 60-300 minutes.

[0076] Mesoporous SSZ-91 can be made directly by contacting calcined SSZ-91 molecular sieve with an organic base, a quaternary ammonium salt, a quaternary ammonium base, an inorganic base, ammonium fluoride, or a combination thereof under solution conditions effective to desilicate the molecular sieve, and contacting the desilicate molecular sieve with an ammonium salt under solution conditions effective to form an ammonium-exchanged mesoporous molecular sieve. Preferred mesoporous SSZ-91 molecular sieves according to the present invention have a total pore volume (measured at a P / P of 0.95) of at least about 0.2 cc / g in the mesopore diameter range (2-50 nm) and a micropore volume of at least 0.05 cc / g, although the foregoing method can also be used to produce mesoporous SSZ-91 (or other ZSM-48 zeolites) with different pore volume characteristics.

[0077] In the aforementioned method, the ammonium salt may include, for example, an ammonium halide such as ammonium chloride or ammonium fluoride, ammonium acetate, ammonium nitrate, or ammonium sulfate. The concentration of the ammonium salt, for example, ammonium fluoride, may generally be in the range of 0.01 to 80 wt%, or in the range of 1 to 60 wt%, or in the range of 10 to 50 wt%.

[0078] The organic base may be, but is not limited to, ammonia, a compound of the general formula R 3-n NH n where R is alkyl and n is 0-2, such as methylamine, dimethylamine, trimethylamine, and / or amines including mono-, di-, and trialkylamines having the general formula [R 4-n NH n ] +(wherein R is alkyl and n is 1 to 3), and combinations thereof. Representative ammonium cations include tetraalkylammonium compounds such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, and the like, as well as tri- and tetraalkylammonium compounds containing longer chain alkyl groups, e.g., cetyltrialkylammonium compounds such as cetyltrimethylammonium. Ammonium counteranions include F - , Cl - , Br - , and I - Halides such as OH - , P.F. 6- , B.F. 4-- , CH3COO - , SO4 - , R.C.O.O. - (wherein R is an alkyl group), as well as combinations thereof. The concentration of the organic base can generally be in the range of 0.001 to 5 mol / liter, or in the range of 0.01 to 2 mol / liter, or in the range of 0.02 to 1.0 mol / liter.

[0079] Suitable inorganic bases include, for example, hydroxides having suitable metal cations such as sodium, potassium, lithium, and / or other cations such as ammonium, and combinations thereof. The concentration of the inorganic base can generally be in the range of 0.001 to 5 mol / liter, or in the range of 0.01 to 2 mol / liter, or in the range of 0.02 to 1.0 mol / liter.

[0080] Suitable quaternary ammonium salts include, for example, those represented by the general formula [R 4-n NH n ] +(wherein R is alkyl and n is 1 to 3), and combinations thereof. Representative ammonium cations include tetraalkylammonium compounds such as tetramethylammonium, tetraethylammonium, and tetrapropylammonium, as well as tri- and tetraalkylammonium compounds containing longer chain alkyl groups, e.g., cetyltrialkylammonium compounds such as cetyltrimethylammonium. Ammonium counteranions include F - , Cl - , Br - , and I - Halides such as OH - , P.F. 6- , B.F. 4-- , CH3COO - , SO4 - , R.C.O.O. - (wherein R is an alkyl group), as well as combinations thereof. The concentration of the quaternary ammonium salt can generally be in the range of 0.001 to 5 mol / L, or in the range of 0.01 to 2 mol / L, or in the range of 0.02 to 1.0 mol / L.

[0081] Suitable quaternary ammonium bases include, for example, those represented by the general formula [R 4-n NH n ] + ammonium compounds containing hydroxide anions, such as alkylammonium hydroxide compounds, including those containing cations having the formula (where R is alkyl and n is 1 to 3), and combinations thereof. Representative ammonium cations include tetraalkylammonium compounds, such as tetramethylammonium, tetraethylammonium, and tetrapropylammonium, as well as tri- and tetraalkylammonium compounds containing longer chain alkyl groups, e.g., cetyltrialkylammonium compounds, such as cetyltrimethylammonium. In addition to hydroxide anions, suitable ammonium counteranions include F -, Cl - , Br - , and I - Halides such as PF 6- , B.F. 4-- , CH3COO - , SO4 - , R.C.O.O. - (wherein R is an alkyl group), as well as combinations thereof. The concentration of the quaternary ammonium base can generally be in the range of 0.001 to 5 mol / L, or in the range of 0.01 to 2 mol / L, or in the range of 0.02 to 1.0 mol / L.

[0082] Generally, but not exclusively, the ratio of molecular sieve to solution (wt / wt) is in the range of 0.001 to 1.0, or in the range of 0.005 to 0.2, or in the range of 0.01 to 0.1. Similarly, the hydroxide (OH) provided by the inorganic base - ) to molecular sieve ratio is generally 2.5 × 10 -4 ~1.0×10 -2 mol OH - / g - molecular sieve range, or 2.5 x 10 -4 ~5.0x10 -3 mol OH - / g - molecular sieve range, or 2.5x10 -4 ~3.0x10 -3 mol OH - / g-molecular sieve range.

[0083] Suitable process conditions include, but are not limited to, a solution temperature typically in the range of 1 to 95°C, or 5 to 95°C, or ambient to 95°C, or a desilication temperature up to the boiling point of the solution, typically in the range of 1 to 95°C, or 5 to 95°C, or ambient to 95°C. Mixing of the solution is typically accomplished by, for example, stirring, tumbling, sonication, or a combination thereof. Separation and recovery of the mesoporous sieve may be accomplished by any effective means, for example, filtration, centrifugation, sedimentation, or a combination thereof.

[0084] The X-ray diffraction pattern lines in Table 4 represent calcined mesoporous SSZ-91 prepared according to the methods described herein. [Table 4]

[0085] Catalysts can be formed from mesoporous SSZ-91 (or other mesoporous ZSM-48 zeolites according to the present invention) by any technique known in the art. Suitable catalysts include those supported with one or more metals from Groups 7-10 and 14 of the Periodic Table, including, for example, platinum and / or palladium, or other noble and / or base metals.

[0086] Mesoporous SSZ-91 (or other mesoporous ZSM-48 zeolites according to the present invention) generally have a silicon oxide to aluminum oxide molar ratio of 40 to 220, and comprise at least 70% polytype 6 of the total ZSM-48 type material present in the molecular sieve, and an additional EUO type molecular sieve phase in an amount of 0 to 3.5% by weight of the molecular sieve, the molecular sieve having a morphology characterized as polycrystalline aggregates collectively comprising crystallites having an average aspect ratio of about 1 to 8, and the molecular sieve has a total pore volume (measured at a P / P of 0.95) of at least about 0.2 cc / g in the mesoporous material diameter range (2 to 50 nm) and a micropore volume of at least 0.05 cc / g. In some cases, the mesoporous SSZ-91 molecular sieve (or other mesoporous ZSM-48 zeolites according to the present invention) may have a pore volume in the mesopore diameter range at a P / P of 0.95 of at least about 0.2-0.6 cc / g, or about 0.22-0.55 cc / g, or about 0.22-0.50 cc / g. In some cases, the mesoporous SSZ-91 molecular sieve (or other mesoporous ZSM-48 zeolites according to the present invention) may have a total pore volume at a P / P of 0.95 of at least about 0.25 cc / g, or in the range of about 0.25-0.8 cc / g, or in the range of about 0.28-0.65 cc / g, or in the range of about 0.28-0.60 cc / g. In some cases, the mesoporous SSZ-91 molecular sieve (or other mesoporous ZSM-48 zeolites according to the present invention) may have a micropore volume in the range of about 0.05 to 0.100 cc / g, or in the range of about 0.05 to 0.090 cc / g, or in the range of about 0.05 to 0.085 cc / g. In some cases, the mesoporous SSZ-91 molecular sieve (or other mesoporous ZSM-48 zeolites according to the present invention) may have a micropore volume of at least about 275 m 2 / g, or approximately 275-500m 2 / g range, or approximately 275-450m 2 / g range, or approximately 275-400m 2 / g。 In some cases, the mesoporous SSZ-91 molecular sieve (or other mesoporous ZSM-48 zeolites according to the present invention) may have a BET surface area in the range of at least about 175 mmol / g, or in the range of about 175 to 500 mmol / g, or in the range of about 175 to 400 mmol / g, or in the range of about 175 to 300 mmol / g. In some cases, the mesoporous SSZ-91 molecular sieve (or other mesoporous ZSM-48 zeolites according to the present invention) may have a silica-to-alumina ratio (SAR) in the range of about 40 to 200, or in the range of about 40 to 150, or in the range of about 40 to 120, or in the range of about 50 to 200, or in the range of about 50 to 150, or in the range of about 50 to 120.

[0087] Mesoporous SSZ-91 (or other mesoporous ZSM-48 zeolites according to the present invention) provides advantageous hydroconversion capabilities. In one aspect, a hydroconversion process useful for hydroisomerizing a hydrocarbon feed may be carried out using a catalyst comprising a mesoporous molecular sieve, for example, by contacting the hydrocarbon feed with a hydroisomerization catalyst under hydroisomerization conditions to produce a product, wherein the hydroisomerization catalyst comprises a mesoporous molecular sieve belonging to the ZSM-48 family of zeolites, the molecular sieve having a total pore volume (measured at a P / P of 0.95) of mesoporous material in the diameter range (2-50 nm). , at least about 0.2 cc / g, and a micropore volume of at least 0.05 cc / g, the molecular sieve having a silicon oxide to aluminum oxide molar ratio of 40 to 220, at least 70% polytype 6 of the total ZSM-48 type material present in the molecular sieve, and an additional EUO type molecular sieve phase in an amount of 0 to 3.5 wt% of the total product, the molecular sieve having a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of about 1 to 8. Suitable catalysts according to the above include a mesoporous zeolite and a metal selected from Groups 7 to 10 and 14 metals, such as Pt, Pd, or a combination thereof, or other noble and / or base metals. While not limited thereto, the metal content is typically 0.01 to 5.0 wt%, or 0.01 to 2.0 wt%, or 0.1 to 2.0 wt% (based on the total catalyst weight). The mesoporous material can be combined with other molecular sieves, for example, for use as a catalyst. Other matrix or support materials may also be included, including materials such as alumina, silica, titania, or combinations thereof. Generally, the catalyst can include 0.01-5.0 wt% metal, 1-80 wt% matrix / support material, and 0.1-99 wt% molecular sieve.

[0088] The hydroconversion process can utilize many conventional petroleum and / or bio-feedstocks, including, for example, gas oils, vacuum gas oils, long residues, vacuum residues, atmospheric distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crude oils, charges obtained from thermal or catalytic conversion processes, shale oils, cycle oils, fats, oils and waxes of animal and vegetable origin, petroleum and slack waxes, or combinations thereof.

[0089] Generally, mesoporous molecular sieves can be used to prepare catalysts that provide advantageous catalytic performance benefits. For example, in some cases, catalysts according to the present invention can be used to prepare catalysts with selectivity of 90% or greater, catalytic activity temperatures of 585°F or less as measured at 96% conversion, or C produced. 4- The present invention provides a hydroisomerized hydrocarbon product having 0.9% or less light ends production, as measured as cracked products, or a combination thereof. In some cases, the selectivity is 90% or greater and the catalyst activation temperature is 585°F or less, or the selectivity is 90% or greater and the C produced is 0.9% or less light ends production, as measured as cracked products, or a combination thereof. 4- The light ends produced as measured by decomposition products are 0.9% or less, or the catalyst activation temperature is 585°F or less, and the C produced 4- Light ends production as measured by cracking products is 0.9% or less, or a combination thereof. In some cases, selectivity is 90% or greater, the catalyst activation temperature is 585°F or less, and the C produced is 4- Light ends production, as measured as cracked products, is 0.9% or less. In some cases, selectivity is 91% or 92% or greater, or the catalyst activity temperature is 582°F, or 580°F, or 575°F, or 570°F or less, or C 4- Light end production of decomposition products is less than or equal to 0.85%, or 0.8%, or 0.7%, or 0.6%, or 0.5%, or 0.4%, 0.3%, or 0.2%, or any combination thereof. [Example]

[0090] Examples 1-40 demonstrate that catalysts comprising mesoporous ZSM-48 materials having the three unique combinations of properties of SSZ-91 (low aspect ratio, low EU-1 content, and high polytype 6 composition) and the mesoporosity described and exemplified herein exhibit improved catalytic performance. The following illustrative examples are intended to be non-limiting.

[0091] The micropore volume was measured by subjecting the dried product to micropore volume analysis by the t-plot method using N2 as the adsorbent, and was expressed in cm 3 The micropore volume in units of / g was obtained. See, e.g., Lippens, Bo C., and JH De Boer. "Studies on pore systems in catalysts: V. The t method." Journal of Catalysis 4, no. 3 (1965): 319-323.

[0092] The total pore volume was determined by Gurvich's law based on the amount of adsorbed inert gas at a relative pressure of 0.95 (i.e., P / P = 0.95). See, for example, Thommes, Matthias, et al., "Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)," Pure and Applied Chemistry 87.9-10 (2015): 1051-1069.

[0093] The BET surface area was determined according to known procedures. See, for example, Thommes, Matthias, et al., "Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)," Pure and applied chemistry 87.9-10 (2015): 1051-1069.

[0094] The Bronsted acid site density was determined by temperature-programmed desorption of n-propylamine. See, e.g., Farneth, W. E., and R. J. Gorte. "Methods for characterizing zeolite acidity." Chemical reviews 95, no. 3 (1995): 615-635, WO2016 / 069073A1.

[0095] The silica to alumina (SAR) molar ratio was determined by inductively coupled plasma spectroscopy according to known techniques.

[0096] Example 1 - Comparative Evaluation of SSZ-91 A sample of ammonium form zeolite SSZ-91 was prepared according to U.S. Patent No. 9,802,830. The material was calcined in air by placing a thin bed in a calcination dish and heating in a muffle furnace from room temperature to 120°C at a rate of 1°C / min and holding for 2 hours. The temperature was then increased at a rate of 1°C / min to 540°C and held for 5 hours. The temperature was again increased at 1°C / min to 595°C and held at that temperature for 5 hours. The material was then allowed to cool to room temperature.

[0097] The material was then converted to the ammonium form by heating in an ammonium nitrate solution (typically 1 g NH4NO3 / 1 g zeolite in 10 mL HO at 95°C for at least 3 hours). The material was then filtered. This was repeated twice for a total of three exchanges. Finally, the material was washed with deionized (DI) water until the conductivity of the water was less than 50 μS / cm.

[0098] Nitrogen isotherm analysis showed a t-plot micropore volume of 0.067 cc / g and a t-plot external surface area of 99 m 2 / g, and BET surface area 245 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.26. The silica to alumina molar ratio was 116.

[0099] The nitrogen isotherm is shown in Figure 1, and the pore size distribution (PSD) calculated from the nitrogen isotherm is shown in Figure 2. The PSD was calculated from density functional theory (DFT), a method well known in the art for calculating PSD. For more details, see, but are not limited to, Landers, John, Gennady Yu Gor, and Alexander V. Neimark. "Density functional theory methods for characterization of porous materials." Colloids and Surfaces A: Physicochemical and Engineering Aspects 437 (2013): 3-32 and Kupgan, Grit, Thilanga P. Liyana-Arachchi, and Coray M. Colina. "NLDFT pore size distribution in amorphous microporous materials." Langmuir 33, no. 42 (2017): 11138-11145. The shape of the nitrogen isotherm shown in Figure 1 is typical for microporous materials, and the sharp increase in volume near P / P = 1 is due to intracrystalline condensation. The mesopore size distribution shown in Figure 2 also does not indicate significant mesoporosity.

[0100] The material was then converted to the ammonium form by heating in an ammonium nitrate solution (typically 1 g NH4NO3 / 1 g zeolite in 10 mL HO at 95°C for at least 3 hours). The material was then filtered. This was repeated twice for a total of three exchanges. Finally, the material was washed with DI water until the conductivity of the water was less than 50 μS / cm.

[0101] Nitrogen isotherm analysis showed a t-plot micropore volume of 0.067 cc / g and a t-plot external surface area of 112 m 2 / g, and BET surface area 260 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.26. The silica to alumina molar ratio was 114.

[0102] The ammonium-exchanged samples were subjected to palladium ion exchange using tetraamminepalladium(II) nitrate (0.5 wt% Pd). After ion exchange, the samples were dried at 95 °C and then calcined in air at 482 °C for 3 h to convert the tetraamminepalladium(II) nitrate to palladium oxide. Finally, the material was pelletized, crushed, and sieved to 20-40 mesh.

[0103] Example 2 - Preparation of mesoporous SSZ-91 A 100 mL solution of 0.12 M NaOH and 0.08 M tetrapropylammonium bromide was prepared and heated to 75°C. Next, 4 g of the ammonium form of SSZ-91 from Example 1 was added, and the solution was stirred at 75°C for 60 minutes. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95°C. The material was converted to the ammonium form by heating in an ammonium nitrate solution (typically 1 g NH4NO3 / 1 g zeolite in 10 mL HO at 95°C for at least 3 hours). The material was then filtered. This was repeated twice for a total of three exchanges. Finally, the material was washed with DI water until the conductivity of the water was less than 50 μS / cm. The yield was 59% based on the weight of the recovered solid.

[0104] Nitrogen isotherm analysis showed a t-plot micropore volume of 0.030 cc / g and a t-plot external surface area of 141 m 2 / g, and BET surface area 211 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.51 cc / g. The mesopore diameter determined by PSD was calculated to be 119 Å. The Brønsted acid site density determined by temperature-programmed desorption of n-propylamine was 166 μmol H + / g.

[0105] Analysis of the nitrogen isotherms and the PSD calculated from the nitrogen isotherms showed only small changes in the micropore volume and surface area of the material, but a significant increase in the total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen PSD suggesting the presence of mesopores.

[0106] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0107] Example 3 A sample of ammonium form of zeolite SSZ-91 was prepared according to Example 1.

[0108] Nitrogen isotherm analysis showed a t-plot micropore volume of 0.071 cc / g and a t-plot external surface area of 85 m 2 / g, and BET surface area 240 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.23. The silica-to-alumina molar ratio was 121. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 185 μmol H + / g.

[0109] Example 4 A solution of 0.1 M NaOH was heated to 50° C., then 5 g of SSZ-91 from Example 3 was added (50 mL / g-zeolite) and stirred for 60 minutes at 50° C. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0110] The yield based on recovered solids was 79%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.063 cc / g and a t-plot external surface area of 166 m 2 / g, and BET surface area 305 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.40 cc / g. The silica to alumina molar ratio was 92. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 248 μmol H + / g.

[0111] Analysis of the nitrogen and argon isotherms and the PSD calculated from the isotherms showed that the material exhibited only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen and argon PSD suggesting the presence of mesopores.

[0112] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0113] Example 5 A solution of 0.3 M NaOH was heated to 50° C., then 10 g of SSZ-91 from Example 3 was added (50 mL / g-zeolite) and stirred for 60 minutes at 50° C. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0114] The yield based on recovered solids was 45%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.071 cc / g and a t-plot external surface area of 176 m 2 / g, and BET surface area 333 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.61 cc / g. The mesopore diameter, from which the PSD was determined, was calculated to be 105 Å. The silica-to-alumina molar ratio was 68. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 284 μmol H + / g.

[0115] The nitrogen isotherm is shown in Figure 3, and the PSD calculated from the nitrogen isotherm is shown in Figure 4. The material showed only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores. This is consistent with the nitrogen and argon PSD, which also suggests the presence of mesopores.

[0116] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0117] Example 6 A solution of equal amounts of 0.1 M NaOH and 0.1 M tetrabutylammonium hydroxide (total hydroxide concentration 0.1 M) was prepared and heated to 50° C. Next, 10 g of SSZ-91 from Example 3 was added (50 mL / g-zeolite) and the solution was stirred at 50° C. for 60 minutes. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0118] The yield based on recovered solids was 77%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.082 cc / g and a t-plot external surface area of 196 m 2 / g, and BET surface area 379 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.46 cc / g. The silica to alumina molar ratio was 97. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 242 μmol H + / g.

[0119] Analysis of the nitrogen and argon isotherms and the PSD calculated from the isotherms showed that the material exhibited only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen and argon PSD suggesting the presence of mesopores.

[0120] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0121] Example 7 A sample of as-prepared zeolite SSZ-91 was prepared according to U.S. Patent No. 9,802,830. The material was calcined in air by placing a thin bed in a calcination dish and heating in a muffle furnace from room temperature to 120°C at a rate of 1°C / min and holding for 2 hours. The temperature was increased at a rate of 1°C / min to 540°C and held for 5 hours. The temperature was again increased at 1°C / min to 595°C and held at that temperature for 5 hours. The material was then allowed to cool to room temperature. The material was not ammonium exchanged.

[0122] A small portion was then converted to the ammonium form for analysis according to the procedure described in Example 1. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.082 cc / g and a t-plot external surface area of 85 m 2 / g, and BET surface area 263 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.25 cc / g. The silica to alumina molar ratio was 119.

[0123] Example 8 A solution of 0.1 M NaOH was heated to 50° C., then 50 g of SSZ-91 from Example 7 was added (10 mL / g-zeolite) and stirred at 50° C. for 60 minutes. Ice was added at the end of the treatment to rapidly cool the solution. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form according to the procedure described in Example 1.

[0124] The yield based on recovered solids was 73%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.052 cc / g and a t-plot external surface area of 98 m 2 / g, and BET surface area 213 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.26 cc / g. The Bronsted acid site density measured by temperature-programmed desorption of n-propylamine was 198 μmol H + / g.

[0125] Analysis of the nitrogen isotherms and the PSD calculated from the isotherms shows that the materials exhibit only small changes in micropore volume and surface area, and a modest increase in total pore volume, suggesting limited formation of mesopores, which is consistent with the nitrogen PSD.

[0126] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0127] Example 9 A solution of 0.1 M NaOH was heated to 50° C., then 10 g of the as-synthesized SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred at 50° C. for 60 minutes. At the end of the procedure, ice was added to rapidly cool the solution. The solid was collected by centrifugation, washed thoroughly with DI water, and then dried in air at 95° C. The material was then converted to the ammonium form according to the procedure described in Example 1.

[0128] The yield based on recovered solids was 73%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.071 cc / g and a t-plot external surface area of 125 m 2 / g, and BET surface area 293 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.29 cc / g. The mesopore diameter determined by PSD was calculated to be 47 Å. The Brønsted acid site density, determined by temperature-programmed desorption of n-propylamine, was 231 μmol H + / g.

[0129] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0130] Example 10 A solution of 0.1 M NaOH was heated to 50° C., then 10 g of SSZ-91 from Example 3 was added (50 mL / g-zeolite) and stirred for 60 minutes at 50° C. Ice was added to quench the solution, and the solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0131] The yield based on recovered solids was 69%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.061 cc / g and a t-plot external surface area of 184 m 2 / g, and BET surface area 321 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.47 cc / g. The mesopore diameter, from which the PSD was determined, was calculated to be 91 Å. The silica-to-alumina molar ratio was 80. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 228 μmol H + / g.

[0132] Analysis of the nitrogen isotherms and the PSD calculated from the isotherms showed that the materials exhibited only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen PSD suggesting the presence of mesopores.

[0133] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0134] Example 11 A solution of 0.1 M NaOH was heated to 50° C., then 5 g of SSZ-91 from Example 3 was added (100 mL / g-zeolite) and stirred for 60 minutes at 50° C. Ice was added to quench the solution, and the solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0135] The yield based on recovered solids was 55%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.071 cc / g and a t-plot external surface area of 207 m 2 / g, and BET surface area 364 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.66 cc / g. The mesopore diameter determined by PSD was calculated to be 107 Å. The Brønsted acid site density determined by temperature-programmed desorption of n-propylamine was 269 μmol H + / g.

[0136] The nitrogen isotherm is shown in Figure 5, and the PSD calculated from the nitrogen isotherm is shown in Figure 6. The material showed only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores. This is consistent with the nitrogen PSD, which suggests the presence of mesopores.

[0137] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0138] Example 12 A solution of 0.05 M NaOH was heated to 50° C., then 10 g of SSZ-91 from Example 3 was added (50 mL / g-zeolite) and stirred for 60 minutes at 50° C. Ice was added to quench the solution, and the solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0139] The yield based on recovered solids was 83%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.061 cc / g and a t-plot external surface area of 143 m 2 / g, and BET surface area 278 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.33 cc / g. The mesopore diameter determined by PSD was calculated to be 49 Å. The Brønsted acid site density determined by temperature-programmed desorption of n-propylamine was 231 μmol H + / g.

[0140] Analysis of the nitrogen isotherms and the PSD calculated from the isotherms showed that the materials exhibited only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen PSD suggesting the presence of mesopores.

[0141] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0142] Example 13 A solution of 0.1 M tetrapropylammonium hydroxide was heated to 50° C., then 10 g of SSZ-91 from Example 3 was added (50 mL / g-zeolite) and stirred for 60 minutes at 50° C. Ice was added to quench the solution, and the solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0143] The yield based on recovered solids was 95%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.062 cc / g and a t-plot external surface area of 95 m 2 / g, and BET surface area 230 m 2 The total pore volume was measured at P / P = 0.95 and found to be 0.24 cc / g. The Bronsted acid site density measured by temperature-programmed desorption of n-propylamine was 212 μmol H + / g.

[0144] Analysis of the nitrogen isotherms and the PSD calculated from the isotherms shows that the materials exhibit only small changes in micropore volume and surface area, and a modest increase in total pore volume, suggesting limited formation of mesopores, which is consistent with the nitrogen PSD.

[0145] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0146] Example 14 A solution of 0.1 M NaOH was heated to 50° C., then 10 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred for 30 minutes at 50° C. Ice was added to quench the solution, and the solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0147] The yield based on recovered solids was 66%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.057 cc / g and a t-plot external surface area of 186 m 2 / g, and BET surface area 315 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.51 cc / g. The mesopore diameter, determined by PSD, was calculated to be 83 Å. The silica-to-alumina molar ratio was 81. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 255 μmol H + / g.

[0148] Analysis of the nitrogen isotherms and the PSD calculated from the isotherms showed that the materials exhibited only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen PSD suggesting the presence of mesopores.

[0149] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0150] Example 15 A solution of 0.1 M NaOH was heated to 50° C., then 10 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred for 120 minutes at 50° C. Ice was added to quench the solution, and the solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The material was then converted to the ammonium form following the procedure described in Example 1.

[0151] The yield based on recovered solids was 64%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.060 cc / g and a t-plot external surface area of 168 m 2 / g, and BET surface area 300 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.49 cc / g. The mesopore diameter, from which the PSD was determined, was calculated to be 87 Å. The silica-to-alumina molar ratio was 80. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 248 μmol H + / g.

[0152] Analysis of the nitrogen isotherms and the PSD calculated from the isotherms showed that the materials exhibited only small changes in micropore volume and surface area, but a significant increase in total pore volume, suggesting the formation of mesopores, which is consistent with the nitrogen PSD suggesting the presence of mesopores.

[0153] The palladium converted material, following the procedure of Example 1, contained 0.5 wt% Pd.

[0154] Example 16 To a solution of 0.1 M NaOH at ambient temperature of 26° C., 30 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred for 60 minutes at a temperature of 26° C. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The product yield based on the recovered solid for this step was 91%. The material was then converted to the ammonium form according to the procedure described in Example 1.

[0155] The yield based on recovered solids was 75%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.055 cc / g and a t-plot external surface area of 115 m 2 / g, and BET surface area 237 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.29 cc / g. The silica to alumina molar ratio was 104. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 220 μmol H + / g.

[0156] Example 17 A solution of 0.1 M NaOH was heated to 50° C., then 30 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred at 50° C. for 30 minutes. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The product yield based on the recovered solid for this step was 73%. The material was then converted to the ammonium form according to the procedure described in Example 1.

[0157] The yield based on the recovered solids was 65%. The nitrogen isotherm and the PSD calculated from the isotherm are shown in Figures 7 and 8. Analysis of the nitrogen isotherm revealed a t-plot micropore volume of 0.058 cc / g and a t-plot external surface area of 161 m. 2 / g, and BET surface area 289 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.35 cc / g. The mesopore diameter, determined by PSD, was calculated to be 83 Å. The silica-to-alumina molar ratio was 81. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 247 μmol H + / g.

[0158] Example 18 A solution of 0.1 M NaOH was heated to 50° C., then 30 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred at 50° C. for 15 minutes. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The product yield based on the recovered solid for this step was 76%. The material was then converted to the ammonium form according to the procedure described in Example 1.

[0159] The yield based on recovered solids was 68%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.058 cc / g and a t-plot external surface area of 155 m 2 / g, and BET surface area 285 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.42 cc / g. The mesopore diameter, determined by PSD, was calculated to be 79 Å. The silica-to-alumina molar ratio was 85. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 240 μmol H + / g.

[0160] Example 19 A solution of 0.05 M NaOH was heated to 50° C., then 80 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred at 50° C. for 45 minutes. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The product yield based on the recovered solid for this step was 80%. The material was then converted to the ammonium form according to the procedure described in Example 1.

[0161] The yield based on recovered solids was 74%. Nitrogen isotherm analysis showed a t-plot micropore volume of 0.063 cc / g and a t-plot external surface area of 174 m 2 / g, and BET surface area 315 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.36 cc / g. The mesopore diameter, determined by PSD, was calculated to be 47 Å. The silica-to-alumina molar ratio was 93. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 236 μmol H + / g.

[0162] Example 20 A solution of 0.05 M NaOH was heated to 50° C., then 80 g of SSZ-91 from Example 7 was added (50 mL / g-zeolite) and stirred at 50° C. for 60 minutes. The solid was collected by filtration, washed thoroughly with DI water until the conductivity was less than 50 μS / cm, and then dried in air at 95° C. The product yield based on the recovered solid was 65%. The material was then converted to the ammonium form following the procedure described in Example 1.

[0163] Nitrogen isotherm analysis revealed a t-plot micropore volume of 0.064 cc / g and a t-plot external surface area of 211 m 2 / g, and BET surface area 353 m 2 / g. The total pore volume was measured at P / P = 0.95 and found to be 0.53 cc / g. The mesopore diameter, from which the PSD was determined, was calculated to be 77 Å. The silica-to-alumina molar ratio was 74. The Bronsted acid site density, measured by temperature-programmed desorption of n-propylamine, was 269 μmol H + / g.

[0164] Example 21 - Hydroisomerization of n-hexadecane according to Example 1 0.5 g of each palladium-exchanged sample from Example 1 was loaded into the center of a 23-inch long, 0.25-inch outer diameter stainless steel reactor tube, and alundum was loaded upstream of the catalyst to preheat the feed (total pressure 1200 psig; downflow hydrogen rate of 160 mL / min (measured at 1 atmosphere and 25°C); downflow liquid feed rate of 1 mL / hr). All materials were first reduced in flowing hydrogen at approximately 315°C for 1 hour. Products were analyzed by online capillary gas chromatography (GC) once every 30 minutes. Raw data from the GC was collected by an automatic data acquisition and processing system, and hydrocarbon conversion was calculated from the raw data.

[0165] The conversion can be carried out by reacting to form other products (iso-nC 16 The yield was defined as the amount of hexadecane produced (including isomers). 16 expressed as the weight percent of products other than iso-C as the product produced 16 The results at 96% conversion are reported in Table 5.

[0166] Examples 22-40 - Hydroisomerization of n-hexadecane based on Examples 2-20 Catalyst testing was performed in the same manner as in Example 21 (using the material of Example 1), except that the catalysts used the materials of Examples 2-20, respectively. Results at 96% conversion are reported in Table 5. The desired isomerization selectivity at 96% conversion for the preferred materials of this invention is at least 87%. A good balance between isomerization selectivity and temperature at 96% conversion is important in this invention. The desired temperature at 96% conversion is less than 600°F. The lower the temperature at 96% conversion, the more desirable the catalyst. Optimal catalyst performance depends on the synergistic effect of isomerization selectivity and temperature at 96% conversion. Undesirable catalyst cracking with concomitant high gas production is reported in Table 5. 4- Desired C values for the materials of the present invention are indicated by an increased level of degradation. 4- Decomposition is no more than 1.0%, or less than 0.9%. [Table 5]

[0167] It is understood that the present invention is not limited to the above-described embodiments, and that various changes and modifications may be made without departing from the concepts described herein. Except where mutually exclusive, any feature may be used individually or in combination with other features, and the present disclosure extends to and includes all combinations and subcombinations of one or more features described herein.

[0168] Further details regarding the invention and the scope of the present disclosure can be found from the appended claims.

[0169] The above description of one or more embodiments of the present invention is primarily for purposes of illustration, and it is recognized that variations may be employed and are incorporated into the essence of the present invention. Reference should be made to the following claims in determining the scope of the present invention.

[0170] For purposes of United States patent practice, and where permitted in other patent offices, any patents and publications cited in the above description of the invention are hereby incorporated by reference to the extent that any information contained therein is consistent with and / or supplements the above disclosure.

Claims

1. A mesoporous molecular sieve belonging to the ZSM-48 family of zeolites, a molar ratio of silicon oxide to aluminum oxide of 40 to 220; at least 70% polytype 6 of the total ZSM-48 type material present in said molecular sieve; and an additional EUO-type molecular sieve phase in an amount of 0 to 3.5 wt. % of said molecular sieve; Including, the molecular sieve has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of about 1 to 8; The molecular sieve has a P / P of 0.95 ０ The mesoporous molecular sieve has a total pore volume in the mesopore diameter range of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g.

2. 2. The mesoporous SSZ-91 molecular sieve according to claim 1.

3. P / P of 0.95 ０ The mesoporous SSZ-91 molecular sieve has a total pore volume in the mesopore diameter range of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g.

4. P / P of 0.95 ０ 4. The molecular sieve of claim 1, wherein the total pore volume at 1000 rpm is at least about 0.25 cc / g, or in the range of about 0.25 to 0.8 cc / g, or in the range of about 0.28 to 0.65 cc / g, or in the range of about 0.28 to 0.60 cc / g.

5. P / P of 0.95 ０ 5. The molecular sieve of claim 1, wherein the total pore volume in said mesopore diameter range is at least about 0.2 to 0.6 cc / g, or about 0.22 to 0.55 cc / g, or about 0.22 to 0.50 cc / g.

6. 6. The molecular sieve of claim 1, wherein the molecular sieve has a micropore volume in the range of about 0.05 to 0.100 cc / g, or in the range of about 0.05 to 0.090 cc / g, or in the range of about 0.05 to 0.085 cc / g.

7. The molecular sieve has a molecular sieve content of at least about 275 m ２ / g, or about 275-500m ２ / g range, or about 275-450 m ２ / g range, or about 275-400 m ２ 7. The molecular sieve of claim 1, having a BET surface area in the range of 1 / g.

8. 8. The molecular sieve of claim 1, wherein the molecular sieve has a Bronsted acidity of at least about 175 mmol / g, or in the range of about 175 to 500 mmol / g, or in the range of about 175 to 400 mmol / g, or in the range of about 175 to 300 mmol / g.

9. 9. The molecular sieve of claim 1, wherein the molecular sieve has a silica-to-alumina ratio (SAR) in the range of about 40 to 200, or in the range of about 40 to 150, or in the range of about 40 to 120.

10. 1. A method for making a mesoporous molecular sieve belonging to the ZSM-48 family of zeolites, said molecular sieve having a P / P ratio of 0.

95. ０ a total pore volume in the mesopore diameter range of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g; preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one element source selected from Groups 1 and 2 of the Periodic Table, hydroxide ions, hexamethonium cations, and water; subjecting said reaction mixture to crystallization conditions sufficient to form crystals of said molecular sieve; subjecting the molecular sieve to calcination conditions sufficient to form a calcined molecular sieve; contacting the calcined molecular sieve with an organic base, a quaternary ammonium salt, a quaternary ammonium base, an inorganic base, ammonium fluoride, or a combination thereof under solution conditions effective to desilicate the molecular sieve; and contacting the desilicate molecular sieve with an ammonium salt under solution conditions effective to form an ammonium-exchanged mesoporous molecular sieve.

11. 11. The method of claim 10, wherein the calcination conditions include heating the molecular sieve to a temperature in the range of 80 to 140°C for 60 to 200 minutes, heating the molecular sieve to a temperature in the range of 450 to 550°C for 60 to 300 minutes, heating the molecular sieve to a temperature in the range of 560 to 600°C for 60 to 300 minutes, or a combination thereof.

12. 12. The method of claim 11, wherein the calcination conditions include heating the molecular sieve to a temperature in the range of 80 to 140°C for 60 to 200 minutes, heating the molecular sieve to a temperature in the range of 450 to 550°C for 60 to 300 minutes, and heating the molecular sieve to a temperature in the range of 560 to 600°C for 60 to 300 minutes.

13. 11. The method of claim 10, wherein the mesoporous molecular sieve is SSZ-91.

14. 11. The method of claim 10, wherein the ammonium salt contacted with the desilicate molecular sieve comprises an ammonium halide, ammonium chloride, ammonium acetate, ammonium nitrate, or ammonium sulfate.

15. Total pore volume in the mesopore diameter range (P / P of 0.95) ０ 1. A method for making a mesoporous SSZ-91 molecular sieve having a densitometric coefficient of resorption (measured by densitometric coefficient of resorption) of at least about 0.2 cc / g, comprising: contacting the calcined SSZ-91 molecular sieve with an organic base, a quaternary ammonium salt, a quaternary ammonium base, an inorganic base, ammonium fluoride, or a combination thereof under solution conditions effective to desilicate the molecular sieve; and contacting the desilicate molecular sieve with an ammonium salt under solution conditions effective to form an ammonium-exchanged mesoporous molecular sieve.

16. 16. The method of claim 15, wherein the calcination conditions of the calcined SSZ-91 include heating the molecular sieve to a temperature in the range of 80 to 140°C for 60 to 200 minutes, and a) heating the molecular sieve to a temperature in the range of 450 to 550°C for 60 to 300 minutes, or b) heating the molecular sieve to a temperature in the range of 560 to 600°C for 60 to 300 minutes, or a combination thereof.

17. 16. The method of claim 15, wherein the calcination conditions for the calcined SSZ-91 include heating the molecular sieve to a temperature in the range of 80 to 140°C for 60 to 200 minutes, heating the molecular sieve to a temperature in the range of 450 to 550°C for 60 to 300 minutes, and heating the molecular sieve to a temperature in the range of 560 to 600°C for 60 to 300 minutes.

18. 18. The method according to any one of claims 10 to 17, wherein the concentration of the inorganic base is in the range of 0.001 to 5 mol / liter, or in the range of 0.01 to 2 mol / liter, or in the range of 0.02 to 1.0 mol / liter.

19. 18. The method of any one of claims 10 to 17, wherein the concentration of the ammonium salt contacted with the desilicate molecular sieve is in the range of 0.01 to 80 wt%, or in the range of 1 to 60 wt%, or in the range of 10 to 50 wt%.

20. 19. The method of any one of claims 10 to 18, wherein the ratio of the molecular sieve to the solution (wt / wt) is in the range of 0.001 to 1.0, or in the range of 0.005 to 0.2, or in the range of 0.01 to 0.

1.

21. The hydroxide (OH) provided by the inorganic base to the molecular sieve － ) is 2.5 × 10 －４ ~1.0 x 10 －２ mol OH － / g - molecular sieve range, or 2.5 x 10 －４ ~5.0 x 10 －３ mol OH － / g - molecular sieve range, or 2.5 x 10 －４ ~3.0 x 10 －３ mol OH － The method according to any one of claims 10 to 19, wherein the molecular sieve content is in the range of 1 / g-molecular sieve.

22. 21. The method of any one of claims 10 to 20, wherein the solution temperature is in the range of 1 to 95°C, or in the range of 5 to 95°C, or in the range of ambient temperature to 95°C, and the solution temperature is up to the boiling point of the solution.

23. 22. The method of any one of claims 10 to 21, wherein the desilication temperature is in the range of 1 to 95°C, or in the range of 5 to 95°C, or in the range of ambient temperature to 95°C.

24. 23. The method of any one of claims 10 to 22, wherein the method comprises mixing the solution by stirring, tumbling, sonication, or a combination thereof.

25. 24. The method of any one of claims 10 to 23, wherein the method comprises separating the molecular sieve from the solution by filtration, centrifugation, sedimentation, or a combination thereof.

26. A catalyst comprising the molecular sieve of any one of claims 1 to 9 and a metal selected from metals of groups 7 to 10 and 14 of the periodic table.

27. 27. The catalyst of claim 26, wherein the metal comprises Pt, Pd, or a combination thereof.

28. A method for making the catalyst of claim 26 or claim 27, wherein the molecular sieve is made according to the method of any one of claims 10 to 25.

29. 1. A hydroconversion process useful for hydroisomerizing a hydrocarbon feedstock, comprising: contacting a hydrocarbon feed with a hydroisomerization catalyst under hydroisomerization conditions to produce a product; The hydroisomerization catalyst comprises a mesoporous molecular sieve belonging to the ZSM-48 family of zeolites, the molecular sieve having a P / P ratio of 0.

95. ０ a total pore volume in the mesopore diameter range of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g; The molecular sieve is a molar ratio of silicon oxide to aluminum oxide of 40 to 220; at least 70% polytype 6 of the total ZSM-48 type material present in said molecular sieve; and an additional EUO-type molecular sieve phase in an amount of 0-3.5 wt. % of the total product; The process wherein the molecular sieve has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of about 1-8.

30. 30. The process of claim 29, wherein the molecular sieve is SSZ-91.

31. 1. A hydroconversion process useful for hydroisomerizing a hydrocarbon feedstock, comprising: contacting a hydrocarbon feed with a hydroisomerization catalyst under hydroisomerization conditions to produce a product; The hydroisomerization catalyst has a total pore volume in the mesopore diameter range (P / P of 0.95 ０ and a mesoporous SSZ-91 molecular sieve having a pore volume (measured by pore size) of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g.

32. 32. The process of any one of claims 29 to 31, wherein the catalyst comprises a metal selected from metals in groups 7 to 10 and 14 of the periodic table.

33. 33. The process of any one of claims 29 to 32, wherein the catalyst comprises Pt, Pd, or a combination thereof.

34. The molecular sieve is at least 80% or 90% polytype 6 of the total ZSM-48 type material; 0.1-2wt% EU-1, crystallites having an average aspect ratio of 1 to 5 or 1 to 3; or a combination thereof, The process of any one of claims 29 to 33, comprising:

35. 35. The process of any one of claims 29 to 34, wherein the catalytic metal content is 0.01 to 5.0 wt%, or 0.01 to 2.0 wt%, or 0.1 to 2.0 wt% (based on total catalyst weight).

36. 36. The process of any one of claims 29 to 35, wherein the silica to alumina molar ratio (SAR) of the molecular sieve is in the range of about 40 to 200, or in the range of about 40 to 150, or in the range of about 40 to 120, or in the range of about 50 to 200, or in the range of about 50 to 150, or in the range of about 50 to 120.

37. 37. The process of any one of claims 29 to 36, wherein the catalyst further comprises a matrix material selected from alumina, silica, titania, or combinations thereof.

38. 38. The process of claim 37, wherein the catalyst comprises 0.01 to 5.0 wt % of the metal, 1 to 80 wt % of the matrix material, and 0.1 to 99 wt % of the molecular sieve.

39. 39. The process of any one of claims 29 to 38, wherein the hydrocarbon feed comprises gas oil, vacuum gas oil, long residue, vacuum residue, atmospheric distillate, heavy fuels, oils, waxes and paraffins, used oil, deasphalted residue or crude oil, charge obtained from thermal or catalytic conversion processes, shale oil, cycle oil, fats, oils and waxes of animal and vegetable origin, petroleum and slack wax, or combinations thereof.

40. Isomerization selectivity of 90% or more (96% n-C １６ conversion), catalytic activity temperature below 585°F (96% n-C １６ conversion), or the generated C ４－ 41. A process for producing hydroisomerized hydrocarbon products having 0.9% or less light ends production, measured as cracked products, or a combination thereof, comprising subjecting a hydrocarbon feed to the process of any one of claims 30 to 40.

41. The selectivity is 90% or more and the catalyst activation temperature is 585°F or less, or the selectivity is 90% or more and the C produced ４－ the light ends produced as measured by decomposition products is 0.9% or less, or the catalyst activation temperature is 585°F or less, and the C produced ４－ 41. The process of claim 40, wherein the light ends production, as measured as decomposition products, is 0.9% or less, or a combination thereof.

42. The selectivity is 90% or more, the catalyst activation temperature is 585°F or less, and the C produced ４－ 41. The process of claim 40, wherein the light ends production, as measured as decomposition products, is 0.9% or less.

43. The selectivity is 91% or 92% or more, or the catalyst activity temperature is 582°F, 580°F, 575°F, or 570°F or less, or ４－ 43. The process of any one of claims 41 or 42, wherein the light ends production of decomposition products is less than or equal to 0.85%, or 0.8%, or 0.7%, or 0.6%, or 0.5%, or 0.4%, 0.3%, or 0.2%, or a combination thereof.

44. 41. A hydroconversion catalyst for use in the process of any one of claims 29 to 40, wherein the catalyst comprises a mesoporous molecular sieve belonging to the ZSM-48 family of zeolites, the molecular sieve having a P / P ratio of 0.

95. ０ a pore volume in the mesopore diameter range of at least about 0.2 cc / g and a micropore volume of at least 0.05 cc / g, and the molecular sieve is a molar ratio of silicon oxide to aluminum oxide of 40 to 220; at least 70% polytype 6 of the total ZSM-48 type material present in said molecular sieve; and an additional EUO-type molecular sieve phase in an amount of 0 to 3.5 wt. % of the total molecular sieve; The catalyst wherein the molecular sieve has a morphology characterized as polycrystalline aggregates comprising crystallites collectively having an average aspect ratio of about 1-8.

45. 45. The catalyst of claim 44, wherein the molecular sieve is SSZ-91.

46. 42. A hydroconversion catalyst for use in the process of any one of claims 30 to 41, wherein the catalyst has a total pore volume in the mesopore diameter range (P / P of 0.95). ０ The catalyst comprises a mesoporous SSZ-91 molecular sieve having a surface area (measured by pore size) of at least about 0.2 cc / g and said micropore volume is at least 0.05 cc / g.

47. 47. The catalyst of any one of claims 44 to 46, wherein the metal comprises Pt, Pd, or a combination thereof.

48. A method for making a catalyst according to any one of claims 44 to 46, wherein the molecular sieve is made according to the method according to any one of claims 10 to 25.

49. 49. The method of claim 48, wherein the molecular sieve is preparing a reaction mixture containing at least one silicon source, at least one aluminum source, at least one element source selected from Groups 1 and 2 of the Periodic Table, hydroxide ions, hexamethonium cations, and water; and subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve; subjecting the molecular sieve to calcination conditions sufficient to form a calcined molecular sieve; contacting the calcined molecular sieve with an organic base, a quaternary ammonium salt, a quaternary ammonium base, an inorganic base, ammonium fluoride, or a combination thereof under solution conditions effective to desilicate the molecular sieve; and contacting the desilicate molecular sieve with an ammonium salt under solution conditions effective to form an ammonium-exchanged mesoporous molecular sieve; The method according to any one of claims 1 to 4, wherein the polymer is produced by the method comprising:

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