Method for manufacturing CON framework molecular sieve

Abstract

The present disclosure relates to a method for producing a CON framework type molecular sieve, using 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation as a structure directing agent. The present disclosure also relates to a molecular sieve material obtained by such a method, and a molecular sieve material containing a structure directing agent in its pore structure.

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims priority and the benefit thereof based on U.S. Provisional Application No. 63 / 359,255, filed on July 8, 2022, the entire content of which is incorporated herein by reference.

[0002] [Technical Field] The present disclosure relates to a method for producing a CON framework type (or framework type) molecular sieve using a novel structure - directing agent (or structure - directing agent). The present disclosure also relates to a molecular sieve material obtained by the above method and a molecular sieve material containing the structure - directing agent in its pore structure.

Background Art

[0003] Both natural and synthetic molecular sieve materials can be used as adsorbents and can have catalytic properties for hydrocarbon conversion reactions. Certain molecular sieves, such as zeolites, AlPOs, and mesoporous (or mesoporous) materials, are regularly arranged, porous crystalline materials and have an obvious crystal structure measured by X - ray diffraction (XRD). Certain molecular sieves are regularly arranged and produce a unique and distinguishable XRD pattern. Inside certain molecular sieves, a large number of cavities can exist, and these cavities can be interconnected by many channels or pores (or pores or pores). These cavities and pores are of uniform size within a particular molecular sieve material. The dimensions of these pores allow molecules of a particular dimension to be adsorbed while rejecting molecules of a larger dimension, so these materials have come to be known as "molecular sieves" and are used in various industrial processes such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

[0004] Molecular sieves applied to catalysts and adsorption include any of natural or synthetic crystalline molecular sieves. Examples of these molecular sieves include extra-large pore zeolites, large pore zeolites, medium pore zeolites, and small pore zeolites. These zeolites and their isotypes are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, framework type zeolites with established structures and other crystalline microporous molecular sieves are assigned a three-letter code and are described in the "Atlas of Zeolite Framework Types" (edited by Ch. Baerlocher, L.B., et al., Elsevier, 6th edition, 2007), which is incorporated herein by reference. Also, these zeolites and their isotypes are described in the zeolite structure database, which provides structural information on all zeolite framework types approved by the Structure Commission of the International Zeolite Association (IZA-SC).

[0005] The ideal inorganic framework structure of zeolite is a silicate (or silicate) framework structure in which all tetrahedral atoms are connected by oxygen atoms to four adjacent nearest tetrahedral atoms. The term "silicate" as used herein refers to a substance that contains at least silicon and oxygen atoms, which are alternately bonded to each other (i.e., -O-Si-O-Si-), and optionally contains other atoms such as boron, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc) within the inorganic framework structure. Atoms other than silicon and oxygen in the framework silicate (or framework silicate) occupy a portion of the lattice sites, which would otherwise be occupied by silicon atoms in an "all-silica" framework silicate. Thus, the term "framework silicic acid" as used herein refers to an atomic lattice containing any of silicate, borosilicate, gallosilicate, ferrisilicate, aluminosilicate, titanosilicate, zincosilicate, vanadosilicate, or the like.

[0006] The structure of the framework silicate within a given zeolite determines the size of the pores or channels present therein. The size of the pores or channels can determine the type of process for which a given zeolite can be applied. Currently, over 200 unique zeolite framework silicate structures are known and recognized by the Structure Commission of the International Zeolite Association, thereby defining a variety of pore structures and orientation ranges.

[0007] The framework silicates of zeolites or molecular sieves are generally characterized in terms of their ring size, which means the number of silicon atoms (or alternative atoms as described above), and the silicon atoms are tetrahedrally coordinated with oxygen atoms in the loop, defining the pores or channels inside the zeolite. For example, an "8-membered ring (or 8-ring)" zeolite means a zeolite having pores or channels defined by 8 alternating tetrahedral atoms and 8 oxygen atoms in the loop. The pores and channels defined within a given zeolite can be symmetric or asymmetric depending on the various structural constraints present in the particular framework silicate.

[0008] Zeolites can be classified as having small, medium, large, and extra-large pore structures, respectively, with respect to pore windows defined by 8, 10, 12, and more than 12 T atoms. Extra-large pore zeolites (>12R) include, for example, AET (14R, such as ALPO-8), SFN (14R, such as SSZ-59), VFI (18R, such as VPI-5), CLO (20R, such as cloverite), and ITV (30R, such as ITQ-37) framework type zeolites. Extra-large pore zeolites generally have a free pore diameter greater than about 0.8 nm. Large pore zeolites (12R) include, for example, LTL, MAZ, FAU, EMT, OFF, *It includes BEA and MOR framework zeolites, such as mazzite, offretite, zeolite L, zeolite Y, zeolite X, omega, ZSM-2, zeolite T, and beta. The large-pore zeolites generally have a free pore diameter of 0.6 to 0.8 nm. The medium (or intermediate) pore size zeolites (10R) include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework zeolites, such as ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite-1, and silicalite-2. The medium pore size zeolites generally have a free pore diameter of 0.45 to 0.6 nm. The small pore size zeolites (8R) include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework zeolites, such as ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, and ALPO-17. The small pore size zeolites generally have a free pore diameter of 0.3 to 0.45 nm.

[0009] The synthesis of molecular sieve materials typically involves hydrothermal crystallization from a synthesis mixture that includes not only a silica source but also sources of all the elements present in the molecular sieve (or zeolite), such as an alumina source. Also, in many cases, a structure-directing agent (SDA) is present. The structure-directing agent is a compound that is thought to facilitate the formation of the molecular sieve and is considered to act as a template (or mold) around which a specific molecular sieve can be generated, thereby promoting the formation of the desired molecular sieve. Various compounds are used as structure-directing agents, including various types of quaternary ammonium cations. Typically, molecular sieve (or zeolite) crystals are formed around the structure-directing agent, and when crystallization is complete, the structure-directing agent occupies the pores within the molecular sieve. Therefore, as-synthesized (or as-made) molecular sieves contain the structure-directing agent within their pores, and after crystallization, the as-synthesized molecular sieves are usually subjected to a treatment step such as a calcination step to remove the structure-directing agent.

[0010] For example, macroporous zeolites include CON framework type zeolites such as aluminosilicate SSZ-26, borosilicate SSZ-33, or borosilicate CIT-1, and are characterized by a three-dimensional pore system composed of intersecting 10-membered and 12-membered ring pores. Such macroporous materials with intersecting channels have attracted great interest for catalytic applications in the petrochemical industry and the like. For example, U.S. Patent Application No. 8,198,501 discloses the use of a CON type zeolite for catalyzing the isomerization of light paraffins. Also, such macroporous materials with intersecting channels are thought to have increased fouling resistance and improved intracrystalline diffusion properties compared to materials with one-dimensional channels.

[0011] The SSZ-26 and SSZ-33 materials can be characterized as members of a family of materials whose two end portions are formed by the stacking of layers in an ABAB arrangement ("polymorph A") or an ABCABC arrangement ("polymorph B"). Between these end polymorphs, there exists an entire family of materials ("SSZ-26 / 33 family") characterized by a defect probability "p" where 0% < p < 100%. When the defect probability is 0%, the end polymorph B is obtained, and when p = 100%, the end polymorph A is obtained. SSZ-26 and SSZ-33 are members of this disorder family of materials. More specifically, SSZ-33 and SSZ-26 are intergrowths of polymorph A and polymorph B where polymorph B is dominant, and the defect probabilities are close to 30% and 15% respectively. SSZ-26 and SSZ-33 use, as a structure directing agent (SDA), hexamethyl[4.3.3.0]propellane-8,11-diammonium cation or tricyclo[5.2.1.0 2,6They were first synthesized using decane quaternary ammonium cations respectively. For example, see Lobo et al., "SSZ-26 and SSZ-33: Two Molecular Sieves with Intersecting 10- and 12-Ring Pores", Science, v.262(5139), p. 1543-1546, December 3, 1993; US Patent Application No. 4,910,006; US Patent Application No. 4,963,337; US Patent Application No. 5,007,997. The SSZ-26 / 33 family was further synthesized from various SDAs such as 1,5-bis(N,N-dimethylcyclohexylammonium)pentane dication, 1,4-bis(N-cyclohexylpiperidinium)butane dication, 1,4-bis(N-chloropentylpiperidinium)butane dication, or 1-benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane (see US Patent Application No. 7,648,694 and US Patent Application No. 10,730,757). US Patent Application No. 8,647,601 describes the synthesis of SSZ-33 using 1,1'-(pentane-1,5-diyl)bis(3-methylcyclohexyl)piperidinium dication as the SDA. US Patent Application No. 7,837,978 describes a process for directly preparing ammonium-containing molecular sieves using cis-N,N-diethyldecahydroquinolinium cation, or a mixture of cis-N,N-diethyldecahydroquinolinium cation and trans-N,N-diethyldecahydroquinolinium cation as the SDA. And US Patent Application No. 10,189,717 describes the synthesis of aluminosilicate SSZ-26 by zeolite conversion (or interzeolite transformation) from FAU framework type zeolite in the presence of 1,4-bis(N-cyclohexylpyrrolidinium)butane dication as the SDA.

[0012] CIT-1 corresponds to pure or nearly pure polymorph B and is synthesized using N,N,N-trimethyl-(-)-cis-myrtanilammonium hydroxide as the SDA. See Lobo et al., "CIT-1: A New Molecular Sieve with Intersecting Pores Bounded by 10- and 12-Rings", J. Am. Chem. Soc, v.117, p.3766-3779, 1995.

[0013] Despite these advances, there remains a need for more effective synthesis methods for molecular sieves, such as new structure-directing agents and CON framework types, particularly lower-cost alternatives like molecular sieves.

[0014] In accordance with the present disclosure, it has been found that the relatively simple cations described herein can be effective as structure-directing agents in the synthesis of CON framework type molecular sieves or zeolites. SUMMARY OF THE INVENTION

[0015] In accordance with the present disclosure, it has been found that the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation can be suitably used as a structure-directing agent (SDA) for the preparation of CON framework type molecular sieves (or zeolites), including the direct synthesis of CON framework type aluminum-containing molecular sieves such as aluminosilicates and aluminoborosilicates. This is particularly advantageous because the SDA can be generated in a single step, thus considerably facilitating the synthesis of CON framework type materials compared to previous art processes using more complex SDAs. Further, this SDA enables the preparation of CON framework type molecular sieves in the presence of fluoride ions. The production of zeolites in the presence of fluoride ions is advantageous because it results in fewer defects in hydrophilic silanols (Si-OH) and higher hydrothermal stability compared to zeolites prepared by the hydroxide route. Also, a higher Si / Al ratio can be obtained in the presence of fluoride ions and can be advantageous, for example, when low acidity is required in hydrogen isomerization.

[0016] In a first aspect, the present disclosure relates to a method for producing a CON framework type molecular sieve, the method comprising the following steps: (a) preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure-directing agent (Q), a mineralizing agent, and optionally a source of an alkali and / or alkaline earth element (M), wherein the mineralizing agent is selected from the group consisting of hydroxide ions (OH), fluoride ions (F), and mixtures thereof, and the structure-directing agent (Q) is the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of formula 1:

Chemical formula

[0017] In a second aspect, the present disclosure relates to a molecular sieve (or zeolite), particularly a CON framework type molecular sieve (or zeolite), which has at least one 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of Formula 1 within its pore structure.

[0018] In a further aspect, the present disclosure relates to a CON framework type molecular sieve, which can be obtained (or is obtained) by the methods disclosed herein.

[0019] These and other features, properties, and their advantageous applications and / or uses of the present disclosure will become apparent from the following detailed description. Of course, the features described with respect to one aspect of the invention may be incorporated into other aspects of the invention. In particular, any two or more of the features described herein, including the summary of the invention, can be combined to form combinations of features not specifically described herein.

Brief Description of the Drawings

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Modes for Carrying Out the Invention

[0021] [Detailed Description] In a first aspect, the present disclosure relates to a method for manufacturing a CON framework type molecular sieve, the method comprising the following steps: (a) preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure directing agent (Q), a mineralizing agent, and optionally a source of alkali and / or alkaline earth elements (M), wherein the mineralizing agent is selected from the group consisting of hydroxide ions (OH), fluoride ions (F), and mixtures thereof, and the structure directing agent (Q) comprises the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of formula 1

Chemical formula

[0022] The structure directing agent (Q) may be present in any suitable form, such as a halide such as fluoride, chloride, iodide, or bromide, a hydroxide, or a nitrate, for example in the form of a hydroxide of the structure directing agent. The structure directing agent (Q) may be present in the synthesis mixture at a Q / Si molar ratio of 0.01 to 1.0, such as 0.05 to 1.0 or 0.05 to 0.8 or 0.1 to 0.7, such as 0.05 or 0.1 or 0.15 to 0.5, such as 0.15 or 0.2.

[0023] The synthesis mixture comprises at least one source of silica. Suitable silica sources (e.g., silicon oxide sources) include silicates such as tetraalkyl orthosilicates (e.g., tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS)), fumed silicas such as Aerosil® (available from Evonik), Cabosperse® (available from Cabot), and Cabosil® (available from DMS), precipitated silicas such as Ultrasil® and Sipernat® 340 (available from Evonik), alkali metal silicate silicas such as potassium silicate and sodium silicate, and aqueous colloidal suspensions such as those sold under Ludox® by E.I. du Pont de Nemours or under Aerodisp® by Evonik, preferably including silicates, fumed silicas, alkali metal silicates, and especially colloidal silica and tetraalkyl orthosilicates such as TEOS.

[0024] The synthesis mixture includes at least one source of alumina. Suitable sources of alumina (e.g., aluminum oxide sources) include aluminum hydroxide, aluminum salts, especially water-soluble salts such as aluminum sulfate and aluminum nitrate, alkali metal aluminates such as sodium aluminate, aluminum alkoxides such as aluminum isopropoxide, hydrated aluminum oxides such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other sources of aluminum include other water-soluble aluminum salts, sodium aluminate, aluminum alkoxides such as aluminum isopropoxide, or aluminum metal such as chip-shaped aluminum, but are not limited thereto. Particularly suitable sources of alumina are aluminum hydroxide, water-soluble salts such as aluminum sulfate and aluminum nitrate, and alkali metal aluminates such as sodium aluminate and potassium aluminate.

[0025] In addition to or instead of the Si and Al sources described above, sources containing both Si and Al elements can also be used. Examples of suitable sources containing both Si and Al elements include amorphous silica alumina gel or dried silica alumina powder, silica alumina, clays such as kaolin and metakaolin, and zeolites such as synthetic faujasite and ultrastable faujasite, such as Ultrastable Y (USY), beta, or other large-pore to medium-pore molecular sieves or zeolites, especially aluminosilicates.

[0026] The synthesis mixture may have an Si / Al molar ratio of 5 to 100, such as 5 to 75, such as 10 to 50 or 10 to 35, such as 10, 15, 20, 25, 30, or 35.

[0027] Alternatively, the synthesis mixture may optionally contain at least one source of boron oxide, such as at least one boric acid and borate, such as sodium tetraborate, or borax and potassium tetraborate. The boron source tends to be more soluble than the aluminum source in the synthesis system via the hydroxide. In embodiments where the synthesis mixture contains boron, the molecular sieve is an aluminoborosilicate, and boron may be present in the synthesis mixture at an Si / B molar ratio of 5 to 100, such as 5 to 75, such as 10 to 50 or 10 to 35, such as 10, 15, 20, 25, 30 or 35. In a further embodiment, the synthesis mixture may have an Si / [Al + B] molar ratio of 5 to 100, such as 5 to 75, such as 10 to 50 or 10 to 35, such as 10, 15, 20, 25, 30 or 35.

[0028] The synthesis mixture contains at least one mineralizer selected from the group consisting of hydroxide ions (OH), fluoride ions (F), and mixtures thereof. The synthesis mixture may contain a mineralizer in an amount represented by an (OH + F) / Si molar ratio of 0.05 to 1.5, most often 0.1 to 1.0, such as 0.15 or 0.2 to 1.0.

[0029] When the mineralizer contains hydroxide ions (OH), the synthesis mixture contains at least one hydroxide ion (OH) source. For example, the hydroxide ions can be present as counterions of the structure-directing agent (Q), or by the use of aluminum hydroxide or sodium aluminate as the alumina source. Also, suitable hydroxide ion sources can be selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof, more often sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and mixtures thereof, most often sodium hydroxide and / or potassium hydroxide. The synthesis mixture may contain a hydroxide ion source at an OH / Si molar ratio of 0.05 to 1.5, such as 0.1 to 1.0, such as 0.15 to 0.7, such as 0.1 or 0.15 to 0.6 or 0.5. When the mineralizer contains hydroxide ions (OH), the synthesis mixture may be substantially free of fluoride ions (F).

[0030] When the mineralizing agent contains fluoride ions (F), the synthesis mixture contains at least one source of fluoride ions (F). The source of fluoride ions (F) can be any compound capable of releasing fluoride ions in the molecular sieve synthesis mixture. For example, fluoride ions can be present as counterions of the structure-directing agent (Q). Non-limiting examples of sources of fluoride ions (F) include hydrogen fluoride (HF), salts containing one or more fluoride ions such as metal fluorides, preferably salts in which the metal is an alkali metal or alkaline earth metal such as sodium, potassium, calcium, magnesium, strontium or barium, salts in which the metal is a metal such as aluminum (AlF3, Al2F6) or tin (SnF2), ammonium fluoride (NH4F) and ammonium bifluoride (NH4HF2). Particularly convenient sources of fluoride ions are HF, NH4F and NH4HF2, especially HF. Also, small amounts of fluoride ions (F) can be present as impurities in any source of alkali metal or alkaline earth metal cations (M), for example. Fluoride ions (F) may be present in an F / Si molar ratio of 0.05 to 1.5, such as 0.1 to 1.0, such as 0.15 to 0.7, such as “0.1 to 0.15” to 0.6 or 0.5. When the mineralizing agent contains fluoride ions (F), the synthesis mixture may further contain hydroxide ions (OH), or may not substantially contain hydroxide ions (OH), preferably further containing hydroxide ions (OH).

[0031] Optionally, the synthesis mixture may contain a source of one or more alkali or alkaline earth metal cations (M). When present, M is preferably selected from the group consisting of sodium, potassium, lithium, rubidium, calcium, magnesium, strontium, barium, and mixtures thereof, and is preferably sodium and / or potassium. The sodium source, when present, may be sodium hydroxide, sodium aluminate, sodium silicate, sodium aluminate, or a sodium salt such as NaCl, NaBr, or sodium nitrate. The potassium source, when present, may be potassium hydroxide, potassium aluminate, potassium silicate, a potassium salt such as KCl, KBr, or potassium nitrate. The lithium source, when present, may be lithium hydroxide, or a lithium salt such as LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate. The rubidium source, when present, may be rubidium hydroxide or a rubidium salt such as RbCl, RbBr, RbI, or rubidium nitrate. The calcium source, when present, may be calcium hydroxide. The magnesium source, when present, may be magnesium hydroxide. The strontium source, when present, may be strontium hydroxide. The barium source, when present, may be barium hydroxide. Also, the alkali or alkaline earth metal cation (M) may be present in one or more alumina or boron oxides such as sodium aluminate, sodium tetraborate, potassium tetraborate, and / or one or more silicon sources such as potassium silicate and / or sodium silicate. The alkali or alkaline earth metal cation (M) source is preferably water-soluble. The synthesis mixture may contain the alkali or alkaline earth metal cation (M) source at an M / Si molar ratio of 0 to 1.0, for example, when M is present, at an M / Si molar ratio of 0.01 to 0.5, particularly 0.05 to 0.5, for example, 0.05 to 0.2. In another embodiment, the synthesis mixture may be substantially free of alkali or alkaline earth metal cations (M).More specifically, in the above-described first embodiment, the synthesis mixture may contain an alkali or alkaline earth metal cation (M) source at an M / Si molar ratio of 0.01 to 1.0, for example 0.01 or 0.05 to 0.5, for example 0.05 or 0.1 to 0.2 or 0.15. On the other hand, in the above-described second or third embodiment, the synthesis mixture may contain an alkali or alkaline earth metal cation (M) source in such an amount, or in more cases, may substantially contain no alkali or alkaline earth metal cation (M).

[0032] The synthesis may be carried out with or without adding a nucleating seed. When a nucleating seed is added to the synthesis mixture, the seed may have the same or a different framework type as the molecular sieve obtained by the method, and may be, for example, a molecular sieve obtained from a different synthesis or a previous synthesis, and may appropriately be present in a weight relative to the synthesis mixture of 0.01 to 10,000 ppm, for example 100 to 5,000 ppm.

[0033] The synthesis mixture typically contains water at an H2O / Si molar ratio of from 1 to 100, such as from 4 or 5 to 80 or 70 or 50, such as from 4 or 5 to 30 or 20. More specifically, in the first embodiment described above, the synthesis mixture may contain water at an H2O / Si molar ratio of from 1 to 100, such as from 4 to 80 or 5 to 70, such as from 10 to 80 or 20 to 70, such as 20, 25, or 30, while in the second or third embodiment described above, the synthesis mixture may contain water at an H2O / Si molar ratio of from 1 to 100, such as from 2 to 50 or 3 to 30, such as from 3 to 20 or 4 to 15, such as from 4 to 10. Depending on the nature of the components of the base mixture, the amount of the solvent of the base mixture (e.g., water from the hydroxide solution, methanol and ethanol optionally by hydrolysis of the silica source) may be removed so as to obtain the desired molar ratio of the solvent to Si in the synthesis mixture. Suitable methods for reducing the solvent content may include evaporation under ambient air, dry nitrogen, dry air or such air streams, or spray drying or freeze drying. Also, if too much water is removed during the solvent removal process, water may be added to the resulting mixture to achieve the desired H2O / Si molar ratio. In some examples, if the preparation has a sufficient H2O / Si molar ratio, removal of water is not necessary.

[0034] Carbon in the form of CH2 may be present in various sources of the components used in the preparation of the synthesis mixtures of the present disclosure, such as silica sources and trivalent element sources, and may be incorporated as a bridging atom into the resulting molecular sieve framework. Nitrogen atoms may be incorporated as bridging atoms into the framework of the molecular sieve material after removal of the SDA.

[0035] In one or more aspects, the synthesis mixture after solvent adjustment (e.g., when the desired ratio of water to silica has been achieved) may be mixed by mechanical means such as stirring or high shear blending, ensuring suitable homogenization of the base mixture, for example, using a dual asymmetric centrifugal mixer (e.g., FlackTek speedmixier) having a mixing speed of from 1000 to 3000 rpm (e.g., 2000 rpm).

[0036] Thereafter, the synthesis mixture is subjected to crystallization conditions suitable for the formation of the molecular sieve material. Crystallization of the molecular sieve material may be carried out under static or stirred conditions in a suitable reactor, for example, in a Teflon®-lined or stainless steel autoclave placed in a convection oven maintained at a suitable temperature.

[0037] Crystallization in step (b) of the method is typically carried out at a temperature of 100 to 200 °C, for example 120 to 180 °C, for example 160 or 170 °C, for a sufficient time for crystallization to occur at the temperature used. For example, at higher temperatures, the crystallization time can be shortened. For example, the crystallization conditions in step (b) of the method may include heating for a period of 1 to 100 days, for example 1 to 50 days, for example 1 to 30 days, for example at least 1 or at least 5 days, up to 30 days or 20 days. The crystallization time can be established by known methods in the art, for example, by sampling the synthesis mixture at various times and measuring the yield of the precipitated solid and the X-ray crystallinity. Unless otherwise specified herein, the measurement temperature is the temperature of the ambient environment of the substance being heated, for example, the temperature of the atmosphere in which the material is heated.

[0038] Typically, the molecular sieve is formed in solution and can be recovered by standard means such as centrifugation or filtration. Also, the separated molecular sieve can be washed, recovered by centrifugation or filtration, and dried.

[0039] The molecular sieve of the present disclosure may be at least partially dehydrated (e.g., dried) when employed as an adsorbent or catalyst in an organic compound conversion process. This can be done by heating to a temperature in the range of 80 to 500 °C, 90 to 370 °C, for example, in an atmosphere such as air, nitrogen, etc., and at atmospheric pressure, a pressure lower than atmospheric pressure, or a pressure higher than atmospheric pressure for 30 minutes to 48 hours. Also, dehydration may be carried out at room temperature simply by placing the molecular sieve in a vacuum, although a longer time is required for sufficient dehydration.

[0040] As a result of the crystallization process, the recovered product contains at least a portion of the structure-directing agent used in the synthesis within its pores. The as-synthesized molecular sieve recovered from step (c) may thus be subjected to heat treatment or other treatments to remove some or all of the SDA incorporated within its pores during synthesis. Heat treatment (e.g., calcination) of the as-synthesized molecular sieve typically involves exposing the material to a sufficiently high temperature in an atmosphere selected from air, nitrogen, ozone, and mixtures thereof within a furnace to remove some or all of the SDA. A pressure lower than atmospheric pressure may be employed in the heat treatment, but atmospheric pressure is desirable for reasons of convenience. The heat treatment may be carried out at a temperature up to 925 °C, for example 300 - 700 °C or 400 - 600 °C. The measured temperature is the temperature of the ambient environment of the sample. The heat treatment (e.g., calcination) may be carried out in a box furnace in air attached to a drying tube containing a desiccant to remove water from the dry air. The heating is usually carried out for at least 1 minute, generally less than 1 day, or at most a few days. The heating may be carried out first under a nitrogen atmosphere and then the atmosphere may be switched to air and / or ozone.

[0041] Also, the molecular sieve may be subjected to an ion exchange treatment, for example, using aqueous ammonium salts such as ammonium nitrate, ammonium chloride, and ammonium acetate to remove any residual alkali metal cations and / or alkaline earth metal cations present in the synthesis mixture and replace them with protons, thereby producing the acid form of the molecular sieve. To the desired extent, the original cations of the as-synthesized material such as alkali metal cations may be replaced by other cations by ion exchange. Preferred replacement cations may include hydrogen ions, hydrogen precursors (e.g., ammonium ions), and mixtures thereof. The ion exchange step may be carried out after the as-synthesized molecular sieve has been dried. The ion exchange step may be carried out before or after the calcination step.

[0042] Also, the molecular sieve may be subjected to other treatments such as steam treatment and / or cleaning treatment using a solvent. Such treatments are well known to those skilled in the art and are performed to modify the properties of the molecular sieve as desired.

[0043] In a second aspect, the present disclosure relates to a molecular sieve, and more specifically, to a CON framework type molecular sieve having at least one 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of Formula 1 in its pores. [Chemical formula]

[0044] The molecular sieve may be an aluminosilicate or an aluminoborosilicate and can be represented by the molecular formula of Formula 2. (q)Q:(m)Al2O3:(n)B2O3:SiO2 Formula 2 where 0 < q ≤ 1.0, 0.005 < m ≤ 0.1, 0 ≤ n ≤ 0.1, and Q is the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of Formula 1. The oxygen atoms of Formula 2 may be substituted by carbon atoms (e.g., in the form of CH2) and may be derived from the sources of the components used to prepare the as-made molecular sieve. Also, the oxygen atoms of Formula 2 can be substituted by nitrogen atoms, for example, after removing the SDA. Formula 2 can represent the framework of a typical molecular sieve having a structure-directing agent (Q) in the intracrystalline structure and does not mean the only representation of such materials. The molecular sieve material may contain impurities that are not described in Formula 2. Further, Formula 2 does not include protons and charge compensating ions that may be present in the molecular sieve material.

[0045] The variable m represents the molar ratio relationship of Al2O3 to SiO2 in Formula 2. For example, when m is 0.005, the molar ratio of SiO2 to Al2O is 200, and the Si / Al molar ratio is 100. m can vary in the range of 0.005 to 0.1, for example 0.007 to 0.1, for example 0.01 to 0.05 or 0.015 to 0.05. The molar ratio of Si to Al can be 5 to 100, specifically 5 to 75, for example 10 to 50, for example 10 to 35.

[0046] The variable n represents the molar ratio relationship of B2O3 to SiO2 in Formula 2. When n is 0, boron is absent, and the molecular sieve is aluminosilicate. When n is greater than 0, boron is present, and the molecular sieve is aluminoborosilicate. For example, when n is 0.005, the molar ratio of SiO2 to B2O3 is 200, and the Si / B molar ratio is 100. When boron is present, n can vary in the range of 0.005 to 0.1, for example 0.007 to 0.1, for example 0.01 to 0.05 or 0.015 to 0.05. When boron is present, the molar ratio of Si to B can be 5 to 100, specifically 5 to 75, for example 10 to 50, for example 10 to 35.

[0047] The variable q represents the molar ratio relationship of Q to SiO2 in Formula 2. For example, when n is 0.1, the Q / Si molar ratio is 0.1. The molar ratio of Q to SiO2 can be 0 to 1.0, for example 0.01 to 0.8 or 0.02 to 0.7, for example 0.1 to 0.5.

[0048] In a further aspect, the present disclosure relates to a CON framework type molecular sieve obtainable (or obtained) by the method disclosed herein.

[0049] Specifically, when the molecular sieve material is prepared in the presence of hydroxide ions, in its as-synthesized form (e.g., when the SDA has not been removed) and / or its calcined form (e.g., when at least a portion of the SDA has been removed), it has an X-ray diffraction pattern similar to that of SSZ-26 zeolite (including about 15% polymorph A), which is disclosed in Tables 3 and 5 of U.S. Patent No. 10,730,757, the entire content of which is incorporated herein by reference. When prepared in the presence of fluoride ions, the molecular sieve material, in its as-synthesized form (e.g., when the SDA has not been removed) and / or its calcined form (e.g., when at least a portion of the SDA has been removed), has an X-ray diffraction pattern similar to that of SSZ-33 zeolite (including about 30% polymorph A), which is disclosed in Tables 1(a) and 1(b) of U.S. Patent No. 4,963,337, the entire content of which is incorporated herein by reference.

[0050] The molecular sieves obtained by the method disclosed herein may contain impurities such as amorphous materials, unit cells with different topologies (e.g., quartz or molecular sieves of different framework types that may or may not affect the performance of the resulting catalyst), and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). Those skilled in the art will understand this. Typical examples of molecular sieves of different framework types that may coexist with the molecular sieves of the present disclosure include, for example, molecular sieves of the MTW, BEA, FAU, or MOR framework types, such as ZSM-12, zeolite beta, undissolved faujasite, or mordenite. The molecular sieves of the present disclosure preferably contain substantially no impurities. As used herein, the term "substantially impurity-free" (or alternatively "substantially pure") means a small proportion (less than 50 wt%), preferably less than 20 wt%, more preferably less than 10 wt%, even more preferably less than 5 wt%, and most preferably less than 1 wt% (e.g., less than 0.5 wt% or 0.1 wt%) of such impurities (or "non-CON" framework type materials), and this weight percentage (wt%) value is based on the total weight of the impurities and the weight of the pure molecular sieve. The amount of impurities can be appropriately determined by powder XRD, rotational electron diffraction, and / or SEM / TEM (e.g., various crystal morphological methods).

[0051] The molecular sieves obtained by the method described in this specification are substantially crystalline. As used herein, the term "crystalline" is used with respect to the crystalline solid form of a material and includes, but is not limited to, crystalline forms of single or multiple components (e.g., solvates, hydrates, and co-crystals). Crystalline means having a regular repetition of molecules and / or an ordered arrangement of molecules and having a distinguishable crystal lattice. For example, the molecular sieves can have various water or solvent contents. Various crystal lattices can be confirmed by solid property evaluation methods such as XRD (e.g., powder XRD). Other property evaluation methods known to those skilled in the relevant art can be further useful for confirming the crystalline form, as well as for determining stability and solvent / water content. As used herein, the term "substantially crystalline" means that a majority amount (greater than 50 wt%) of the weight of the material sample being described is crystalline and the remainder of the sample is in an amorphous form. In one or more aspects, a substantially crystalline sample has a crystallinity of at least 95% (e.g., 5% amorphous form), at least 96% (e.g., 4% amorphous form), at least 97% (e.g., 3% amorphous form), at least 98% (e.g., 2% amorphous form), at least 99% (e.g., 1% amorphous form), and 100% (e.g., 0% amorphous form).

[0052] The gist of the present disclosure will be described in more detail by specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present disclosure in any way. Those skilled in the relevant art will readily recognize that various parameters can be changed or modified to obtain essentially the same results.

Examples

[0053] The present disclosure will be further described below without limiting its scope thereto.

[0054] In these examples, the X-ray diffraction (XRD) patterns of the as-synthesized and calcined materials were recorded in continuous mode on an X-ray powder diffractometer (Bruker DaVinci D8 Discovery instrument), using a Bragg-Bentano configuration with a Vantec500 detector in the 2θ range of 4-36 degrees with CuKα radiation. The interplanar spacing and d-spacing were calculated in angstrom units, and the relative intensity of the lines I / I0 is the ratio of the peak intensity to the peak intensity of the strongest line. The intensity was not corrected for the Lorentz and polarization effects. The position of the diffraction peaks at 2θ, and the relative peak area intensity of the lines, I / I0 (where I0 is the intensity of the strongest line above the background), were determined using the MDI Jade peak search algorithm. It should be understood that diffraction data described as a single line (single line) may consist of multiple overlapping lines, which may appear as resolved or partially resolved lines under certain conditions, for example, differences such as crystallographic changes. Typically, crystallographic changes can include small changes in the unit cell parameters, and / or changes in the crystal symmetry, without a change in the framework connectivity. These small effects can include changes in the relative intensity and can occur as a result of differences in the cation content, framework composition, and the nature and extent of pore filling, crystal size and shape, preferred orientation, and thermal and / or hydrothermal history.

[0055] Scanning electron microscope (SEM) images of the as-synthesized materials were obtained on a Hitachi4800 scanning electron microscope. The SEM images were used to evaluate the purity of the product. The presence of clearly different crystal morphologies in the SEM images can indicate impurities in the form of other crystalline materials. Such appropriate analysis can be useful in identifying the presence of the formation of relatively small amounts of crystalline impurities, which may not be confirmed by the XRD pattern of the product, in particular.

[0056] The following measurements were carried out on ion-exchanged (when alkali metals are present in the synthetic mixture) and calcined samples. The procedure used for each sample that was ion-exchanged and calcined is as follows. The as-prepared sample was calcined at 560 °C for 8 hours to remove SDA, and then ion-exchanged twice with 1 M ammonium nitrate aqueous solution, and then calcined at 500 °C for 4 hours.

[0057] The total BET surface area (S BET ) of the material was measured by the BET method as described in S. Brunauer, P.H. Emmett et al., J. Am. Chem. Soc., 1938, v.60, pg.309, using nitrogen adsorption-desorption (desorption) at liquid nitrogen temperature. The content of this reference is incorporated herein by reference. The external surface area (S ext ) of the material was obtained by the t-plot method.

[0058] The micropore volume (V micro ) of the material can be determined using methods known in the relevant art. For example, the micropore volume of the material can be measured using physical adsorption of nitrogen, and the data can be analyzed by the t-plot method, which is described in Lippens, B.C. et al., "Studies on pore system in catalysts: V. The t method" J. Catal., v.4, pg.319, 1965, which describes the micropore volume method and is incorporated herein by reference.

[0059] The alpha value is a measure of the decomposition activity of the catalyst and is described in U.S. Patent Application No. 3,354,078 and Journal of Catalysis, v.4, pg. 527, 1965, v.6, pg. 278, 1966 and v.61, pg. 395, 1980, each of which is incorporated herein by reference with respect to its description. The test conditions used herein include a constant temperature of 538 °C and a variable flow rate as detailed in Journal of Catalysis, v.61, pg. 395.

[0060] Example 1: Synthesis of 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium hydroxide 45 g of K2CO3 was added to a solution of 20 g of 4,5,6,7-tetrahydroindazole in acetonitrile (250 mL). After stirring for 30 minutes at ambient temperature, 70 g of 1,4-dibromobutane was added. The reaction mixture was stirred at ambient temperature for about 4 hours, then the temperature was raised to 90 °C and stirred for about 24 hours. Thereafter, the mixture was cooled substantially to atmospheric temperature and the solvent was evaporated under reduced pressure. The residue was taken up in dichloromethane and the resulting suspension was filtered. The solvent was removed in vacuo to give a solid corresponding to 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium bromide.

[0061] The vacuum-dried bromide salt was then ion-exchanged into the hydroxide form using an ion-exchange resin in the hydroxide form of Amberlite® IRN78 OH at a weight ratio of bromide: resin: water of 1:3.5:5. The exchange was carried out overnight at room temperature.

[0062] The molar ratios and conditions used for the synthesis of Examples 2 - 13 are detailed below and summarized in Table 2.

[0063] Example 2: Synthesis of CON framework type molecular sieve from USY zeolite in the presence of NaOH (Si / Al = 15) In a 23 mL PTFE liner for a Steel Parr autoclave, the following were mixed together: 1.90 g of SDAOH solution (13.9 wt%), 1.35 g of sodium hydroxide (NaOH, 4 wt%), 1.10 g of deionized water, and 0.64 g of Ultrastable Y (USY) zeolite (available from Zeolyst as CBV720) having a Si / Al molar ratio of 15. A synthesis mixture having the following composition in molar ratio was produced. 25H2O:1SiO2:0.033Al2O3:0.15SDAOH:0.15NaOH

[0064] Subsequently, the liner was closed and sealed inside a 23 mL Parr autoclave and placed in the spit inside a convection oven. The reactor was heated at 160 °C for 10 days under tumbling conditions (about 30 rpm). The as-synthesized material was separated by filtration, rinsed with deionized water, and dried at 90 °C in a vented drying oven.

[0065] XRD analysis of the as-synthesized product indicated that the material had a CON framework type. Figure 1 shows the powder XRD pattern of the as-synthesized material. Figure 2 shows the SEM image of the as-synthesized material.

[0066] XRF analysis of the calcined and ion-exchanged material indicated that the zeolite product had a Si / Al molar ratio of 21.

[0067] The BET specific surface area (S BET ) of the ion-exchanged and calcined material was 609 m 2 / g, the external surface area (S EXT ) was 92 m 2 / g, the micropore volume (V micro ) was 0.22 cc / g, and the Alpha Value was 1600. The observed micropore volume and specific surface area (S BET ) were consistent with the values reported for CON framework type zeolites, indicating that the current structure-directing agent was able to bring about sufficient crystallization.

[0068] The absorption of n-hexane, 2,2-dimethylbutane (2,2-DMB), and 2,3-dimethylbutane (2,3-DMB) was determined for the ion-exchanged and calcined material. The material was placed under a nitrogen stream, and then the hydrocarbons were introduced via a sparger to saturate the nitrogen stream and measure hydrocarbon absorption. Each hydrocarbon was absorbed at a different temperature: n-hexane at 90 °C, 2,2-DMB at 120 °C, and 2,3-DMB at 130 °C. The n-hexane absorption was 133 mg / g, the 2,2-DMB absorption was 141 mg / g, and the 2,3-DMB absorption was 142 mg / g.

[0069] Example 3: Synthesis of CON framework type molecular sieve from silica and USY zeolite in the presence of NaOH (Si / Al = 16) This example was carried out under the same conditions as Example 2, except that silica was used in combination with USY zeolite in the presence of more water. In the PTFE liner of a 23 mL Steel Parr autoclave, the following were mixed together: 2.17 g of SDAOH solution (13.9 wt%), 0.52 g of Cab-O-Sil® M5 (medium surface fused silica, available from Spectrum Chemical), 1.54 g of sodium hydroxide (NaOH, 4 wt%), 2.16 g of deionized water, and 0.19 g of Ultrastable Y (USY) zeolite (available from Zeolyst as CBV500) having a Si / Al molar ratio of 2.5. A synthetic mixture having the following composition by moles was obtained. 30H2O:1SiO2:0.031Al2O3:0.15SDAOH:0.15NaOH

[0070] Thereafter, the liner was closed, sealed inside a 23 mL Parr autoclave, and placed in a spit inside a convection oven. The reactor was heated at 160 °C for 18 days under tumbling conditions (about 30 rpm). The as-synthesized material was separated by filtration, rinsed with deionized water, and dried at 90 °C in a ventilated drying oven.

[0071] This material had an XRD pattern similar to that of the as-synthesized material of Example 2. Figure 3 shows the SEM image of the as-synthesized material.

[0072] Example 4: Synthesis of CON molecular sieve from silica and USY zeolite in the presence of NaOH (Si / Al = 16) This example was carried out under the same conditions as Example 4, except that the synthetic mixture contained a lower amount of NaOH and a higher amount of SDAOH, and a synthetic mixture having the following composition by molar ratio was obtained. 30H2O:1SiO2:0.031Al2O3:0.2SDAOH:0.1NaOH

[0073] After heating at 160 °C for 18 days, a CON framework-type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 was obtained.

[0074] Example 5: Synthesis of CON framework-type molecular sieve from colloidal silica and sodium aluminate in the presence of NaOH (Si / Al = 25) This example was carried out under the same conditions as the previous example, but the synthesis mixture contained Ludox® HS40 (40 wt% colloidal silica suspension) as the Si source and sodium aluminate (NaAlO2, 25 wt% Al2O3, 19.3 wt% Na2O) as the Al source. The synthesis mixture had the following composition in molar ratio. 25H2O:1SiO2:0.02Al2O3:0.15SDAOH:0.1NaOH

[0075] After heating at 160 °C for 18 days, a CON framework-type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 was obtained.

[0076] Example 6: Synthesis of CON framework-type molecular sieve from colloidal silica and sodium aluminate in the presence of NaOH (Si / Al = 20) This example was carried out under the same conditions as Example 6, but the synthesis mixture had a slightly different molar ratio. 30H2O:1SiO2:0.02Al2O3:0.2SDAOH:0.1NaOH

[0077] After heating at 160 °C for 18 days, a CON framework-type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 was obtained.

[0078] Example 7: Synthesis of CON framework type molecular sieve from colloidal silica and aluminum hydroxide in the presence of KOH (Si / Al = 16) This example was carried out under the same conditions as the previous example, but the synthesis mixture contained Ludox® HS40 (40 wt% colloidal silica suspension) as the Si source, aluminum hydroxide (Al(OH)3, Sigma, 54 wt% Al2O3) as the Al source, and potassium hydroxide (KOH, 20 wt%). The synthesis mixture had the following composition in molar ratio. 30H2O:1SiO2:0.031Al2O3:0.15SDAOH:0.15KOH

[0079] After heating at 160 °C for 18 days, a CON framework type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 was obtained.

[0080] Example 8: Synthesis of CON framework type molecular sieve from colloidal silica and aluminum hydroxide in the presence of KOH (Si / Al = 15) This example was carried out under the same conditions as Example 7, but the synthesis mixture had the following composition in molar ratio. 25H2O:1SiO2:0.033Al2O3:0.15SDAOH:0.15KOH

[0081] After heating at 170 °C for 10 days, a CON framework type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 was obtained.

[0082] Example 9: Synthesis of CON framework type molecular sieve from colloidal silica and aluminum hydroxide in the presence of KOH (Si / Al = 10) This example was carried out under the same conditions as Example 9, but the synthesis mixture contained a larger amount of Al. The synthesis mixture had the following composition in molar ratio. 25H2O:1SiO2:0.05Al2O3:0.15SDAOH:0.15KOH

[0083] After heating at 170 °C for 10 days, a CON framework type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 was obtained.

[0084] Example 10: Synthesis of CON framework type molecular sieve from TEOS and aluminum hydroxide in the presence of HF (Si / Al = 33) In a 23 mL PTFE liner for a Steel Parr autoclave, 4.75 g of SDAOH solution (13.9 wt%), 1.41 g of tetraethyl orthosilicate (TEOS, >99 wt%), and aluminum hydroxide (Al(OH)3, 54% wt, Sigma) were stirred at room temperature for 3 hours, and then the temperature was raised to 60 °C, and 1.24 g of ethanol and 3.45 g of H2O were removed. Finally, 0.14 g of HF (48 wt% solution) was added to the gel to obtain a synthesis mixture having the following composition in molar ratio. 4H2O:1SiO2:0.015Al2O3:0.5SDAOH:0.5HF

[0085] Thereafter, the liner was closed and sealed in a 23 mL Parr autoclave, placed in a spit in a convection oven, and heated at 160 °C for 16 days under tumbling conditions (about 30 rpm). The obtained as-synthesized material was determined to be a CON framework type molecular sieve having an XRD pattern similar to that of the as-synthesized material of Example 2 in addition to a minimal amount of impurity phase identified as zeolite beta.

[0086] Example 11: Synthesis of CON framework type molecular sieve from TEOS and aluminum hydroxide in the presence of HF (Si / Al = 17) This example was carried out under the same conditions as Example 11, but the synthesis mixture contained a larger amount of Al. The synthesis mixture had the following composition in molar ratio. 4H2O:1SiO2:0.029Al2O3:0.5SDAOH:0.5HF

[0087] After heating at 160 °C for 9 days, XRD analysis of the as-synthesized and calcined products showed materials with a CON framework type, as explained by Figures 4 and 5.

[0088] Example 12: Synthesis of CON framework type molecular sieves from USY zeolite and boric acid in the presence of KOH (Si / Al = 30, Si / B = 20) In a 23 mL PTFE liner for a Steel Parr autoclave, the following were mixed together: 1.98 g of SDAOH solution (9.8 wt%), 0.36 g of potassium hydroxide (KOH, 20 wt%), 1.9 g of deionized water, 0.69 g of H3BO3 (3.9 wt%) and 0.54 g of Ultrastable Y (USY) zeolite (available from Zeolyst as CBV760) with a Si / Al molar ratio of 30. A synthesis mixture with the following composition in molar ratio was produced. 30H2O:1SiO2:0.0167Al2O3:0.025B2O3:0.15SDAOH:0.15KOH

[0089] Thereafter, the liner was closed and sealed in a 23 mL Parr autoclave and placed in a spit in a convection oven. The reactor was heated at 170 °C for 12 days under tumbling conditions (about 30 rpm). The as-synthesized material was separated by filtration, rinsed with deionized water, and dried at 90 °C in a ventilated drying oven. XRD analysis of the as-synthesized product obtained showed a material with a CON framework type, as explained by Figure 6.

[0090] Example 13: Synthesis of CON framework type molecular sieves using USY zeolite and boric acid in the presence of KOH (Si / Al = 30, Si / B = 33) In a PTFE liner for a 23 mL Steel Parr autoclave, the following were mixed together: 1.98 g of an SDAOH solution (9.8 wt%), 0.36 g of potassium hydroxide (KOH, 20 wt%), 2.16 g of deionized water, 0.41 g of H3BO3 (3.9 wt%) and 0.54 g of Ultrastable Y (USY) zeolite (available from Zeolyst as CBV760) having a Si / Al molar ratio of 30. A synthetic mixture having the following composition in molar ratio was produced. 30H2O:1SiO2:0.0167Al2O3:0.015B2O3:0.15SDAOH:0.15KOH

[0091] Thereafter, the liner was closed and sealed inside a 23 mL Parr autoclave and placed in a spit inside a convection oven. The reactor was heated at 170 °C for 12 days under tumbling conditions (about 30 rpm). The as-synthesized material was separated by filtration, rinsed with deionized water, and dried at 90 °C in a ventilated drying oven. XRD analysis of the obtained as-synthesized product was determined to be a CON framework type molecular sieve having an XRD pattern similar to the as-synthesized XRD pattern of Example 12.

[0092]

Table 1

[0093] The present invention has been described and illustrated with reference to specific embodiments, but those skilled in the art will understand that the present invention is suitable for many various changes, modifications, and variations not specifically described herein. Also, when numerical lower and upper limits are described herein, it will be apparent to those skilled in the art to envision ranges from any lower limit to any upper limit. Also, all numerical values in the detailed description herein are to be modified as being values "about" and to account for experimental error and variations envisioned by those skilled in the art.

[0094] In the above description, when referring to an integer or element having known, obvious, or foreseeable equivalents, thereafter, such equivalents are incorporated herein as if individually recited. Reference should be made to the claims to determine the true scope of the present invention, and the true scope should be understood to encompass any of such equivalents. Also, the reader should understand that features or integers of the invention such as "preferred", "advantageous", "convenient", etc. are optional and do not limit the scope of the independent claims. Furthermore, such optional integers or features may be beneficial in some embodiments of the invention, while being undesirable in other embodiments, and therefore may be omitted.

[0095] Additionally or alternatively, the present invention relates to the following embodiments:

[0096] Embodiment 1: A method for producing a CON framework type molecular sieve, the method comprising the following (a) to (c): (a) Preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure-directing agent (Q), a mineralizing agent, and optionally an alkali and / or alkaline earth metal element (M), wherein the mineralizing agent is selected from the group consisting of hydroxide ions (OH), fluoride ions (F), and mixtures thereof, and the structure-directing agent (Q) comprises the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of Formula 1. [Chemical formula] (b) Heating the synthesis mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve; and (c) Recovering at least a portion of the molecular sieve from (b).

[0097] Embodiment 2: The method of Embodiment 1, wherein the structure-directing agent (Q) is in the form of a halide, hydroxide, or nitrate, and preferably, the structure-directing agent (Q) is in the form of a hydroxide.

[0098] Embodiment 3: The method of embodiment 1 or 2, wherein the mineralizer comprises hydroxide ions (OH).

[0099] Embodiment 4: The method of embodiment 3, wherein the hydroxide ion source comprises at least one of the structure directing agent (Q) in the hydroxide form, sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide, preferably the structure directing agent (Q) in the hydroxide form, sodium hydroxide and / or potassium hydroxide.

[0100] Embodiment 5: The method of any one of embodiments 1 to 4, wherein the mineralizer comprises fluoride ions (F).

[0101] Embodiment 6: The method of embodiment 5, wherein the fluoride ion source comprises at least one of HF, NH4F, and NH4HF2, preferably HF.

[0102] Embodiment 7: The method of any one of embodiments 1 to 6, wherein the synthesis mixture has the following composition, expressed in molar ratios: [Table 2]

[0103] Embodiment 8: The method of any one of embodiments 1 to 7, wherein the synthesis mixture further comprises at least one source of boron oxide.

[0104] Embodiment 9: The process of embodiment 8, wherein boron is present in the synthesis mixture in a Si / B molar ratio of from 5 to 100, preferably from 10 to 50, more preferably from 10 to 35.

[0105] Embodiment 10: The method of any one of the preceding embodiments 1 to 9, further comprising treating the molecular sieve recovered in (c) to remove at least a portion of the structure directing agent (Q).

[0106] Embodiment 11: A molecular sieve having at least one of the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cations of Formula 1 in its pore structure.

[0107] Embodiment 12: The molecular sieve of Embodiment 10, which is of the CON framework type.

[0108] Embodiment 13: The molecular sieve of Embodiment 10 or 11, wherein the molecular sieve is as follows (Formula 2): (q)Q:(m)Al2O3:(n)B2O3:SiO2 (Formula 2) [wherein 0 < q ≦ 1.0, 0.005 < m ≦ 0.1, 0 ≦ n ≦ 0.1, and Q is the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of Formula 1. ] is a molecular sieve.

[0109] Embodiment 14: The molecular sieve of any one of Embodiments 10 to 13, which can be obtained by the method of any one of Embodiments 1 to 9.

Claims

1. A method for producing a CON framework type molecular sieve, comprising: (a) preparing a synthesis mixture comprising water, a silica source, an alumina source, a structure-directing agent (Q), a mineralizing agent, and optionally a source of an alkali and / or alkaline earth metal element (M); (b) heating the synthesis mixture under crystallization conditions including a temperature of 100°C to 200°C for a time sufficient to form crystals of the molecular sieve; (c) recovering at least a portion of the molecular sieve from step (b); wherein the mineralizing agent is selected from the group consisting of hydroxide ions (OH), fluoride ions (F), and combinations thereof, and the structure-directing agent (Q) comprises a 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of formula 1: 【Chemical 1】 A method.

2. The method according to claim 1, wherein the structure-directing agent (Q) is in the form of a halide, hydroxide, or nitrate, and preferably, the structure-directing agent (Q) is in the form of a hydroxide. A method.

3. The method according to claim 1 or 2, wherein the mineralizing agent comprises hydroxide ions (OH). A method.

4. The method according to claim 3, wherein the hydroxide ion source comprises at least one of the structure-directing agent (Q) in the form of a hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide, and preferably, the hydroxide ion source comprises the structure-directing agent (Q) in the form of a hydroxide, sodium hydroxide, and / or potassium hydroxide. A method.

5. The method according to any one of claims 1 to 4, wherein the mineralizing agent comprises fluoride ions (F). A method.

6. The method according to claim 5, wherein the fluoride ion source is HF, NH ４ F, and NH ４ HF ２ and at least one of which preferably comprises HF.

7. The method according to any one of claims 1 to 6, wherein the synthesis mixture has the following composition in molar ratio. A method. 【Table 1】

8. The method according to any one of claims 1 to 7, wherein the synthesis mixture comprises at least one source of boron oxide. A method.

9. The method according to claim 8, wherein boron is present in the synthesis mixture at a Si / B molar ratio of 5 to 100, preferably 10 to 50, more preferably 10 to 35. A method.

10. The method according to any one of claims 1 to 9, further comprising treating the molecular sieve recovered in step (c) to remove at least a portion of the structure-directing agent (Q). A method.

11. A molecular sieve having at least one of the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cations of Formula 1 within its pore structure.

12. The molecular sieve according to claim 10, which is of the CON backbone type.

13. The molecular sieve according to claim 10 or 11, The molecular sieve is as follows (Formula 2): (q) Q: (m) Al ２ O ３ : (n) B ２ O ３ : SiO ２ (Formula 2) [wherein 0 < q ≤ 1.0, 0.005 < m ≤ 0.1, 0 ≤ n ≤ 0.1, and Q is the 1,2,3,4,6,7,8,9-octahydropyridazino[1,2-a]indazol-10-ium cation of Formula 1. ] is a molecular sieve.

14. The molecular sieve according to any one of claims 10 to 13, which can be obtained by the method according to any one of claims 1 to 9.

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