阅读说明：本技术 Emm-37材料及其方法和用途 (EMM-37 materials and methods and uses thereof ) 是由 艾伦·W·伯顿 赫尔达·B·弗罗芒 尤金·特雷芬科 于 2019-01-23 设计创作，主要内容包括：本公开涉及EMM-37材料,其制备方法和用途,以及可用于制备所述EMM-37材料的结构导向剂,用于制备此类结构导向剂的方法和中间体。(The present disclosure relates to EMM-37 materials, methods of making and uses thereof, as well as structure directing agents useful in making the EMM-37 materials, processes and intermediates for making such structure directing agents.)

1. A crystalline material having at least six XRD peaks selected from table 1:

TABLE 1

Wherein some or all of the structure directing agent has been removed from the crystalline material.

2. A crystalline material having a framework defined by the following connectivity in table 2 for tetrahedral (T) atoms in the unit cell, the tetrahedral (T) atoms being connected by bridging atoms:

TABLE 2

3. The material of claim 1 or 2, having a micropore volume of from 0.10cc/g to 0.28 cc/g.

4. The material of any one of claims 1 to 3, wherein five of the six XRD peaks comprise the peaks in Table 1B:

TABLE 1B

And the crystalline material has a micropore volume of from 0.10cc/g to 0.28 cc/g.

5. The material according to any one of claims 1 to 4, having a composition comprising formula I:

(m)X₂O₃:YO₂(formula I) is shown in the specification,

wherein m is more than or equal to 0.01 and less than or equal to 0.25, X is trivalent element, and Y is tetravalent element.

6. The material of claim 5, wherein the ratio of Y to X is from 5 to 25.

7. A as-synthesized crystalline material having at least six XRD peaks selected from table 3:

TABLE 3

8. The material of claim 7 having a triclinic cell a parameter of

9. The material of claim 7 or 8, wherein the six XRD peaks comprise the peaks in Table 3B:

TABLE 3B

And the crystallizationThe triclinic cell a parameter of the material isb parameter is

10. The material according to any one of claims 7 to 9, having a composition comprising formula II:

(n)G:(v)X₂O₃:YO₂(formula II) in the formula (III),

wherein v is not less than 0.01 and not more than 0.25, n is not less than 0.03 and not more than 0.25, G is an organic structure directing agent, X is a trivalent element, and Y is a tetravalent element.

11. The material of claim 10, wherein the ratio of Y to X is from 5 to 25.

12. The material of claim 10, wherein the ratio of G to Y is 0.05 to 0.15.

13. A method of preparing the crystalline material of any one of claims 7 to 12, the method comprising mixing a source comprising a hydroxide ion source, a source of an oxide of a tetravalent element Y, a source of a trivalent element X, and a source comprising bispyrrolidineA composition of a biscationic structure directing agent (G).

14. The method of claim 13, further comprising removing some or all of the structure directing agent from the crystalline material.

15. A structure directing agent comprising compound H or being compound H:

wherein A is an ion.

16. The structure directing agent of claim 15, wherein compound H comprises or is an RS isomer.

17. A process for preparing compound H of claim 15, comprising converting compound 3 to compound H:

18. the method of claim 17, further comprising separating RS isomer of compound H from the reaction product of converting compound 3.

19. The method of claim 17 or 18, wherein compound 3 is prepared by a process comprising converting compound 2 to compound 3:

20. the method of claim 19, wherein compound 2 is prepared by a process comprising converting compound 1 to compound 2:

21. a method of converting an organic compound to a conversion product, the method comprising contacting the organic compound with the crystalline material of any one of claims 1 to 6.

Technical Field

The present disclosure relates to materials, referred to as EMM-37, methods of making such materials, uses of these materials, Structure Directing Agents (SDAs) for making such materials, and processes and intermediates for making such structure directing agents.

Background

Zeolites can be used as adsorbents and catalysts for hydrocarbon conversion or as supports for catalysts. Zeolites have uniform cavities and pores, which are interconnected by channels. The size and dimensions of the cavities and pores enable adsorption of molecules of certain sizes. Since zeolites are capable of adsorbing molecules by size selection, they have many uses, including hydrocarbon conversion, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

Zeolites that may be used in catalysis and adsorption include any naturally occurring or synthetic crystalline zeolite. Examples of such zeolites include large pore zeolites, medium pore zeolites, and small pore zeolites. These zeolites and their isoforms are described in http:// america. IZA-structure. org/IZA-SC/ftc _ table. php. The pore size of the large pore zeolite is typically at least aboutAnd include LTL, VFI, MAZ, FAU, OFF, BEA, and MOR framework type zeolites (IUPAC commission on zeolite nomenclature), examples of large pore zeolites include mazzite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and βTo less than aboutAnd include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites (IUPAC zeolite nomenclature Commission). Examples of medium pore zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, and silicalite 2. The pore size of the small pore zeolite is aboutTo less than aboutAnd include, for example, CHA, ERI, KFI, LEV, SOD, and LTA framework-type zeolites (IUPAC zeolite nomenclature committee). Examples of small pore zeolites include ZK-4, ZSM-2, SAP0-34, SAP0-35, ZK-14, SAP0-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, zeolite T, gmelinite, ALPO-17, and clinoptilolite. However, there is still a need for new zeolites.

Disclosure of Invention

In one aspect, the present disclosure provides EMM-37 materials, methods of making these materials, and uses thereof. The present disclosure provides a porous crystalline EMM-37 material having at least six X-ray diffraction (XRD) peaks in degrees 2 θ selected from Table 1, wherein some or all of the SDA has been removed.

TABLE 1

In another aspect, provided herein is a crystalline EMM-37 material having a framework defined by the following connectivity for tetrahedral (T) atoms in the unit cell in table 2, the tetrahedral (T) atoms being connected by bridging atoms:

TABLE 2

In another aspect, the present disclosure provides a porous crystalline EMM-37 material in which some or all of the SDA has been removed, the porous crystalline EMM-37 material having a composition comprising formula I:

(m)X₂O₃:YO₂(formula I) is shown in the specification,

wherein m is more than or equal to 0.01 and less than or equal to 0.25, X is trivalent element, and Y is tetravalent element. The EMM-37 material may comprise components other than the trivalent and tetravalent oxides of formula I, such as those described in the detailed description and examples section.

In yet another aspect, provided herein is a crystalline EMM-37 material in as-synthesized form having at least six XRD peaks in degrees 2-theta selected from table 3:

TABLE 3

In yet another aspect, provided herein is a crystalline EMM-37 material in as-synthesized form having a composition comprising formula II:

(n)G:(v)X₂O₃:YO₂(formula II) in the formula (III),

wherein v is more than or equal to 0.01 and less than or equal to 0.25, n is more than or equal to 0.03 and less than or equal to 0.25, G is an organic structure directing agent, X is a trivalent element, and Y is a tetravalent element. The EMM-37 material may comprise components other than the trivalent and tetravalent oxides of formula II, such as those described in the detailed description and examples section.

In yet another aspect, the present disclosure provides methods of making the materials described herein.

In another aspect, provided herein is an SDA material comprising or being compound H having the structure:

(compound H) wherein a is an ion; and a method for preparing the same.

Any two or more features described in this specification, including features in this summary, may be combined to form a combination of features not specifically described herein. The details of one or more features are set forth in the accompanying drawings and the description below. Other features and advantages will be apparent from the description and drawings, and from the claims.

Drawings

Figure 1 shows the powder XRD pattern of the as-synthesized EMM-37 material.

Figure 2 shows the powder XRD pattern of the heat treated EMM-37 material calcined to 515 ℃.

Figure 3 shows the powder XRD pattern of the heat treated EMM-37 material calcined to 515 ℃, 540 ℃ and 600 ℃.

Detailed Description

Provided herein are materials, referred to as EMM-37, methods of making these materials, uses thereof, structure directing agents for making EMM-37, methods and intermediates for making such SDAs. The EMM-37 material is crystalline and porous. The EMM-37 material in which some or all of the SDA has been removed (e.g., thermally or otherwise treated to remove Structure Directing Agent (SDA) from the pores) may comprise a variety of components, such as the components described herein, including oxides of trivalent elements (e.g., X)₂O₃) And oxides of tetravalent elements (e.g. YO)₂) Wherein the oxides may be present in different molar ratios. X is a trivalent element and Y is a tetravalent element. EMM-37 as-synthesized (i.e., prior to heat treatment or other treatment to remove the SDA from the pores) may include the SDA, i.e., one of the components of the synthesis mixture, in its pores. In one aspect, the as-synthesized EMM-37 material may be heat treated or otherwise treated to remove some or all of the SDA. The heat treatment (e.g. calcination) of the as-synthesized EMM-37 material typically entails subjecting the material to a high temperature, e.g. 400-700 c, in an atmosphere selected from air, nitrogen or mixtures thereof in a furnace. On the other hand, ozone treatment of the as-synthesized EMM-37 material can be used to remove some or all of the SDA. The EMM-37 material, from which some or all of the SDA has been removed, may be used as an adsorbent and catalyst or catalyst support for hydrocarbon conversion (e.g., conversion of organic compounds to conversion products). EMM-37 described herein is a small pore zeolite capable of separating small molecules.

The EMM-37 material from which some or all of the SDA has been removed has at least 6 XRD peaks in degrees 2 theta selected from table 1:

TABLE 1

In one or more aspects, the EMM-37 material (in which some or all of the SDA has been removed) may have at least six XRD peaks with 2-theta degrees and d-spacing values selected from table 1A, where the d-spacing values have a deviation based on the corresponding deviation in 2-theta degrees ± 0.20, as determined when converted to the corresponding value of d-spacing using bragg's law:

TABLE 1A

XRD patterns with XRD peaks described herein use Cu (K)_α) And (4) irradiating. The EMM-37 material may have at least seven, at least eight, or nine XRD peaks selected from table 1 or table 1A.

The framework of the EMM-37 material (e.g., containing SDA, or with some or all of SDA removed) is defined by the connectivity in table 2 for the tetrahedral (T) atoms in the unit cell, where the tetrahedral (T) atoms are connected by bridging atoms. Connectivity can be calculated by the computer algorithm zeoTsites, which is the Fortran code for topological and crystallographic tetrahedral site analysis of zeolites and zeolite-like. See, e.g., g.sastre, j.d.gale, "microporous and mesoporous materials" 2001, 43, pages 27-40. The tetrahedral atoms may comprise one or more elements selected from B, Al, Fe, Ga, Si, Ge, Sn, Ti and Zr, or mixtures thereof. For example, the tetrahedral atoms may be selected from B, Al or Si, or mixtures thereof. For example, the tetrahedral atom may comprise or be Si or Al. The bridging atom may be selected from O, N and C, or mixtures thereof. The bridging atoms can comprise or be oxygen atoms (e.g., at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the bridging atoms can be oxygen). The bridging atoms C may be introduced from various components used to make the zeolite, such as sources of silica. After removal of the SDA, the bridging atom N may be introduced into the zeolite.

In one or more aspects, the micropore volume of an EMM-37 material (in which some or all of the SDA has been removed by heat treatment or other treatment) can be from 0.10cc/g to 0.28cc/g, such as from 0.20cc/g to 0.28 cc/g. The micropore volume can be from 0.10cc/g to 0.20cc/g (e.g., 0.12cc/g) or from 0.20cc/g to 0.25cc/g (e.g., 0.21cc/g or 0.22 cc/g). The EMM-37 material may have at least six, at least seven, at least eight, or nine XRD peaks selected from table 1 or table 1A; micropore volume is from 0.10cc/g to 0.28cc/g, for example from 0.20cc/g to 0.28 cc/g.

In one or more other aspects, the EMM-37 material (in which some or all of the SDA has been removed) may have five XRD peaks selected from table 1B:

TABLE 1B

And the micropore volume is from 0.10 to 0.28 cc/g.

The EMM-37 material (in which some or all of the SDA has been removed) may have a composition optionally represented by formula I:

(m)X₂O₃:YO₂(formula I) is shown in the specification,

wherein m is more than or equal to 0.01 and less than or equal to 0.25, X is trivalent element, and Y is tetravalent element. X may be selected from B, Al, Fe and Ga, or mixtures thereof. For example, X may comprise or be Al. Y may be selected from Si, Ge, Sn, Ti and Zr, or mixtures thereof. For example, Y may comprise or be Si. The oxygen atom in formula I may be replaced by a carbon atom (e.g., with CH)₂Form(s) may be derived from the source of the components used to prepare the as-synthesized EMM-37. The oxygen atom in formula I may also be replaced by a nitrogen atom, for example after removal of the SDA. Formula I may represent the skeleton of a typical EMM-37 material in which part or all of the SDA has been removed, and is not meant to represent only the EMM-37 material. The EMM-37 material may also contain SDA and/or impurities after appropriate treatment to remove SDA and impurities, which is not shown in formula I. Further, formula I excludes protons and charge compensating ions that may be present in the EMM-37 material.

The variable m represents X in formula I₂O₃With YO₂The molar ratio of (a). For example, when m is 0.01, the molar ratio of Y to X is 50 (e.g., the molar ratio of Si/Al is 50). When m is 0.25, the molar ratio of Y to X is 2 (e.g., the molar ratio of Si/Al is 2). The molar ratio of Y to X may be 5 to 40, 5 to 25, or 4 to 15 (e.g., the molar ratio of Si/Al is 5 to 40, 5 to 25, or 4 to 15). The molar ratio of Y to X may be 4, 5,6, 7, 8, 9, 10, 11, or 12 (e.g., the Si/Al molar ratio is 4, 5,6, 7, 8, 9, 10, 11, or 12).

The as-synthesized (e.g., non-heat treated) EMM-37 material has at least six XRD peaks in degrees 2 theta selected from table 3:

TABLE 3

In one or more aspects, the as-synthesized (e.g., untreated to remove SDA) EMM-37 material may have at least six XRD peaks with 2-theta degrees and d-spacing values selected from table 3A, where the d-spacing values have a deviation based on a corresponding deviation in 2-theta degrees ± 0.20, as determined when converted to a corresponding value of d-spacing using bragg's law:

TABLE 3A

The as-synthesized EMM-37 material may have at least seven, at least eight, at least nine, or ten XRD peaks selected from table 3 or table 3A.

In one or more aspects, the as-synthesized EMM-37 material may be described as follows: the a parameter of the triclinic cell isb parameter isc parameter is

α is 104 + -6 deg., β is 100 + -6 deg., and gamma is 100 + -6 deg. the as-synthesized EMM-37 material may have at least six, at least seven, at least eight, at least nine, or ten XRD peaks selected from Table 3 or Table 3A, and the a-parameter of the triclinic cell isb parameter is

c parameter isα is 104 +/-6 degrees, β is 100 +/-6 degrees, and gamma is 100 +/-6 degrees.

In one or more other aspects, the as-synthesized EMM-37 material may have six XRD peaks selected from table 3B:

TABLE 3B

And the a parameter of the triclinic cell isb parameter isc parameter is

α is 104 +/-6 degrees, β is 100 +/-6 degrees, and gamma is 100 +/-6 degrees.

Optionally, the as-synthesized EMM-37 material may have a composition represented by formula II:

(n)G:(v)X₂O₃:YO₂(formula II) in the formula (III),

wherein v is more than or equal to 0.01 and less than or equal to 0.25, n is more than or equal to 0.03 and less than or equal to 0.25, G is an organic structure directing agent, and X is a trivalent elementElement, Y is tetravalent element. X may be selected from B, Al, Fe and Ga, or mixtures thereof. For example, X may comprise or be Al. Y may be selected from Si, Ge, Sn, Ti and Zr, or mixtures thereof. For example, Y may comprise or be Si. Formula II may represent the backbone of a typical as-synthesized EMM-37 material with SDA and is not meant to represent only such material. The as-synthesized EMM-37 material may contain impurities not shown in formula II. Further, formula II does not include protons and charge compensating ions that may be present in the as-synthesized EMM-37 material. Similar to formula I, the oxygen atom in formula II may be replaced by a carbon atom (e.g., with CH)₂Form(s) may be derived from the source of the components used to prepare the as-synthesized EMM-37.

The variable v represents X in formula II₂O₃With YO₂The molar ratio of (a). For example, when v is 0.01, the molar ratio of Y to X is 50 (e.g., the molar ratio of Si/Al is 50). When v is 0.25, the molar ratio of Y to X is 2 (e.g., the molar ratio of Si/Al is 2). The molar ratio of Y to X may be 5 to 40, 5 to 25, or 4 to 15 (e.g., the molar ratio of Si/Al is 5 to 40, 5 to 25, or 4 to 15). The molar ratio of Y to X may be 4, 5,6, 7, 8, 9, 10, 11, or 12 (e.g., the Si/Al molar ratio is 4, 5,6, 7, 8, 9, 10, 11, or 12).

The variable n represents the organic structure directing agents G and YO in formula II₂The molar ratio of (a). For example, when n is 0.03, the molar ratio of G to Y is 0.03. When n is 0.25, the molar ratio of G to Y is 0.25. The molar ratio of G to Y may be 0.05 to 0.15, 0.10 to 0.25, 0.15 or 0.25.

The process for preparing the as-synthesized EMM-37 material can be described as follows:

(i) mixing a source of hydroxide ions, a source of an oxide of a tetravalent element Y, a source of a trivalent element X and optionally a dipyrrolidine(ii) a biscationic structure directing agent (G);

(ii) heating the mixed composition; and

(iii) crystals of EMM-37 material are isolated.

The composition may have a YO of 2 to 50 (e.g., 5 to 30, 4 to 25, or 5 to 20)₂And X₂O₃In a molar ratio of (a). The composition may also have a H of 1 to 50 (e.g., 10 to 40)₂O and YO₂In a molar ratio of (a). The composition may also have an OH of 0.05 to 0.5 (e.g., 0.10 to 0.30)^-With YO₂In a molar ratio of (a). The composition can have a G and YO of 0.03 to 0.25 (e.g., 0.10 to 0.25)₂In a molar ratio of (a).

CH₂The carbon in form may be present in various sources for the preparation of the components of EMM-37, for example a source of tetravalent element (silica source) and introduced as bridging atoms into the EMM-37 framework. After removal of the SDA, the nitrogen atoms can be introduced as bridging atoms into the framework of the EMM-37 material.

In one or more other aspects, the as-synthesized EMM-37 material may be prepared by first mixing a trivalent element X source with a hydroxide solution of SDA, and then adding a tetravalent Y source to the mixture to form a base mixture of components. Optionally, seeds of EMM-37 material may be added to the base mixture. In one or more aspects, the solvent-adjusted mixture (e.g., where the desired water to silica ratio is achieved) can be mixed by mechanical means such as stirring or high shear blending to ensure proper homogenization of the base mixture, e.g., using double asymmetric centrifugal mixing (e.g., flaktek speed mixer) at a mixing speed of 1000 to 3000rpm (e.g., 2000 rpm). Depending on the nature of the components in the base mixture, an amount of solvent (e.g., water in the hydroxide solution, and optionally methanol and ethanol from hydrolysis of the silica source) may be removed from the base mixture to achieve the desired solvent and YO for the resulting mixture₂The molar ratio. Suitable methods for reducing the solvent content may include evaporation under static or flowing atmosphere (e.g. ambient air, dry nitrogen, dry air), or by spray drying or freeze drying. When too much water is removed during solvent removal, water may be added to the resulting mixture to achieve the desired H₂O/YO₂The molar ratio. In some embodiments, when the formulation has sufficient H₂O/YO₂At the molar ratio, water need not be removed.

The mixed mixture is then subjected to crystallization conditions suitable for the formation of EMM-37 material. Crystallization of the EMM-37 material may be carried out under static or stirring conditions in a suitable reactor vessel, e.g., a polypropylene jar placed in a convection oven or an autoclave lined with Teflon or stainless steel, maintained at a temperature of about 100 ℃ to about 200 ℃ for a time sufficient for crystallization to occur, e.g., about 1 day to about 30 days (e.g., 1 day to 1 to 14 days, or 1 day to 7 days). Thereafter, the solid crystals of the as-synthesized EMM-37 material are separated from the liquid (e.g. by filtration or centrifugation) and recovered.

Examples of sources of tetravalent element Y may be selected from colloidal suspensions of: silica, precipitated silica, fumed silica, alkali metal silicates, tetraalkyl orthosilicates (e.g., tetraethyl orthosilicate, tetramethyl orthosilicate, etc.), and germanium oxide, or mixtures thereof. Other examples of silica sources may include(e.g. in

LS-30、

AS-40) colloidal silica,

Precipitated silica, CARBOSPERSE^TMA fumed silica suspension, or a mixture thereof.

The trivalent element X may comprise aluminum or be aluminum. Suitable aluminium sources may be selected from metakaolin, alkali metal aluminates, aluminium alkoxides and water soluble aluminium salts, for example aluminium nitrate, or mixtures thereof. Additionally or alternatively, the trivalent element X may comprise or be boron. Suitable boron sources may be selected from boric acid, sodium tetraborate and potassium tetraborate, or mixtures thereof.

Some or all of the SDA introduced into the pores during synthesis of the as-synthesized EMM-37 material may be removed to form a heat-treated EMM-37 material. The removal of SDA may be performed using a heat treatment (e.g., calcination) during which the as-synthesized EMM-37 material is heated in an atmosphere selected from air, nitrogen, or a mixture thereof at a temperature sufficient to remove some or all of the SDA. Although sub-atmospheric pressures may be employed for the heat treatment, it is desirable to use atmospheric pressure for reasons of convenience. The heat treatment may be carried out at a temperature of up to 700 c, for example 400 c to 700 c. The measured temperature is the temperature of the environment surrounding the sample. The heat treatment (e.g., calcination) may be carried out in a box furnace in dry air that has been treated with a drying tube containing a desiccant that removes water from the air. The heating may be carried out at 400 ℃ to 700 ℃ (e.g., 515 ℃ or 540 ℃) for 1 day to 14 days. The heating may first be performed under a nitrogen atmosphere up to 400 c, and then the atmosphere may be switched to 400 c air.

The as-synthesized EMM-37 material may contain a structure directing agent, such as dipyrrolidine

A dication. An alternative method of synthesizing porous crystalline EMM-37 material may be performed without the use of SDA. Suitable sources of structure directing agents may be selected from the hydroxides and/or salts of the relevant diquaternary ammonium compounds. For example, the structure directing agent may comprise or be compound H having the structure:

(Compound H) wherein A is an ion.

For example, a may be tosylate, OH (hydroxyl), or a halide, such as I or Br. In one or more aspects, a can comprise or be a hydroxyl group (OH). Compound H has two stereocenters and therefore has RS, SS or RR configuration. For example, compound H may comprise or be in the RS configuration. The SDA used to prepare the as-synthesized EMM-37 material may be compound H having the RS configuration.

A method of preparing compound H, or a particular stereoisomer thereof, may comprise:

(i) converting compound 1 to compound 2:

(ii) converting compound 2 to compound 3:

(iii) converting compound 3 to compound H:

and

(iv) compound H is optionally purified to the desired stereoisomer (e.g., RS isomer).

Compound 2 can be prepared by converting compound 1 to compound 2. For example, compound 1 can be reacted with methylamine and methanol in the presence of a solvent. The solvent may comprise or be a protic solvent, for example water. Methylamine may be used in an amount of 1 to 3 molar equivalents (e.g., 1.6 molar equivalents) of methylamine based on 1 molar equivalent of compound 1. The conversion of compound 1 to compound 2 may comprise microwaving compound 1 with methylamine. The microwave treatment may be at a temperature of 150 ℃ to 170 ℃ (e.g., heating the reaction mixture to a temperature of 150 ℃ to 170 ℃ in a closed vessel). The microwave treatment may include raising the temperature to 150 ℃ to 170 ℃ (e.g., 160 ℃) for 15 minutes and holding the temperature to 150 ℃ to 170 ℃ (e.g., 160 ℃) for 1 to 3 hours (e.g., 1 hour).

Compound 3 can be prepared by converting compound 2 to compound 3. The conversion of compound 2 to compound 3 may comprise reacting compound 2 with a reducing agent in the presence of a solvent. For example, the reducing agent may comprise or be Lithium Aluminum Hydride (LAH). The reducing agent may be used in an amount of 2 to 5 molar equivalents (e.g., 3 to 4 molar equivalents or 3.5 molar equivalents) of the reducing agent based on 1 molar equivalent of compound 2. The solvent may comprise or be an ether, such as Tetrahydrofuran (THF).

Compound H can be prepared by converting compound 3 to compound H. For example, compound 3 can be reacted with a haloalkane source in the presence of a solvent. The haloalkane source may comprise or be an iodide source, such as methyl iodide. The haloalkane source can be used in an amount of 2 to 4 molar equivalents (e.g., 3 molar equivalents) of haloalkane source based on 1 molar equivalent of compound 3. The solvent may comprise or be a protic solvent, such as methanol.

Compound H can optionally be purified to obtain the desired stereoisomer, e.g., SS, RR or RS. For example, compound H can be obtained substantially pure to the RS stereoisomer. "substantially pure" with respect to compound H means at least 80%, 90%, 95%, 96%, 97%, 98%, or 99% pure to the SS, RR, or RS stereoisomer. Purification may include precipitation of the desired stereoisomer (e.g., RS stereoisomer) from the solvent or mixture of one or more solvents. The solvent may comprise or be a protic solvent. For example, the protic solvent may be selected from methanol, water or mixtures thereof. For example, compound H can be dissolved in hot methanol (e.g., methanol at a temperature above room temperature) and then deionized water can be added to the methanol solution of compound H to precipitate or crystallize compound H. Using a methanol/water mixture as solvent system for the crystallization or precipitation of compound H, the RS isomer can first be isolated in solid form (e.g. crystals or precipitate) and the remaining isomer can then be separated from the residual solution by, for example, removing the solvent in vacuo. As described above, RS isomers can be separated from RR and SS isomers. The RR and SS enantiomers can be separated from each other by chiral separating agents.

The anion of compound H can be converted to other anions. For example, the anionic iodide may be converted to the hydroxide anion by standard methods known to those of ordinary skill in the art, such as resin exchange.

General features

The EMM-37 material (with some or all of the SDA removed) may be combined with a hydrogenation component. The hydrogenation component may be selected from molybdenum, tungsten, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium, in which the hydrogenation-dehydrogenation function is to be performed. Such hydrogenation components may be incorporated into the composition by one or more of the following methods: co-crystallizing; exchange into the composition to the extent that the group IIIA element (e.g., aluminum) is in the structure; impregnated therein or physically mixed therewith. In one or more aspects, such hydrogenation components may be impregnated into the EMM-37 material. In the case of platinum, the EMM-37 material may be impregnated with a solution containing platinum-containing metal ions. Suitable platinum compounds for impregnation may be selected from chloroplatinic acid, platinous chloride and compounds containing a platinum amine complex.

The EMM-37 material (with some or all of the SDA removed) may be at least partially dehydrated when used as an adsorbent or catalyst. This dehydration can be achieved by heating to a temperature in the range of 200 ℃ to 370 ℃ (e.g., the temperature of the environment surrounding the sample) in an atmosphere selected from air, nitrogen, or mixtures thereof and at atmospheric, subatmospheric, or superatmospheric pressure for 30 minutes to 48 hours. Dehydration can also be carried out at room temperature by placing the EMM-37 material in a vacuum; however, a long time is required to obtain a sufficient amount of dehydration.

The EMM-37 material (with some or all of the SDA removed) can be used as an adsorbent or as a catalyst in the form of an aluminosilicate to catalyze a variety of organic compound conversion processes. Examples of chemical conversion processes that are effectively catalyzed by the modified EMM-37 materials described herein, either alone or in combination with one or more other catalytically active species (including other crystallization catalysts), include those that require a catalyst with acid activity. Examples of organic conversion processes that may be catalyzed by the modified EMM-37 materials described herein include cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

The EMM-37 material (with some or all of the SDA removed) may be used in combination with another material that is resistant to the temperatures and other conditions employed in the organic conversion process. Such resistant materials may be selected from active materials, inactive materials, synthetic zeolites, naturally occurring zeolites, inorganic materials or mixtures thereof. Examples of such resistant materials may be selected from clays, silica, metal oxides (such as alumina) or mixtures thereof. The inorganic material may be naturally occurring or in the form of a gelatinous precipitate or gel, including mixtures of silica and metal oxides. The use of a resistant material in combination with the EMM-37 material (i.e. in combination therewith or present during the synthesis of the as-synthesized EMM-37 crystals, which are active) alters the conversion and/or selectivity of the catalyst in certain organic conversion processes. Non-reactive resistant materials are suitable for use as diluents to control the amount of conversion in a given process so that the product can be obtained in an economical and orderly manner without the need to otherwise control the rate of reaction. These materials can be incorporated into naturally occurring clays, such as bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. The inactive refractory materials, i.e., clay, oxide, etc., are used as binders for the catalyst. Catalysts with good crush strength can be beneficial because in commercial applications, it is desirable to prevent the catalyst from decomposing into a powdery material.

Naturally occurring clays which may be composited with the EMM-37 material include the montmorillonite and kaolin families which include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or other clays in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used as originally mined or initially subjected to calcination, acid treatment or chemical modification. Suitable binders for compounding with EMM-37 materials also include inorganic oxides selected from silica, zirconia, titania, magnesia, beryllia, alumina, or mixtures thereof.

The EMM-37 material (e.g., as-synthesized or calcined, or any other EMM-37 material) may be compounded with: porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania; and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

The relative proportions of the EMM-37 material and the inorganic oxide matrix can vary widely, with the EMM-37 material being present in an amount of from about 1% to about 90% by weight of the composite, or when the composite is prepared in the form of beads, the EMM-37 material being present in an amount of from about 2% to about 80% by weight of the composite.

As used herein, and unless otherwise indicated, a value or range of values can have a degree of deviation that is deemed reasonable by one of ordinary skill in the relevant art. It is well known that variations in instrumentation and other factors can affect the values. Unless otherwise indicated, such deviations may be ± 2%, ± 5%, ± 10% or ± 15% of the indicated value or range of values.

The EMM-37 material described herein may be at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, or at least 99 wt% (e.g., 99.5 wt% or 99.9 wt%) pure EMM-37 material based on the total weight of the composition, quantified by using XRD or NMR spectroscopy (e.g., by measuring the area or relative intensity of the relevant peaks), or by other known methods suitable for such determination. The remainder of the material is non-EMM-37 material and may be a structure directing agent, an amorphous material, other impurities, or mixtures thereof.

The EMM-37 material described herein is substantially crystalline. As used herein, the term "crystalline" refers to a crystalline solid form of a material, including but not limited to single or multicomponent crystalline forms, including, for example, solvates, hydrates, and co-crystals. Crystallization may refer to having a regular repeating and/or ordered arrangement of molecules, and having a distinguishable crystal lattice. For example, crystalline EMM-37 may have different water or solvent contents. The different crystal lattices can be identified by solid state characterization methods, such as by XRD (e.g., powder XRD). Other characterization methods known to those of ordinary skill in the relevant art may further aid in identifying crystalline forms and in determining stability and solvent/water content.

As used herein, the term "substantially crystalline" means that a majority (greater than 50 weight percent) of the sample weight of the material is crystalline, while the remainder of the sample is in a non-crystalline form. In one or more aspects, a substantially crystalline sample has a crystallinity of at least 95% (e.g., 5% amorphous form), a crystallinity of at least 96% (e.g., 4% amorphous form), a crystallinity of at least 97% (e.g., 3% amorphous form), a crystallinity of at least 98% (e.g., about 2% amorphous form), a crystallinity of at least 99% (e.g., 1% amorphous form), and a crystallinity of 100% (e.g., 0% amorphous form).

The micropore volume of the EMM-37 materials described herein can be determined using methods known in the relevant art. For example, the material can be measured by nitrogen physisorption and can be measured by the methods described in Lippens, b.c. et al, "investigation of pore systems in catalysts: v.t method ", J.Catal., 4,319(1965), which describes the micropore volume method and is incorporated herein by reference.

The X-ray diffraction data reported herein were obtained using a Bruker D4 Endevidor instrument in continuous mode using CuK α radiation at 0.01796 ° steps through a lens having an effective area of 50mm × 16mm

Collected by a gas detector. Fig. 1 and 2 were collected with an effective count time of 278 seconds per step and fig. 3 was collected with an effective count time of 347.5 seconds per step. The interplanar spacing d is calculated in angstroms and the relative intensity of the lines, I/Io, is the ratio of the peak intensity to the intensity of the strongest line above background. The intensity is not corrected for lorentz and polarization effects. The position of the 2 theta diffraction peak and the relative peak area intensity of the spectral line, I/I (o), were determined using the MDI Jade peak search algorithm, where Io is the intensity of the strongest spectral line above background. It will be appreciated that diffraction data listed as a single line may consist of multiple overlapping lines that may appear as resolved lines or partially resolved lines under certain conditions, such as differences in crystallographic changes. Typically, crystallographic changes can include minor changes in unit cell parameters and/or changes in crystal symmetry, without structural changes. These minor effects, including being relatively strongVariations in degree may also occur due to differences in cation content, framework composition, nature and extent of pore filling, crystal size and shape, preferred orientation, and thermal and/or hydrothermal history.

Aspects of the present disclosure are described in more detail by specific embodiments. The following examples are provided for illustrative purposes only and are not intended to limit the present disclosure in any way. One skilled in the relevant art will readily recognize that various parameters may be changed or modified to produce substantially the same result.