JPWO2021119380A5 - - Google Patents

Description

Cross-reference to related applications

This application claims priority from US Provisional Patent Application No. 62/947,434 filed December 12, 2019, the contents of which are incorporated by reference for all purposes.

(Government rights)
none

The present disclosure relates to germanosilicates designated CIT-13/OH and CIT-14 and the conversion of the former to the latter by inverse sigma transformation.

Zeolites play an important role as heterogeneous catalysts and are used in various industrial settings. Initially, these materials were developed primarily to assist the petroleum industry in its quest to create more selective and robust catalysts for making gasoline and other fuels. These solids are now emerging as specialty materials with properties based on their structure and chemical composition that make them amenable to specific large-scale applications. A great deal of effort is required from the stage of discovering a new substance to a catalyst that has been commercialized. are also left.

One goal for discovering new materials is the hope that larger pores that retain some catalytic properties on their internal surfaces will be able to process larger feed molecules in the petroleum upgrade field.

Therefore, there remains interest in finding new crystalline phases for use in these applications. This research aims to address deficiencies in the technology in this area.

Synthetic molecular sieves typically contain inorganic (Na+, K+, etc.) and organic structure-directing agents (OSDA), mineralizers (OH- or F-), heteroatoms (Al, B, Ge , Ti, Sn, etc.). The synthesis of crystalline molecular sieves is complicated. Although advances have been made in designing certain parts of recipes and assembly processes, it is difficult to predict the results from that approach.

Topotactic conversion of existing zeolites has played a role as a method to prepare new zeolite frameworks that could not be synthesized by conventional hydrothermal methods. A typical example of this is the assembly-decomposition-assembly-reassembly (ADOR) of germanosilicate transformations that take advantage of the property that germanium moieties preferably occupy small compositional building units (CBUs), such as the double 4-ring (d4r). ) strategies, and these transformations are shown schematically in FIGS. 1(A) and 1(B), respectively.

In the process of investigating the function of imidazolium-derived compounds with benzyl pendant groups as OSDAs, CIT-13 (*CTH: an asterisk (*) indicates an ultra-large pore structure with 14 MR and 10 MR channels). ) was found. Isostructural germanosilicates, NUD-2 and SAZ-1, crystallized from imidazolium-based OSDA and fluoride-based gels have also been reported. CIT-13 is a structure in which a Si-rich cfi layer is bridged with a two-dimensional array of Ge-rich d4r units. The structure of the cfi layer gives the d4r unit two crystallographically equivalent positions. This equivalence was revealed by perturbation of the position of the d4r unit of the CIT-13 backbone and conversion of *CTH to CFI (Fig. 1(C)). Most importantly, the structure of CIT-13 resembles that of IM-12, showing the rich chemistry of germanosilicate conversion.

We previously reported the similarities between *CTH and UTL, two novel scaffolds CIT-14 and CIT with two-dimensional 12/8 MR and one-dimensional 10 MR channel systems, respectively, prepared based on ADOR transformations. -15 disclosed. However, ADOR products of sufficient quality for Rietveld refinement from powder X-ray diffraction (PXRD) have never been prepared. This is believed to be due to the possible presence of Si--O--Si linkages within the interlayer region, which may lead to incomplete exfoliation. Liu et al. reported that a weak base solution such as ammonium hydroxide dissociates the inter-layer Si—O—Si bond that prevents the complete exfoliation of the cfi-type layer of CIT-13, resulting in a structure called ECNU-21 (equivalent structure to CIT-15). reported that it was obtained. We also found that a weak base solution exfoliates the cfi-type layer from the germanosilicate Ge-CIT-5, which has double zigzag chain (dzc) composition building units instead of d4r units. Most recently, the formation of partially degermanated ECNU-23 (isostructural to CIT-14) from the d4r unit of CIT-13 and its structural solution (based on electron diffraction) was also reported. This synthesis was similar to the inverse sigma transformation of IM-12. However, due to the unique germanium arrangement within the d4r unit of CIT-13, inverse sigma conversion by leaching pure Ge-4-rings with strong acid has not been previously reported.

The present disclosure describes a recently reported crystalline microporous germanium with CIT-13 topology prepared by a fluoride-free hydroxide route, as described in US Pat. No. 10,828,625. A novel germanosilicate derived from silicate is targeted. This reference is hereby incorporated by reference in its entirety for all purposes including characterization of materials of CIT-13 topology and methods of manufacture and use. These CIT-13 germanosilicates are hydrothermally prepared using benzylimidazolium organic structure-directing agents and are characterized by having a three-dimensional framework with pores defined by 10- and 14-membered rings. (with pore sizes of 6.2×4.5 Å and 9.1×7.2 Å, respectively). This is the first known crystalline silicate with such a structure. These structures were characterized by powder X-ray diffraction (PXRD) patterns, unit cell parameters, SEM micrographs, ²⁹ Si MAS NMR spectroscopy and adsorption/desorption isotherms.

This disclosure describes a germanium-containing ultra-large pore molecular sieve CIT-13 synthesized without the use of fluoride. After removing the occluded organics, the CIT-13 obtained from the fluoride-free preparation shows a difference from the CIT-13 sample prepared in the presence of fluoride. CIT-13 prepared by the fluoride-free method undergoes an inverse sigma transformation to produce mesopore-free CIT-14, while Ge-CIT- It was found to convert to CIT-5 type germanosilicate much faster than 13. Rietveld refinement structural analysis of CIT-14 confirmed that it has 12- and 8-membered ring channels, although the unit call parameters of this material were slightly different from previous reports. ¹⁹ F magic angle spinning (MAS) and ¹ H- ²⁹ Si cross-polarization (CP) MAS nuclear magnetic resonance (NMR) spectroscopy showed that CIT-13 crystallized without fluoride was synthesized in the presence of fluoride. It was found to have different germanium positions than CIT-13.

The present disclosure is further directed to methods of engineering the structure of these CIT-13 germanosilicates prepared by the fluoride-free hydroxide route. Si/Ge ratios range from 3.8 to 10 by exposure to heat and steam under reaction conditions suitable to effect inverse sigma conversion. This mechanism for this substance is hitherto unknown. The disclosure is also directed to the germanosilicate CIT-14 product resulting from such manipulations. Previously, the germanosilicate CIT-14 was disclosed in US Pat. No. 10,293,33, the contents of which are incorporated herein by reference for all purposes or at least for methods of preparation and characterization of CIT-14. was obtained by ADOR transformation (assembly-disaggregation-assembly-reassembly) of a phyllosilicate called CIT-13P, as described in 2001.

Certain embodiments of the present disclosure include those crystalline microporous germanosilicate compositions, designated CIT-14/IST, with 8- and 12-membered ring channels. The CIT-14/IST composition, in some embodiments, is 7.59±0.5, 8.07±0.5, 12.88±0.5, 19.12±0.5, 19. at 32±0.5, 20.73±0.5, 22.33±0.5, 24.37±0.5, 27.19±0.5 and 27.69±0.5 degrees 2-theta Characterized by an X-ray powder diffraction (RD) pattern having at least 5, 7 or 10 characteristic peaks. The present disclosure also provides a more complete disclosure of the various uncertainties associated with the peaks, the full range of characteristic peaks and the relative intensities and selection of peaks that characterize these materials.

CIT-14/IST compositions, in some embodiments, have a Si:Ge ratio in the range of 12:1 to 20:1 or 14:1 to 18:1 or subranges within these ranges. characterized by being

The CIT-14/IST composition is in some embodiments characterized by claims 1-4, wherein the crystals are orthorhombic. In some embodiments, the CIT-14/IST crystals have a Cmmm space group or a Cmcm space group or an intracrystalline mixture of the two domains (disorder). In some embodiments, the crystalline microporous germanosilicate CIT-14/IST composition has the following unit cell parameters.

In some embodiments, the 8-membered ring channel has a CIT-14/IST composition pore size of about 3.3 Å×3.9 Å and the 12-membered ring channel has a pore size of about 4.9 Å×6.4 Å. have Physical strain (eg, compression) or the Si:Ge ratio can change these values.

In some embodiments, the crystalline microporous germanosilicate CIT-14/IST composition is derived from the inverse sigma transformation of a crystalline microporous germanosilicate designated CIT-13/OH, or It is inducible. In some embodiments, the crystalline microporous germanosilicate CIT-14/IST composition is derived or derivable from a crystalline microporous germanosilicate designated CIT-13/OH. and CIT-13/OH germanosilicate concentrated aqueous mineral or Isolating this as-formed "-CIT-14" germanosilicate by subjecting it to other strong aqueous acid conditions and calcining to form a crystalline microporous germanosilicate CIT-14/IST composition. according to. Exemplary conditions for effectively performing these transformations are described elsewhere in this disclosure.

Although the specific morphology, properties and manufacturing conditions of the crystalline microporous CIT-13/OH germanosilicates are more clearly defined in this disclosure, these compositions are free of fluoride ions and have specific It needs to be manufactured within a range of Si:Ge ratios. The synthesis of these CIT-13/OH germanosilicates is conveniently accomplished using the specific substituted benzylimidazolium organic structure-directing agent (OSDA) cations defined herein. In some preferred embodiments, the precursor CIT-13/OH germanosilicate is fluoride-free and has d4r units with an average of at least and preferably more than 4 Ge atoms, and in the d4r units Allows for the presence of the Ge-4-ring.

In other embodiments, the crystalline microporous germanosilicate CIT-14/IST composition comprises at least one alkali metal salt, alkaline earth metal cation salt, transition metal, transition metal oxide, transition metal salt, or Contains micropores containing combinations.

In another embodiment, the crystalline microporous germanosilicate CIT-14/IST
are used in either their acid or metal-containing forms as catalysts or adsorbents in a range of processes described elsewhere herein.

The present disclosure also includes other embodiments relating to the preparation of the crystalline microporous germanosilicate CIT-14/IST, wherein the crystalline microporous germanosilicate CIT-13/OH germanosilicate as-produced "-CIT -14" composition comprising contacting the crystalline microporous CIT-13/OH germanosilicate with a concentrated strong aqueous mineral acid at an elevated temperature for a time sufficient to convert it to a composition. The present disclosure also encompasses pre-baked, as-produced "-CIT-14" compositions.

The present disclosure also includes embodiments of CIT-13/OH germanosilicates prepared by the hydroxide route specifically described herein. The present disclosure also provides CIT-13/ characterized as having d4r units containing on average at least and preferably more than 4 Ge atoms per d4r, allowing for the presence of a Ge-4-ring in the d4r unit. OH germanosilicate embodiments are included. The present disclosure also includes embodiments of CIT-13/OH germanosilicates that exhibit previously unobserved reactivity characteristics that are the result of the new and unique physical characteristics defined herein.

The patent or application file contains at least one drawing/photograph executed in color. Copies of this patent or patent application publication with color drawings/photographs will be provided by the United States Patent Office upon request and payment of the necessary fee.

The present application will be better understood when read in conjunction with the accompanying drawings. For purposes of explaining the subject matter, the drawings depict exemplary embodiments of the subject matter, however, the presently disclosed subject matter is not limited to the particular methods, apparatus and systems disclosed. . Additionally, the drawings are not necessarily drawn to scale. In the drawing:

We provide a schematic description of known germanosilicate transformations: FIG. 1(A) is the inverse sigma transformation, FIG. 1(B) is the ADOR transformation, and FIG. Fig. 3 shows the conversion to CFI); * CTH type skeleton is displayed as a model base material. 1 is a schematic representation of the studies conducted and reported herein; FIG. FIG. 3 illustrates the structure of CIT-14/ESP (ESP stands for ethoxysilylated pillar ring) and its theoretical PXRD data (FIG. 3(A)) described in US Pat. No. 10,293,33. ) and pore channel dimensions (FIG. 3(B)). (a) SEM of CIT-14/IST samples derived from CIT-13/OH [3.71] (Fig. 4(A)); and CIT-13/OH [3.56] (Fig. 4(B)). FIG. 4 is a diagram showing an image; CIT-13/OH samples: CIT-13/OH[3.71] (FIG. 5(A)); CIT-13/OH[3.56] (FIG. 5(A)) and CIT-13/OH[4 .33] (Fig. 5(C)). CIT-13/OH [4.33], ¹ H- ¹³ C 8 kHz CPMAS spectra of the as-produced version of CIT-13/F [4.33] and 1,2-dimethyl-3- in chloroform-d. FIG. 13 shows the ¹³ C solution spectrum of (3-methylbenzyl)imidazolium chloride. ¹ H- ²⁹ Si 8 kHz CPMAS spectrum of the as-produced version of CIT-13/OH[4.33]. FIG. FIG. 4 is a diagram showing the results of characterization of CIT-13; FIG. 8(A): Two OSDAs capable of crystallizing CIT-13 without fluoride mineralizers. Figure 8(B-E): PXRD patterns of selected examples of CIT-13/OH samples: (b) as-produced and Figure 8(C): calcined CIT-13/OH [3.88]; Figure 8(D): as-produced and Figure 8(E): calcined CIT-13/OH [4.33]. FIG. 8(F): PXRD profile of reference CIT-13/F with Si/Ge ˜5. FIG. 8(G): Ar adsorption isotherms of CIT-13/OH [3.56] and CIT-13/F [4.18] on a logarithmic scale. PXRD patterns of as-prepared CIT-13/OH samples compared to those of reference CIT-13/F with Si/Ge=˜5. Figure 9(A): Reference CIT-13/F, Figure 9(B): Batch #A, Figure 9(C): Batch #5, Figure 9(D): Batch #7, Figure 9(E): Batch #8, FIG. 9(F): Batch #12, FIG. 9(G): Batch #13, FIG. 9(H): Batch #15, FIG. 9(I): Batch #16, FIG. 9(J): Batch #17 and FIG. 9(K): Batch #18. PXRD patterns of an as-prepared CIT-13/OH sample and its refluorinated version. (310) diffraction is highlighted. FIG. 3 shows structural changes during conversion of *CTH to CFI observed based on PXRD profiles. Calcined CIT-13/OH[4.33] (FIGS. 11(AB)) and (a,c) 4-40° and (b,d) 5-9° after 10 days exposure to atmospheric humidity. PXRD profile of CIT-13/OH [3.88] (Fig. 11 (CD)) in the range of . Changes in the d200 interlayer distance of CIT-13/OH[4.33] compared to CIT-13/F[4.31] (FIG. 11(E)). ²⁹ Si 8 kHz MAS spectra of calcined CIT-13/OH[3.88] and Ge-CIT-5 prepared therefrom. FIG. ²⁹ Si MAS NMR is qualitatively identical to that of CIT-14/ESP germanosilicate prepared by ADOR synthesis described in US Pat. A small amount of Q ³ Si species within the region and multiple Q ⁴ Si environments are shown. FIG. 13 illustrates the inverse sigma transformation of CIT-13 to CIT-14; Schematic of inverse sigma transformation of CIT-13/OH leading to CIT-14/IST (Fig. 13(A)); ). PXRD profiles of parent CIT-13 sample (black), 12M HCl fresh material (fuchsia) and calcined sample (blue): CIT-13/F [3.87] (FIG. 14(A)). and CIT-13/OH[4.33] (FIG. 14(B)). CIT-13/OH [3.56] (top), CIT-14/IST from CIT-13/F [4.33] (middle) and optimized “random” CIT based on GULP algorithm PXRD profile of a theoretical model of -14 in the range of (a) 4-40°, (b) 6-10° and (c) 10.0-12.5°. (d) ²⁹ Si NMR spectra of CIT-14/IST and CIT-14/ESP samples. ( ^29Si MAS spectrum of CIT-14/ESP is taken from US Patent Application Publication No. 20170252729). FIG. 4 shows the effect of elemental composition on the intensity of the PXRD peaks of CIT-14. Germanium at (a) the seven T sites of CIT-14 and (b) T1, (c) T2, (d) T3, (e) T4, (f) T5, (g) T6 and (h) T7 sites Simulated PXRD profiles of 0% (black), 10% (cyan) and 20% (red) CIT-14 scaffolds. Peak-1, peak-2 and peak-3 represent (110), (200) and (001) diffraction, respectively. FIG. 17 shows the experimental design and PXRD patterns in the range 4-40° (FIG. 17(B)) and 6-9° (FIG. 17(C)) of the resulting CIT-14/ESP samples. IM-12 [3.80] (Fig. 18 (A)), IM-12 [4.79] (Fig. 18 (B)), COK-14 from IM-12 [3.80] (Fig. 18 (C ))) and COK-14 from IM-12 [4.79] (Fig. 18(D)). PXRD profiles of COK-14 from IM-12 [3.80] and COK-14 from IM-12 [4.79]. Ar-adsorption and desorption isotherms of parent CIT-13/OH, CIT-14/IST and CIT-14/ESP are shown on: linear scale (Fig. 20(A)) and logarithmic scale (Fig. 20(B)). It is a diagram. FIG. 2 shows the results of structural analysis of CIT-14/IST. (FIG. 21(A)) Observed profile (top), calculated profile (middle) and difference profile (bottom) in the Rietveld refinement of CIT-14. (FIG. 21(B)) Projections along the crystallographic principal axes [001], [010] and [100] of CIT-14 (3×3×3 unit cells). (FIG. 21(C)) Two-dimensional 12-/8-ring channel system in the idealized structure of CIT-14. (FIG. 21(D)) Schematic representation of the disorganization of CIT-14. FIG. 2 shows the idealized structure of CIT-14/IST. Silicon, germanium and oxygen atoms are shown in blue, green and red respectively. FIG. 22(BC) shows the pore sizes of the 12- and 8-membered rings of CIT-14/IST, respectively. As-formed CIT-13/F [4.33], fluorinated CIT-13/OH [4.33] (FIG. 23(B)) and fluorinated CIT-13/OH [3.56] (FIG. 23 FIG. 19 shows the ¹⁹ F 12k MAS NMR spectrum of (C)). (Asterisks (*) indicate rotating sidebands of the fluorinated silica (19F—Si) surface formed as a result of fluorination with ammonium fluoride). ¹ H- ²⁹ Si CPMAS spectra of water-degermanated CIT-13/OH, CIT-13/F and IM-12 samples with different germanium contents. FIG. The parent germanosilicate sample and its acid-leached product are shown on the left and right sides of the spectrum, respectively. Schematic of a possible germanium arrangement within the d4r unit. Green balls and silver nodes indicate germanium and silicon sites, respectively (not all possibilities shown).

The present disclosure is directed to novel compositions of matter comprising crystalline microporous germanosilicates and methods of making and using these compositions.

Disclosed herein is a new method of synthesizing *CTH-type germanosilicate molecular sieves without the use of fluoride. Eliminating fluoride from the synthesis narrows the previously reported compositional range and slows the crystallization time for CIT-13 crystallization. However, CIT-13 prepared from hydroxide media (designated CIT-13/OH) cannot be achieved with CIT-13 synthesized in the presence of fluoride (designated CIT-13/F). exhibit interesting properties. Fluoride-free CIT-13/OH, upon exposure to ambient humidity after calcination, converts to CFI-type germanium much faster than conventional CIT-13/F from fluoride-containing gels with approximately the same Si/Ge ratio. Convert to nosilicate (Ge-CIT-5). Also, CIT-13/OH from the fluoride-free pathway can undergo a reverse sigma conversion to CIT-14, another scaffold with 12MR and 8MR ring channels, upon contact with a strong acid. CIT-14 from the inverse sigma transformation (referred to as CIT-14/ist) did not exhibit the mesoporosity present in the isostructural analogs obtained from the ADOR-type transformation. Since these transformations are based on the presence and placement of germanium sites within the d4r unit, the presence of fluoride anions in the synthesis mixture may affect the elemental (Ge and Si) composition and/or placement within the d4r unit of CIT-13. It can be concluded that it affects These results also support the presence of Ge—O—Ge bonds and germanium tetracycles within the d4r unit of CIT-13/OH synthesized from a hydroxide-based gel, similar to that observed with IM-12. indirectly confirms its existence. FIG. 2 summarizes the studies reported in this disclosure.

The present disclosure may be more readily understood by reference to the following description taken in conjunction with the accompanying figures and examples, all forming part of the present disclosure. The disclosure is not limited to the specific products, methods, conditions or parameters described or illustrated herein, and the terminology used herein is for the purpose of illustratively describing the particular embodiments and is not intended to limit the disclosure of any claim. Similarly, unless otherwise stated, any description of possible mechanisms or modes of action or reasons for improvement is intended to be exemplary only, and the disclosure herein does not cover any such implied mechanism or mode of action. It is not bound by the right or wrong of the reason for the form or improvement. It is recognized that throughout this text the description refers to compositions and methods of making and using said compositions. That is, where the disclosure describes or claims features or embodiments relating to compositions or methods of making or using the compositions, such descriptions or claims shall not include those features or embodiments in their context ( That is, it is intended to extend to embodiments in each of the composition, method of manufacture, and method of use). Where a treatment method is described, unless otherwise excluded, additional embodiments provide that the product composition is isolated and optionally post-treated in a manner consistent with molecular sieve or zeolite synthesis. .

The present disclosure encompasses compositions designated "CIT-13/OH," "-CIT-14," and "CIT-14/IST," and methods of converting the former to the latter.

(Crystalline microporous germanosilicate composition referred to as CIT-14/IST and "-CIT-14")
A particular embodiment includes a crystalline microporous germanosilicate composition designated CIT-14/IST with 8- and 12-membered ring channels. These include compositions derived or derivable from CIT-13/OH through the use of concentrated strong acids.

In certain embodiments, the CIT-14/IST germanosilicate composition comprises pure germanosilicate. In other independent embodiments, the CIT-14/IST germanosilicate composition has a framework comprising one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium. include. These additional oxides may come from the precursor CIT-13/OH used to prepare the CIT-14/IST germanosilicate composition. Methods of incorporating these oxides into precursor CIT-13/OH compositions are described elsewhere herein.

These crystalline microporous germanosilicate CIT-14/IST compositions had a 19.32±0.5, 20.73±0.5, 22.33±0.5, 24.37±0.5, 27.19±0.5 and 27.69±0.5 degrees 2- It can be characterized by an X-ray powder diffraction (XRD) pattern having at least five characteristic peaks in θ. In certain independent embodiments, the X-ray powder diffraction (XRD) pattern exhibits at least 5 characteristic peaks in 5, 6, 7, 8, 9 or 10 of these characteristic peaks described above. In certain independent embodiments, peak position uncertainty is independently (for each peak) ±0.5 degrees 2-theta, ±0.4 degrees 2-theta, ±0.3 degrees 2-theta , ±0.2 degrees 2-theta, ±0.15 degrees 2-theta, or ±0.15 degrees 2-theta.

Table 1 provides a list of powder XRD data from samples of the crystalline germanosilicate CIT-14/IST composition. These data are considered representative of these materials. Various permutations of these data can be used to characterize these compositions, for example, by including multiple peaks selected by their relative intensities. Additionally, these crystalline microporous germanosilicate CIT-14/IST compositions can be characterized by comparison with the powder XRD pattern shown in FIG.

For example, in certain other embodiments, the crystalline microporous germanosilicate CIT-14/IST composition has 7.59±0.5, 8.07±0.5, 19.12±0.5 optionally 12.88 ± 0.5, 19.32 ± Characterized by at least three characteristic peaks at 0.5, 24.37±0.5, 27.19±0.5 and 27.69±0.5 degrees 2-theta. The peaks at 7.59 and 8.07 degrees 2-theta, corresponding to Miller indices of (110 and (200) respectively, are the strongest peaks in the pattern. can help distinguish.

The observed intensity values in Table 1 are based on the complete random orientation of the crystallites, perfect long-range order in all crystallographic directions and the ideal linkage of the CIT-14/IST framework. it is conceivable that. However, the crystallite morphology of CIT-14/IST is very flat and exhibits a high aspect ratio, indicating that in fact the intensity may be convoluted by the preferential orientation of the sample. ing. Furthermore, the intensity of the first peak (110) (7.67) appears to increase as the crystallinity (quality) of the CIT-14 sample improves. This is because the diagonal long-range order of the connecting unit (single four-ring in CIT-14) contributes to (110) diffraction. The relatively chemically inert Si-rich layer is attributed to the (200) peak at 8.08°. (thus generally strong).

In certain embodiments, the crystalline microporous germanosilicate CIT-14/IST compositions prepared from CIT-13/OH described herein are 12:1 to 13:1, 13:1 to 14 : 1, 14:1-15:1, 15:1-16:1, 16:1-17:1, 17:1-18:1, 18:1-19:1, 19:1-20:1 or any combination of two or more of these aforementioned subranges, eg, having a Si:Ge ratio ranging from 14:1 to 18:1. Certain compositions described in the examples are also considered to be within these ranges.

The crystals of the crystalline microporous germanosilicate CIT-14/IST are orthorhombic. In some cases, as described in the examples, the crystals can be disordered, including crystals of the Cmmm or Cmcm space groups or intracrystalline mixtures of the two domains (disordered).

In this context, crystals of the crystalline microporous germanosilicate CIT-14/IST composition have been found to exhibit the following unit cell parameters.

The Å values in the far right column are those actually determined (or estimated) based on the Rietveld refinement (see Examples) and those shown in the middle column are for the specific composition It provides an estimated variance that may occur as a function of (eg, Si:Ge ratio or any metal oxide substitution).

The channels within these crystalline microporous germanosilicate CIT-14/IST compositions are also characterized as follows: 8-membered ring channels have pore sizes of about 3.3 Å x 3.9 Å; has a pore size of about 4.9 Å x 6.4 Å. The respective pore sizes have been experimentally determined to be 3.26 Å x 3.93 Å and 4.86 Å x 6.44 Å, respectively, but for example physical strain (such as compression) or the ratio of Si:Ge may reduce these values. can change, so a wider dispersion is needed. In addition, the average metal-oxygen (TO) bond length in the skeleton is 1.55 to 1.65 Å, the average oxygen-metal-oxygen (OT-O) is 98 ^o to 116 ^o , the average metal-oxygen- Metal (TOT) ranges from 139 ^° to 180 ^° where T is Si or Ge.

To date, crystalline microporous germanosilicate CIT-14/IST compositions have been characterized by their physical attributes. However, the present disclosure also contemplates embodiments in which these compositions are characterized by the method of making them from the reaction of germanosilicate CIT-13/OH and concentrated strong acid. Such embodiments include those in which structure is considered independently of the physical parameters mentioned (i.e., pure product-by-process descriptions) and those in which structure is considered simultaneously with one or more of the physical attributes. includes those that are

In these embodiments, the crystalline microporous germanosilicate CIT-14/IST composition comprises a crystalline microporous germanosilicate referred to as CIT-13/OH at elevated temperature and an as-formed microporous germanosilicate. It was prepared by contact with concentrated aqueous mineral acid for a time sufficient to form the nosilicate "-CIT-14". Compositions of both CIT-13/OH (described and used herein) and "-CIT-14" are described elsewhere herein. The following description also relates to methods of preparing germanosilicate CIT-14/IST compositions from germanosilicate CIT-13/OH compositions, and of germanosilicate CIT-14/IST compositions according to these methods. It will be appreciated that the method of preparation constitutes an independent embodiment. This composition of CIT-13/OH germanosilicate, as well as the composition designated "-CIT-14," as well as its use in the preparation of CIT-14/IST, are independent practice of the present disclosure. regarded as a form.

To prepare the CIT-14/IST composition from the germanosilicate CIT-13/OH composition, the method includes one or more of the following conditions.

(1) The CIT-13/OH composition is conveniently dispersed in a strong acid aqueous solution. The reaction mixture can then be static or mixed more efficiently in a moving reactor, such as a rotating reactor. As emphasized in the examples, it may be useful to physically disperse the reaction medium at intermediate points.

(2) Mineral acids are strong acids; ie, those that dissociate substantially completely in aqueous solution, as distinguished from weak acids that only partially ionize in aqueous solution. HCl or HNO ₃ are typical acids used in this volume, but other strong acids may be used. These strong acids are those with anions that can be incorporated into the framework lattice (eg, phosphoric acid), but are not considered where such incorporation is considered undesirable.

(3) The use of concentrated acid appears to be important. In a preferred embodiment, the mineral acid concentration ranges from 6-12M. Higher concentrations are preferred (eg, 10-12M) as these appear to improve reaction rates and yields.

(4) The elevated temperature is a temperature in the range of 80°C to 120°C, preferably about 95°C. Considering the volatility of water at this temperature, it is necessary to use a closed reactor.

(5) Time sufficient to effect conversion ranges from 4 hours to 96 hours, preferably from 6 hours to 24 hours. Clearly, there is a balance between the time, temperature and type and concentration of acid required for the reaction to proceed to an adequate yield of product. Conditions equivalent to 95° C. for 6 hours using 12M aqueous HCl have been found to be adequate.

(6) Isolating the resulting degermanated germanosilicate, designated "-CIT-14", following contacting the germanosilicate with an acid. This is conveniently done by centrifugation, but other separation methods can be used.

(7) The isolated "-CIT-14" material is then rinsed or washed repeatedly with water (preferably distilled or deionized water) until the wash is pH neutral. This "-CIT-14" material is also considered a separate embodiment of this disclosure, and representative features of this material are described in the Examples.

(8) Preparing CIT-14/IST from the as-produced "-CIT-14" material comprises heating the isolated and washed "-CIT-14" material to a temperature of about 450°C to 650°C. It can be carried out by heating at a temperature in the range for a time in the range from 2 hours to 12 hours, preferably at 580° C. for 6 hours, or substantially equivalent conditions. In a preferred embodiment, heating is performed at a temperature ramp rate of 1-5°C/min, preferably 1°C/min.

Conversion of CIT-13/OH to CIT-14/IST is accompanied by a decrease in micropore volume of approximately 25-30 vol%.

The foregoing method yields CIT-14/IST germanosilicates consistent with a mechanism characterized as the inverse sigma transformation of crystalline microporous CIT-13/OH germanosilicates, for reasons discussed in the discussion section of the Examples. offer. As such, the methods and products may be characterized using that term.

(Crystalline microporous germanosilicate composition called CIT-13/OH)
Compositions generally defined as CIT-13 and their reactivity under various processing conditions have been previously reported. See, for example, U.S. Pat. Nos. 10,293,330 and 10,828,625 and U.S. Patent Application Publication No. 2017-0252729, each of which is intended for all or at least germanosilicate CIT-13 shall be incorporated herein by reference with respect to information relating to

US Pat. No. 10,293,330 states that CIT-13 has a three-dimensional framework with pore channels defined by 10- and 14-membered rings and powder XRD patterns as shown in Table 2. is described as indicating

The CIT-13/OH germanosilicates described herein also have a 10-membered ring and a 1
It has a three-dimensional framework with pores defined by four-membered rings, but is fluoride-free. Consistent with other CIT-13 germanosilicates, they are 6.45±0.2, 7.18±0.2, 12.85±0.2, 20.78±0.2, 26. A powder XRD (X-ray diffraction) pattern with at least five peaks at 01±0.2, and 26.68±0.2 degrees 2-theta is shown. See Table 2. These CIT-13/OH germanosilicates have powder XRD patterns with peaks at 6.45±0.2 and 7.18±0.2 degrees 2-theta, and among other peaks shown in Table 2: May be characterized by 5, 6 or 7.

As discussed in the Examples, the powder XRD pattern of CIT-13/OH described herein shows some differences from the data presented in Table 2, particularly the (200) peak of the as-formed material. is shown with respect to the strength of This observation is further elaborated in the examples. In some embodiments, the peak at 6.45±0.2 degrees 2-theta is less intense (weaker) than the peak at 7.18±0.2 degrees 2-theta, the latter peak being strongest within the pattern (see examples). In another embodiment, the powder XRD pattern of CIT-13/OH germanosilicate exhibits an additional peak at 11.58 degrees ±0.2 degrees 2-theta of moderate to weak intensity attributed to the (310) index. show.

CIT-13/OH germanosilicate also exhibits ^{a 29} Si MAS-nmr spectrum consistent with the spectrum shown in FIG. 12 (top). This is explained further in the examples.

The Si:Ge ratios of these CIT-13/OH germanosilicates are 3.5-3.6, 3.6-3.7, 3.7-3.8, 3.8-3.9, 3 .9-4.0, 4.0-4.1, 4.1-4.2, 4.2-4.3, 4.3-4.4, 4.4-4.5, 4.5 ~4.6, 4.6 to 4.7, 4.7 to 4.8, 4.8 to 4.9, 4.9 to 5.0, 5.0 to 5.2, or Ranges defined by any two or more of the foregoing ranges, such as 3.5 to 5.2 or 3.5 to 3.9. These ranges are similar to those reported previously for the CIT-13 substance.

However, unlike those previously reported materials, the present fluoride-free CIT-13/OH germanosilicate has an average of at least 4 and preferably more than 4 Ge atoms per d4r unit. It contains a structural unit, allowing the presence of a Ge-4-ring in the d4r unit. This feature allows unexpected conversion of these substances to the corresponding CIT-5 and "-CIT-14"/CIT-14/IST substances. Again, these features are further illustrated in the Examples.

One such method for determining the average number of Ge atoms in the d4r unit is described in the Examples, adding fluoride ions to CIT-13/OH germanosilicate and the resulting dope Including measuring the ¹⁹ F MAS-nmr spectrum of the material.

（ｅ）任意選択で、少なくとも１つの組成的に一致した種結晶；及び
（ｆ）水
の混合物から得られる水性組成物を、ＣＩＴ－１３／ＯＨと称される結晶性マイクロポーラスゲルマノシリケート組成物を結晶化させるのに有効な条件下で水熱処理することを含む方法によって調製される；ここで、水性組成物は、
（ａ）２～４、好ましくは２．５～３．０の範囲のＳｉ：Ｇｅのモル比；
（ｂ）水：Ｓｉのモル比が８：１～１２：１の範囲にある水；
（ｃ）水：（ＳｉＯ₂＋ＧｅＯ₂）のモル比が６：１～７：１の範囲にある水；
（ｃ）ＯＨ：（ＳｉＯ₂＋ＧｅＯ₂）のモル比が約０．３：１～０．７：１の範囲にある水酸化物イオン（ＯＨ）
を含有する；ここで、水性組成物は、フッ化物イオンを本質的に含まない。 Critical to the final structure of the CIT-13/OH materials is their method of preparation in the complete absence of fluoride ions. As described herein, the crystalline microporous germanosilicate CIT-13/OH composition comprises
(a) a source of silicon oxide ( _SiO2 );
(b) a source of germanium oxide ( _GeO2 ); and (c) aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations thereof. or an optional source of a mixture;
(d) at least one hydroxide salt of a substituted benzylimidazolium organic structure-directing agent (OSDA) cation having the structure:

(e) optionally at least one compositionally matched seed crystal; hydrothermally treated under conditions effective to crystallize the composition; wherein the aqueous composition comprises
(a) Si:Ge molar ratio in the range 2 to 4, preferably 2.5 to 3.0;
(b) water having a water:Si molar ratio in the range of 8:1 to 12:1;
(c) water having a molar ratio of water:(SiO ₂ +GeO ₂ ) in the range of 6:1 to 7:1;
(c) hydroxide ions (OH) having an OH:(SiO ₂ +GeO ₂ ) molar ratio in the range of about 0.3:1 to 0.7:1;
wherein the aqueous composition is essentially free of fluoride ions.

These ranges are narrower than previously reported. These narrower ranges are important for producing Ge-rich d4r units.

Within this skeleton, the method includes one or more of the following features.

(1) The source of silicon oxide can be any source known to be suitable for molecular sieve synthesis, but in preferred embodiments silicic acid, silica hydrogel, silicic acid, fumed silica, Colloidal silica, tetraalkyl orthosilicate, silica hydroxide or combinations thereof (or equivalent sources), preferably sodium silicate or tetraalkyl orthosilicate, even more preferably tetraethyl orthosilicate (TEOS).

(2) The source of germanium oxide can be any source known to be suitable for molecular sieve synthesis, the source of germanium oxide being _GeO2 or its hydrated derivatives (or equivalent). source).

(3) Substituted benzylimidazolium organic structure directing agent (OSDA) cations range from about 0.3:1 to 0.7:1, preferably from about 0.4:1 to 0.6:1 OSDA: It exists in a molar ratio of (SiO ₂ +GeO ₂ ).

(4) The aqueous composition is essentially free of alkali metal cations, alkaline earth metal cations or dications or combinations thereof.

(5) The at least one substituted benzylimidazolium organic structure directing agent (OSDA) cation preferably has the structure

(6) The aqueous composition is a suspension or gel.

(7) Effective crystallization conditions include subjecting the mixture to a temperature of about 140° C. to about 180° C. for about 4 days to about 4 weeks.

(7) hydrothermally treating the aqueous composition in a rotary oven;

(8) A method further comprising isolating the crystalline microporous germanosilicate solid composition.

The CIT-14/IST described herein was previously reported in US Patent Application Publication No. 2017/0252729, which is hereby incorporated by reference for all purposes or at least for these disclosures. It is compositionally different from the CIT-14/ESP (ESP stands for ethoxysilylated pillar ring) structure. These previously reported preparations of CIT-14/ESP prepared phyllosilicates of CIT-13P topology in the presence of concentrated aqueous mineral acids (eg HCl or preferably HNO ₃ ) in a source of silica. , at one or more temperatures ranging from about 165° C. to about 225° C. for times ranging from 12 hours to 48 hours to form an intermediate composition, and then a crystalline microparticle of CIT-14/ESP topology. This was done by isolating and calcining the intermediate composition to form a porous silicate composition.

In particular, CIT-14/ESP germanosilicate is formed using CIT-13P phyllosilicate, which has a much higher Si:Ge ratio than described by the present method, but with a much higher Si:Ge ratio; CIT-14/ESP germanosilicates with Si:Ge ratios ranging from about 25 to substantially infinity are obtained, including Si:Ge ratios from about 25 to about 150, or from about 75 to about 150. An embodiment was included. The quality of crystals formed by the ADOR process was lower than reported here.

These CIT-14/ESP germanosilicates exhibited powder X-ray diffraction (XRD) patterns not significantly different from those reported for the CIT-14/IST germanosilicates, 7.7, 8.2, 13. At least five characteristic peaks were found at 1, 19.5, 21.1, 22.7 and 27.6 degrees 2-theta. Due to the structural disorder of matter,
The observed diffraction peaks were broad and the error assigned to these peaks was ±0.5 degrees 2-theta. In another embodiment, the error associated with these peaks was ±0.3 degrees 2-theta. Consistent with other structures prepared by pillaring and how they can be made, the structure of this new material is a three-dimensional scaffold with pores defined by 8- and 12-membered rings. described from the point of view. Based on the theoretical structure, the dimensions of the 8- and 12-membered rings were calculated to be 4.0×3.4 Å and 6.9×5.4 Å, respectively (see FIGS. 3(AB)). The PXRD patterns identified from the isolated products are not identical, but are consistent with the theoretical value associated with this structure (predicted by the General Utility Lattice Program, GULP (Gale, 1997)), namely silica. It has silica pillars separating the cfi-rich layers. It was believed that such pattern differences could be explained by structural disorder and/or imperfect silica pillar rings. In this case, the version of CIT-14/ESP can also be described in terms of the crystallographic parameters shown in FIGS. 3(A) and 3(B).

(Other changes in the microcrystalline composition)
In certain embodiments, the crystalline microporous solids described in this disclosure, including CIT-13/OH germanosilicate and the newly described microcrystalline CIT-14/IST germanosilicate, exist in their hydrogen form. do. In other embodiments, the crystalline microporous solid comprises at least one metal cation salt or transition metal or salt within its micropores. In other specific embodiments, the metal cation salts are K ⁺ , Li ⁺ , Rb ⁺ , Ca ²⁺ , Cs ⁺ : Co ²⁺ , Cu ²⁺ , Mg ²⁺ , Sr ²⁺ , Ba ²⁺ , Ni ²⁺ or Fe ²⁺ salts, copper salts such as Schweiser reagent (tetraamminediaqua copper dihydroxide, [Cu(NH ₃ ) ₄ (H ₂ O) ₂ ](OH) ₂ ]), Copper (II) nitrate or copper (II) carbonate may be included. Such metal cations can be incorporated, for example, using techniques known to be suitable for this purpose (eg, ion exchange).

In other embodiments, the micropores can contain transition metals or transition metal oxides. Addition of such substances can be accomplished by, for example, chemical vapor deposition or chemical precipitation. In certain independent embodiments, the transition metal or transition metal oxide comprises a Group 6, 7, 8, 9, 10, 11 or 12 element. In another independent embodiment, the transition metal or transition metal oxide is scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium. , platinum, copper, silver, gold or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au and mixtures thereof are preferred. In independent embodiments, the aqueous ammonium or metal salts or chemical vapor deposited or precipitated materials are independently Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga, In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu or R4 _-n N ⁺ _Hn cations (at least some of the pores in which R is alkyl and n=0 to 4).

Although the term "transition metal" is defined elsewhere herein, in certain other independent embodiments the transition metal or transition metal oxide is a 6, 7, 8, 9, 10 , 11 or 12 elements. In yet another independent embodiment, the transition metal or transition metal oxide is scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, Including palladium, platinum, copper, silver, gold or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au and mixtures thereof are preferred dopants.

In other embodiments, the optionally doped crystalline solid is 400° C.-500° C., 500° C.-600° C., 600° C.-700° C., 700° C.-800° C., 800° C.-900° C., 900° C.- Fired in air at a temperature defined to range from at least one of 1000°C, 1000°C to 1200°C, 500°C to about 1200°C. Selection of a particular temperature may in some cases be limited by the stability of a particular solid with respect to decomposition or conversion to another crystalline phase.

Other methods of modifying molecular sieves for use as catalysts are known to those skilled in the art, and such additional modifications are considered within the scope of this disclosure.

(Use of the compositions of the invention - catalytic conversion/separation)
In various embodiments, crystalline microporous germanosilicate solids as disclosed herein are calcined, doped or treated as described herein to mediate or Acts as a catalyzing catalyst. All such combinations of compositions and catalysis are considered individual embodiments of the present disclosure as if they were individually depicted separately. The use of these germanosilicates for these purposes is also within the scope of this disclosure. Such conversions/separations include carbonylation of DME (dimethyl ether) with CO at low temperatures, reduction of NOx with methane (e.g. for exhaust applications), cracking, hydrocracking, dehydrogenation, aromatics of paraffins. dewaxing of hydrocarbon feeds, MTO (methanol to olefins), isomerization of aromatics (e.g. xylenes), disproportionation of aromatics (e.g. toluene), alkylation of aromatics, alkenes amination of lower alcohols, separation and sorption of lower alkanes, hydrocracking of hydrocarbons, dewaxing of hydrocarbon feedstocks, isomerization of olefins, production of high molecular weight hydrocarbons from low molecular weight hydrocarbons, Hydrocarbon reforming, conversion of lower alcohols or other oxygenated hydrocarbons to produce olefin products, epoxidation of olefins with hydrogen peroxide, content of nitrogen oxides in gas streams in the presence of oxygen or separation of nitrogen from a nitrogen-containing gas mixture, wherein the respective feedstock is converted to any one of the substances described herein under conditions sufficient to affect the specified conversion. Separations carried out by contact with a catalyst comprising a crystalline microporous solid are included. Particularly attractive applications in which these germanosilicates are expected to be useful include catalytic cracking, hydrocracking, dewaxing, alkylation, and olefin and aromatic forming reactions. Additional uses include gas drying and separation.

Certain embodiments provide hydrocracking processes, each process contacting a hydrocarbon feedstock under hydrocracking conditions with a catalyst comprising a crystalline microporous solid of the present disclosure, preferably predominantly in hydrogen form. Including.

Yet other embodiments provide processes for dewaxing a hydrocarbon feedstock, each process comprising contacting the hydrocarbon feedstock under dewaxing conditions with a catalyst comprising the crystalline microporous solids of the present disclosure. include. Yet other embodiments provide processes for improving the viscosity index of dewaxed products of waxy hydrocarbon feedstocks, each process comprising converting a waxy hydrocarbon feedstock to the crystallinity of the present disclosure under isomerization dewaxing conditions. Including contacting with a catalyst comprising a microporous solid.

Additional embodiments include processes for producing C20+ lubricants from C20+ olefin feedstocks, each process comprising at least one transition metal catalyst and isomerization conditions over a catalyst comprising a crystalline microporous solid of the present disclosure. and isomerizing said olefin feedstock in.

The present disclosure also includes processes for isomerizing dewaxing a raffinate, each process comprising, in the presence of added hydrogen, converting said raffinate, such as bright stock, to at least one transition metal and the present disclosure. with a catalyst comprising a crystalline microporous solid of

Other embodiments provide for dewaxing a hydrocarbon oil feed boiling above about 350 ^° F. and containing straight chain hydrocarbons and slightly branched chain hydrocarbons at a hydrogen pressure of about 15-3000 psi. contacting said hydrocarbon oil feedstock with a catalyst comprising at least one transition metal and a crystalline microporous solid of the present disclosure, preferably predominantly in the hydrogen form, in the presence of hydrogen gas added in .

The disclosure also includes hydrocracking a hydrocarbon feedstock in a hydrocracking zone to obtain an effluent comprising a hydrocracked oil; catalytically dewaxing said effluent comprising hydrocracked oil in the presence of added hydrogen gas at a temperature of at least about 400 ^° F. and a pressure of from about 15 psig to about 3000 psig using a catalyst comprising Also included are processes for oil preparation.

The present disclosure also includes processes for octane enrichment of a hydrocarbon feedstock to produce products with increased aromatic content, each process comprising a boiling point range of greater than about 40°C and about 200°C. C. C. under aromatic conversion conditions with a catalyst comprising the crystalline microporous solids of the present disclosure. In these embodiments, the crystalline microporous solid is preferably rendered substantially acid free by neutralizing the solid with a basic metal. Also provided in this disclosure are processes in which the crystalline microporous solid comprises a transition metal component.

Catalytic cracking processes are also provided by the present disclosure, each process contacting a hydrocarbon feedstock with a catalyst comprising the crystalline microporous solids of the present disclosure in a reaction zone under catalytic cracking conditions in the absence of added hydrogen. Including. The present disclosure also includes catalytic cracking processes in which the catalyst further comprises a large crystalline cracking component.

The present disclosure further provides isomerization processes for isomerizing C4-C7 hydrocarbons, each process comprising, under isomerization conditions, a feedstock having linear and slightly branched C4-C hydrocarbons, preferably contacting a catalyst comprising a crystalline microporous solid of the present disclosure primarily in hydrogen form. A crystalline microporous solid may be impregnated with at least one transition metal, preferably platinum. The catalyst can be calcined at elevated temperature in a steam/air mixture after impregnation with the transition metal.

Also provided by the present disclosure are processes for alkylating aromatic hydrocarbons, each process comprising, under alkylation conditions, at least a molar excess of aromatic hydrocarbons and C2-C20 olefins, at least partial liquid phase conditions, under, preferably in the presence of a catalyst comprising a crystalline microporous solid of the present disclosure primarily in hydrogen form. The olefin can be a C2-C4 olefin, and the aromatic hydrocarbon and olefin can be present in a molar ratio of about 4:1 to about 20:1, respectively. Aromatic hydrocarbons may be selected from the group consisting of benzene, toluene, ethylbenzene, xylenes or mixtures thereof.

Further provided in accordance with the present disclosure are processes for transalkylating aromatic hydrocarbons, each of the processes comprising, under transalkylating conditions, converting aromatic hydrocarbons and polyalkylaromatic hydrocarbons into at least a partial contacting in the presence of a catalyst comprising the crystalline microporous solids of the present disclosure, preferably predominantly in the hydrogen form, under liquid phase conditions. The aromatic hydrocarbon and polyalkylaromatic hydrocarbon may be present in molar ratios of about 1:1 to about 25:1, respectively. The aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene or mixtures thereof and the polyalkylaromatic hydrocarbon may be dialkylbenzene.

Further, the present disclosure provides processes for converting paraffins to aromatics, each of which comprises contacting paraffins with a catalyst comprising the crystalline microporous solids of the present disclosure under conditions that convert the paraffins to aromatics. and the catalyst comprises gallium, zinc, or a compound of gallium or zinc.

Also provided in accordance with the present disclosure are processes for isomerizing an olefin, each process comprising contacting the olefin with a catalyst comprising the crystalline microporous solids of the present disclosure under conditions that cause isomerization of the olefin. include.

Further provided in accordance with the present disclosure are processes for isomerizing an isomerization feedstock, each process comprising an aromatic C8 stream of xylene isomers or a mixture of xylene isomers and ethylbenzene, wherein ortho, meta and A more equilibrium ratio of para-xylene is obtained, the process comprising contacting the feedstock with a catalyst comprising the crystalline microporous solids of the present disclosure at isomerization conditions.

The present disclosure further provides processes for oligomerizing olefins, each process comprising contacting an olefin feedstock with a catalyst comprising the crystalline microporous solids of the present disclosure under oligomerization conditions.

The present disclosure also provides processes for converting lower alcohols and other oxygenated hydrocarbons, each process comprising the conversion of said lower alcohol (e.g., methanol, ethanol or propanol) or other oxygenated hydrocarbons under conditions that produce a liquid product. comprising contacting an oxygenated hydrocarbon with a catalyst comprising a crystalline microporous solid of the present disclosure.

Also provided by the present disclosure are processes for reducing nitrogen oxides contained in a gas stream in the presence of oxygen, each process comprising contacting the gas stream with the crystalline microporous solid of the present disclosure. The crystalline microporous solid may contain metals or metal ions (such as cobalt, copper or mixtures thereof) capable of catalyzing the reduction of nitrogen oxides, carried out in the presence of a stoichiometric excess of oxygen. obtain. In a preferred embodiment, the gas stream is the exhaust stream of an internal combustion engine.

Catalysts comprising any of the germanosilicates described herein, including those having a CIT-13 backbone, and Fischer-Tropsch catalysts are also used to produce syngas comprising hydrogen and carbon monoxide, also called syngas. A process for converting to a liquid hydrocarbon fuel is also provided. Such catalysts are described in US Pat. No. 9,278,344, which is incorporated by reference for its teachings of catalysts and methods of using catalysts. The Fischer-Tropsch component comprises a group 8-10 transition metal component (ie Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), preferably cobalt, iron and/or ruthenium. The optimum amount of catalytically active metal present depends, inter alia, on the particular catalytically active metal. Typically, the amount of cobalt present in the catalyst may range from 1 to 100 parts by weight per 100 parts by weight of support material, preferably from 10 to 50 parts by weight per 100 parts by weight of support material. In one embodiment, 15-45 wt% cobalt is deposited on the hybrid support as the Fischer-Tropsch component. In another embodiment, 20-45 wt% cobalt is deposited on the hybrid support. The catalytically active Fischer-Tropsch component may be present in the catalyst along with one or more metal promoters or cocatalysts. Promoters may be present as metals or metal oxides, depending on the particular promoter involved. Suitable promoters include metal or transition metal oxides, including lanthanides and/or actinides or oxides of lanthanides and/or actinides. Alternatively, or in addition to metal oxide promoters, the catalyst may comprise metal promoters selected from Group 7 (Mn, Tc, Re) and/or Groups 8-10. In some embodiments, the Fischer-Tropsch component further comprises a cobalt reduction accelerator selected from the group consisting of platinum, ruthenium, rhenium, silver, and combinations thereof. The method employed to deposit the Fischer-Tropsch component on the hybrid support requires the use of soluble cobalt Including impregnation techniques using aqueous or non-aqueous solutions containing salts and optionally solubility-promoting metal salts such as platinum salts.

Still further process embodiments include those for reducing the halogen compound concentration in the initial hydrocarbon product containing undesirable levels of organohalogen compounds, wherein the process reduces at least a portion of the hydrocarbon product to , under organohalogen compound absorption conditions, with a composition comprising any of the germanosilicate structures described herein, including CIT-13, to reduce the halogen concentration in the hydrocarbon. Initial hydrocarbon products may be produced by hydrocarbon conversion processes using ionic liquid catalysts comprising halogen-containing acidic ionic liquids. In some embodiments, the organic halide content in the initial hydrocarbon product ranges from 50 to 4000 ppm, and in other embodiments the halogen concentration is reduced to provide a product of less than 40 ppm. . In other embodiments, production may be reduced by 85%, 90%, 95%, 97% or more. The initial hydrocarbon stream may comprise alkylate or gasoline alkylate. Preferably, the hydrocarbon alkylate or alkylate gasoline product is not cracked during contacting. Any of the materials or process conditions described in US Pat. No. 8,105,481 are believed to illustrate the range of materials and process conditions of the present disclosure. US Pat. No. 8,105,481 is incorporated by reference for at least its teachings regarding methods and materials used to effect such transformations (both alkylation and halogen reduction).

Still further process embodiments include a process for octane enrichment of a hydrocarbon feedstock to produce a product with increased aromatic content, which under aromatic conversion conditions
It comprises contacting a hydrocarbon feed comprising linear hydrocarbons and slightly branched hydrocarbons having a boiling range greater than about 40°C and less than about 200°C with a catalyst.

The specific conditions for many of these transformations are known to those skilled in the art. Exemplary conditions for such reactions/transformations are described in WO/1999/008961, U.S. Pat. , 827,843, each of which is hereby incorporated by reference in its entirety for at least these purposes.

Depending on the type of reaction catalyzed, the microporous solid may be predominantly in the hydrogen form, partially acidic, or have substantially no acid. Those skilled in the art will be able to define these conditions without undue effort. As used herein, "predominantly in the hydrogen form" means that after calcination (which can also include exchanging the pre-calcined material with NH ₄ ⁺ before calcination), at least 80% of the cationic sites are hydrogen ions and/or or occupied by rare earth ions.

The germanosilicates of the present disclosure can also be used as adsorbents for gas separation. For example, these germanosilicates can also be used as hydrocarbon traps, such as cold start hydrocarbon traps in combustion engine pollution control systems. In particular, such germanosilicates are believed to be particularly useful for capturing _C3 fragments. Such embodiments may include processes and apparatus for capturing low molecular weight hydrocarbons from an incoming gas stream, wherein the process produces an effluent having a reduced concentration of low molecular weight hydrocarbons compared to the incoming gas stream. comprising passing a gas stream across or through a composition comprising any one of the crystalline microporous germane silicate compositions described herein to provide the gas stream. In this context, the term "low molecular weight hydrocarbons" refers to C1-C6 hydrocarbons or hydrocarbon fragments.

The germanosilicates of the present disclosure may also be used in processes for treating cold start engine exhaust gas streams containing hydrocarbons and other pollutants, which process reduces the engine exhaust gas stream to flowing over one of the germanosilicate compositions of the present disclosure that preferentially adsorb hydrocarbons to provide a first exhaust stream; flowing the first exhaust gas stream over a catalyst; comprising or consisting of converting contained residual hydrocarbons and other pollutants into harmless products to provide a treated exhaust stream; and discharging the treated exhaust stream to the atmosphere.

The germanosilicates of the present disclosure can also be used to separate gases. For example, they can be used to separate water, carbon dioxide and sulfur dioxide from fluid streams such as low grade natural gas streams, and carbon dioxide from natural gas. Typically, molecular sieves are used as components of membranes used to separate gases. Examples of such membranes are disclosed in US Pat. No. 6,508,801.

For each of the aforementioned processes described above, additional corresponding embodiments include those that include devices or systems that include or contain the materials described for each process. For example, in gas trap gases, additional embodiments include devices known in the art as hydrocarbon traps that can be placed in the exhaust gas flow path of a vehicle. In such devices, hydrocarbons are adsorbed in a trap and stored until the engine and exhaust reach temperatures sufficient for desorption. The device can also include a membrane comprising a germanosilicate composition useful in the processes described.

(the term)
In this disclosure, the singular forms “a,” “an,” and “the” include plural references and references to a particular numerical value refer to at least that particular numerical value unless the context clearly indicates otherwise. including. Thus, for example, reference to "a substance" is a reference to at least one such substance and/or equivalents thereof, etc., known to those skilled in the art.

It will be understood that when values are expressed as approximations through the use of the descriptor "about," the particular value forms another embodiment. In general, use of the term "about" indicates an approximation that may vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the particular context in which it is used, based on its function. It is a thing. Those skilled in the art will be able to interpret this as routine. In some cases, the number of significant digits used for a particular value can be one non-limiting way of determining the scope of the word "about." In other cases, gradations used in series of values can be used to determine the intended range available for the term "about" for each value. Where present, all ranges are inclusive and combinable. That is, reference to values stated in ranges include every value within that range.

It is understood that specific features of the disclosure that are, for clarity, described in this specification in the context of separate embodiments can also be provided in combination in a single embodiment. That is, each individual embodiment is considered combinable with any other embodiment, and such combination is considered an alternative embodiment, unless clearly incompatible or expressly excluded. . Conversely, various features of this disclosure that, for brevity, are described in the context of a single embodiment can also be provided separately or in any subcombination. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step is also an independent embodiment in its own right, and other It can also be considered that it can be combined with

The transition terms "comprising," "consisting essentially of, and "consisting of" are intended to imply their generally accepted meaning in patent terminology. That is, (i) "comprising," synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and includes additional, unrecited elements or method steps; does not exclude (ii) “consisting of” excludes any element, step or ingredient not specified in the claim; (iii) "consisting essentially of" limits the scope of the claim to the specified materials or processes and "not materially affecting the basic and novel characteristics" of the claimed disclosure; Embodiments described with respect to the phrase "comprising" (or its equivalents) also provide embodiments independently described with respect to "consisting of" and "consisting essentially of". For the embodiments provided for "consisting essentially of", the basic and novel property is the facile manipulation of the method or composition/system to provide germanosilicate compositions in meaningful yields. performance, or the ability of the system to use only the listed ingredients.

The term "meaningful product yield" is intended to reflect product yields as described herein, including those greater than 20%, but where specified , the term may also refer to yields of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% or more relative to the amount of original substrate.

When a list is presented, unless otherwise stated, each individual element of that list, and all combinations of that list, are understood to be separate embodiments. For example, a list of embodiments presented as "A, B or C" may be designated as separate embodiments "A", "B", "C", "A or B", "A or C", " B or C" or "A, B or C" embodiments are intended to be included.

Throughout this specification, words are to be given their ordinary meanings as understood by those of ordinary skill in the art. However, for the avoidance of doubt, the meaning of certain terms is specifically defined or clarified.

The term “alkyl” as used herein, although not necessarily containing from 1 to about 6 carbon atoms, typically refers to straight, branched or cyclic saturated hydrocarbon groups such as methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.

The term "aromatic" refers to cyclic moieties that satisfy the Hückel 4n+2 rule for aromaticity, and includes both aryl (ie, carbocyclic) and heteroaryl structures.

The term "halide" is used in its conventional sense to refer to chloride, bromide, fluoride or iodide.

"Lower alcohol" or lower alkane means an alcohol or alkane having 1 to 10 carbon atoms, linear or branched, preferably 1 to 6 carbon atoms, preferably linear, respectively. Methanol, ethanol, propanol, butanol, pentanol and hexanol are examples of lower alcohols. Methane, ethane, propane, butane, pentane and hexane are examples of lower alkanes.

As used herein, unless otherwise specified, the term "elevated temperature" typically refers to at least one temperature within the range of about 170°C to about 230°C. The term "firing" is reserved for higher temperatures. Unless otherwise specified, it refers to one or more temperatures ranging from about 450°C to about 800°C.

As used herein, the term "metal or metalloid" refers to the 4th, 5th, 8th , 13, 14 and 15 elements. These elements are usually included as oxides in molecular sieves and include, for example, aluminum, boron, gallium, hafnium, iron, silicon, tin, titanium, vanadium, zinc, zirconium, or combinations thereof.

Typical sources of silicon oxide for the reaction mixture include alkoxides, hydroxides or oxides of silicon or combinations thereof. Exemplary compounds also include silicates (including sodium silicate), silica hydrogels, silicic acid, fumed silica, colloidal silica, tetraalkyl orthosilicates, silica hydroxide, or combinations thereof. Sodium silicates or tetraalkyl orthosilicates such as tetraethyl orthosilicate (TEOS), diethoxydimethylsilane (DEDMS) and/or 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane (DETMDS) are A preferred source.

Sources of germanium oxide include alkali metal orthogermanates, M ₄ GeO ₄ containing isolated GeO ₄ ^4- ions, GeO(OH) ₃ ^- , GeO ₂ (OH) ₂ ^2- , [(Ge(OH) ₄ ) ₈ (OH) ₃ ] ^3- , or a neutral solution of germanium dioxide containing Ge(OH) ₄ or its alkoxide or carboxylate derivatives.

Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, aluminum alkoxides, aluminum oxide coated on silica sol, hydrated alumina gels such as Al(OH) ₃ and sodium aluminate. is included. The source of aluminum oxide can also include alkoxides, hydroxides or oxides of aluminum or combinations thereof. Additionally, the source of alumina may also contain other ligands as well, such as acetylacetonate, carboxylates and oxalic acid; such compounds are well known to be useful in hydrothermal or sol-gel synthesis. It is Additional sources of aluminum oxide may include aluminum salts such as _AlCl3 , Al(OH) ₃ , Al( _NO3 ) ₃ and _Al2 ( _SO4 ) ₃ .

Sources of boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide and/or zirconium oxide can be added in forms corresponding to their aluminum and silicon counterparts. be.

_As used herein, the term "mineral acid" refers to mineral acids conventionally used in molecular sieve zeolite synthesis, such as HCl, HBr, HF, _HNO3 or _H2SO4 . Also, oxalic acid and other strong organic acids can be used in place of mineral acids. Generally, HCl and _HNO3 are the preferred mineral acids. As used throughout this specification, the terms "concentrated" and "diluted" with respect to mineral acids mean concentrations greater than 0.5M and concentrations less than 0.5M, respectively. In some embodiments, the term "enriched" is between 0.5-0.6, 0.6-0.7, 0.7-0.8, 0.8-0.9, 0.9-1 .0, 1.0-1.1, 1.1-1.2, 1.2-1.3, 1.3-1.4, 1.4-1.5, 1.5-1.6 , 1.6-1.7, 1.7-1.8, 1.8-1.9, 1.9-2.0 or more. In the experiments and preferred embodiments described herein, concentrated acids refer to those in the composition range of 0.9-1.1M. Similarly, the term “dilution” includes 0.5-0.4, 0.4-0.3, 0.3-0.2, 0.2-0.15, 0.15-0.1 and 0 means one or more concentrations in the range of .1 to 0.05. In the experiments and preferred embodiments described herein, dilute acids refer to those in the composition range of 0.5-0.15M.

The term "CIT-13" topology describes a crystalline microporous composition similar to that described in US Pat. No. 10,293,330 with a set of orthogonally oriented 14-membered pores. The term "phyllosilicate" refers to a two-dimensional layered structure of silica-containing oxides, as described in US Patent Application Publication No. 2017/0252729.

The terms "oxygenated hydrocarbons" or "oxygenated additives" as known in the hydrocarbon processing art are those present in the hydrocarbon stream or from other sources of the biomass stream (e.g., from fermented sugars). (ethanol) containing alcohols, aldehydes, carboxylic acids, ethers and/or ketones.

The term "separate" or "separated" means to physically separate or separate a solid product material from other starting materials or co-products or by-products (impurities) associated with the reaction conditions that produce the material. To the extent it is meant to separate, it has its ordinary meaning as will be understood by those skilled in the art. Accordingly, it is assumed that the person skilled in the art will at least be aware of the presence of the product and take specific actions to separate or isolate it from the starting materials and/or co- or by-products. Absolute purity is not required, but is preferred. When these terms are used in the context of gas processing, the term "separate" or "separated" can be by adsorption based on size or physical or chemical properties, or It refers to gas distribution by permeation.

Unless otherwise specified, the term "isolated" means physically separated from other components so as to be at least free of solvents or other impurities such as starting materials, co-products or by-products. means. In some embodiments, isolated crystalline materials are considered isolated if, for example, they are separated from the reaction mixture that gave rise to their preparation, from mixed phase co-products, or both. can be done. In some of these embodiments, the pure germanosilicate (including structures with or without incorporated OSDA) is
It can be prepared directly from the method described. In some cases, the crystalline phases may not be separated from each other, in which case the term "isolated" may refer to their separation from their source composition.

According to the IUPAC notation, the term "microporous" means a material with a pore size of less than 2 nm. Similarly, the term "macroporous" refers to materials with pore sizes greater than 50 nm. The term "mesoporous" also refers to materials whose pore sizes are intermediate between microporous and macroporous. In the context of the present disclosure, material properties and applications are determined by scaffold properties such as pore size and diameter, cage dimensions and material composition. As such, there is often only one scaffold and composition that provides optimum performance in a desired application.

"Optional" or "optionally" means that the subsequently described situation may or may not occur, and thus the description includes instances where the situation does and does not occur. means. For example, the phrase "optionally substituted" means that non-hydrogen substituents may or may not be present on a given atom; It is meant to include structures with no substituents.

The terms "method" and "process" are considered interchangeable within this disclosure.

As used herein, the term "crystalline microporous solid" or "crystalline microporous germanosilicate" refers to a crystalline structure having a highly regular pore structure of molecular dimensions, i.e., less than 2 nm. is. The maximum size of species that can enter the pores of a crystalline microporous solid is controlled by the channel dimensions. These terms may also refer specifically to CIT-13 compositions.

As used herein, the term “pillaring” generally refers to the process of introducing stable metal oxide structures (“so-called “pillars”) between substantially parallel crystalline silicate layers. The metal oxide structure maintains separation of the silicate layers and is created by spacings between the layers of molecular dimensions. The term is generally used in the context of clay chemistry and is well understood by those skilled in the art of clays and zeolites, especially when applied to catalysis.

The term "germanosilicate" means any composition containing silicon and germanium oxides in its framework. The term "pure" and "pure germanosilicate" means that these compositions contain, as far as practicable, only germania and silica, respectively, with other metal oxides in the framework free of unavoidable unintentional impurities. means to exist as The germanosilicate may be "pure germanosilicate" or optionally substituted with other metal oxides or metalloid oxides. Similarly, the terms aluminosilicate, borosilicate, ferrosilicate, stannosilicate, titanosilicate or zincosilicate structures are intended to include oxides of silicon oxide and aluminum, boron, iron, tin, titanium and zinc, respectively. When described as "optionally substituted," each framework is aluminium, boron, gallium, germanium, hafnium, substituted with one or more atoms or oxides not already in the parent framework. It may contain iron, tin, titanium, indium, vanadium, zinc, zirconium or other atoms or oxides.

As used herein, the term "transition metal" refers to any element in the d-block of the periodic table, including groups 3-12 of the periodic table. In practice, the f-block lanthanide and actinide series are also considered transition metals and are termed "internal transition metals". This definition of transition metal also includes the elements of Groups 3-12. In certain other independent embodiments, the transition metal or transition metal oxide comprises a Group 6, 7, 8, 9, 10, 11 or 12 element. In yet another independent embodiment, the transition metal or transition metal oxide is scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, Contains palladium, platinum, copper, silver, gold or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au and mixtures thereof are preferred dopants.

The following list of embodiments is intended to supplement rather than replace or supersede the previous discussion.

(Embodiment 1)
A crystalline microporous germanosilicate composition designated CIT-14/IST with 8- and 12-ring channels.

(Embodiment 2)
Powder X-ray diffraction (XRD) patterns of 7.59±0.5, 8.07±0.5, 12.88±0.5, 19.12±0.5, 19.32±0.5, At least five characteristic peaks at 20.73±0.5, 22.33±0.5, 24.37±0.5, 27.19±0.5 and 27.69±0.5 degrees 2-theta The crystalline microporous germansylate CIT-14/IST composition of embodiment 1, comprising: In certain aspects of this embodiment, the CIT-14/IST germanosilicate composition comprises pure germanosilicate. In another independent aspect of this embodiment, the CIT-14/IST germanosilicate composition contains one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium. Including a skeleton containing. In certain independent aspects of this embodiment, the powder X-ray diffraction (XRD) pattern exhibits at least 5 characteristic peaks at 5, 6, 7, 8, 9 or 10 of these characteristic peaks described above . In certain independent aspects of this embodiment, peak position uncertainties are independently (for each peak) ±0.5 degrees 2-theta, ±0.4 degrees 2-theta, ±0.3 degrees 2-θ, ±0.2 degrees 2-θ, ±0.15 degrees 2-θ, or ±0.15 degrees 2-θ.

(Embodiment 3)
Powder X-ray diffraction (XRD) patterns of 7.59±0.5, 8.07±0.5, 19.12±0.5, 20.73±0.5 and 22.33±0.5 degrees 2-theta and optionally 12.88±0.5, 19.32±0.5, 24.37±0.5, 27.19±0.5 and 27.69±0.5 degrees 2 The crystalline microporous germanosilicate CIT-14/IST composition according to embodiment 1 or 2, characterized in that it exhibits at least three characteristic peaks at -θ. The data in Table 1 and the comments above relating to that table are considered independent aspects of this embodiment.

(Embodiment 4)
12:1-13:1, 13:1-14:1, 14:1-15:1, 15:1-16:1, 16:1-17:1, 17:1-18:1, 18: Embodiments 1-1 having a Si:Ge ratio ranging from 1 to 19:1, 19:1 to 20:1, or any combination of two or more of these aforementioned subranges, such as from 14:1 to 18:1. 4. The crystalline microporous germanosilicate CIT-14/IST composition according to any one of 3. Each of these ranges is considered an independent aspect within the present embodiments.

(Embodiment 5)
The crystalline microporous germanosilicate according to any one of embodiments 1-4, wherein the crystals are orthorhombic and have a Cmmm space group or a Cmcm space group or an intracrystalline mixing (disorder) of the two domains. CIT-14/IST composition.

(Embodiment 6)
The crystalline microporous germanosilicate CIT-14/IST composition of any one of embodiments 1-5, having unit cell parameters according to:

(Embodiment 7)
7. Any one of embodiments 1-6, wherein the 8-membered ring channel has a pore size of about 3.3 Å×3.9 Å and the 12-membered ring channel has a pore size of about 4.9 Å×6.4 Å. A crystalline microporous germanosilicate CIT-14/IST composition. In certain aspects of this embodiment, the respective pore sizes are 3.26 Å×3.93 Å and 4.86 Å×6.44 Å. Physical strain (eg, compression) or the Si:Ge ratio can change these values. In certain aspects of this embodiment, the average metal-oxygen (TO) bond length in the framework is in the range of 1.55-1.65 Å, and the average oxygen-metal-oxygen (OT- O) ranges from 98 ^° to 116 ^° and the average metal-oxygen-metal (TOT) in the framework ranges from 139 ^° to 180 ^° . ]

(Embodiment 8)
8. The crystal of any one of embodiments 1-7, which is derived or derivable from a reaction characterized as an inverse sigma transformation of a crystalline microporous germanosilicate designated CIT-13/OH. 14/IST composition. Specific properties of CIT-13/OH are described in more detail elsewhere herein, and these descriptions are incorporated herein as if physically incorporated. .

(Embodiment 9)
A crystalline microporous germanosilicate designated CIT-13/OH (described elsewhere herein) was added to a concentrated aqueous mineral acid (e.g., as a dispersion of germanosilicate in aqueous acid). and at elevated temperatures to form an as-formed microporous germanosilicate "-CIT-14" (also described elsewhere herein and incorporated herein by reference). The crystalline microporous germano-silicon CIT-14/IST composition of any one of embodiments 1-8 prepared by contacting for a time sufficient to

In certain aspects of this embodiment, (a) the mineral acid is aqueous HCl or HNO ₃ or an equivalent strong acid; (b) the concentration of the mineral acid ranges from 6-12M; , a temperature in the range of 80°C to 120°C, preferably a temperature of about 95°C; (d) a sufficient time in the range of 4 to 96 hours, preferably 4 to 24 hours; 6 hours at 95°C (e) contact with acid followed by isolation of the resulting degermanated germanosilicate, a material designated "-CIT-14": (f) The "-CIT-14" material is rinsed with water (preferably distilled or deionized water) until the pH of the wash solution is neutral; further comprising heating the material to a temperature in the range of about 450° C. to 650° C. for a time in the range of 2 to 12 hours, preferably at 580° C. for 6 hours, more preferably at a temperature ramp rate of 1° C./min. include.

(Embodiment 10)
5. A crystalline microporous germanosilicate designated CIT-13/OH, which is fluoride-free and has a three-dimensional framework with pores defined by 10- and 14-membered rings; At 45±0.2, 7.18±0.2, 12.85±0.2, 20.78±0.2, 26.01±0.2 and 26.68±0.2 degrees 2-θ A crystalline microporous germanosilicate that exhibits an X-ray powder diffraction (XRD) pattern with at least five peaks. In some aspects of this embodiment, the peak at 6.45±0.2 degrees 2-theta is less intense (weaker) than the peak at 7.18±0.2 degrees 2-theta, the latter becomes the strongest in the pattern (see Examples). In another aspect of this embodiment, the powder XRD pattern exhibits an additional peak at 11.58°±0.2° 2-θ. The data in Table 2 and the comments associated therewith are considered independent aspects of this embodiment.

This composition of CIT-13/OH germanosilicate, as well as its use in the preparation of CIT-14/IST, are considered independent embodiments of the present disclosure.

（ｅ）任意選択で、少なくとも１つの組成的に一致した種結晶；及び
（ｆ）水
の混合物から得られる水性組成物を、ＣＩＴ－１３／ＯＨと称される結晶性マイクロポーラスゲルマノシリケート組成物を結晶化させるのに有効な条件下で水熱処理することを含む方法によって調製され、ここで、水性組成物が、
（ａ）２～４、好ましくは２．５～３．０の範囲のＳｉ：Ｇｅのモル比；
（ｂ）水：Ｓｉのモル比が８：１～１２：１の範囲にある水；
（ｃ）水：（ＳｉＯ₂＋ＧｅＯ₂）のモル比が６：１～７：１の範囲にある水；
（ｃ）ＯＨ：（ＳｉＯ₂＋ＧｅＯ₂）のモル比が約０．３：１～０．７：１の範囲にある水酸化物イオン（ＯＨ）
を含有し；ここで、水性組成物は、フッ化物イオンを本質的に含まない、実施形態８又は９の結晶性マイクロポーラスゲルマノシリケートＣＩＴ－１４／ＩＳＴ組成物又は実施形態１０の結晶性マイクロポーラスゲルマノシリケートＣＩＴ－１３／ＯＨ。 (Embodiment 11)
The crystalline microporous germanosilicate CIT-14/IST composition of embodiment 8 or 9 or the crystalline microporous germanosilicate CIT-13/OH of embodiment 10, referred to as CIT-13/OH Crystalline microporous germanosilicate
(a) a source of silicon oxide ( _SiO2 );
(b) a source of germanium oxide ( _GeO2 ); and (c) aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations thereof. or an optional source of a mixture;
(d) at least one hydroxide salt of a substituted benzylimidazolium organic structure-directing agent (OSDA) cation having the structure:

(e) optionally at least one compositionally matched seed crystal; hydrothermally treated under conditions effective to crystallize a substance, wherein the aqueous composition comprises
(a) Si:Ge molar ratio in the range 2 to 4, preferably 2.5 to 3.0;
(b) water having a water:Si molar ratio in the range of 8:1 to 12:1;
(c) water having a molar ratio of water:(SiO ₂ +GeO ₂ ) in the range of 6:1 to 7:1;
(c) hydroxide ions (OH) having an OH:(SiO ₂ +GeO ₂ ) molar ratio in the range of about 0.3:1 to 0.7:1;
wherein the aqueous composition comprises the crystalline microporous germanosilicate CIT-14/IST composition of embodiment 8 or 9 or the crystalline microporous germanosilicate CIT-14/IST composition of embodiment 10, essentially free of fluoride ions. Porous germanosilicate CIT-13/OH.

In an independent aspect of this embodiment,

(1) The source of silicon oxide is silicic acid, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetraalkyl orthosilicate, silica hydroxide or combinations thereof (or equivalent sources), preferably silicic acid Sodium or tetraalkyl orthosilicate, more preferably tetraethyl orthosilicate (TEOS).

(2) Sources of germanium oxide include GeO ₂ or its hydrated derivatives (or equivalent sources).

(3) Substituted benzylimidazolium organic structure directing agent (OSDA) cations range from about 0.3:1 to 0.7:1, preferably from about 0.4:1 to 0.6:1 OSDA: It exists in a molar ratio of (SiO ₂ +GeO ₂ ).

(4) The aqueous composition is essentially free of alkali metal cations, alkaline earth metal cations or dications or combinations thereof.

(5) at least one substituted benzylimidazolium organic structure directing agent (OSDA) cation has the structure:

(6) The aqueous composition is a suspension or gel.

(7) Effective crystallization conditions include subjecting the mixture to a temperature of about 140° C. to about 180° C. for about 4 days to about 4 weeks.

(7) hydrothermally treating the aqueous composition in a rotary oven;

(8) A method further comprising isolating the crystalline microporous germanosilicate solid composition.

(Embodiment 12)
A crystalline microporous germanosilicate designated CIT-13/OH is fluoride-free and has d4r units with an average of at least 4 and preferably more than 4 Ge atoms per d4r unit, The crystalline microporous germanosilicate CIT-14/IST composition of embodiment 8, 9 or 11 or the crystalline microporous germanosilicate CIT- of embodiment 10 or 11 that allows the presence of Ge4 rings in the 13/OH. A method for determining the average number of Ge atoms in a d4r unit has been described elsewhere and is incorporated into this embodiment. In some independent aspects of this embodiment, the Si:Ge ratio is 3.5-3.6, 3.6-3.7, 3.7-3.8, 3.8-3.9, 3.9-4.0, 4.0-4.1, 4.1-4.2, 4.2-4.3, 4.3-4.4, 4.4-4.5, 4. 5 to 4.6, 4.6 to 4.7, 4.7 to 4.8, 4.8 to 4.9, 4.9 to 5.0, 5.0 to 5.2, or ranges defined by any two or more of the foregoing ranges, eg, 3.5 to 3.9. Each of these ranges is considered an independent aspect within the present embodiments.

(Embodiment 13)
The crystallinity of embodiment 8, 9, 11, or 12 containing micropores optionally containing alkali metal cation salts, alkaline earth metal salts, transition metals, transition metal oxides, transition metal salts, or combinations thereof. The microporous germanosilicate CIT-14/IST composition, or the crystalline microporous germanosilicate CIT-13/OH of any one of embodiments 10-12. The properties of salts, metals and metal oxides are discussed elsewhere in this specification and incorporated into this embodiment. In a particular aspect of this embodiment, each germanosilicate is in its hydrogen form. In another aspect of this embodiment, each germanosilicate contains one or more of salts, metals or metal oxides within its micropores.

(Embodiment 14)
The crystalline microporous germanosilicate CIT-14/IST composition according to any one of embodiments 1-9 or 11-13 or the crystalline microporous according to any one of embodiments 10-13 A catalyst comprising the germanosilicate CIT-13/OH.

(Embodiment 15)
A process for influencing organic transformations or separating substances, comprising:
(a) carbonylation of DME with CO at low temperature;
(b) reducing NOx with methane;
(c) cracking, hydrocracking or dehydrogenating hydrocarbons;
(d) dewaxing the hydrocarbon feedstock;
(e) converting the paraffins to aromatics;
(f) isomerizing or heterogenizing the aromatic feedstock;
(g) alkylating the aromatic hydrocarbon;
(h) oligomerizing the alkene;
(i) aminating a lower alcohol;
(j) separating and sorbing lower alkanes from a hydrocarbon feedstock;
(k) isomerizing the olefin;
(l) producing high molecular weight hydrocarbons from low molecular weight hydrocarbons;
(m) reforming the hydrocarbon;
(n) converting lower alcohols or other oxygenated hydrocarbons to produce olefin products (including MTO);
(o) epoxidizing the olefin with hydrogen peroxide;
(p) reducing the content of nitrogen oxides in the gas stream in the presence of oxygen;
(q) separating nitrogen from a nitrogen-containing gas mixture; or (r) converting synthesis gas containing hydrogen and carbon monoxide into a hydrocarbon stream; or (s) organic 15. A process comprising reducing the concentration of halide, conducted by contacting each feed with the catalyst of embodiment 14 under conditions sufficient to affect the specified conversion.

(Embodiment 16)
The crystalline microporous germanosilicate CIT-14/IST composition of any one of embodiments 1-9 or 11-13 (or of the composition referred to elsewhere herein as CIT-14/IST) any one) of the crystalline microporous designated CIT-13/OH according to at least any one of embodiments 10-12 (or described elsewhere herein). The germanosilicate is combined with a concentrated aqueous mineral acid (e.g., as a dispersion of germanosilicate in aqueous acid) at elevated temperature with the as-formed microporous germanosilicate "-CIT-14" (also herein described elsewhere, which descriptions are also incorporated herein).

In certain aspects of this embodiment, (a) the mineral acid is aqueous HCl or HNO ₃ or an equivalent strong acid; (b) the concentration of the mineral acid ranges from 6-12M; , a temperature in the range of 80°C to 120°C, preferably a temperature of about 95°C; (d) a sufficient time in the range of 4 to 96 hours, preferably 4 to 24 hours; 6 hours at 95°C (e) contact with acid followed by isolation of the resulting degermanated germanosilicate, a material designated "-CIT-14": (f) The "-CIT-14" material is rinsed with water (preferably distilled or deionized water) until the pH of the wash solution is neutral.

(Embodiment 17)
calcining the as-produced washed "-CIT-14" composition for a time and temperature sufficient to form a crystalline microporous germanosilicate CIT-14/IST composition. Form 16 method. In certain independent embodiments, these conditions comprise subjecting the isolated and washed "-CIT-14" material to a temperature ranging from about 450°C to 650°C for a period of time ranging from 2 hours to 12 hours. Further comprising heating, preferably at 580° C. for 6 hours, more preferably at a temperature ramp rate of 1° C./min.

The present disclosure also includes embodiments of CIT-13/OH germanosilicates prepared by the hydroxide route specifically described herein. The present disclosure is also characterized by having d4r units containing at least and preferably more than 4 Ge atoms on average per d4r, allowing for the presence of a Ge-4-ring in the d4r unit. /OH germanosilicate embodiments. The present disclosure also includes embodiments of CIT-13/OH germanosilicates that exhibit previously unobserved reactivity characteristics that are the result of the new and unique physical characteristics defined herein.

The following examples provide experimental methods used to characterize these novel substances and their transformations, and illustrate some of the concepts described within this disclosure. Although in each example both those provided in the examples and elsewhere in the text of this specification are considered to provide specific individual embodiments of compositions, methods of preparation and uses. None of the examples should be considered limiting of the more general embodiments described herein.

Unless otherwise specified, powder XRD patterns, nmr-spectra or other representations of structures shown herein for particular compositions are believed to be representative of those attributed to the general structure with which they are associated. be done.

In the following examples, efforts have been made to ensure accuracy with respect to numbers used (eg amounts, temperature, etc.) but some experimental errors and deviations should be accounted for. Unless indicated otherwise, temperatures are in degrees Celsius and pressures are at or near atmospheric.

(Example 1. Experiment)
(Example 1.1. Material preparation)
1,2-dimethyl-3-(2-methylbenzyl)imidazolium hydroxide (denoted as "orthomethylbenzyl") or 1,2-dimethyl-3-(3-methylbenzyl)imidazolium hydroxide ("metamethyl Benzyl”) was used as an OSDA to crystallize CIT-13 from a fluoride-free gel (labeled CIT-13/OH), which gives CIT-13 in fluoride media. was the same as A synthesis protocol for the two OSDAs is provided elsewhere. The gel composition ratio is x/(x+1) _SiO2 :1/(x+1)GeO2:0.5ROH: _yH2O , where x is the Si/Ge ratio of the gel and y is _{the H2O} /(Si+Ge ) ratio. Preferred values for x and y are given below. Detailed procedures and gel compositions are as follows. A CIT-13/OH sample is denoted as CIT-13/OH[z], where z is the Si/Ge ratio of the CIT-13 crystal measured using energy dispersive spectroscopy (EDS).

CIT-13 from a conventional fluoride-containing gel (denoted CIT-13/F) was also prepared for comparative analysis with CIT-13/OH and was based on previously reported methods. As with the CIT-13/OH samples, the CIT-13/F samples are denoted as CIT-13/F[z], where z represents the crystalline Si/Ge ratio measured using EDS.

IM-12 samples were also prepared according to protocols previously reported in the literature for comparison with CIT-13. Similar to CIT-13, the IM-12 sample was also denoted as IM-12[z] (z=EDS Si/Ge ratio).

(Example 1.2. Detailed Synthesis of CIT-13/OH)
In the final stages of gel preparation, the dry weight of the liner and stir bar should be characterized because the desired water level should be adjusted based on the total weight (liner + stir bar + gel).

Germanium dioxide (99.999%, Strem) was completely dissolved in the OSDA solution in a Parr steel autoclave 23 mL PTFE liner. 1,2-dimethyl-3-(2-methylbenzyl)imidazolium hydroxide and 1,2-dimethyl-3-(3-methylbenzyl)imidazolium hydroxide were used as OSDA for CIT-13/OH. The methods used to prepare these OSDAs are known. The desired amount of TEOS was added to the solution and the mixture was stirred overnight until the TEOS phase was completely hydrolyzed. Excess water and ethanol were allowed to evaporate under a stream of air at room temperature until the gel became thick and viscous. Ethanol, a hydrolysis product of TEOS, appears to adversely affect both crystallization rate and product purity. To maximize the extent of ethanol removal, purified water (approximately 10 mL) was added to the viscous gel and evaporated again with stirring until the gel became viscous. This water addition-evaporation process was repeated a total of 5 times. (Note: this ethanol removal step is not necessary if fumed silica was used as the Si source). Finally, the desired moisture content was adjusted based on the above total weight (liner + stir bar + gel). The final gel composition is x/(x+1) _SiO2 :1/(x+1)GeO2:0.5ROH: _yH2O , where x is the Si/Ge ratio of the gel and y is _{the H2O} /( Si+Ge) ratio. The values of x and y are as shown in Table 4. Optimal ranges for x and y are described in the text. CIT-13 seed crystals (5 wt% relative to the total weight of SiO ₂ +GeO ₂ ) were added as needed. The gel was sealed in a steel autoclave and placed in an oven preheated to the desired temperature.

After 1 week of crystallization, the gel was taken out. Usually after the first week of crystallization the gel turned dark brown and solidified. Using a clean, hard PTFE rod, the solidified gel was thoroughly ground into a powder. The crushed gel was placed back into the oven to resume crystallization. Aliquots were taken weekly to monitor the extent of crystallization. The final product was washed repeatedly using distilled water and acetone and dried in a 100°C convection oven.

The gel composition, crystallization conditions and corresponding results are summarized in Table 4.

Example 1.2. Germanosilicate Conversion and CIT-14/IS of CIT-13/OH
post-synthetic modification to T)
Conversion of CTH to CFI was accomplished by exposing freshly calcined CIT-13/OH samples to an atmosphere containing moisture. Here, only one condition (30% relative humidity (pH ₂ O=7.1 Torr) at 25° C.) was used to ensure consistency with results from previous studies. The degree of conversion was monitored based on PXRD. CIT-14/ESP (ESP stands for ethoxysilylated pillar ring) and CIT-14/IST (IST stands for inverse sigma transformation) are weakly acidic ADOR-type transformations of CIT-13/F and CIT-13/ Each was prepared based on the inverse sigma transformation of OH. Inverse sigma conversion of CIT-13/OH was performed by treating freshly calcined CIT-13/OH with 12 M HCl at 95° C. for 48 hours. The resulting solid (“-CIT-14”) was recovered using a centrifuge and washed repeatedly with distilled water until the pH became neutral. The final material, CIT-14/IST (IST stands for Inverse Sigma Transformation), was obtained by heating to 580° C. for 6 hours at a temperature ramp rate of 1° C. min ⁻¹ . For comparison, an inverse sigma transformation from UTL to OKO was also performed using the prepared IM-12 sample. SEM images of the CIT-14/IST samples are shown in Figure 4 (AB).

¹⁹ F magic angle spinning (MAS) and ¹ H- ²⁹ Si cross-polarization (CP) MAS NMR studies were performed on the degermanization and fluorination of germanosilicates. Cold water degermanization of calcined germanosilicates was performed as follows: 100 mg of freshly calcined germanosilicate was soaked in 100 mL of distilled water at room temperature and stirred overnight. The resulting solid was collected using a centrifuge and washed repeatedly with distilled water. Degermanated samples were vacuum dried at room temperature. Post-synthetic fluorination of germanosilicates crystallized in fluoride-free media was carried out as follows: 100 mg of as-prepared CIT-13/OH was mixed with 20-25 mg of ammonium fluoride. It was ground and heated at 150° C. for 24 hours. Excess ammonium fluoride was removed by washing with cold distilled water and the recovered solid was dried at 100°C.

(Example 1.3. Characteristic evaluation)
Powder X-ray diffraction (PXRD) profiles were collected using a Rigaku Miniflex II diffractometer (CuKα radiation λ=1.5418 A). High-resolution PXRD data were collected at the 2-1 powder diffraction beamline of the Stanford Synchrotron Radiation Light Source (SSRL) using a wavelength of 0.9998A. For high-resolution PXRD experiments, calcined CIT-14 powder samples were packed and sealed in 1.0 mm glass capillaries.

Scanning electron microscopy (SEM) images and elemental analysis data were obtained with Oxford X-max
Collected on a ZEISS 1550VP field emission (FE)-SEM microscope equipped with an SDD EDS system. Ar-sorption isotherms were acquired at 87.45 K using a Quantachrome Autosorb iQ analyzer. Solid Magic Angle Rotation (MAS)
Nuclear magnetic resonance (NMR) spectra were acquired on a Bruker Avance 500 MHz spectrometer (field = 11.2 T). Molecular sieve samples were loaded into a 4 mm diameter zirconia rotor with a Kel-FR cap. ¹ H- ¹³ C cross-polarization (CP) MAS spectra, ²⁹ Si MAS spectra and ¹ H- ²⁹ Si CPMAS spectra were collected at a MAS spinning speed of 8 kHz and ¹⁹ F MAS spectra were collected at 12 kHz.

(Example 2. Results and discussion)
(Example 2.1 Consideration of Synthesis)
CIT-13 can be crystallized in hydroxide media by omitting fluoride and altering other gel compositions from those of the fluoride route of CIT-13. Unlike CIT-13/F, which can crystallize over a moderately high range of gel compositions, CIT-13/OH is obtained over a much narrower gel composition range. The range of gel Si/Ge ratio and gel _H2O /(Si+Ge) ratio is 2<Si/Ge<4 and 6< _H2O /(Si+Ge)<7 when OSDA/(Si+Ge)=0.5. , preferably 2.5<Si/Ge<3.0 and 6.0<H ₂ O/(Si+Ge)<6.5, respectively. Gel compositions outside this compositional range resulted in amorphous germanosilicates or unknown high-density phases. Crystallization of pure CIT-13 phase was observed at 160°C and 175°C. Details of the synthesis (eg, gel composition, etc.) are shown in Table 4. CIT-13/OH had a plate-like crystal morphology, as shown in Figure 5 (A-C), similar to CIT-13 obtained from fluorine-containing preparations and their isostructural germanosilicates. . The ¹ H- ¹³ C CPMAS spectrum of as-formed CIT-13/OH [4.33] and the solution-phase ¹³ C NMR of OSDA (FIG. 6) revealed the structure of OSDA during the crystallization of CIT-13/OH. confirmed to be retained. In addition, the same as-formed material ¹ H- ²⁹ Si
The CPMAS spectrum also confirmed the presence of connectivity defects that compensated for the absence of fluoride. (Fig. 7)

The PXRD profiles of as-prepared calcined CIT-13/OH[3.88] and CIT-13/OH[4.33] are displayed in FIGS. 8(BE). Another PXRD pattern is provided in FIG. All PXRD profiles were obtained under ambient conditions. The positions of the diffraction peaks agreed well with those of the reference CIT-13/F shown in FIG. 8(F). However, there was a difference in peak intensity between CIT-13/F and CIT-13/OH. With the exception of the only CIT-13/OH[3.88] crystallized using ortho-methylbenzyl OSDA (FIGS. 8(A) and 9(B)), other prepared compounds synthesized from meta-methylbenzyl OSDA As-is CIT-13/OH showed a very weak (200) peak at 2θ=6.44°, as shown in FIGS. 8(D) and 9(A). 9(CK) shows a very weak (200) peak at 2θ=6.44°. These weak (200) peaks from as-formed CIT-13/OH became stronger after OSDA was removed by calcination. (FIG. 8(E)) In addition, some of the CIT-13/OH samples are clearly identifiable at 2θ=11.58°, as shown in FIGS. 9(DG) and 9(IJ). (310) peak. It can be seen that these (310) diffractions are attenuated by post-synthesis insertion of fluoride using ammonium fluoride. Fluorination of CIT-13/OH also increased the intensity of the (200) peak. (FIG. 10) Therefore, the absence of fluoride in the CIT-13 backbone and the presence of the metamethylbenzyl OSDA cation appear to be responsible for the weak intensity of the (200) peak and the occasional appearance of the (310) peak. It seemed to me.

The argon physisorption isotherm of CIT-13/OH[3.56] obtained at 87.45 K is superimposed with that of CIT-13/F[4.18] for comparison in FIG. 8(G). shown in The micropore volume of CIT-13/OH[3.56] was 0.141 cc/g based on the t-plot method (0.202 cc/g from the Saito-Foley method). This microporosity was slightly lower than the reference CIT-13/F [4.18] (de Boer t-plot: 0.172 cc/g; Saito-Foley: 0.223 cc/g). The characteristic two-step adsorption due to the presence of 10 MR and 14 MR of CIT-13 (marked ↓ in FIG. 8(G)) was also observed with CIT-13/OH as expected.

(Example 2.2. Consideration of conversion from CTH to CFI)
CIT-13-type germanosilicate, unlike other d4r-type germanosilicates such as UTL, IWW and ITH, slowly converted to CFI-type germanosilicate when exposed to environmental humidity (* CTH to CFI change). This transformation occurred through the rearrangement of Ge-rich d4r units into dzc units due to instability of the CIT-13 framework caused by the presence of germanium-rich d4r units and the crystallographic nature of the cfi layer. Interestingly, CIT-13/OH converted to the corresponding germanosilicate CIT-5 much faster than CIT-13/F of comparable germanium content. CIT-13/OH [4.33] completed conversion to CFI within 12 days,
CIT-13/F [4.31] was completely converted to CFI-type germanosilicate over 85 days. PXRD profile of calcined CIT-13/OH[4.33] after exposure of CIT-13/OH[4.33] to environmental humidity (pH2O=7.1 torr at 25° C., 30% relative humidity) for a period of time. are shown in FIGS. 11(A) and 11(B). The (400) peak of CIT-13 was initially overlapped with the (002) diffraction at 2θ=13.07°, but after 2 days it shifted to 2θ=13.69° and appeared separate. After 8 days, the three characteristic diffractions of the CFI scaffold ((301), (002) and (400)) began to appear. The PXRD profile after 10 days of environmental exposure was in good agreement with that of the reference pure silica CIT-5. The time-dependent position of the cfi-cfi interlayer distance estimated from the (200) diffraction position is shown in FIG. It shows faster conversion of CIT-13/OH compared to CIT-13/F.

For CIT-13/F, decreasing the Si/Ge ratio from 4.31 to 3.87 reduced the time required to achieve full conversion from about 4 months to 12 days. This acceleration of the conversion rate can be attributed to an increase in germanium sites within the d4r unit, the structural building unit that converts to the dzc unit of the CFI backbone. As with CIT-13/F, decreasing the Si/Ge ratio of CIT-13/OH further accelerated the conversion of *CTH to CFI. CIT-13/OH[3.88] converted to the corresponding CIT-5-type germanosilicate within 2 days, as shown in FIGS. 11(C) and 11(D). This was at least 6 times faster than a similar conversion with CIT-13/F [3.87]. ²⁹ Si NMR spectra of the calcined CIT-13/OH[3.88] and the resulting Ge-CIT-5 were obtained to investigate the Si site environment within these germanosilicates (FIG. 12). Similar to CIT-13/F, CIT-13/OH showed three groups of signals at -104.2, -109.4 and -113.9 ppm. This spectral shape was consistent with previously reported CIT-13 (see Figure 3 above) and related substances synthesized in fluoride media. Unlike Ge-CIT-5 from CIT-13/F, which showed a single broad signal cluster at −110.61 ppm, Ge-CIT-5 from CIT-13/OH[3.88] is about It showed two separate groups of peaks at -109.0 and -112.2 ppm. The disappearance of the shoulder at −104.2 ppm in the spectrum of CIT-13 can be attributed to the rearrangement of the d4r unit to the dzc bridging unit also seen in the conversion of CIT-13/F. Therefore, both signals can be attributed to the cfi layer Si site since they have the same origin as the −113 ppm and −115 ppm signals of pure silica CIT-5.

Based on the fact that the higher the germanium content of the parent CIT-13, the faster the conversion of *CTH to CFI, the CIT-13/OH crystals were similar to those of CIT-13 with similar overall Si/Ge ratios. It can be inferred to have more germanium in its d4r unit compared to the /F crystal. It was also confirmed that the cfi layer has a non-zero germanium occupancy in CIT-13/F. Formation of d4r units is known to be promoted by the presence of fluoride anions, which can stabilize low backbone TOT angles, and/or high germanium content. Formation of the d4r-type CIT-13 framework in the absence of fluoride can result in increased incorporation of germanium into the d4r unit. Indeed, a CIT-13/OH sample with a low Si/Ge ratio underwent inverse sigma transformation in concentrated acid to produce '-CIT-14', an analogue of IM-12-derived COK-14. The ability to undergo this type of transformation strongly suggests not only the high content of clustered germanium sites within the d4r unit, but also the presence of pure Ge-4 rings.

(Example 2.3. Consideration of topotactic conversion from CIT-13 to "-CIT-14" and CIT-14/IST)
Despite the structural similarities between CIT-13 and IM-12, leaching of Ge-4-rings from *CTH-type germanosilicates by strong acids has not yet been reported. Unlike IM-12, it has been suggested that the Si--O--Si interlayer cross-linking of *CTH-type germanosilicates is the major obstacle to such transformation. ADOR conversion of SAZ-1 to IPC-16 and Pawley purification of the latter has emerged. Most recently, it was reported that the T-site within the d4r unit of CIT-13/F was partially removed based on mild base treatment, resulting in ECNU-23. However, the presence of a pure Ge-4-ring within the d4r unit is essential for true inverse sigma conversion by strong acids, and IM-12 is the only d4r-type with such structural and elemental prerequisites. It was germanosilicate.

Ge-rich CIT-13 crystallized in a hydroxide medium undergoes a structural transformation that can be explained by an inverse sigma transformation in which the Ge-4-ring simultaneously detaches from the d4r, as shown schematically in Fig. 13(A). It is possible to receive Two examples (CIT-13/OH[3.71] and CIT-13/OH[3.56]) were demonstrated herein based on the PXRD profile shown in FIG. 13(B). Following the nomenclature used by Verheyen (Nat. Mater. 2012, 11, 1059), the material that has just been acid treated before calcination is denoted as "-CIT-14". Although no Rietveld refinement was performed for "CIT-14", similar to the condensation of -COK-14 to COK-14, after firing of "-CIT-14" A slight decrease in unit cell parameters was observed. Presence or absence of fluoride and germanium content were the two most important synthetic factors for the preparation of CIT-13 germanosilicate, which can produce CIT-14 by inverse sigma transformation. Treatment of calcined CIT-13/F [3.87] with 12M HCl did not yield "-CIT-14" despite the high germanium content. A similar treatment of CIT-13/OH[4.33] also gave a disordered layered material. (Fig. 14 (AB))

For comparison, isostructural material was obtained based on the conventional ADOR transformation of CIT-13, herein denoted as CIT-14/ESP. This conversion was similar to that of SAZ-1 to IPC-16. CIT-14/IST prepared by treating calcined CIT-13/OH[3.56] with 12 M HCl and CIT-14/ESP from the ADOR conversion of CIT-13/F[4.33] PXRD profiles of are shown in FIGS. 15(A) and 15(B) together with those of the reference CIT-14 model based on the GULP geometry optimization algorithm. Apparently, the intensity of the (200) interlayer diffraction of CIT-14/IST was stronger than that of CIT-14/ESP. This difference in diffraction intensity can be attributed to the elemental composition of the single four-ring (s4r) bridging unit of CIT-14. The effect of germanium occupancy in each of the seven T-sites of CIT-14 on the (110) and (200) diffraction intensities was calculated and the results are shown in FIG. It was found that when germanium occupied two T-sites (T3 and T7), the relative intensity of the (110) diffraction of PXRD increased significantly. T7 is the s4r site and T3 is the site directly adjacent to the d4r site. In fact, in the CIT-14/IST Rietveld refinement, the germanium content of T7 is 21%, accounting for 52% of the total germanium count in the entire framework. (Table 5, see above). No significant germanium occupancy was detected for T3. Considering that the inverse sigma transformation displaced the pure Ge-4 ring from the d4r unit of the parent germanosilicate, the d4r unit of CIT-13/OH has an average of more than 4 germanium atoms. It can be concluded that there are However, no significant difference was found in the ¹ H-decoupled ²⁹ Si MAS spectra of CIT-14/IST and CIT-14/ESP (Fig. 15(D)). Both CIT-14 show a broad envelope of signals centered around -112 ppm. This spectral similarity is presumed to be due to the presence of residual germanium sites within the CIT-14 framework. Also, only a very small amount of Q3-type silanol was detected.

As previously mentioned, CIT-14/IST had a higher germanium content than CIT-14/ESP. The EDS Si/Ge ratios of the two CIT-14/IST samples obtained from CIT-13/OH[3.56] and CIT-13/OH[3.71] are 14.5 and 17.5, respectively. It turns out there is. These values correspond to the CIT-14/ESP samples (Si/Ge=50-253, depending on the extent of degermanization, depending on the degree of degermanization, with degermanization exfoliation using mild acid (0.1 M HCl) in the preparation procedure, Fig. 17). The Si/Ge ratios of the COK-14 samples, now prepared using the same procedure for two IM-12 samples (Si/Ge = 3.80 and 4.79), are 17.5 and 29.2, Verheyen et al. (Si/Ge = 110) reported by B. et al., probably due to the lower Si/Ge ratio of the parent IM-12.18 (see Figures 18 and 19). These values are also much lower than IPC-2 (reported as Si/Ge = 97), prepared as an ADOR product from IM-12 that underwent weak acid exfoliation similarly to CIT-14/ESP. there were. These results confirm that the inverse sigma conversion by strong acid leaves extra germanium sites (other than removal of the Ge-4-ring) in the d4r unit unleached out.

Microporosity of CIT-14 was investigated using an argon adsorption isotherm acquired at 87.45K. (FIG. 20) CIT-14/IST showed no adsorption-desorption hysteresis, while CIT-14/ESP showed a desorption curve that clearly deviated from its adsorption curve. A similar hysteresis was observed from IPC-2 formed by the ADOR-type pillaring method. This minor mesology is commonly observed after post-synthetic treatment in nitric acid medium. In addition, the specific micropore volume of CIT-14/IST (0.105 cc/g from t-plot, 0.141 cc/g from Saito-Foley) is the specific micropore volume of CIT-14/ESP (from t-plot 0.065 cc/g, 102 cc/g from Saito-Foley). A similar trend is observed in the conversion from UTL to OKO. Also, as clearly seen in FIG. 20(B), CIT-14/IST is p/p ₀ =about 1×10 ⁻⁴ lower than CIT-13 (p/p ₀ to 3×10 ⁻⁴ ). By the way, I started to absorb argon. This adsorption onset pressure is very similar to 8MR ring zeolite A (LTA) (p/p ₀ ~1×10 ^-4 ). Argon adsorption of CIT-14 was therefore initiated by adsorption into its 8MR pores.

The reduction in micropore volume with inverse sigma transformation from CIT-13 to '-CIT-14' was investigated theoretically and experimentally. For theoretical evaluation, the pore volume reduction was estimated using the TOTOPOL utility for topological analysis developed by Treacy and Foster. Crystallographic information (cif) files obtained from the Rietveld refinement of CIT-13 and CIT-14/IST (this study, see below) were used as computational skeleton models. The results are summarized in Table 6. The experimentally observed decrease in micropore volume (Saito-Foley: 30.2%; t-plot: 25.5%) is comparable to the value estimated using TOTOPOL (30.2%), Although lower, TOTOPOL appeared to underestimate the micropore volume of CIT-13 and CIT-14 compared to the experimentally obtained values.

CIT-14/IST was disordered from its parent CIT-13 because the position of the bridging site, ie, the layer site directly connected to the d4r or s4r unit of CIT-13 or CIT-14, respectively, did not change during the inverse sigma transformation. It should have inherited the pattern directly. Indeed, the (111) and (201) diffraction peaks estimated to be located at 2θ=11.43° and 11.78°, respectively, in the disordered model based on the GULP algorithm are observed in the actual PXRD pattern of CIT-14/IST. it wasn't. (FIG. 15(C)) These diffractions were also not observed for CIT-14/ESP, consistent with the previously reported ADOR conversion of SAZ-1 to IPC-16. However, in the ADOR transformation, the Ge-rich d4r was completely removed by exfoliation in weak acid and the bridging s4r was formed by newly introduced silicon sources such as diethoxydimethylsilane. Therefore, the disorder pattern of CIT-14/IST may not be identical to that of CIT-14/ESP and IPC-16.

The XPD pattern was generated using the software CMPR. The orthorhombic unit cell (a=21.90 A, b=13.74 A, c=10.11 A) could be indexed using the program TREOR35 implemented in 36. The initial CIT-14 backbone model was derived from the CIT-13 backbone structure (assuming all silica) 20 by inverse sigma transformation and no disorder from CIT-13 was introduced. In addition, the program DLS-7637 was used to optimize the shape, assuming the same space group Cmmm as the parent CIT-13 (*CTH). Using this as a starting point, a Rietveld refinement was performed using the program TOPAS. The final structure of CIT-14/IST was obtained based on Rietveld refinement of the powder pattern with agreement values R _F =0.057, R _wp =0.078 and R _exp =0.053 (FIG. 21). (A)).

Since all symmetry elements are preserved, the inverse sigma transform satisfies the IUPAC definition of a topotactic transform. The idealized structure and pore system of CIT-14/IST are shown in Figures 21(B) and 21(C), respectively. CIT-14/IST has a two-dimensional channel system bounded by pores of 12 MR and 8 MR, with critical dimensions of 6.4×4.9 A and 3.9×3.3 A, respectively. Similar to ferrierite (FER), there is a small cage in CIT-14/IST connected to two adjacent straight main channels through small pore openings, whereas other two-dimensional 12/8 MR topologies EON and M
OR does not have such a cage structure. Due to the presence of disorder (illustrated in FIG. 21(D)), the 8-MR subchannels are not linear. The unit cell parameter c can also be defined as c′=c/2=5.0569 A for the average structure, but using smaller unit cells did not improve the refinement (i.e., atomic coordinates and profile The change in goodness of fit is minimal, but the number of parameters undergoing refinement increases). Detailed crystallographic information for CIT-14/IST is provided in Tables 5 and 7 and FIG.

(Example 2.4. Consideration of Ge arrangement in d4r unit)
The inverse sigma transformability of d4r-type germanosilicates can indirectly provide evidence for the existence of layer-parallel pure Ge-4 rings (d4r units). As mentioned in the previous section, Ge-rich CIT-13/OH (Si/Ge ratio < 3.7) undergoes inverse sigma transformation similar to IM-12, resulting in CIT with high crystallinity and well-defined pore system. -14/IST. Also, based on PXRD and structure refinement, the remaining s4r unit of CIT-14 was found to have a germanium moiety. Therefore, the elemental composition of the d4r unit of CIT-13/OH is [Si _n Ge _8-n ]−d4r (n<4) for low Si/Ge ratios, with four Ge completely flanking the d4r. It is inferred that Although CIT-13/F could be converted to CIT-14/ESP using the ADOR strategy, we were unable to achieve inverse sigma conversion with it. Furthermore, as noted above, CIT-13/OH showed a much higher conversion of *CTH to CFI than CIT-13/F samples with similar germanium content. These results suggest that the presence or absence of fluoride, which can also direct and stabilize the d4r unit, plays a major role in organizing the elemental composition and distribution within the d4r unit of the ultra-large pore germanosilicate CIT-13. is shown.

¹⁹ F NMR spectroscopy can be used as a tool to reveal the elemental composition of small ring building units such as the d4r unit. Germanosilicates that do not incorporate fluoride anions from direct synthesis can be modified post-synthesis by inserting fluoride into the as-formed or degermanized backbone. Fluoride-introduced d4r- _type germanosilicates generally show three signals at about −8 ppm (broad), −19 ppm (sharp) and −38 ppm (sharp), respectively [Si ₄ Ge ]-d4r , [Si ₇ Ge]-d4r and [Si ₈ ]-d4r. There is general agreement on the latter two attributions. However, the nature of the former −8 ppm peak, which is usually broad and sometimes accompanied by one or two shoulder signals, remains questionable due to the many possible germanium configurations.

The ¹⁹ F NMR spectra of the as-produced CIT-13/F and fluorinated CIT-13/OH samples are shown in Figures 23 (AC). All CIT-13 samples show a broad peak centered around −8 ppm and no signals at −19 ppm and −38 ppm, indicating that the d4r units of these CIT-13 samples are rich in germanium. . Also, post-synthetic fluorination of CIT-13/OH revealed a sharp signal with multiple rotating sidebands at −123.7 ppm, presumed to originate from surface ¹⁹ F-Si species due to surface etching. be. This surface etch did not result in structural degradation, as also supported by the PXRD profile (Fig. 10). The −8 ppm signal of the CIT-13 sample is broader than that of IM-12, indicating that the placement of germanium within the d4r unit of CIT-13 is similar to that of fluorinated IM-12, regardless of the type of mineralizer used. It shows that it appears to be less uniform than the placement. The −8 ppm signal of the CIT-13 sample was deconvolved into two peaks, line 1 (−7.3 to −8.3 ppm) and line 2 (−11.0 to −11.7 ppm). As shown in FIGS. 23(A) and (B), CIT-13/OH[4.33] (16%) is superior to CIT-13/F[4.33] despite similar germanium contents. 33] (1%) gave a stronger line 2 signal. This result indicates that the absence of fluoride in the CIT-13 synthesis did indeed affect the placement of the germanium sites within the d4r unit. CIT-13/OH[4.33] converts to the corresponding Ge-CIT-5 faster than CIT-13/F with a similar Si/Ge ratio, and this *CTH to CFI conversion is T–O It was shown above to be caused by hydrolysis of -Ge bonds. IM-12 with Ge--O--Ge bonds decayed very quickly (within 1 day) when exposed to environmental conditions. Kasian et al. showed that fluorinated IM-12 exhibited a shoulder peak at -12 ppm next to a main peak at -8 ppm (the -3 ppm shoulder peak observed for fluorinated IM-12 was detected in CIT-13). It has not been). This suggests that the origin of the line 2 signal of CIT-13/OH can be attributed to the highly clustered germanium site arrangement within the d4r unit such as the Ge-4-ring.

The 19F spectrum of CIT-13/OH[3.56] further increased the contribution of line 2 (23%) and underwent inverse sigma transformation to CIT-14/IST (as shown in FIG. 23(C) ). Others investigated the 19F NMR spectra of a series of STW-type germanosilicates from pure silica to pure germania and found that the Si/Ge ratio decreased from 5 to 0.42 resulting in a major 19F signal of -7. reported a shift from 5 ppm to -10.5 ppm. Still others have also reported the presence of an upfield signal at -14 ppm in the ¹⁹ F NMR spectrum of Ge-rich ITQ-21 material. In light of these results, we believe that the high field signals such as line 2 can be attributed to the high germanium content within the d4r unit.

The placement of germanium moieties within the d4r unit of CIT-13/OH was further investigated based on the ¹ H- ²⁹ Si CPMAS NMR spectrum (FIG. 24) of the related germanosilicate degermanized with distilled water. Using this type of treatment, it is speculated that most of the germanium sites are removed from the d4r unit, with the adjacent silicon sites becoming silanol sites. Water-degermanated CIT-13 and IM-12 samples commonly show a strong Q3 signal, in addition to a fully connected Q4 signal. The major difference between the samples is the intensity of the Q2-type (geminal) silanol signal. The degermanated IM-12 samples (Si/Ge = 4.89 and 4.23) exhibited the weakest Q2 signal among the degermanated materials studied, which was consistent with previous studies by other researchers. Consistent with observations. These IM-12 samples were more Ge-rich than IM-12 (Si/Ge=5.3), which was confirmed to undergo inverse sigma transformation. The Q2 signal signature in the ¹ H- ²⁹ Si CPMAS spectrum may be due to excessive degermanization. Unlike IM-12, the four CIT-13 samples shown in Figure 24 gave moderately intense Q2 signals. Of the four studied CIT-13 samples, only CIT-13/OH[3.71] underwent inverse sigma transformation and became CIT-14/IST, showing the weakest Q2 signal among CIT-13. . The two CIT-13/F samples gave stronger Q2 signals than CIT-13/OH[4.33] regardless of the Si/Ge ratio. These CIT-13/F samples did not convert to CIT-14 by inverse sigma transformation as shown above. Also, their degermanated ¹ H- ²⁹ Si CPMAS spectra were similar to those of ITH and IWW in terms of their strong Q2 signals. This observation further supports the premise that the presence or absence of fluoride in the synthetic gel of CIT-13 affected the placement of germanium within the d4r bridging unit.

Three example types of germanium configurations within the [Si ₄ Ge ₄ ]-d4r unit (I, II and III) and two Ge-rich configurations (II-2 and III-2 with 5 and 6 Ge sites, respectively). ) is shown in FIG. Based on their computational results, Corma et al. found that among the possible [Si4Ge4]-d4r configurations of AST germanosilicates, the alternating arrangement of Si and Ge sites within the d4r unit (i.e., the Type I arrangement) is the most energetic. was shown to be advantageous for This germanium arrangement was also suggested by Liu et al. to be present in as-produced CIT-13/F. Types II and III are [Si ₄ Ge ]-d4r configurations suggested to exist in ITH/IWW and UTL, respectively, in fluorinated and _degermanized ITQ-13, ITQ-22 and IM -12 germanosilicate. 28 ¹⁹ F MAS and ¹ H- ²⁹ Si CPMAS spectra. Most importantly, the Type III configuration can explain the extraction of the Ge-4-ring during the inverse sigma transformation of IM-12 and the resulting high Si/Ge ratio of the COK-14 material.

Regarding CIT-13/F, it has been pointed out that the presence of Si--O--Si crosslinks may inhibit complete exfoliation of the cfi-type layered material under an acidic medium. Also, CIT-13/F was not converted to CIT-14 by strong acid treatment as described above. This result suggests that there is no pure Ge-4-ring in the d4r unit of the CIT-13/F sample. Although very slow, CIT-13/F converted completely to Ge-CIT-5 upon exposure to ambient humidity. This transformation mechanistically involves hydrolysis of the TOT bond parallel to the major 14MR channel within the d4r unit. Therefore, it is unlikely that CIT-13/F has Si--O--Si bonds along the main channel direction of d4r. Therefore, it is possible to explain all the conversion behavior exhibited by CIT-13/F in the configuration of type I or type II-2 (when Ge-rich). However, according to DFT-based calculations by Camblor et al., highly clustered germanium moieties such as type II-2 can lead to a large contribution of the line 2 signal in its ¹⁹ F NMR, which CIT-13 /F is not observed (FIG. 23(A)). Therefore, CIT-13/F may have Type I or other possible configurations that could explain its transformation behavior.

As shown in FIGS. 23(B) and 23(C), the fluorinated form of the CIT-13/OH sample has a broader −8 ppm signal (line 1) and extra upfield than that of IM-12,28. It showed a 16-23% contribution of the signal (line 2). These data suggest the presence of highly clustered germanium moieties such as type II-2 and type III-2 within the d4r unit. Also, the fast conversion of CIT-13/OH from *CTH to CFI can be explained by Ge--O--Ge bonds parallel to the channel direction. The type III-2 configuration is also consistent with the pure Ge-4 ring and high germanium content within the s4r site of the resulting CIT-14/IST. Indeed, our fine structure solution obtained from synchrotron PXRD confirms that the Si/Ge ratio of the bridging s4r unit is about 4, which is the pure Ge-4 in the d4r unit of CIT-13/OH. - Means that there are 1 or 2 additional germanium substitutions on the ring. We therefore suggest that the absence of fluoride in the synthetic gel of CIT-13 results in clustered germanium moieties such as type II-2 or type III-2.

As those skilled in the art will appreciate, numerous modifications and variations of the present invention are possible in light of these teachings, and all such are contemplated herein. All references cited herein are hereby incorporated by reference for their teaching at least in the context provided.

Claims (18)

A crystalline microporous germanosilicate composition designated CIT-14/IST, having 8- and 12-membered ring channels with a powder X-ray diffraction (XRD) pattern of 7.59±0.5,8 .07±0.5, 12.88±0.3, 19.12±0.3, 19.32±0.3, 20.73±0.3, 22.33±0.3, 24.37 A crystalline microporous germanosilicate composition characterized by having at least five characteristic peaks at ±0.3, 27.19±0.3 and 27.69±0.3 degrees 2-theta. The crystalline microporous germanosilicate CIT-14/IST composition of claim 1, having a Si:Ge ratio ranging from 12:1 to 20:1. The crystalline microporous germanosilicate CIT-14/IST composition of claim 1, comprising an orthorhombic crystal system. The crystalline microporous germanosilicate CIT-14/IST composition according to claim 3, characterized by a Cmmm space group or a Cmcm space group or an intracrystalline mixture (disordered) of the two domains. The crystalline microporous germanosilicate CIT-14/IST composition of claim 3, wherein the crystals have the following unit cell parameters:

2. The crystalline microporous germano of claim 1, wherein the 8-membered ring channel has a pore size of about 3.3 Å x 3.9 Å and the 12-membered ring channel has a pore size of about 4.9 Å x 6.4 Å. Silicate CIT-14/IST composition. The crystalline microporous germanosilicate CIT-14/IST composition of claim 1, which is substantially free of fluoride. 2. The crystalline microporous germanosilicate of claim 1, having micropores optionally containing alkali metal cation salts, alkaline earth metal salts, transition metals, transition metal oxides, transition metal salts, or combinations thereof. CIT-14/IST composition. A crystalline microporous germanosilicate designated CIT-13/OH, which is fluoride-free and has a three-dimensional framework with pores defined by 10- and 14-membered rings, 6.45± at least 5 A crystalline microporous germanosilicate that exhibits a powder X-ray diffraction (XRD) pattern with two peaks. The crystalline microporous germanosilicate CIT-13/OH according to claim 9, having a Si:Ge ratio ranging from 3.5 to 5.2. 10. The crystalline microporous germanosilicate CIT of claim 9, having d4r units containing on average at least 4 Ge atoms per d4r unit, allowing the presence of Ge-4-rings in said d4r units. -13/OH. 10. The crystalline microporous germanosilicate of claim 9, having micropores optionally containing alkali metal cation salts, alkaline earth metal salts, transition metals, transition metal oxides, transition metal salts, or combinations thereof. CIT-13/OH composition. A method for preparing the crystalline microporous germanosilicate CIT-13/OH according to claim 9, comprising:
(a) a source of silicon oxide ( _SiO2 );
(b) a source of germanium oxide ( _GeO2 ); and (c) aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations thereof. or an optional source of a mixture;
(d) at least one hydroxide salt of a substituted benzylimidazolium organic structure-directing agent (OSDA) cation having the structure:

(e) optionally at least one compositionally matched seed crystal; hydrothermally treating under conditions effective to crystallize a substance, wherein the aqueous composition comprises
(a) Si:Ge molar ratio in the range 2 to 4, preferably 2.5 to 3.0;
(b) water having a water:Si molar ratio in the range of 8:1 to 12:1;
(c) water having a molar ratio of water:(SiO ₂ +GeO ₂ ) in the range of 6:1 to 7:1;
(c) hydroxide ions (OH) having an OH:(SiO ₂ +GeO ₂ ) molar ratio in the range of about 0.3:1 to 0.7:1;
wherein the aqueous composition is essentially free of fluoride ions. A method for preparing the crystalline microporous germanosilicate CIT-14/IST according to claim 1, wherein the crystalline microporous germanosilicate CIT-13/OH according to claim 9 is heated at a high temperature to an intermediate micro A method comprising contacting with a concentrated strong aqueous mineral acid for a time sufficient to form a porous germanosilicate "-CIT-14". 14. The method of claim 13, wherein (a) said mineral acid is aqueous HCl or _HNO3 ; (b) said strong aqueous mineral acid has a concentration in the range of 6-12M; (c) said high temperature is a temperature in the range of 80° C. to 120° C.; and/or (d) said sufficient time is in the range of 4 to 24 hours. 14. The method of claim 13, wherein the intermediate microporous germanosilicate "-CIT-14" is isolated, and the "-CIT-14" material is washed with water until the pH of the wash is neutral. and then heating the isolated and washed "-CIT-14" material at a temperature in the range of about 450°C to 650°C for a time in the range of 2 hours to 12 hours. . Catalyst or vehicle for gas separation of the crystalline microporous germanosilicate CIT-14/IST composition according to claim 8 or the crystalline microporous germanosilicate CIT-13/OH composition according to claim 12 Use as. (a) carbonylation of dimethyl ether (DME) with CO at low temperature;
(b) reducing NOx with methane;
(c) cracking, hydrocracking or dehydrogenating hydrocarbons;
(d) dewaxing the hydrocarbon feedstock;
(e) converting the paraffins to aromatics;
(f) isomerizing or heterogenizing the aromatic feedstock;
(g) alkylating the aromatic hydrocarbon;
(h) oligomerizing the alkene;
(i) aminating a lower alcohol;
(j) separating and sorbing lower alkanes from a hydrocarbon feedstock;
(k) isomerizing the olefin;
(l) producing high molecular weight hydrocarbons from low molecular weight hydrocarbons;
(m) reforming the hydrocarbon;
(n) converting lower alcohols or other oxygenated hydrocarbons to produce olefin products (including methanol to olefin processes);
(o) epoxidizing the olefin with hydrogen peroxide;
(p) reducing the content of nitrogen oxides in the gas stream in the presence of oxygen;
(q) separating nitrogen from a nitrogen-containing gas mixture; or (r) converting synthesis gas containing hydrogen and carbon monoxide into a hydrocarbon stream; or (s) organic 13. A process comprising reducing the concentration of halides, wherein each raw material is the crystalline microporous germanosilicate CIT-14/IST composition of claim 8 or the crystalline microporous of claim 12. A process carried out by contacting with a germanosilicate CIT-13/OH composition.

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