Preparation of the same from Germanosilicate CIT-14 / IST and Germanosilicate CIT-13 / OH

Abstract

The present disclosure relates to large-pore germanosilicate compositions designated as CIT-13 / OH and CIT-14 / IST, wherein each of the two large-pore germanosilicates has a three-dimensional framework having 10- and 14-membered ring channels and 8- and 12-membered channels, respectively. The present disclosure also provides a method for converting the former to the latter under conditions consistent with an inverse sigma transformation. Uses of the large-pore germanosilicate compositions are also disclosed.

Description

Technology Field Cross-reference regarding related applications

[0001] This application claims priority to U.S. provisional patent application No. 62 / 947,434 filed on December 12, 2019, the contents of which are incorporated by reference for all purposes. Government rights

[0002] doesn't exist Technology field

[0003] The present disclosure relates to germanosilicates designated as CIT-13 / OH and CIT-14 and the conversion of the former to the latter by inverse sigma transformation. Background Technology background

[0004] Zeolites play a crucial role as heterogeneous catalysts and are used in various industrial environments. Initially, these materials were primarily developed to support the petroleum industry, which was seeking to create more selective and potent catalysts for the production of gasoline and other fuels. Currently, these solids have emerged as specialty materials possessing properties based on their structural and chemical compositions capable of handling specific large-scale applications. While significant effort is required to bring new materials in the discovery stage into commercially available catalysts, there remains room to discover new structures with the hope that they may prove superior to existing materials.

[0005] One goal in seeking new materials was the hope that increasingly larger pores, which retain some catalytic properties on the internal surface, could handle larger feed molecules in the oil upgrading field.

[0006] Therefore, there is continued interest in the discovery of new crystalline phases for use in these application fields. Current work aims to address technical shortcomings in this field.

[0007] Synthetic molecular sieves are generally prepared using hydrothermal synthesis involving the use of inorganic (Na+, K+, etc.) and organic structure-directing agents (OSDA), mineralizing agents (OH- or F-), heteroatoms (in addition to Si elements such as Al, B, Ge, Ti, Sn, etc.), and so on. The synthesis of crystalline molecular sieves is complex. Although progress has been made in designing recipes and specific parts of the assembly process, this approach makes it difficult to predict the results.

[0008] The topotactic transformation of existing zeolites has served as a method for producing new zeolite frameworks that cannot be synthesized by conventional hydrothermal methods. A typical example is the ADOR (assembly-disassembly-organization-reassembly) strategy for germanosilicate transformation, which utilizes the properties of germanium sites that preferably occupy small complex building units (CBUs), such as double-4-rings (d4r). These transformations are schematically illustrated in Figures 1(a) and 1(b), respectively.

[0009] A super-large pore framework containing CIT-13 (*CTH: the asterisk (*) indicates the presence of crystallographic disorder within the structure), 14MR, and 10MR channels was discovered during the investigation of the ability of imidazolium-derived compounds containing benzyl pendant groups to act as OSDAs. Isostructural germanosilicates NUD-2 and SAZ-1, crystallized from imidazolium-based OSDAs and fluoride-based gels, have also been reported. CIT-13 consists of a Si-rich cfi-layer bridged by the two-dimensional alignment of Ge-rich d4r monomers. The structure of the cfi-layer provides two crystallographically identical positions for the d4r monomers. This equivalence is manifested by the positional disorder of the d4r monomers in the CIT-13 framework and the conversion from *CTH to CFI ( Fig. 1(c) Most importantly, the structure of CIT-13 is similar to the structure of IM-12, which has shown rich chemistry of germanosilicate conversion.

[0010] The inventors previously reported the similarity between *CTH and UTL and disclosed two novel frameworks, CIT-14 and CIT-15, having 2D 12 / 8MR and 1D 10MR channel systems, respectively, prepared based on ADOR transformation. However, ADOR products of sufficient quality for Rietveld refining were not produced from powder X-ray diffraction (PXRD). This may be due to the potential presence of Si-O-Si bonds within the interlayer region, which could lead to incomplete exfoliation. Liu et al. reported that a weakly basic solution, such as ammonium hydroxide, can dissociate the interlayer Si-O-Si bonds that hinder the complete exfoliation of the cfi-type layer of CIT-13, and that the structure ECNU-21 (equistructured with CIT-15) was obtained. The inventors also discovered that a weakly basic solution can exfoliate the cfi-type layer from germanosilicate Ge-CIT-5, which has double zigzag chain (dzc) complex building units instead of d4r units. Very recently, the formation of ECNU-23 (isostructured with CIT-14) and its structural solution (electron diffraction-based) was also reported as a partial degermination from the d4r units of CIT-13. Its synthesis was similar to the inverse sigma transformation of IM-12. Nevertheless, the inverse sigma transformation of CIT-13 by leaching pure Ge-4-rings using strong acids has never been reported due to the intrinsic germanium arrangement within the d4r units. outline

[0011] The present disclosure relates to a novel germanosilicate derived from a recently reported crystalline microporous germanosilicate having a CIT-13 topology prepared by a fluoride-free hydroxide route as described in U.S. Patent No. 10,828,625. This reference is incorporated by reference in its entirety for all purposes, including features and methods for making and using materials of the CIT-13 topology. These CIT-13 germanosilicates were hydrothermally prepared using a benzyl-imidazolium organic structuring agent and were characterized to have a three-dimensional framework having pores defined by 10-membered and 14-membered rings (pore dimensions of 6.2 x 4.5 Å and 9.1 x 7.2 Å, respectively). These are the first crystalline silicates known to have this structure. These structures are their powder X-ray diffraction (PXRD) patterns, their monomer cell parameters, SEM micrographs, 29 It features Si MAS NMR spectroscopy and adsorption / desorption isotherms.

[0012] This disclosure describes a germanium-containing, extra-large porous molecular sieve CIT-13 synthesized without the use of fluoride. After removing clogged organic matter, the CIT-13 obtained from the fluoride-free preparation differs from the CIT-13 samples prepared in the presence of fluoride. CIT-13 produced using the fluoride-free method can undergo an inverse sigma transformation to produce a mesoporous non-containing CIT-14, which is converted into a CIT-5 type germanosilicate much faster than Ge-CIT-13 with a similar Si / Ge ratio from fluoride-containing synthesis. A Rietveld-refined structural solution for CIT-14 confirms that it possesses 12-membered and 8-membered ring channels but provides monomer calling parameters that are slightly different for this material from those previously reported. 19 F Magic-Angle Spinning (MAS) and 1 H- 29The results of Si cross-polarization (CP) MAS nuclear magnetic resonance (NMR) spectroscopy show that crystallized CIT-13 without fluoride has different germanium positions than CIT-13 synthesized in the presence of fluoride.

[0013] The present disclosure also relates to a method for manipulating the structure of such CIT-13 germanosilicate prepared by a fluoride-free hydroxide route. By applying heat and steam under reaction conditions suitable for performing an inverse sigma transformation, the Si / Ge ratio is obtained in the range of 3.8 to 10. This mechanism for the material was previously unknown. The present disclosure also relates to a germanosilicate CIT-14 product derived from this manipulation. Germanosilicate CIT-14 can be accessed by the ADOR transformation (assembly-disassembly-organization-reassembly) of the phylosilicate designated as CIT-13P as described in U.S. Patent No. 10,293,33, the contents of which are incorporated by reference for all purposes, or at least for methods of preparing and characterizing CIT-14.

[0014] Certain embodiments of the present disclosure comprise a crystalline microporous germanosilicate composition designated as CIT-14 / IST having eight-membered and twelve-membered ring channels. In some embodiments, the CIT-14 / IST composition features a powder X-ray diffraction (XRD) pattern having at least five, seven, or ten characteristic peaks at 2-θ at 7.59 ± 0.5, 8.07 ± 0.5, 12.88 ± 0.5, 19.12 ± 0.5, 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. The present disclosure further provides a more complete disclosure of various uncertainties associated with peaks, characteristic peaks across the entire range, and the relative intensity and selection of peaks characterizing these materials.

[0015] The CIT-14 / IST composition is characterized in that, in some embodiments, the Si:Ge ratio is in the range of 12:1 to 20:1 or 14:1 to 18:1, or a sub-range within these ranges.

[0016] The CIT-14 / IST composition is characterized by claims 1 to 4, in which, in some embodiments, the crystal is orthorhombic. In some embodiments, the CIT-14 / IST crystal is Cmmm space group, or Cmcm It has a space group, or an intracrystalline mixture (disorder) of two domains. In some embodiments, the crystalline microporous germanosilicate CIT-14 / IST composition has unit cell parameters according to the following:

[0017] In some embodiments, the 8-membered ring channel of the CIT-14 / IST composition has pore dimensions of about 3.3 Å x 3.9 Å, and the 12-membered ring channel has pore dimensions of about 4.9 Å x 6.4 Å. Physical distortion (e.g., compression) or the Si:G ratio can change these values.

[0018] In some embodiments, the crystalline microporous germanosilicate CIT-14 / IST composition may be derived or derivable from the inverse sigma transformation of the crystalline microporous germanosilicate designated as CIT-13 / OH. In some embodiments, the crystalline microporous germanosilicate CIT-14 / IST composition may be derived or derivable from the crystalline microporous germanosilicate designated as CIT-13 / OH by treating the CIT-13 / OH germanosilicate with a concentrated aqueous mineral or other strong aqueous acid condition at an elevated temperature for a time sufficient to degerminate the CIT-13 / OH germanosilicate to form the "-CIT-14" composition, and then separating and calcining the thus formed "-CIT-14" germanosilicate to form the crystalline microporous germanosilicate CIT-14 / IST composition. Exemplary conditions for performing such transformations are described elsewhere in this disclosure.

[0019] Although specific forms, features, and conditions for preparing crystalline microporous CIT-13 / OH germanosilicates are more explicitly set forth in this disclosure, such compositions must be prepared in the absence of fluoride ions and within a specific Si:Ge ratio. The synthesis of these CIT-13 / OH germanosilicates is conveniently carried out using the specific substituted benzyl-imidazolium organic structure-director (OSDA) cations set forth herein. In some preferred embodiments, the precursor CIT-13 / OH germanosilicate is fluoride-free and has d4r units having an average of at least, preferably more than 4, Ge atoms, allowing for the presence of a Ge-4 ring in the 4dr unit.

[0020] In another embodiment, the crystalline microporous germanosilicate CIT-14 / IST composition contains micropores containing at least one alkali metal salt, alkaline earth metal cation salt, transition metal, transition metal oxide, transition metal salt, or a combination thereof.

[0021] In another embodiment, the crystalline microporous germanosilicate CIT-14 / IST in an acid or metal-containing form is used as a catalyst or adsorbent in the process range set forth elsewhere in this invention.

[0022] The present disclosure also includes other embodiments relating to the preparation of crystalline microporous germanosilicate CIT-14 / IST, which comprises a method comprising contacting crystalline microporous germanosilicate CIT-13 / OH germanosilicate with a concentrated strong aqueous mineral acid at an elevated temperature for a time sufficient to convert the crystalline microporous germanosilicate CIT-13 / OH germanosilicate into an as-prepared "-CIT-14" composition. The present disclosure also comprises a pre-calcined as-prepared "-CIT-14" composition.

[0023] The present disclosure also includes such embodiments of CIT-13 / OH germanosilicate prepared by a hydroxide route as specifically described herein. The present disclosure also includes such embodiments of CIT-13 / OH germanosilicate characterized by having d4r units containing an average of at least, preferably more than 4, Ge atoms per d4r unit, thereby allowing the presence of a Ge-4 ring in the d4r unit. The present disclosure also includes embodiments of CIT-13 / OH germanosilicate exhibiting previously unobserved reactive features, which are a result of the novel and unique physical features presented herein. Brief explanation of the drawing

[0024] The file of this patent or application contains at least one drawing / photograph executed in color. A copy of this patent or patent application publication containing the color drawing(s) / photograph(s) will be provided by the U.S. Patent and Trademark Office upon request and payment of the necessary fees.

[0025] This application is better understood when read together with the accompanying drawings. For the purpose of illustrating the subject matter, exemplary embodiments of the subject matter are depicted in the drawings; however, the subject matter disclosed herein is not limited to the specific methods, devices, and systems disclosed. Also, the drawings are not necessarily drawn to scale. In the drawings:

[0026] Fig. 1(ac) provides a schematic description of the known germanosilicate transformation: Fig. 1(a) Inverse sigma transform; Fig. 1(b) ADOR conversion; and Fig. 1(c) No-diffusion rearrangement of d4r alignment (*conversion from CTH to CFI). * The CTH-type framework is represented as the model material.

[0027] Fig. 2 This shows a schematic diagram of the research conducted and reported at this institution.

[0028] Fig. 3 (ab ) is theoretical PXRD data as described in U.S. Patent No. 10,293,33 ( Fig. 3(a) ) and pore channel dimensions ( Fig. 3(b) Describes the structure of CIT-14 / ESP (ESP represents ethoxysilylated columnarization) containing ).

[0029] Fig. 4(ab) is (a) CIT-13 / OH[3.71]( Fig. 4(a) ); and CIT-13 / OH[3.56]( Fig. 4(b) Shows an SEM image of a CIT-14 / IST sample derived from ).

[0030] Fig. 5(ac) shows the SEM image of the CIT-13 / OH sample: 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) ).

[0031] Fig. 6 This version of CIT-13 / OH[4.33] and CIT-13 / F[4.33] is manufactured as is.1 H- 13 C 8 kHz CPMAS, and 1,2-dimethyl-3-(3-methylbenzyl)imidazolium chloride of chloroform-d 13 Shows the spectrum of C solution.

[0032] Fig. 7 is the manufactured version of CIT-13 / OH[4.33] 1 H- 29 Shows the Si 8kHz CPMAS spectrum.

[0033] Fig. 8 (ag ) shows the characteristics of CIT-13. Fig. 8(a) : Two OSDAs capable of crystallizing CIT-13 without fluoride mineralizing agents. Fig. 8(be) : PXRD patterns of selected examples of CIT-13 / OH samples: (b) As manufactured and Fig. 8(c) : Calcined CIT-13 / OH[3.88], Fig. 8(d) : As manufactured and Fig. 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 log scale.

[0034] Fig. 9 (ak ) shows the PXRD pattern of the prepared CIT-13 / OH sample compared to that of the reference CIT-13 / F having Si / Ge = approximately 5. Fig. 9(a) : See CIT-13 / F, Fig. 9(b) : Ash #A, Fig. 9(c) : Ash #5, Fig. 9(d) : Episode #7, Fig. 9(e) : Episode #8, Fig. 9(f) : Ash #12, Figure 9(g) : Ash #13, Fig. 9(h) : Ash #15, Fig. 9(i) : Sequence #16, Fig. 9(j) : Ash #17 and Fig. 9(k) : Sequence #18.

[0035] Fig. 10 (310) The PXRD patterns of the CIT-13 / OH samples as prepared and their re-fluorinated versions are shown. The diffraction is highlighted.

[0036] Fig. 11(ae) is observed based on the PXRD profile * Shows structural changes during the conversion from CTH to CFI. (a, c) Calcined CIT-13 / OH[4.33]( ) after 10 days of exposure to ambient humidity in the range of 4–40° and (b, d) 5–9° Fig. 11(ab) ) and CIT-13 / OH[3.88]( Fig. 11(cd) PXRD profile of ) Change in d200 interlayer distance of CIT-13 / OH[4.33] compared to that of CIT-13 / F[4.31]( Fig. 11(e) ).

[0037] Fig. 12 is calcined CIT-13 / OH[3.88] and Ge-CIT-5 prepared therefrom 29 Shows the Si 8 kHz MAS spectrum. 29 The Si MAS NMR is qualitatively identical to the CIT-14 / ESP germanosilicate prepared by the ADOR synthesis described in U.S. Patent No. 10,293,33, which has a small amount of Q in the -108 to -120 chemical shift region. 3 Si species and multiple Q 4 Shows the Si environment.

[0038] Fig. 13(ab) shows the inverse sigma transform from CIT-13 to CIT-14. Schematic diagram of the inverse sigma transform of CIT-13 / OH generating CIT-14 / IST ( Fig. 13(a )); PXRD profiles of parent CIT-13 / OH and corresponding CIT-14 / IST samples( Fig. 13(a) .

[0039] Fig. 14(ab)shows the PXRD profiles of the original CIT-13 sample (black), the material immediately after 12M HCl treatment (magenta), and the calcined sample (blue): CIT-13 / F[3.87]( Fig. 14(a) ) and CIT-13 / OH[4.33]( Fig. 14(b) ).

[0040] Fig. 15 (a) shows the PXRD profiles of the theoretical model of "disorder-free" CIT-14 optimized based on the GULP algorithm, CIT-14 / IST from CIT-13 / OH[3.56] in the range of 4-40°, (b) 6-10°, and (c) 10.0-12.5° (top), CIT-14 / ESP from CIT-13 / F[4.33] (middle), and (d) of the CIT-14 / IST and CIT-14 / ESP samples. 29 Si NMR spectrum (of CIT-14 / ESP) 29 The Si MAS spectrum was adopted from U.S. Patent Application Publication No. 20170252729).

[0041] Fig. 16 Figure 1 shows the effect of elemental composition on the PXRD peak intensity of CIT-14. (a) Simulated PXRD profiles of a CIT-14 framework with 0% (black), 10% (cyan), and 20% (red) germanium at 7 T-sites of CIT-14 and (b) T1, (c) T2, (d) T3, (e) T4, (f) T5, (g) T6, and (h) T7-sites. Peaks 1, 2, and 3 represent (110), (200), and (001) diffraction, respectively.

[0042] Fig. 17(a) It shows the experimental design of the PXRD pattern and the CIT-14 / ESP sample generated within the range of 4-40° (Fig. 17(b)) and 6-9° (Fig. 17(c)).

[0043] Fig. 18(ad) is IM-12[3.80]( Fig. 18(a)), IM-12[4.79]( Fig. 18(b) ), IM-12[3.80]'s COK-14( Fig. 18(c) ) and IM-12 [4.79]'s COK-14( Fig. 18(d) Shows the SEM image of ).

[0044] Fig. 19 shows the PXRD profiles of COK-14 of IM-12[3.80] and COK-14 of IM-12[4.79].

[0045] Fig. 20(ab) is a linear scale ( Fig. 20(a) ) and log scale( Fig. 20(b) ...shows the Ar-adsorption and desorption isotherms of the parent bodies CIT-13 / OH, CIT-14 / IST, and CIT-14 / ESP.

[0046] Fig. 21(ad) represents the structural analysis results of CIT-14 / IST. Fig. 21(a Observed (top), calculated (middle), and difference (bottom) profiles for Rietveld refining of CIT-14. Fig. 21(b) Projection of CIT-14 along the principal crystallographic axes

[0001] ,

[0010] , and

[0100] (3x3x3 unit cell). Fig. 21(c) ) Two-dimensional 12- / 8-ring channel system in the ideal structure of CIT-14. Fig. 21(d) Schematic diagram of disorder in CIT-14.

[0047] Fig. 22(a) This shows the ideal structure of CIT-14 / IST. Silicon, germanium, and oxygen atoms are shown in blue, green, and red, respectively. Fig. 22(bc) Figures show the pore dimensions of the 12-membered ring and 8-membered ring of CIT-14 / IST, respectively.

[0048] Fig. 23(ac) CIT-13 / F[4.33] as manufactured, fluorinated CIT-13 / OH[4.33]( Fig. 23(b) ) and fluorinated CIT-13 / OH[3.56] ( Fig. 23(c) )of 19Shows the F 12 k MAS NMR spectrum. (The asterisk (*) indicates the rotational side band on the surface of fluorinated silica (19F-Si) formed as a result of fluorination using ammonium fluoride.)

[0049] Fig. 24(ac) water-degermanized CIT-13 / OH, CIT-13 / F, and IM-12 samples having different germanium contents 1 H- 29 The Si CPMAS spectrum is shown. The mother germanosilicate sample and the acid-leaching product are indicated on the left and right sides of the spectrum, respectively.

[0050] Fig. 25 This shows a schematic diagram of possible germanium arrangements within a d4r unit. (Not all possibilities are shown.) Green balls and silver nodes represent germanium and silicon sites, respectively. Specific details for implementing the invention Detailed description of exemplary implementations

[0051] The present disclosure relates to a novel composition of a material comprising a crystalline microporous germanosilicate, and a method for preparing and using such a composition.

[0052] Here, those that do not contain fluoride *A new method for synthesizing CTH-type germanosilicate molecular sieves is disclosed. The removal of fluoride from the synthesis narrows the previously reported compositional window for the CIT-13 crystallization that occurs and slows down the crystallization time. However, CIT-13 prepared from a hydroxide medium (designated as CIT-13 / OH) exhibits interesting properties that cannot be achieved with CIT-13 samples synthesized in the presence of fluoride (designated as CIT-13 / F). After calcination, fluoride-free CIT-13 / OH is converted into CFI-type germanosilicate (Ge-CIT-5) from a fluoride-containing gel with a similar Si / Ge ratio much faster than the existing CIT-13 / F when exposed to ambient humidity. In addition, CIT-13 / OH of the fluoride-free pathway can undergo inverse sigma transformation into CIT-14, another framework having 12MR and 8MR ring channels, upon contact with a strong acid. CIT-14 from the inverse sigma transformation (designated as CIT-14 / ist) did not exhibit the mesopority present in the isostructural analogs obtained from the ADOR-type transformation. Given that this transformation is based on the presence and arrangement of germanium sites within the d4r unit, we conclude that the presence of fluoride anions in the synthetic mixture influences the elemental (Ge and Si) composition and / or arrangement within the d4r unit in CIT-13. Furthermore, these results indirectly support the presence of Ge-O-Ge bonds and germanium 4-rings within the d4r unit of CIT-13 / OH synthesized in hydroxide-based gels, as observed in IM-12. Fig. 2 This summarizes the research reported in the present disclosure.

[0053] All of the present disclosures may be more easily understood by referring to the following descriptions taken in connection with the accompanying drawings and embodiments, which form part of the present disclosures. It should be understood that the present disclosures are not limited to the specific products, methods, conditions, or parameters described or illustrated herein, and that the terms used herein are merely illustrative of specific embodiments and are not intended to limit any claimed disclosures. Similarly, unless specifically stated otherwise, descriptions of possible mechanisms or modes of operation or reasons for improvement are merely illustrative, and the present disclosures are not limited by the accuracy or inaccuracy of such proposed mechanisms or modes of operation or reasons for improvement. Throughout the text, descriptions are recognized as representing compositions and methods of preparing and using said compositions. That is, where the present disclosures describe or claim features or embodiments related to a composition or a method of preparing or using a composition, such descriptions or claims are understood to be intended to extend such features or embodiments to each of these contexts (i.e., composition, method of preparation, and method of use). Where a processing method is described, additional embodiments provide that, unless specifically excluded otherwise, the product composition is isolated and optionally post-processed in a manner consistent with molecular sieve or zeolite synthesis.

[0054] The present disclosure includes compositions designated as "CIT-13 / OH", "-CIT-14", and "CIT-14 / IST", as well as a method for converting the former to the latter.

[0055] Crystalline microporous germanosilicate composition designated as CIT-14 / IST and "-CIT-14".

[0056] Certain embodiments include crystalline microporous germanosilicate compositions designated as CIT-14 / IST having eight-membered and twelve-membered ring channels. These include compositions derived from or derivable from CIT-13 / OH through the use of concentrated strong acids.

[0057] In a specific embodiment, the CIT-14 / IST germanosilicate composition comprises pure germanosilicate. In another independent embodiment, the CIT-14 / IST germanosilicate composition comprises a framework comprising one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium. These additional oxides may be derived from the precursor CIT-13 / OH used in the preparation of the CIT-14 / IST germanosilicate composition. Methods for incorporating these oxides into the precursor CIT-13 / OH composition are disclosed elsewhere in this invention.

[0058] These crystalline microporous germanosilicate CIT-14 / IST compositions may be characterized by a powder X-ray diffraction (XRD) pattern having at least five characteristic peaks at 2-θ of 7.59 ± 0.5, 8.07 ± 0.5, 12.88 ± 0.5, 19.12 ± 0.5, 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. In certain independent embodiments, the powder X-ray diffraction (XRD) pattern exhibits at least five characteristic peaks out of five, six, seven, eight, nine, or ten of these characteristic peaks described above. In certain independent embodiments, the uncertainty of the peak position is independently ± 0.5° 2-θ, ± 0.4° 2-θ, ± 0.3° 2-θ, ± 0.2° 2-θ, ± 0.15° 2-θ, or ± 0.15° 2-θ (for each peak).

[0059] Table 1...provides a list of powder XRD data derived from samples of crystalline germanosilicate CIT-14 / IST compositions. This data is considered representative of such materials. Various permutations of this data can be used to characterize these compositions, for example, by including multiple peaks selected by relative intensity. Additionally, these crystalline microporous germanosilicate CIT-14 / IST compositions Fig. 15 The characteristics can be identified by comparison with the powder XRD pattern shown in.

[0060] For example, in another specific embodiment, the crystalline microporous germanosilicate CIT-14 / IST composition features a powder X-ray diffraction (XRD) pattern exhibiting characteristic peaks at at least three of the characteristic peaks at 7.59 ± 0.5, 8.07 ± 0.5, 19.12 ± 0.5, 20.73 ± 0.5 and 22.33 ± 0.5 ° 2-θ and optionally at 12.88 ± 0.5, 19.32 ± 0.5, 24.37 ± 0.5, 27.19 ± 0.5 and 27.69 ± 0.5 ° 2-θ. The peaks at 7.59 and 8.07 degrees 2-θ correspond to (110) and (200) Miller indices, respectively, and are the most intense peaks in the pattern. Other individual weaker peaks can also help distinguish it from other materials.

[0061] Observed Table 1The intensity values ​​are believed to be based on the completely randomized orientation of the crystallites, perfect long-range order in all crystallographic directions, and the ideal connectivity of the CIT-14 / IST framework. However, the crystallite morphology of CIT-14 / IST is very flat, exhibiting a high aspect ratio, which actually indicates the possibility of intensity convolution by the preferred orientation of the sample. Furthermore, the intensity (7.67) of the first peak (110) indicates that it increases as the crystallinity (quality) of the CIT-14 sample improves. This is because the long-range order of the diagonal connecting units (single-4-rings of CIT-14) contributes to the (110) diffraction. The relatively chemically inert Si-rich layer is attributed to the (200) peak at 8.08°. (Therefore, it is generally strong.)

[0062] In certain embodiments, crystalline microporous germanosilicate CIT-14 / IST compositions prepared from CIT-13 / OH as described herein have a Si:Ge ratio of 12:1 to 13:1, 13:1 to 14:1, 14:1 to 15:1, 15:1 to 16:1, 16:1 to 17:1, 17:1 to 18:1, 18:1 to 19:1, 19:1 to 20:1, or any combination of two or more of these aforementioned sub-ranges, for example, 14:1 to 18:1. The specific compositions presented in the Examples are also considered to be within these ranges.

[0063] The crystals of the crystalline microporous germanosilicate CIT-14 / IST are orthorhombic. As described in the examples, the crystals may be disordered in some cases, and this Cmmm space group or Cmcm It may include the determination of a space group, or the mixing (disorder) within the determination of two domains.

[0064] In this context, the crystallization of the crystalline microporous germanosilicate CIT-14 / IST composition was found to exhibit unit cell parameters according to the following: The Å values ​​provided in the far right column are values ​​actually determined (or estimated) based on Rietveld refining (see Examples); the values ​​provided in the middle column represent the estimated variance that may occur as a function of specific composition (e.g., Si:Ge ratio or optional metal oxide substitution).

[0065] The channels within this crystalline microporous germanosilicate CIT-14 / IST composition also have the following characteristics: the eight-membered ring channels have pore dimensions of approximately 3.3 Å x 3.9 Å, and the twelve-membered ring channels have pore dimensions of approximately 4.9 Å x 6.4 Å. Although the respective pore sizes were experimentally determined to be 3.26 Å x 3.93 Å and 4.86 Å x 6.44 Å, respectively, a wider deviation is ensured to accommodate, for example, physical distortion (e.g., compression) or Si:Ge ratios that can change these values. In addition, within the framework, the average metal-oxygen (TO) bond length of the framework is in the range of 1.55 to 1.65 Å, the average oxygen-metal-oxygen (OTO) bond length of the framework is in the range of 98° to 116°, and the average metal-oxygen-metal (TOT) bond length of the framework is in the range of 139° to 180°, where T is Si or Ge.

[0066] Up until now, crystalline microporous germanosilicate CIT-14 / IST compositions have been characterized by physical properties. However, the present disclosure also considers embodiments in which such compositions are characterized by a method of preparing the composition from the reaction of germanosilicate CIT-13 / OH with a concentrated strong acid. Such embodiments include embodiments in which the structure is considered independently of the cited physical parameters (i.e., descriptions by pure product) and embodiments in which the structure is considered together with one or more physical properties.

[0067] In these embodiments, the crystalline microporous germanosilicate CIT-14 / IST composition is prepared by contacting the crystalline microporous germanosilicate designated as CIT-13 / OH with a concentrated aqueous mineral acid for a time sufficient to form the microporous germanosilicate "-CIT-14" as prepared at an elevated temperature. Compositions of both CIT-13 / OH (as described and used herein) and "-CIT-14" are described elsewhere in this application. It should be understood that the following description is also appropriate and relates to a method for preparing a germanosilicate CIT-14 / IST composition from a germanosilicate CIT-13 / OH composition, and that the method of preparing a germanosilicate CIT-14 / IST composition by these methods constitutes an independent embodiment. Compositions of such CIT-13 / OH germanosilicate are also considered independent embodiments of the present disclosure, such as the use in the manufacture of CIT-14 / IST, as with the composition designated as "-CIT-14".

[0068] In the preparation of a CIT-14 / IST composition from a germanosilicate CIT-13 / OH composition, the present method comprises one or more of the following conditions:

[0069] (1) The CIT-13 / OH composition is conveniently dispersed in an aqueous strong acid. The reaction mixture can then be left in a static state or mixed more efficiently in a working reactor, such as a rotary reactor. As highlighted in the examples, it may be useful to physically disperse the reaction medium during intermediate times.

[0070] (2) Mineral acids are strong acids; that is, they dissociate substantially completely in aqueous solution, as is distinguished from weak acids which only partially ionize in aqueous solution. HCl or HNO3 are the original acids used in this dosage, but other strong acids may also be used. Such strong acids (e.g., phosphoric acid) that have anions that can be incorporated into the framework lattice are not considered if such incorporation is undesirable.

[0071] (3) The use of a concentrated acid appears to be important. In a preferred embodiment, the concentration of the mineral acid is in the range of 6 to 12 M. Higher concentrations (e.g., 10 to 12 M) are preferred because they appear to improve the kinetics and yield of the reaction.

[0072] (4) The elevated temperature is in the range of 80°C to 120°C, preferably about 95°C. Given the volatility of water at this temperature, a closed reactor must be used.

[0073] (5) The time sufficient to carry out the conversion is in the range of 4 to 96 hours, preferably 6 to 24 hours. Clearly, there is a balance between the time, temperature, and acid type and concentration required for the reaction to proceed in a suitable yield of the product; conditions corresponding to 95°C for 6 hours using 12M aqueous HCl were found to be suitable.

[0074] (6) After contacting the germanosilicate with acid, the resulting degermaniculated germanosilicate designated as "-CIT-14" is isolated. This is conveniently performed by centrifugation, and other separation methods may be used.

[0075] (7) The separated "-CIT-14" material is then repeatedly rinsed or washed with water (preferably distilled water or deionized water) until the washing solution becomes pH neutral. The "-CIT-14" material is also considered as a separate embodiment of the present disclosure, and representative features of this material are presented in the embodiment.

[0076] (8) CIT-14 / IST can be prepared from the separated and washed "-CIT-14" material by heating it at a temperature in the range of about 450°C to 650°C for 2 to 12 hours, preferably at 580°C for 6 hours or under substantially the same conditions. In a preferred embodiment, heating is performed at a temperature rise rate of 1-5°C / min, preferably 1°C / min.

[0077] The conversion of CIT-13 / OH to CIT-14 / IST entails a reduction in micropore volume of about 25 to 30 volume percent.

[0078] The method described above provides a CIT-14 / IST germanosilicate consistent with the mechanism characterized by the inverse sigma transformation of crystalline microporous CIT-13 / OH germanosilicate for the reasons presented in the discussion section of the examples. Accordingly, the method and the product can be characterized using the relevant terms.

[0079] Crystalline microporous germanosilicate composition designated as CIT-13 / OH

[0080] Compositions generally defined as CIT-13 and their reactivity under various process conditions have been previously reported. For instance, refer to U.S. Patent Nos. 10,293,330 and 10,828,625 and U.S. Patent Application Publication No. 2017-0252729, each of which is incorporated herein by reference for all purposes or at least for information relating to the germanosilicate CIT-13.

[0081] U.S. Patent No. 10,293,330 describes CIT-13 having a three-dimensional framework having pore channels defined by 10-membered and 14-membered rings, and Table 2 It is described as exhibiting a powder XRD pattern as presented in [the document].

[0082] As described herein, CIT-13 / OH germanosilicate also has a three-dimensional framework having pores defined by 10-membered and 14-membered rings, but does not contain fluoride. Consistent with other CIT-13 germanosilicates, they exhibit powder X-ray diffraction (XRD) patterns having at least five peaks at 2-θ of 6.45 ± 0.2, 7.18 ± 0.2, 12.85 ± 0.2, 20.78 ± 0.2, 26.01 ± 0.2, and 26.68 ± 0.2. Table 2 Reference. These CIT-13 / OH germanosilicates also have peaks at 2-θ of 6.45 ± 0.2 and 7.18 ± 0.2 degrees and Table 2 The powder XRD pattern can be characterized by having 5, 6, or 7 of the other peaks presented in ).

[0083] As discussed in the examples, the powder XRD pattern of CIT-13 / OH as described herein is particularly related to the intensity of the (200) peak of the material as prepared. Table 2 It shows a slight difference from the data presented in [the example]. This observation is explained in more detail in the examples. In some embodiments, the peak at 6.45 ± 0.2° 2-θ has reduced intensity (weak) compared to the peak at 7.18 ± 0.2° 2-θ, making the latter peak the strongest in the pattern (see examples). In other embodiments, the powder XRD pattern of CIT-13 / OH germanosilicate shows an additional peak at 11.58° ± 0.2° 2-θ of medium to weak intensity attributed to the index (310).

[0084] CIT-13 / OH germanosilicate also Fig. 12 Matching the spectrum shown in 29 Shows the Si MAS-nmr spectrum (top). This is discussed further in the examples.

[0085] The Si:Ge ratio of these CIT-13 / OH germanosilicates is in the range of 3.5 to 3.6, 3.6 to 3.7, 3.7 to 3.8, 3.8 to 3.9, 3.9 to 4.0, 4.0 to 4.1, 4.1 to 4.2, 4.2 to 4.3, 4.3 to 4.4, 4.4 to 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 a range defined by any two or more of the above ranges, e.g., 3.5 to 5.2 or 3.5 to 3.9. This range is similar to the range previously reported for CIT-13 materials.

[0086] However, unlike previously reported materials, the fluoride-free CIT-13 / OH germanosilicate of the present invention contains d4r structural units having an average of at least 4 and preferably more than 4 Ge atoms per d4r unit, allowing for the presence of Ge-4 rings in the d4r units. These characteristics allow for unexpected conversion of these materials into the corresponding CIT-5 and "-CIT-14" / CIT-14 / IST materials. Again, these characteristics are further described in the examples.

[0087] One method for determining the average number of Ge atoms in a d4r monomer involves adding fluoride ions to CIT-13 / OH germanosilicate, and the resulting doped material 19 An example of measuring the F MAS-nmr spectrum is presented.

[0088] An important aspect of the final structure of CIT-13 / OH materials is the manner in which these materials are formed in the complete absence of fluoride ions. As presented herein, the crystalline microporous germanosilicate CIT-13 / OH composition is (a) Source of silicon oxide (SiO2); (b) a source of germanium oxide (GeO2); and (c) an optional source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations or mixtures thereof; (d) At least one hydroxide salt of a substituted benzyl-imidazolium organic structure-deriver (OSDA) cation having the following structure: (e) at least one compositionally consistent seed determination at any time; and (f) Aqueous composition derived from a mixture of water A crystalline microporous germanosilicate composition designated as CIT-13 / OH is prepared by a method comprising hydrothermal treatment under conditions effective for crystallization; said aqueous composition (a) Si:Ge in a molar ratio in the range of 2 to 4, preferably 2.5 to 3.0; (b) Water with a water:Si molar ratio in the range of 8:1 to 12:1; (c) Water in a molar ratio of (SiO2+GeO2) in the range of 6:1 to 7:1; (c) containing hydroxide ions (OH) in an OH:(SiO2+GeO2) molar ratio in the range of about 0.3:1 to 0.7:1; The above aqueous composition essentially does not contain fluoride ions.

[0089] This range is stricter than previously reported. This narrower range is important for generating Ge-rich d4r monomers.

[0090] Within this framework, methods include one or more of the following attributes:

[0091] (1) The silicon oxide source may be any source known to be suitable for molecular sieve synthesis, but in a preferred embodiment comprises silicate, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, silica hydroxide or a combination thereof (or equivalent source), preferably sodium silicate or tetraalkyl orthosilicate, and more preferably tetraethyl orthosilicate (TEOS); (2) The source of germanium oxide may be any source known to be suitable for molecular sieve synthesis, and the source of germanium oxide includes GeO2, or a hydrated derivative thereof (or an equivalent source thereof);

[0093] (3) The substituted benzyl-imidazolium organic structure-directing agent (OSDA) cations are present in an OSDA:(SiO2+GeO2) molar ratio in the range of about 0.3:1 to 0.7:1, preferably in the range of about 0.4:1 to 0.6:1;

[0094] (4) The aqueous composition essentially does not contain alkali metal cations, alkaline earth metal cations or divalent cations, or a combination thereof;

[0095] (5) At least one substituted benzyl-imidazolium organic structure-derived agent (OSDA) cation preferably has the following structure:

[0096] (6) The aqueous composition is a suspension or a gel;

[0097] (7) Effective crystallization conditions include treating the mixture at a temperature of about 140°C to about 180°C for a period of about 4 days to about 4 weeks;

[0098] (7) The aqueous composition is treated with hot water in a rotary oven;

[0099] (8) The above method further includes separating a crystalline microporous germanosilicate solid composition.

[0100] The CIT-14 / IST described herein is compositionally different from the CIT-14 / ESP structure (ESP represents an ethoxylylated pillar) previously disclosed in U.S. Patent Application Publication No. 2017 / 0252729, which is incorporated herein by reference for all purposes or at least for such disclosure. This previously reported CIT-14 / ESP was prepared by treating a phyllosilicate of the CIT-13P topology with a silica source in the presence of a concentrated aqueous mineral acid (e.g., HCl or preferably HNO3) for 12 to 48 hours at one or more temperatures in the range of about 165°C to about 225°C to form an intermediate composition, and then separating and calcining the intermediate composition to form a crystalline microporous silicate composition of the CIT-14 / ESP topology.

[0101] In particular, CIT-14 / ESP germanosilicate was formed using CIT-13P phylosilicate having a much higher Si:Ge ratio (although a much higher Si / Ge ratio than that described by the method of the present invention), resulting in CIT-14 / ESP germanosilicate having a Si:Ge ratio in the range of about 25 to substantially infinite, including embodiments in which the Si:Ge ratio is about 25 to about 150, or about 75 to about 150. The quality of the crystals formed by the ADOR process was lower than that reported herein.

[0102] These CIT-14 / ESP germanosilicates exhibited powder X-ray diffraction (XRD) patterns reported to be not significantly different from those reported for CIT-14 / IST germanosilicates, and have at least five of the characteristic peaks at 7.7, 8.2, 13.1, 19.5, 21.1, 22.7, and 27.6 at 2-θ. Due to the structural disorder of the material, the observed diffraction peaks were broad, and the error assigned to these peaks was ± 0.5 at 2-θ. In another embodiment, the error associated with these peaks was ± 0.3 at 2-θ. Consistent with other structures prepared by pillaring and the methods by which they can be formed, the structure of this new material was described with respect to a three-dimensional framework having pores defined by eight-membered and twelve-membered rings. Based on the theoretical structure, the eight-membered and twelve-membered rings were calculated to have dimensions of 4.0 x 3.4 Å and 6.9 x 5.4 Å, respectively ( Fig. 3(ab) (Reference). The PXRD pattern identified from the isolated product is not identical but is consistent with theoretical values ​​associated with this structure (predicted by the General Utility Lattice Program, GULP (Gale, 1997)), that is, silica-rich cfi- It has silica pillars separating the layers. Furthermore, differences in these patterns were thought to be explained by structural disorder and / or structurally incomplete silica pillars. In this case, the version of CIT-14 / ESP also Fig. 3(a) and 3(b) It may also be described in terms of the crystallographic parameters shown in. Other modifications to microcrystalline compositions.

[0103] In certain embodiments, the crystalline microporous solids described in this disclosure, comprising CIT-13 / OH germanosilicate and the newly described microcrystalline CIT-14 / IST germanosilicate, exist in their hydrogen form. In other embodiments, the crystalline microporous solid contains at least one metal cation salt or transition metal or salt in its micropores. In other specific embodiments, the metal cation salt is K + , Li + , Rb + , Ca 2+ , Cs + : Co 2+ , Cu 2+ , Mg 2+ , Sr 2+ , Ba 2+ , Ni 2+ or Fe 2+ The copper salt is a salt, and the copper salt may include, for example, Schweiser's reagent (tetraammin diaquacopper dihydroxide, [Cu(NH3)4(H2O)2](OH)2]), copper(II) nitrate, or copper(II) carbonate. These metal cations may be incorporated, for example, using a technique known to be suitable for this purpose (e.g., ion exchange).

[0104] In other embodiments, the micropores may contain a transition metal or a transition metal oxide. The addition of such material may be achieved, for example, by chemical vapor deposition or chemical precipitation. In certain independent embodiments, the transition metal or transition metal oxide comprises elements of Group 6, 7, 8, 9, 10, 11, or 12. In other independent embodiments, the transition metal or transition metal oxide comprises scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, or a mixture thereof. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred. In an independent embodiment, the aqueous ammonium or metal salt or chemically vapor-deposited or precipitated material is 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 R in at least a portion of its pores. 4-n N + H n It contains a cation (where R is alkyl and n = 0-4).

[0105] Although the term “transition metal” is defined elsewhere in this invention, in certain other independent embodiments, the transition metal or transition metal oxide comprises elements of Group 6, 7, 8, 9, 10, 11, or 12. In further other independent embodiments, the transition metal or transition metal oxide comprises scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, or mixtures thereof. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.

[0106] In another embodiment, an optionally doped crystalline solid is calcined in air at a temperature defined as at least one range of 400°C to 500°C, 500°C to 600°C, 600°C to 700°C, 700°C to 800°C, 800°C to 900°C, 900°C to 1000°C, 1000°C to 1200°C, and 500°C to about 1200°C. In some cases, the selection of any particular temperature may be limited by the stability of the particular solid with respect to decomposition or conversion to another crystalline phase.

[0107] Other methods of modifying molecular sieves for use as catalysts are known to those skilled in the art, and any such additional modifications are considered within the scope of this disclosure. Uses of the composition of the present invention - Catalytic conversion / separation

[0108] In various embodiments, calcined, doped, or treated crystalline microporous germanosilicate solids disclosed herein act as catalysts that mediate or catalyze the alignment of chemical transformations or separations. All such combinations of compositions and catalytic reactions are considered individual embodiments of the present disclosure as if they were described separately. The use of these germanosilicates for such purposes is also within the scope of the present disclosure. These conversions / separations include carbonylating DME (dimethyl ether) with CO at low temperatures, reducing NOx with methane (e.g., in exhaust applications), cracking, hydrocracking, dehydrogenating, converting paraffins to aromatics, dewaxing hydrocarbon feedstocks, MTO (methanol to olefin), isomerizing aromatics (e.g., xylene), disproportionating aromatics (e.g., toluene), alkylating aromatic hydrocarbons, oligomerizing alkenes, aminating lower alcohols, separating and adsorbing lower alkanes, hydrocracking hydrocarbons, dewaxing hydrocarbon feedstocks, isomerizing olefins, generating high molecular weight hydrocarbons from low molecular weight hydrocarbons, modifying hydrocarbons, converting lower alcohols or other oxygenated hydrocarbons to produce olefin products, This may include epoxidizing olefins with hydrogen peroxide, reducing the oxide content of nitrogen contained in a gas stream in the presence of oxygen, or separating nitrogen from a nitrogen-containing gas mixture by contacting each feedstock with a catalyst comprising any one of the crystalline microporous solids described herein under conditions sufficient to influence the named conversion. Particularly attractive applications where such germanosilicates are expected to be useful include catalytic cracking, hydrocracking, dewaxing, alkylation, and olefin and aromatic formation reactions. Additional applications include gas drying and separation.

[0109] Specific embodiments provide a hydrocracking method, each method comprising contacting a hydrocarbon feedstock under hydrocracking conditions with a catalyst preferably comprising the crystalline microporous solid of the present disclosure, preferably in the form of hydrogen.

[0110] Another embodiment provides a method for dewaxing a hydrocarbon feedstock, each method comprising contacting the hydrocarbon feedstock with a catalyst comprising the crystalline microporous solid of the present disclosure under dewaxing conditions. Another embodiment provides a process for improving the viscosity index of a dewaxed product of a waxy hydrocarbon feedstock, each process comprising contacting the waxy hydrocarbon feedstock with a catalyst comprising the crystalline microporous solid of the present disclosure under isomerizing dewaxing conditions.

[0111] Further embodiments include a method for producing C20+ lubricating oil from a C20+ olefin feed, each method comprising isomerizing the olefin feed under isomerizing conditions on a catalyst comprising at least one transition metal catalyst of the present disclosure and a crystalline microporous solid.

[0112] Additionally, the present disclosure includes a method for isomerizing and dewaxing a raffinate, each method comprising contacting said raffinate, e.g., bright stock, with a catalyst comprising at least one transition metal and a crystalline microporous solid of the present disclosure in the presence of added hydrogen.

[0113] Another embodiment provides a dewaxing of a hydrocarbon oil feedstock containing straight-chain and slightly branched-chain hydrocarbons, comprising boiling at a temperature greater than about 350°F and contacting the hydrocarbon oil feedstock with a catalyst comprising at least one transition metal and, preferably, a crystalline microporous solid of the disclosure in the form of hydrogen, preferably, mainly hydrogen, in the presence of added hydrogen gas at a hydrogen pressure of about 15 to 3000 psi.

[0114] The present disclosure also includes a method for producing a lubricating oil comprising hydrocracking a hydrocarbon feedstock in a hydrocracking zone to obtain an effluent containing hydrocracking oil, and catalytically dewaxing the effluent containing hydrocracking oil at a temperature of at least about 400°F at a pressure of about 15 psig to about 3000 psig in the presence of added hydrogen gas with a catalyst comprising at least one transition metal and a crystalline microporous solid of the present disclosure.

[0115] Additionally, the present disclosure includes a method for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatic content, each method comprising contacting a hydrocarbon feedstock comprising normal and slightly branched hydrocarbons having a boiling range of about 40°C to about 200°C under aromatic conversion conditions with a catalyst comprising the crystalline microporous solid of the present disclosure. In such embodiments, the crystalline microporous solid is preferably neutralized with a basic metal to make the solid substantially non-acidic. Additionally, the present disclosure provides a method in which the crystalline microporous solid contains a transition metal component.

[0116] Additionally, catalytic decomposition processes are provided by the present disclosure, each method comprising contacting a hydrocarbon feedstock in a reaction zone with a catalyst comprising the crystalline microporous solid of the present disclosure under catalytic decomposition conditions without hydrogen addition. Additionally, catalytic decomposition methods are provided in the present disclosure, wherein the catalyst further comprises an additional large-pore crystalline decomposition component.

[0117] The present disclosure further provides isomerization methods for isomerizing C4 to C7 hydrocarbons, each method comprising contacting a feed having ordinary and slightly branched C4 to C7 hydrocarbons under isomerization conditions with a catalyst comprising the crystalline microporous solid of the present disclosure, preferably in the form of hydrogen. The crystalline microporous solid may be impregnated with at least one transition metal, preferably platinum. The catalyst may be calcined in a steam / air mixture at an elevated temperature after impregnation with the transition metal.

[0118] Additionally, the present disclosure provides a method for alkylating an aromatic hydrocarbon, each method comprising contacting at least a molar excess of an aromatic hydrocarbon with a C2 to C20 olefin under alkylation conditions in the presence of a catalyst, preferably comprising the crystalline microporous solid of the present disclosure mainly in the form of hydrogen, at least under partial liquid phase conditions. The olefin may be a C2 to C4 olefin, and the aromatic hydrocarbon and the olefin may each be present in a molar ratio of about 4:1 to about 20:1. The aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof.

[0119] A method for transalkylating an aromatic hydrocarbon is further provided according to the present disclosure, each of which comprises contacting the aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under transalkylation conditions in the presence of a catalyst preferably comprising the crystalline microporous solid of the present disclosure mainly in the form of hydrogen. The aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon may each be present in a molar ratio of about 1:1 to about 25:1. The aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the polyalkyl aromatic hydrocarbon may be dialkylbenzene.

[0120] A method for converting paraffin into an aromatic form is further provided by the present disclosure, each method comprising contacting the paraffin with a catalyst comprising a crystalline microporous solid of the present disclosure under conditions that cause the paraffin to be converted into an aromatic form, said catalyst comprising gallium, zinc, or a compound of gallium or zinc.

[0121] According to the present disclosure, a method for isomerizing an olefin is also provided, each method comprising contacting said olefin with a catalyst comprising the crystalline microporous solid of the present disclosure under conditions that cause isomerization of the olefin.

[0122] According to the present disclosure, a method for isomerizing a feed is further provided, wherein each method comprises an aromatic C8 stream of xylene isomer or a mixture of xylene isomer and ethylbenzene, wherein a more nearly equilibrium ratio of ortho-, meta-, and para-xylene is obtained, and the method comprises contacting the feed with a catalyst comprising the crystalline microporous solid of the present disclosure under isomerizing conditions.

[0123] The present disclosure further provides a method for oligomerizing an olefin, each method comprising contacting an olefin feed with a catalyst comprising the crystalline microporous solid of the present disclosure under oligomerizing conditions.

[0124] The present disclosure also provides a method for converting lower alcohols and other oxygenated hydrocarbons, each method comprising contacting said lower alcohol (e.g., methanol, ethanol, or propanol) or other oxygenated hydrocarbon with a catalyst comprising the crystalline microporous solid of the present disclosure under conditions that produce a liquid product.

[0125] Additionally, the present disclosure provides a method for reducing oxides of nitrogen contained in a gas stream in the presence of oxygen, wherein each method comprises contacting the gas stream with a crystalline microporous solid of the present disclosure. The crystalline microporous solid may contain a metal or metal ions (e.g., cobalt, copper, or a mixture thereof) capable of catalyzing the reduction of oxides of nitrogen, and may be carried out in the presence of stoichiometric excess oxygen. In a preferred embodiment, the gas stream is an exhaust stream of an internal combustion engine.

[0126] Additionally, a method is provided for converting synthesis gas containing hydrogen and carbon monoxide, also referred to as syngas or synthesis gas, into a liquid hydrocarbon fuel using a catalyst comprising any of the germanosilicates described herein, including having a CIT-13 framework, and a Fischer-Tropsch catalyst. Such a catalyst is described in U.S. Patent No. 9,278,344, which is incorporated by reference for teaching of the catalyst and the method of using the catalyst. The Fischer-Tropsch component comprises transition metal components of Group 8–10 (i.e., Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), preferably cobalt, iron, and / or ruthenium. The optimal amount of the catalytically active metal present is particularly dependent on the specific catalytically active metal. Typically, the amount of cobalt present in the catalyst may be in the range of 1 to 100 parts by weight per 100 parts by weight of support material, preferably 10 to 50 parts by weight per 100 parts by weight of support material. In one embodiment, 15 to 45 weight percent of cobalt is deposited on the hybrid support as a Fischer-Tropsch component. In another embodiment, 20 to 45 weight percent of cobalt is deposited on the hybrid support. The catalytically active Fischer-Tropsch component may be present in the catalyst together with one or more metal promoters or co-catalysts. The promoter may be present as a metal or a metal oxide depending on the specific promoter involved. Suitable promoters include oxides of transition metals or metals comprising lanthanides and / or actinides or oxides of lanthanides and / or actinides. As an alternative to or in addition to metal oxide promoters, the catalyst may include a metal promoter selected from Group 7 (Mn, Tc, Re) and / or Groups 8-10. In some embodiments, the Fischer-Tropsch component further comprises a cobalt reduction promoter selected from the group consisting of platinum, ruthenium, rhenium, silver, and combinations thereof.The method used to deposit Fischer-Tropsch components on a hybrid support comprises an impregnation technique using an aqueous or non-aqueous solution containing a soluble cobalt salt and, if desired, a soluble promoter metal salt, e.g., a platinum salt, to achieve the necessary metal loading and distribution required to provide a highly selective and active hybrid synthesis gas conversion catalyst.

[0127] Another additional method embodiment comprises a method for reducing the halogen concentration in an initial hydrocarbon product containing undesirable levels of organic halogens, said method comprising contacting at least a portion of the hydrocarbon product with a composition comprising any germanosilicate structure described herein, including CIT-13, under conditions of organic halogen absorption to reduce the halogen concentration in the hydrocarbon. The initial hydrocarbon product may be produced by a hydrocarbon conversion method using an ionic liquid catalyst comprising a halogen-containing acidic ionic liquid. In some embodiments, the organic halogen content in the initial hydrocarbon product is in the range of 50 to 4000 ppm; in other embodiments, the halogen concentration is reduced to provide a product having less than 40 ppm. In other embodiments, the product may achieve a reduction of 85%, 90%, 95%, 97% or more. The initial hydrocarbon stream may contain an alkylate or a gasoline alkylate. Preferably, the hydrocarbon alkylate or alkylate gasoline product is not decomposed during contact. Any material or method conditions described in U.S. Patent No. 8,105,481 are deemed to describe the scope of material and method conditions of this disclosure. U.S. Patent No. 8,105,481 is incorporated by reference for teaching of methods and materials used to perform at least these conversions (both alkylation and halogen reduction).

[0128] Another method embodiment includes a method for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatic content, comprising contacting a hydrocarbon feedstock containing ordinary and slightly branched hydrocarbons having a boiling range greater than about 40°C and less than about 200°C with a catalyst under aromatic conversion conditions.

[0129] Specific conditions for many of these transformations are known to those skilled in the art. Exemplary conditions for such reactions / transformations can also be found in WO / 1999 / 008961, U.S. Patents No. 4,544,538, 7,083,714, 6,841,063, and 6,827,843, each of which is incorporated herein by reference in its entirety at least for this purpose.

[0130] Depending on the type of reaction being catalyzed, the microporous solid may exist primarily in the form of hydrogen, be partially acidic, or be substantially acidic. A skilled technician will be able to define these conditions without excessive effort. As used herein, "primarily in the form of hydrogen" refers to the material after calcination (the material pre-calcined before calcination is NH4). + It means that at least 80% of the cation sites are occupied by hydrogen ions and / or rare earth ions, which may also include exchanging with hydrogen ions.

[0131] The germanosilicates of the present disclosure may also be used as adsorbents for gas separation. For example, such germanosilicates may also be used as hydrocarbon traps, for example, as cold start hydrocarbon traps in combustion engine pollution control systems. In particular, such germanosilicates may be particularly useful for trapping C3 fragments. Such embodiments may include methods and apparatus for capturing low molecular weight hydrocarbons from an incoming gas stream, the method comprising passing the gas stream across or through a composition comprising any one of the crystalline microporous germanosilicate compositions to provide an exhaust gas stream having a reduced concentration of low molecular weight hydrocarbons compared to the incoming gas stream. In this context, the term "low molecular weight hydrocarbons" refers to C1-C6 hydrocarbons or hydrocarbon fragments.

[0132] The germanosilicate of the present disclosure may also be used in a method for treating a cold-start engine exhaust gas stream containing hydrocarbons and other contaminants, wherein the method comprises or consists of: flowing the engine exhaust gas stream over one of the germanosilicate compositions of the present disclosure to preferentially adsorb hydrocarbons over water to provide a first exhaust stream; flowing the first exhaust gas stream over a catalyst to convert any residual hydrocarbons and other contaminants contained in the first exhaust gas stream into harmless products and providing a treated exhaust stream; and releasing the treated exhaust stream into the atmosphere.

[0133] 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 to separate carbon dioxide from natural gas. Generally, molecular sieves are used as components of membranes used to separate gases. An example of such a membrane is disclosed in U.S. Patent No. 6,508,860.

[0134] For each of the prior methods described, additional corresponding embodiments include a device or system comprising or containing the material described for each method. For example, in the case of gas trapping, additional embodiments include a device known in the art as a hydrocarbon trap that may be located in the exhaust gas passage of a vehicle. In such a device, hydrocarbons are adsorbed to the trap and stored until the engine and exhaust gas reach a temperature sufficient for desorption. The device may also include a membrane comprising a germanosilicate composition useful for the described process. terminology

[0135] In the present disclosure, the singular forms "a," "an," and "the" include plural objects, and references to specific numerical values ​​include at least that specific value unless the context clearly indicates otherwise. Thus, for example, a reference to "substance" is a reference to at least one of such substance and / or equivalents thereof, and others known to those skilled in the art.

[0136] You will understand that when a value is expressed as an approximation using the predicate "approximately," a specific value forms a different implementation example. Generally, the use of the term "about" indicates an approximation that may vary depending on the desired characteristics sought to be obtained from the disclosed subject matter, and should be interpreted within the specific context in which it is used based on its function. Those skilled in the art may interpret this as a matter of convention. In some cases, the number of significant figures used for a specific value may be a non-restrictive method for determining the scope of the word "about." In other cases, the variation used for a series of values ​​may 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, a reference to a value specified in a range includes all values ​​within that range.

[0137] For the sake of clarity, it should be understood that certain features of the disclosure described herein in the context of separate embodiments may also be provided in combination in a single embodiment. That is, unless explicitly incompatible or specifically excluded, each individual embodiment is considered to be combinable with any other embodiment(s), and such combination is considered another embodiment. Conversely, for the sake of brevity, various features of the disclosure described herein in the context of a single embodiment may also be provided individually or in any sub-combination. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered as an independent embodiment in itself that can be combined with others.

[0138] The conjunctions “comprising,” “essentially constituting,” and “constituting” are intended to imply the meanings generally accepted in patent language; that is, (i) “comprising,” which is synonymous with “comprising,” “containing,” or “characterizing,” is inclusive or open and does not exclude additional unquoted elements or method steps; (ii) “constituting” excludes any elements, steps, or components not specified in the claim; and (iii) “essentially constituting” limits the claim to a specific material or step that does not substantially affect the “basic and novel feature(s)” of the claimed disclosure. An embodiment described in connection with the phrase “comprising” (or its equivalent) is also provided as an embodiment described independently in connection with “constituting” and “essentially constituting.” In these embodiments provided with respect to "essentially constituted," the basic and novel characteristic(s) are the ease of operation of the method or composition / system for providing a germanosilicate composition in a meaningful yield or the ability of the system to use only these listed components.

[0139] The term “meaningful product yield” is intended to reflect a product yield such as that described herein, but also includes greater than 20%, but where specified, this term also refers to a yield of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or more relative to the amount of the original material.

[0140] When a list is presented, unless otherwise specified, each individual element of the list and all combinations of the list shall be understood as distinct embodiments. For example, a list of embodiments presented as "A, B, or C" shall be interpreted as including embodiments "A," "B," "C," "A or B," "A or C," or "A, B, or C" as distinct embodiments.

[0141] Throughout this specification, words are to be given their normal meanings as understood by those skilled in the relevant art. However, to avoid misunderstanding, the meanings of specific terms will be specifically defined or clarified.

[0142] As used herein, the term "alkyl" refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert - It does not necessarily have to contain 1 to about 6 carbon atoms, such as butyl, etc., but typically represents a linear, branched, or cyclic saturated hydrocarbon group.

[0143] The term "aromatic" refers to aromaticity. It refers to a ring moiety that satisfies the 4n + 2 rule, and includes both aryl (i.e., carbon-cyclic) and heteroaryl structures.

[0144] The term "halide" is used in the common sense to refer to chloride, bromide, fluoride, or iodide.

[0145] "Lower alcohols" or "lower alkanes" each refer to alcohols or alkanes having 1 to 10 carbons, linear or branched, preferably 1 to 6 carbon atoms, preferably linear. Methanol, ethanol, propanol, butanol, pentanol, and hexanol are examples of lower alcohols. Methane, ethane, propane, butane, pentane, and hexane are examples of lower alkanes.

[0146] As used herein, unless otherwise specified, the term “elevated temperature” typically refers to at least one temperature in the range of about 170°C to about 230°C. The term “calcined” is designated for higher temperatures. Unless otherwise specified, it refers to one or more temperatures in the range of about 450°C to about 800°C.

[0147] The term “metal or metalloid” as used herein, such as in “source of metal or metalloid” or “oxide of metal or metalloid,” refers to elements of groups 4, 5, 8, 13, 14, and 15 of the periodic table. These elements are generally found as oxides in molecular sieves, for example, aluminum, boron, gallium, hafnium, iron, silicon, tin, titanium, vanadium, zinc, zirconium, or combinations thereof.

[0148] Typical sources of silicon oxide for reaction mixtures include silicon alkoxides, hydroxides, or oxides, or combinations thereof. Exemplary compounds also include silicates (including sodium silicates), silica hydrogels, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates, silica hydroxides, or combinations thereof. Sodium silicates or tetraorthosilicates, such as tetraethyl orthosilicate (TEOS), diethoxydimethylsilane (DEDMS), and / or 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane (DETMDS) are preferred sources.

[0149] The source of germanium oxide is individual GeO4 4- Ion, GeO(OH)3 - , GeO2(OH)2 2- , [(Ge(OH)4)8(OH)3] 3- Alkali metal orthogermanate containing M4GeO4, or a neutral solution of germanium dioxide containing Ge(OH)4 or its alkoxide or carboxylate derivative.

[0150] Typical sources of aluminum oxide for reaction mixtures include aluminates, alumina, aluminum colloids, aluminum alkoxides, aluminum oxide coated on silica sol, hydrated alumina gels, such as Al(OH)3 and sodium aluminate. Sources of aluminum oxide may also include aluminum alkoxides, hydroxides, or oxides, or combinations thereof. Additionally, sources of alumina may also include other ligands, such as acetylacetonates, carboxylates, and oxalates; these compounds are well known to be useful for hydrothermal or sol-gel synthesis. Additional sources of aluminum oxide may include aluminum salts, such as AlCl3, Al(OH)3, Al(NO3)3, and Al2(SO4)3.

[0151] Sources of boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide and / or zirconium oxide may be added in a form corresponding to their aluminum and silicon counterparts.

[0152] As used herein, the term “mineral acid” refers to mineralizing acids commonly used in the synthesis of molecular sieve zeolites, such as HCl, HBr, HF, HNO3, or H2SO4. Oxalic acid and other strong organic acids may also be used instead of mineral acids. Generally, HCl and HNO3 are preferred mineral acids. As used throughout this specification, the terms “concentrated” and “diluted” in relation to mineral acids refer to concentrations greater than and less than 0.5 M, respectively. In some embodiments, the term “concentrated” refers to a concentration in one or more of the ranges of 0.5 to 0.6, 0.6 to 0.7, 0.7 to 0.8, 0.8 to 0.9, 0.9 to 1.0, 1.0 to 1.1, 1.1 to 1.2, 1.2 to 1.3, 1.3 to 1.4, 1.4 to 1.5, 1.5 to 1.6, 1.6 to 1.7, 1.7 to 1.8, 1.8 to 1.9, and 1.9 to 2.0 or greater. In the experiments and preferred embodiments described herein, concentrated acid refers to one in the compositional range of 0.9 to 1.1 M. Similarly, the term “dilute” refers to one or more concentrations in the ranges of 0.5 to 0.4, 0.4 to 0.3, 0.3 to 0.2, 0.2 to 0.15, 0.15 to 0.1, and 0.1 to 0.05. In the experiments and preferred embodiments described herein, the dilute acid refers to a composition in the range of 0.5 to 0.15 M.

[0153] The term "CIT-13" topology describes a crystalline microporous composition similar to that described in U.S. Patent No. 10,293,330, which has an orthogonally oriented set of 14 pores. The term "phylosilicate" refers to a two-dimensional layered structure of a silica-containing oxide as described in U.S. Patent Application Publication No. 2017 / 0252729.

[0154] The terms “oxygenated hydrocarbon” or “oxygenate” as known in the field of hydrocarbon processing refer to components including alcohols, aldehydes, carboxylic acids, ethers, and / or ketones known to be present in a hydrocarbon stream or derived from other sources in a biomass stream (e.g., ethanol from fermented sugars).

[0155] The terms "separating" or "separated" have the ordinary meaning understood by those skilled in the art, insofar as they mean physically splitting or separating a solid product material from a crude product or byproduct (impurity) associated with reaction conditions that produce another starting material or material. Accordingly, it means that a skilled technician recognizes the presence of the product and takes specific measures to separate or isolate the product from the starting material and / or byproduct. Absolute purity is not required but is desirable. When this term is used in the context of gas processing, the terms "separating" or "separated" mean the splitting of a gas by adsorption or permeation based on size or physical or chemical properties, as understood by those skilled in the art.

[0156] Unless otherwise specified, the term “isolated” means physically separated from other components so as not to contain at least solvent or other impurities, such as starting materials, crude products, or by-products. In some embodiments, for example, the isolated crystalline material may be considered isolated if it is separated from the reaction mixture, the mixed-phase crude product, or both that give rise to its production. In some of these embodiments, pure germanosilicate (including structures with or without incorporated OSDA) may be produced directly from the described method. In some cases, it may be impossible to separate the crystalline phases from one another, in which case the term “isolated” may refer to their separation from the source composition.

[0157] Under IUPA notation, the term "microporous" refers to a material having a pore diameter of less than 2 nm. Similarly, the term "macroporous" refers to a material having a pore diameter greater than 50 nm. The term "mesoporous" refers to a material with a pore size intermediate between microporous and macroporous. Within the context of this disclosure, material properties and applications depend on the characteristics of the framework, such as pore size and dimensions, cage dimensions, and material composition. Consequently, there are often only a single framework and composition that provides optimal performance for a desired application.

[0158] "Arbitrary" or "arbitrarily" implies that the situation described later may or may not occur; therefore, the description includes cases where the situation occurs and cases where it does not. For example, the phrase "arbitrarily substituted" implies that a non-hydrogen substituent may or may not be present on a given atom; thus, the description includes structures in which non-hydrogen substituents are present and structures in which non-hydrogen substituents are not present.

[0159] The terms "method(s)" and "method(s)" are considered interchangeable in this disclosure.

[0160] The terms "crystalline microporous solid" or "crystalline microporous germanosilicate" as used herein refer to crystalline structures having molecular dimensions, i.e., a very regular pore structure of less than 2 nm. The maximum size of species that can enter the pores of the crystalline microporous solid is controlled by the dimensions of the channels. These terms may also specifically refer to CIT-13 compositions.

[0161] The term “pillar” as used herein generally refers to a process of introducing a stable metal oxide structure (“so-called “pillar”) between substantially parallel crystalline silicate layers. The metal oxide structure keeps the silicate layers separated, creating a molecular-level interlayer distance. This term is generally used in the context of clay chemistry and is well understood by those skilled in the art of clay and zeolite, particularly when applied to catalysts.

[0162] The term "germanosilicate" refers to any composition containing silicon oxide and germanium oxide within a framework. The terms "pure" and "pure germanosilicate" mean that such compositions contain only germania and silica, respectively, as much as possible, and that any other metal oxide within the framework is present as an inevitable and unintended impurity. Germanosilicate may be "pure-germanosilicate" or optionally substituted with other metal or metalloid oxides. Likewise, the terms aluminosilicate, borosilicate, ferrosilicate, stannosilicate, titanosilicate, or zincosilicate structures are those containing silicon oxide and oxides of aluminum, boron, iron, tin, titanium, and zinc, respectively. Where described as “arbitrarily substituted,” each framework may contain aluminum, boron, gallium, germanium, hafnium, iron, tin, titanium, indium, vanadium, zinc, zirconium, or other atoms or oxides substituted for one or more atoms or oxides not already contained in the parent framework.

[0163] The term “transition metal” as used herein refers to any element of the d-block of the periodic table, including groups 3 through 12. In practice, the f-block lanthanide and actinide series are also considered transition metals and are referred to as “internal transition metals.” This definition of transition metal also includes elements of groups 3 through 12. In certain other independent embodiments, the transition metal or transition metal oxide comprises elements of groups 6, 7, 8, 9, 10, 11, or 12. In further other independent embodiments, the transition metal or transition metal oxide comprises scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, or a mixture thereof. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.

[0164] The following list of implementation examples is intended to supplement, rather than replace, the previous description.

[0165] Embodiment 1. Crystalline microporous germanosilicate composition designated as CIT-14 / IST having 8-membered and 12-membered ring channels

[0166] Example 2. A crystalline microporous germanosilicate CIT-14 / IST composition of Example 1, characterized by a powder X-ray diffraction (XRD) pattern having at least five characteristic peaks at 2-θ of 7.59 ± 0.5, 8.07 ± 0.5, 12.88 ± 0.5, 19.12 ± 0.5, 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. In a specific aspect of this embodiment, the CIT-14 / IST germanosilicate composition comprises pure germanosilicate. In another independent embodiment of the present embodiment, the CIT-14 / IST germanosilicate composition comprises a framework comprising one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium. In a specific independent embodiment of the present embodiment, the powder X-ray diffraction (XRD) pattern exhibits at least 5 characteristic peaks out of 5, 6, 7, 8, 9, or 10 of these characteristic peaks presented above. In a specific independent embodiment of the present embodiment, the uncertainty in the peak position is independently ± 0.5° 2-θ, ± 0.4° 2-θ, ± 0.3° 2-θ, ± 0.2° 2-θ, ± 0.15° 2-θ, or ± 0.15° 2-θ (for each peak).

[0167] Embodiment 3. A crystalline microporous germanosilicate CIT-14 / IST composition of Embodiment 1 or 2, characterized by a powder X-ray diffraction (XRD) pattern showing at least three characteristic peaks at 7.59 ± 0.5, 8.07 ± 0.5, 19.12 ± 0.5, 20.73 ± 0.5, and 22.33 ± 0.5 ° 2-θ, and optionally at 12.88 ± 0.5, 19.32 ± 0.5, 24.37 ± 0.5, 27.19 ± 0.5, and 27.69 ± 0.5 ° 2-θ. The above-mentioned Table 1 The data of, and the comments related to this table are presented above as can be viewed as independent aspects of the present embodiment.

[0168] Example 4. A crystalline microporous germanosilicate CIT-14 / IST composition of any one of Examples 1 to 3, having a Si:Ge ratio in the range of 12:1 to 13:1, 13:1 to 14:1, 14:1 to 15:1, 15:1 to 16:1, 16:1 to 17:1, 17:1 to 18:1, 18:1 to 19:1, 19:1 to 20:1, or any combination of two or more of the aforementioned sub-ranges, for example, 14:1 to 18:1. Each of these ranges is considered an independent mode within the present embodiment.

[0169] Example 5. A crystalline microporous germanosilicate CIT-14 / IST composition of any one of Examples 1 to 4, wherein the crystal is orthorhombic, and Cmmm space group, or Cmcm A crystalline microporous germanosilicate CIT-14 / IST composition having a space group, or an intracrystalline mixture (disorder) of these two domains.

[0170] Example 6. A crystalline microporous germanosilicate CIT-14 / IST composition of any one of Examples 1 to 5, wherein the crystalline microporous germanosilicate CIT-14 / IST composition has monomer cell parameters according to the following:

[0171] Example 7. A crystalline microporous germanosilicate CIT-14 / IST composition of any one of Examples 1 to 6, wherein the 8-membered ring channels have pore dimensions of about 3.3 Å x 3.9 Å and the 12-membered ring channels have pore dimensions of about 4.9 Å x 6.4 Å. In a specific aspect of this embodiment, the respective pore sizes are 3.26 Å x 3.93 Å and 4.86 Å x 6.44 Å. Physical distortion (e.g., compression) or the Si:G ratio may change these values. In a specific aspect of the present embodiment, the average metal-oxygen (TO) bond length in the framework is in the range of 1.55 to 1.65 Å, the average oxygen-metal-oxygen (OTO) bond length in the framework is in the range of 98° to 116°, and the average metal-oxygen-metal (TOT) bond length in the framework is in the range of 139° to 180°.

[0172] Example 8. A crystalline microporous germanosilicate CIT-14 / IST composition of any one of Examples 1 to 7, wherein the crystalline microporous germanosilicate CIT-14 / IST composition is derived or may be derived from a reaction characterized by the inverse sigma transformation of the crystalline microporous germanosilicate designated as CIT-13 / OH. Specific features of CIT-13 / OH are described in more detail elsewhere in this invention, and such description is incorporated herein by way of being in its entirety.

[0173] Example 9. A crystalline microporous germanosilicate CIT-14 / IST composition of Examples 1 to 8, prepared by contacting a crystalline microporous germanosilicate designated as CIT-13 / OH (described elsewhere in this application) with a concentrated aqueous mineral acid (e.g., a dispersion of germanosilicate in an aqueous acid) at an elevated temperature for a time sufficient to form the microporous germanosilicate "-CIT-14" (also described elsewhere in this application, such description is incorporated into the present embodiment).

[0174] In a specific aspect of the present embodiment: (a) the mineral acid is aqueous HCl or HNO3 or an equivalent strong acid; (b) the concentration of the mineral acid is in the range of 6 to 12 M; (c) the elevated temperature is in the range of 80°C to 120°C, preferably about 95°C; (d) the sufficient time is in the range of 4 to 96 hours, preferably 4 to 24 hours; conditions corresponding to 95°C for 6 hours are suitable; (e) the degermaniculated germanosilicate generated after contact with the acid is separated as a substance designated as "-CIT-14"; and (f) the "-CIT-14" substance is rinsed with water (preferably distilled water or deionized water) until the washing solution becomes pH neutral; (g) The conditions further include 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 to 12 hours, preferably at 580°C for 6 hours, more preferably at a temperature ramp rate of 1°C / min.

[0175] Example 10. A crystalline microporous germanosilicate designated as CIT-13 / OH, which does not contain fluoride, has a three-dimensional framework having pores defined by 10-membered and 14-membered rings, and exhibits a powder X-ray diffraction (XRD) pattern having at least 5 peaks at 2-θ of 6.45 ± 0.2, 7.18 ± 0.2, 12.85 ± 0.2, 20.78 ± 0.2, 26.01 ± 0.2, and 26.68 ± 0.2. In some aspects of this embodiment, the peak at 6.45 ± 0.2° 2-θ has reduced intensity (weakness) compared to the peak at 7.18 ± 0.2° 2-θ, making the latter peak the strongest in the pattern (see Examples). In another aspect of this embodiment, the powder XRD pattern shows an additional peak at 11.58° ± 0.2° 2-θ. Table 2 The data and related comments are considered as independent modes of this embodiment.

[0176] Such compositions of CIT-13 / OH germanosilicate are considered independent embodiments of the present disclosure, such as use in the manufacture of "-CIT-14".

[0177] Embodiment 11. As the crystalline microporous germanosilicate CIT-14 / IST composition of Embodiment 8 or 9 or the crystalline microporous germanosilicate CIT-13 / OH of Embodiment 10, the crystalline microporous germanosilicate designated as CIT-13 / OH (a) Source of silicon oxide (SiO2); (b) a source of germanium oxide (GeO2); and (c) an optional source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations or mixtures thereof; (d) At least one hydroxide salt of a substituted benzyl-imidazolium organic structure-deriver (OSDA) cation having the following structure: (e) at least one compositionally consistent seed determination at any time; and (f) an aqueous composition derived from a mixture of water is prepared by a method comprising hydrothermal treatment of the crystalline microporous germanosilicate composition designated as CIT-13 / OH under conditions effective for crystallizing the composition; said aqueous composition (a) Si:Ge in a molar ratio in the range of 2 to 4, preferably 2.5 to 3.0; (b) Water with a water:Si molar ratio in the range of 8:1 to 12:1; (c) Water in a molar ratio of (SiO2+GeO2) in the range of 6:1 to 7:1; (c) containing hydroxide ions (OH) in an OH:(SiO2+GeO2) molar ratio in the range of about 0.3:1 to 0.7:1; The above aqueous composition essentially does not contain fluoride ions.

[0178] In an independent aspect of the present embodiment:

[0179] (1) The silicon oxide source comprises silicate, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, silica hydroxide or a combination thereof (or an equivalent source), preferably sodium silicate or tetraalkyl orthosilicate, more preferably tetraethyl orthosilicate (TEOS);

[0180] (2) The source of germanium oxide comprises GeO2, or a hydrated derivative thereof (or an equivalent source thereof);

[0181] (3) The substituted benzyl-imidazolium organic structure-directing agent (OSDA) cations are present in an OSDA:(SiO2+GeO2) molar ratio in the range of about 0.3:1 to 0.7:1, preferably in the range of about 0.4:1 to 0.6:1;

[0182] (4) The aqueous composition does not essentially contain alkali metal cations, alkaline earth metal cations or divalent cations, or a combination thereof;

[0095] (5) At least one substituted benzyl-imidazolium organic structure-derived agent (OSDA) cation has the following structure:

[0184] (6) The aqueous composition is a suspension or a gel;

[0185] (7) Effective crystallization conditions include treating the mixture at a temperature of about 140°C to about 180°C for a period of about 4 days to about 4 weeks;

[0186] (7) The aqueous composition is treated with hot water in a rotary oven;

[0187] (8) The above method further includes separating a crystalline microporous germanosilicate solid composition.

[0188] Embodiment 12. A crystalline microporous germanosilicate CIT-14 / IST composition of Embodiment 8, 9, or 11 or a crystalline microporous germanosilicate CIT-13 / OH of Embodiment 10 or 11, wherein the crystalline microporous germanosilicate designated as CIT-13 / OH does not contain fluoride and has d4r units having an average of at least and preferably more than 4 Ge atoms per d4r unit, allowing for the presence of Ge-4-rings in the d4r units. A method for determining the average number of Ge atoms in the d4r units is presented elsewhere and is included in this embodiment. In some independent embodiments of this embodiment, the Si:Ge ratio is in the range of 3.5 to 3.6, 3.6 to 3.7, 3.7 to 3.8, 3.8 to 3.9, 3.9 to 4.0, 4.0 to 4.1, 4.1 to 4.2, 4.2 to 4.3, 4.3 to 4.4, 4.4 to 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 a range defined by any two or more of the above ranges, e.g., 3.5 to 3.9. Each of these ranges is considered an independent embodiment within this embodiment.

[0189] Embodiment 13. A crystalline microporous germanosilicate CIT-14 / IST composition of Embodiments 8, 9, 11 or 12, or a crystalline microporous germanosilicate CIT-13 / OH of any one of Embodiments 10 to 12, wherein the crystalline microporous germanosilicate CIT-14 / IST composition or crystalline microporous germanosilicate CIT-13 / OH having micropores optionally containing an alkali metal cation salt, an alkaline earth metal salt, a transition metal, a transition metal oxide, a transition metal salt, or a combination thereof. The properties of the salt, metal, and metal oxide are considered elsewhere in this specification and are included in this embodiment. In a specific aspect of this embodiment, each germanosilicate exists in the form of hydrogen. In another aspect of this embodiment, each germanosilicate contains one or more of a salt, a metal, or a metal oxide within its micropores.

[0190] Example 14. A catalyst comprising a crystalline microporous germanosilicate CIT-14 / IST composition of any one of Examples 1 to 9 or 11 to 13, or a crystalline microporous germanosilicate CIT-13 / OH of any one of Examples 10 to 13.

[0191] Embodiment 15. A method for separating substances or influencing organic conversion, wherein the method By contacting each feedstock with the catalyst of Example 14 under conditions sufficient to influence the named conversion, (a) Carbonylation of DME with CO at low temperatures; (b) Reduction of NOx to methane; (c) Decomposing, hydrolyzing, or dehydrogenating hydrocarbons; (d) Dewaxing the hydrocarbon feedstock; (e) Converting paraffin into aromatics: (f) isomerizing or disproportionating aromatic feedstocks; (g) Alkylating aromatic hydrocarbons; (h) Oligomerizing alkenes; (i) Amination of lower alcohols; (j) Separating and adsorbing lower alkanes from a hydrocarbon feedstock; (k) isomerizing olefins; (l) Producing high molecular weight hydrocarbons from low molecular weight hydrocarbons; (m) Reforming hydrocarbons; (n) converting lower alcohols or other oxygenated hydrocarbons to produce olefin products (including MTO); (o) Epoxideizing an olefin with hydrogen peroxide; (p) Reducing the content of nitrogen oxides contained in a 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) A method comprising reducing the concentration of organic halides in the initial hydrocarbon product.

[0192] Embodiment 16. A method for preparing a crystalline microporous germanosilicate CIT-14 / IST composition (or any composition designated as CIT-14 / IST elsewhere in this invention) of any one of Embodiments 1 to 9 or 11 to 13, the method comprising contacting a crystalline microporous germanosilicate designated as CIT-13 / OH as presented in at least one of Embodiments 10 to 12 (or described elsewhere in this invention) with a concentrated aqueous mineral acid (e.g., as a dispersion of germanosilicate in an aqueous acid) at an elevated temperature for a time sufficient to form the microporous germanosilicate "-CIT-14" as prepared (also described elsewhere herein, such description also incorporated into this embodiment).

[0193] In a specific aspect of this embodiment: (a) the mineral acid is aqueous HCl or HNO3 or an equivalent strong acid; (b) the concentration of the mineral acid is in the range of 6 to 12 M; (c) the elevated temperature is in the range of 80 to 120°C, preferably about 95°C; (d) the sufficient time is in the range of 4 to 96 hours, preferably 4 to 24 hours; conditions corresponding to 95°C for 6 hours are suitable; (e) the degermaniculated germanosilicate produced after contact with the acid is separated as a substance designated as "-CIT-14"; and (f) the "-CIT-14" substance is rinsed with water (preferably distilled water or deionized water) until the washing solution becomes pH neutral.

[0194] Embodiment 17. A method according to Embodiment 16, further comprising the step of calcining a “-CIT-14” composition prepared and washed at a time and temperature sufficient to form a crystalline microporous germanosilicate CIT-14 / IST composition. In a specific independent embodiment, these conditions further comprise 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 to 12 hours, preferably at 580°C for 6 hours, more preferably at a temperature ramp rate of 1°C / min.

[0195] The present disclosure also includes embodiments of CIT-13 / OH germanosilicate prepared by a hydroxide route as specifically described herein. The present disclosure also includes such embodiments of CIT-13 / OH germanosilicate characterized by having d4r units containing an average of at least, preferably more than 4, Ge atoms per d4r unit, thereby allowing the presence of Ge-4-rings in these d4r units. The present disclosure also includes embodiments of CIT-13 / OH germanosilicate exhibiting previously unobserved reactive features, which are a result of the novel and unique physical features presented herein. Examples

[0196] The following examples provide experimental methods used to characterize these novel materials and their transformations and to exemplify parts of the concepts described within this disclosure. Each example provided in the body of this specification and elsewhere in the body of this specification is considered to provide a specific individual embodiment of the composition, method of preparation, and use, but none of the examples should be considered to limit the more general embodiments described herein.

[0197] Unless otherwise specified, powder XRD patterns, nmr spectra, or other representations of structures presented herein for a particular composition are considered to be attributable to the general structures associated with them.

[0198] In the following examples, efforts have been made to ensure accuracy regarding the numbers used (e.g., quantities, temperatures, etc.), but some experimental errors and deviations must be taken into account. Unless otherwise indicated, temperatures are in degrees Celsius and pressures are at or near atmospheric pressure.

[0199] Example 1. Experiment

[0200] Example 1.1. Material Preparation

[0201] CIT-13 (representing CIT-13 / OH) was crystallized from fluoride-free gels using 1,2-dimethyl-3-(2-methylbenzyl)imidazolium hydroxide (denoted "orthomethylbenzyl") or 1,2-dimethyl-3-(3-methylbenzyl)imidazolium hydroxide (denoted "metamethylbenzyl") as the OSDA, which is equivalent to generating CIT-13 in a fluoride medium. Synthesis protocols for the two OSDAs are provided elsewhere. The gel composition ratio was x / (x+1) SiO2: 1 / (x+1) GeO2: 0.5 ROH: y H2O, where x is the gel Si / Ge ratio and y is the gel H2O / (Si+Ge) ratio. Standard values ​​for x and y are provided below. Detailed procedures and gel compositions are provided below. CIT-13 / OH samples are denoted as CIT-13 / OH[z], where z is the Si / Ge ratio of the CIT-13 crystal measured using energy dispersive spectroscopy (EDS).

[0202] CIT-13 from a conventional fluoride-containing gel (denoted as CIT-13 / F) was also prepared for comparative analysis with CIT-13 / OH, based on a previously reported method. Similar to the case of the CIT-13 / OH sample, the CIT-13 / F sample was denoted as CIT-13 / F[z], where z is the crystalline Si / Ge ratio measured using EDS.

[0203] IM-12 samples were also prepared for comparison with CIT-13 based on protocols previously reported in the literature. Similar to CIT-13, the IM-12 samples were also denoted as IM-12[z] (z = EDS Si / Ge ratio).

[0204] Example 1.2. Detailed synthesis of CIT-13 / OH

[0205] The dry weight of the liner and stirring rod must be characterized because the desired water level must be adjusted based on the total weight (liner + stirring rod + gel) at the final stage of gel preparation.

[0206] Germanium dioxide (99.999%, Strem) was completely dissolved in an OSDA solution in a 23-mL PTFE liner for a Parr steel autoclave. 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 method used to prepare these OSDAs is 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 evaporated under an airflow at room temperature until the gel became thick and viscous. Ethanol, a hydrolysis product of TEOS, appears to have a negative effect on both the crystallization rate and purity of the product. To maximize the degree of ethanol removal, additional purified water (approx. 10 mL) was added to the viscous gel and evaporated again while stirring until the gel became viscous. This water addition-evaporation step was repeated a total of five times. (Note: If fumed silica is used as the Si source, this ethanol removal step is not strictly necessary.) Finally, as mentioned above, the desired moisture content was adjusted based on the total weight (liner + stirring rod + gel). The final gel composition was x / (x+1) SiO2: 1 / (x+1) GeO2: 0.5 ROH : y H2O, where x is the gel Si / Ge ratio and y is the gel H2O / (Si+Ge) ratio. The values ​​of x and y are Table 4 It can be found in [location]. The optimized ranges for x and y are given in the text. If necessary, CIT-13 seed crystals (5 wt% relative to total SiO2+GeO2 weight) were added. The gel was tightly sealed in a steel autoclave and placed in an oven preheated to the desired temperature.

[0207] After one week of crystallization, the gel was removed. Generally, the gel turned dark brown and solidified one week after the initial crystallization. The solidified gel was thoroughly ground into a powder using a clean, rigid PTFE rod. The ground gel was placed back into the oven to resume crystallization. Aliquots were taken weekly to monitor the degree of crystallization. The final product was repeatedly washed with distilled water and acetone and dried in a 100°C convection oven.

[0208] Gel composition, crystallization conditions, and corresponding results Table 4 It was summarized in.

[0209] Example 1.2. Germanosilicate conversion and transformation of CIT-13 / OH to CIT-14 / IST after synthesis

[0210] * The conversion from CTH to CFI was performed by exposing freshly calcined CIT-13 / OH samples to ambient air containing moisture. To ensure consistency with the results of previous work, only one condition (30% relative humidity at 25°C (pH2O = 7.1 Torr)) was used. The degree of conversion was monitored based on PXRD. CIT-14 / ESP (ESP represents the ethoxysilylation column) and CIT-14 / IST (IST represents the inverse sigma conversion) were prepared based on the weak acid ADOR-type conversion of CIT-13 / F and the inverse sigma conversion of CIT-13 / OH, respectively. The 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 repeatedly washed with distilled water until the pH became neutral. CIT-14 / IST, the final material where IST signifies the inverse sigma transformation, is "-CIT-14" at 1℃ min -1It was obtained by heating at 580°C for 6 hours at a temperature ramping rate. For comparison, an inverse sigma transform from UTL to OKO was also performed using the prepared IM-12 sample. SEM images of the CIT-14 / IST sample Fig. 4(ab) It was built in.

[0211] 19 F Magic-Angle Spinning (MAS) and 1 H- 29 For Si cross-polarization (CP) MAS NMR studies, degermination and fluorination of germanosilicate were performed. Cold water degermination of calcined germanosilicate was carried out as follows: 100 mg of freshly calcined germanosilicate was immersed in 100 mL of distilled water at room temperature and stirred overnight. The resulting solid was recovered using a centrifuge and washed repeatedly with distilled water. The degerminated sample was dried under vacuum at room temperature. Post-synthesis fluorination of germanosilicate crystallized in fluoride-free medium was carried out as follows: 100 mg of the prepared raw CIT-13 / OH was finely ground with 20–25 mg of ammonium fluoride 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.

[0212] Example 1.3. Characterization

[0213] Powder X-ray diffraction (PXRD) profiles were collected using a Rigaku Miniflex II diffractometer (Cu Kα radiation λ = 1.5418 A). High-resolution PXRD data were collected at the 2-1 Powder Diffraction beamline of the Stanford Synchrotron Radiation Lightsource (SSRL) using a wavelength of 0.9998 A. For high-resolution PXRD experiments, calcined CIT-14 powder samples were packed and sealed in 1.0 mm glass capillaries.

[0214] Scanning electron microscope (SEM) images and elemental analysis data were collected using a ZEISS 1550VP field emission (FE)-SEM microscope equipped with an Oxford X-max SDD EDS system. Ar-adsorption isotherms were acquired at 87.45 K using a Quantachrome Autosorb iQ analyzer. Solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were obtained using a Bruker Avance 500 MHz spectrometer (magnetic 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 Spectrum, 29 Si MAS spectrum and 1 H- 29 Si CPMAS spectra are collected at a MAS rotation speed of 8 kHz, and 19 The F MAS spectrum was collected at 12 kHz.

[0215] Example 2. Results and Discussion

[0216] Example 2.1 Discussion of Synthesis

[0217] CIT-13 can be crystallized in a hydroxide medium by omitting the fluoride and further modifying the gel composition from that of the fluoride pathway for CIT-13. Unlike CIT-13 / F, which can be crystallized in a moderately high range of gel compositions, CIT-13 / OH is obtained in a much narrower range of gel compositions. The ranges of the gel Si / Ge ratio and the gel H2O / (Si+Ge) ratio are 2 < Si / Ge < 4 and 6 < H2O / (Si+Ge) < 7, respectively, when OSDA / (Si+Ge) = 0.5, preferably 2.5 < Si / Ge < 3.0 and 6.0 < H2O / (Si+Ge) < 6.5. Gel compositions outside this range produced amorphous germanosilicate or an unknown dense phase. Crystallization of the pure CIT-13 phase was observed at 160°C and 175°C. Synthesis details (e.g., gel composition, etc.) are Table 4 It is provided in. CIT-13 / OH is similar to CIT-13 obtained from fluoride-containing preparations and their isostructural germanosilicates. Fig. 5(ac) As shown in [4.33], it had a plate-like crystal form. CIT-13 / OH [4.33] as manufactured 1 H- 13 C CPMAS spectrum and OSDA solution phase 13 C NMR( Fig. 6 ) confirmed that the structure of OSDA was preserved during the crystallization of CIT-13 / OH. of the same material as manufactured. 1 H- 29 The Si CPMAS spectrum also revealed the presence of connection defects compensating for the absence of fluoride. (Fig. 7)

[0218] The PXRD profiles of manufactured and calcined CIT-13 / OH[3.88] and CIT-13 / OH[4.33] are Fig. 8(be) It was indicated in. Other PXRD patterns are Fig. 9Provided in. All PXRD profiles were obtained under ambient conditions. The positions of the diffraction peaks Fig. 8(f) It matched well with the position of the reference CIT-13 / F shown in [Figure]. However, there was a difference in peak intensity between CIT-13 / F and CIT-13 / OH. Except for CIT-13 / OH[3.88], the only CIT-13 / OH crystallized using ortho-methylbenzyl OSDA ( Fig. 8(a) and Fig. 9(b) ), all other manufactured CIT-13 / OH synthesized from meta-methylbenzyl OSDA Fig. 8(d) and Fig. 9(ck) As shown in [figure], a very weak (200) peak was exhibited at 2θ = 6.44°. This weak (200) peak from the CIT-13 / OH as prepared became stronger after removing OSDA by calcination. ( Fig. 8(e) Also, some of the CIT-13 / OH samples Fig. 9(dg) and 9(ij) As exemplified in [Figure], it shows a clearly identifiable (310) peak at 2θ = 11.58°. This (310) diffraction was attenuated by insertion after the synthesis 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 within the CIT-13 framework and the presence of meta-methylbenzyl OSDA cations appear to be responsible for the weak intensity of the (200) peak and the occasional appearance of the (310) peak.

[0219] The argon physisorption isotherm of CIT-13 / OH[3.56] obtained at 87.45 K is Figure 8(g)It is illustrated in and superimposed with CIT-13 / F[4.18] for comparison. The micropore volume of CIT-13 / OH[3.56] was 0.141 cc / g based on the t-plot method (0.202 cc / g by the Saito-Foley method). This micropority is slightly lower than that of reference CIT-13 / F[4.18] (de Boer t-plot: 0.172 cc / g; Saito-Foley: 0.223 cc / g). Characteristic two-step adsorption due to the presence of 10 MR and 14 MR of CIT-13 ( Indicated by ↓ in Fig. 8(g). ) was also observed as CIT-13 / OH as expected.

[0220] Example 2.2. * Discussion on the conversion from CTH to CFI

[0221] Unlike other d4r-type germanosilicates such as UTL, IWW, and ITH, which are known not to undergo similar conversion, CIT-13 type germanosilicate slowly converts to CFI-type germanosilicate when exposed to ambient moisture. * Conversion from CTH to CFI). This conversion occurred by rearranging Ge-rich d4r units into dzc units due to instability in the CIT-13 framework induced by the presence of germanium-rich d4r units and the crystallographic properties of the cfi-layer. Interestingly, CIT-13 / OH converted to its corresponding germanosilicate CIT-5 much faster than CIT-13 / F, which has a similar germanium content. CIT-13 / OH [4.33] completed the conversion to CFI within 12 days, whereas CIT-13 / F [4.31] took 85 days to fully convert to the CFI-type germanosilicate. The PXRD profile of calcined CIT-13 / OH [4.33] after exposure to ambient moisture (pH2O = 7.1 torr, 30% relative humidity at 25°C) for a certain period of time Fig. 11(a) and 11(b)It is shown in [figure]. The (400) peak of CIT-13, initially superimposed with the (002) diffraction at 2θ = 13.07°, shifted to 2θ = 13.69° and could be seen separately after 2 days. After 8 days, three characteristic diffractions of the CFI framework—(301), (002), and (400)—began to appear. After 10 days of ambient exposure, the PXRD profile matched well with the profile of the reference pure silica CIT-5. The time-dependent position of the cfi-cfi interlayer distance estimated from the location of the (200) diffraction is Fig. 11(e) CIT-13 / OH[4.33] and CIT-13 / F[4.31] are shown, demonstrating the faster conversion of CIT-13 / OH compared to that of CIT-13 / F.

[0222] In the case of CIT-13 / F, reducing the Si / Ge ratio from 4.31 to 3.87 shortened the time required to achieve complete transformation from approximately 4 months to 12 days. This acceleration of the transformation speed can be attributed to the increase in germanium sites within the d4r unit, a structural building unit that transforms into the dzc unit of the CFI framework. Similar to the case of CIT-13 / F, the reduction in the Si / G ratio of CIT-13 / OH * It further accelerated the conversion from CTH to CFI. CIT-13 / OH[3.88] Fig. 11(c) and 11(d) As shown in [3.87], it was converted into the corresponding CIT-5 type germanosilicate within 2 days. This is at least 6 times faster than the same conversion using CIT-13 / F [3.88]. of calcined CIT-13 / OH [3.88] and the generated Ge-CIT-5 29 Si NMR spectra were acquired to study the environment of Si-sites within these germanosilicates ( Fig. 12Similar to the case of CIT-13 / F, CIT-13 / OH exhibited three groups of signals at -104.2, -109.4, and -113.9 ppm. This spectral shape is similar to the previously reported CIT-13 (the above). Fig. 3 It was consistent with related materials synthesized in fluoride media (see reference). Unlike Ge-CIT-5 derived from CIT-13 / F, which showed a single broad signal ensemble at -110.61 ppm, Ge-CIT-5 from CIT-13 / OH[3.88] exhibited two separate groups of peaks at approximately -109.0 and -112.2 ppm. The disappearance of the shoulder at -104.2 ppm in the CIT-13 spectrum may be due to the reassembly of d4r units into dzc bridging units, which was also observed in the transformation of CIT-13 / F. Therefore, since both signals share the same origin as the -113 and -115 ppm signals of pure silica CIT-5, they can be assigned to the cfi-layer Si sites.

[0223] The higher the germanium content of the CIT-13, the *Based on the fact that the conversion from CTH to CFI was faster, it can be inferred that CIT-13 / OH crystals contain more germanium within the d4r unit than CIT-13 / F crystals with a similar overall Si / Ge ratio. In CIT-13 / F, the cfi-layer was also confirmed to have a non-zero germanium occupancy rate. The formation of d4r unit is known to be promoted by a high germanium content and / or the presence of fluoride anions, which can stabilize the low framework TOT angle. The formation of a d4r-type CIT-13 framework in the absence of fluoride can increase the incorporation of germanium into the d4r unit. Indeed, CIT-13 / OH samples with a low Si / Ge ratio underwent inverse sigma conversion in concentrated acid to produce "-CIT-14," a COK-14 analogue of IM-12. The ability to undergo this type of transformation strongly suggests that there is a high content of clustered germanium sites within the d4r unit, but also the presence of pure Ge-4 rings.

[0224] Example 2.3. Discussion of phase transition from CIT-13 to "-CIT-14" and CIT-14 / IST

[0225] Despite the structural similarities between CIT-13 and IM-12, due to strong acids * The leaching of Ge-4 rings from CTH-type germanosilicate has been reported. Unlike IM-12 *Si-O-Si interlayer bridging bonds in CTH-type germanosilicates have been proposed as a major obstacle to this transformation. The ADOR-type transformation from SAZ-1 to IPC-16 and the Pawley refinement of the latter have been demonstrated. Very recently, the partial removal of T-sites within the d4r monomers of CIT-13 / F based on weak-base treatment to produce ECNU-23 has been reported. Nevertheless, the presence of a pure Ge-4 ring within the d4r monomer is essential for a true inverse sigma transformation by strong acids, and IM-12 was the only d4r-type germanosilicate possessing these structural and elemental prerequisites.

[0226] Ge-rich CIT-13 crystallized in a hydroxide medium is Fig. 13(a) As schematically illustrated in [Figure], it may undergo a structural transformation that can be explained by the simultaneous removal of the Ge-4-ring from the inverse sigma transformation d4r. Two examples (CIT-13 / OH[3.71] and CIT-13 / OH[3.56]) Fig. 13(b) This has been demonstrated here based on the PXRD profile shown in [figure]. The nomenclature used by Verheyen (Nat. Mater. 2012 According to , 11, 1059), the material freshly acid-treated prior to calcination is designated as "-CIT-14". Although Rietveld refining was not performed on "-CIT-14", monomer cell parameters along the interlaminar direction (i.e., the a-direction) were observed to decrease slightly after calcination of "-CIT-14", similar to the condensation of -COK-14 to COK-14. The presence / absence of fluoride and germanium content were the two most important synthesis factors for the preparation of CIT-13 germanosilicate capable of generating CIT-14 through inverse sigma transformation. Treatment of calcined CIT-13 / F[3.87] with 12M HCl did not produce "-CIT-14" despite the high germanium content. Furthermore, the same treatment of CIT-13 / OH[4.33] resulted in a disordered layered material ( Fig. 14(ab) ).

[0227] For comparison, an isostructural material was obtained based on the conventional ADOR transformation of CIT-13, denoted here as CIT-14 / ESP. This transformation was similar to the transformation from SAZ-1 to IPC-16. The PXRD profile of CIT-14 / ESP from the ADOR-type transformation of CIT-14 / IST and CIT-13 / F[4.33], prepared by treating calcined CIT-13 / OH[3.56] with 12 M HCl, is Fig. 15(a) and Fig. 15(b) This is shown in [Figure], and the reference CIT-14 model is based on the GULP structural optimization algorithm. Clearly, the intensity of the (200) interlayer diffraction of CIT-14 / IST was stronger than that of CIT-14 / ESP. This difference in diffraction intensity may be attributed to the elemental composition of the single-4-ring (s4r) bridging unit of CIT-14. The effect of the germanium occupancy at each of the seven T-sites of CIT-14 on the intensity of (110) and (200) diffraction was calculated, and the results Fig. 16 It was provided in. The germanium occupancy of the two T-regions (T3 and T7) was found to significantly increase the relative intensity of (110) diffraction in PXRD. T7 is the s4r region, and T3 is the region immediately adjacent to the d4r region. In fact, the germanium content of T7 was 21% in the Rietveld refinement of CIT-14 / IST, which accounts for 52% of the total germanium population of the entire framework. (Above Table 5 (Reference). No significant germanium occupation for T3 was detected. Given that the inverse sigma transformation removes the pure Ge-4 ring from the d4r unit of the parent germanosilicate, it can be concluded that the d4r unit of CIT-13 / OH has, on average, more than 4 germanium atoms. However, CIT-14 / IST and CIT-14 / ESP 1 H-separated 29No significant difference was found between the Si MAS spectra. Fig. 15(d) Both CIT-14s exhibit a broad signal envelope centered at approximately -112 ppm. This spectral similarity was likely due to the presence of germanium sites remaining within the CIT-14 framework. Additionally, a negligible amount of Q3-type silanol was detected.

[0228] As mentioned above, 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] were found to be 14.5 and 17.5, respectively. These values ​​are higher than those of CIT-14 / ESP samples (Si / Ge = 50-253, depending on the degree of degermination), for which the manufacturing procedure involves degermination exfoliation using a weak acid (0.1 M HCl). Fig. 17 It is lower than the value (see reference). The Si / Ge ratios of the COK-14 samples prepared here using the same procedure for the two IM-12 samples (Si / Ge = 3.80 and 4.79) were 17.5 and 29.2, which were much lower than the value reported by Verheyen et al. (Si / Ge = 110), likely due to the lower Si / Ge ratio of the parent IM-12.18. Fig. 18 and 19 (Reference). These values ​​were also much lower than those of IPC-2 (reported Si / Ge = 97) prepared from the ADOR product from IM-12 that underwent weak acid exfoliation, just like CIT-14 / ESP. These results support the idea that the inverse sigma transformation by strong acid leaves extra germanium sites (other than the removal of the Ge-4 ring) within the d4r unit without leaching.

[0229] The microporosity of CIT-14 was investigated using the argon adsorption isotherm obtained at 87.45 K ( Fig. 20While CIT-14 / IST did not exhibit adsorption-desorption hysteresis, CIT-14 / ESP showed a desorption curve that deviated significantly from the adsorption curve. Similar hysteresis was observed in IPC-2 formed by the ADOR-type columnarization procedure. Such small mesopority is generally observed after post-synthesis treatment in a nitric acid medium. Furthermore, the specific micropore volume of CIT-14 / IST (0.105 cc / g in the t-plot; 0.141 cc / g in Saito-Foley) is higher than that of CIT-14 / ESP (0.065 cc / g in the t-plot; 102 cc / g in Saito-Foley). A similar trend was observed during the conversion from UTL to OKO. In addition, Fig. 20(b) As can be clearly seen from, CIT-14 / IST is CIT-13 (p / p0~ 3x10 -4 p / p0 = approximately 1x10 lower than ) -4 It began adsorbing argon. This adsorption onset pressure was very similar to that of 8MR cyclic zeolite A (LTA) (p / p0 ~ 1x10⁻⁶). -4 Therefore, argon absorption by CIT-14 was initiated by adsorption onto 8MR pores.

[0230] The reduction in micropore volume associated with the inverse sigma transformation of CIT-13 to "-CIT-14" was investigated theoretically and experimentally. For theoretical evaluation, the reduction in pore volume was estimated using the TOTOPOL utility for topological analysis developed by Treacy and Foster. Crystallographic information (cif) files obtained from Rietveld refining for CIT-13 and CIT-14 / IST (see this work below) were used as a framework model for calculations. The results are Table 6This is summarized in [link]. The experimentally observed reduction in micropore volume (Saito-Foley: 30.2%; t-plot: 25.5%) appears to underestimate the micropore volume of CIT-13 and CIT-14 when compared to experimentally obtained values, but it was similar to or lower than the values ​​estimated using TOTOPOL (30.2%).

[0231] Since the positions of the bridging regions—that is, the layer regions directly connected to the d4r or s4r units of CIT-13 or CIT-14, respectively—did not change during the inverse sigma transformation, CIT-14 / IST directly inherited the disorder pattern from the parent CIT-13. Indeed, the (111) and (201) diffraction peaks, which are estimated to be located at 2θ = 11.43° and 11.78°, respectively, in the disorder-free model based on the GULP algorithm, were not observed in the actual PXRD pattern of CIT-14 / IST. Fig. 15(c) ) Such diffraction was not observed in CIT-14 / ESP either, which is consistent with the previously reported ADOR transformation from SAZ-1 to IPC-16. However, in the ADOR transformation, Ge-rich d4r was completely removed by exfoliation in a weak acid, and bridging s4r was formed by a newly introduced silicon source such as diethoxydimethylsilane. Therefore, the disorder pattern of CIT-14 / IST may not be identical to the disorder patterns of CIT-14 / ESP and IPC-16.

[0232] The XPD pattern can be indexed into orthorhombic monomer cells (a = 21.90 A, b = 13.74 A, and c = 10.11 A) using the program TREOR35 implemented in the software CMPR.36. The initial CIT-14 framework structure model was derived from the CIT-13 framework structure (assumed to be all silica)20 via inverse sigma transformation, without introducing disorder from CIT-13. The geometry was determined using the space group program DLS-7637. Cmmm It was further optimized assuming, and this is the mod CIT-13( * It is identical to the group of CTH). Subsequently, this became the starting point for Rietveld refining using the TOPAS program. The final structure of CIT-14 / IST has a matching value R F = 0.057, R wp = 0.078 and R exp It was obtained based on Rietveld refining of a powder pattern having = 0.053 ( Fig. 21(a) ).

[0233] Since all symmetry elements are preserved, the inverse sigma transform satisfies the IUPAC definition of a phase transformation. The idealized structure and porous system of CIT-14 / IST, respectively Fig. 21(b) and 21(c) As shown in [figure]. CIT-14 / IST has a two-dimensional channel system divided into 12MR and 8MR pores with limiting dimensions of 6.4 x 4.9 A and 3.9 x 3.3 A, respectively. Similar to ferrierite (FER), CIT-14 / IST has small cages connected to two adjacent straight main channels through small pore openings, whereas the other two known 2D 12 / 8MR topologies, EON and MOR, lack such cage structures. Due to the presence of disorder ( Fig. 21(d)(as illustrated in [figure]), the 8-MR minor channel is not linear. The monomer cell parameter c can also be defined as the average structure as c' = c / 2 = 5.0569 A, but using a smaller monomer cell did not improve refinement (i.e., changes in atomic coordinates and profile fitting are minimized, but the number of parameters to be refined increases). Detailed crystallographic information on CIT-14 / IST Table 5 and 7 , and Fig. 22 It was provided to.

[0234] Example 2.4. Discussion of Ge-arrangement in d4r unit

[0235] The inverse sigma transformation of d4r-type germanosilicates can indirectly provide evidence for the presence of pure Ge-4 rings (within the d4r monomers) parallel to the layers. As discussed in the previous section, Ge-rich CIT-13 / OH (Si / Ge ratio < 3.7), like IM-12, underwent inverse sigma transformation to produce CIT-14 / IST, which possesses high crystallinity and a well-defined pore system. Furthermore, the remaining s4r monomers of CIT-14 possess germanium sites based on PXRD and structural refining. Therefore, the elemental composition of the d4r monomers in CIT-13 / OH is [Si n Ge 8-n ]-d4r(n<4), and when the Si / Ge ratio is low, it can be estimated that four Ge atoms occupy a complete face of d4r. Although CIT-13 / F can be converted to CIT-14 / ESP using the ADOR strategy, the inventors were unable to achieve an inverse sigma conversion using this. Furthermore, as mentioned above, CIT-13 / OH is compared to CIT-13 / F samples having a similar germanium content *The conversion rate from CTH to CFI was found to be much higher. These results also indicate that the presence or absence of fluoride, which can structure and stabilize d4r monomers, plays an important role in the composition and distribution of organized elements within the d4r monomers of the superporous germanosilicate CIT-13.

[0236] 19 F NMR spectroscopy can be used as a tool to elucidate the elemental composition of small ring-building units, such as d4r units. Germanosilicates that are not incorporated with fluoride anions in direct synthesis can be modified into their original or degermanized frameworks by inserting fluoride after synthesis. F-integrated d4r-type germanosilicates generally exhibit three signals at approximately -8 ppm (broad), -19 ppm (sharp), and -38 ppm (sharp), which are typically assigned to [Si4Ge4]-d4r, [Si7Ge]-d4r, and [Si8]-d4r, respectively. There has been general consensus regarding the latter two tasks. However, the characterization of the earlier -8 ppm peak, which is generally broad and sometimes accompanied by one or two shoulder signals, remains questionable due to the various possibilities of germanium arrangements.

[0237] of CIT-13 / F and fluorinated CIT-13 / OH samples as prepared 19 The F NMR spectrum is Fig. 23(ac) This is illustrated in [figure]. All CIT-13 samples exhibit a broad peak centered at approximately -8 ppm, with no signal at -19 and -38 ppm, indicating germanium enrichment in the d4r monomers of these CIT-13 samples. Fluorination after the synthesis of CIT-13 / OH also resulted in the appearance of a sharp signal at -123.7 ppm accompanied by multiple rotational side bands, which is likely due to surface etching on the surface 19It appears to have originated from F-Si species. This surface etching did not cause any structural degradation, as 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 germanium arrangement within the d4r monomer of CIT-13 is less uniform than that of fluorinated IM-12, regardless of the type of mineralizing agent used. The -8 ppm signal of the CIT-13 sample was deconvolved into two peak groups: line 1 (-7.3 to -8.3 ppm) and line 2 (-11.0 to -11.7 ppm). Despite similar germanium content, CIT-13 / OH[4.33](16%) is Fig. 23(a) and 23(b) As shown in [Image], it provided a stronger line 2 signal than CIT-13 / F[4.33](1%). These results indicated that the absence of fluoride in CIT-13 synthesis actually affected the arrangement of germanium sites within the d4r unit. As demonstrated above, CIT-13 / OH[4.33] converts to the corresponding Ge-CIT-5 much faster than CIT-13 / F with a similar Si / Ge ratio, and this * The CTH-CFI conversion was driven by the hydrolysis of the TO-Ge bond. IM-12, which has a Ge-O-Ge bond, decayed very rapidly (within 1 day) when exposed to ambient conditions. Kasian et al. showed that fluorinated IM-12 exhibited a -12 ppm shoulder peak next to the main -8 ppm peak (the -3 ppm shoulder peak observed in fluorinated IM-12 was not detected in CIT-13). Therefore, it is believed that the origin of the line 2 signal in CIT-13 / OH can be attributed to a highly clustered arrangement of germanium sites within the d4r unit, such as the Ge-4 ring.

[0238] The contribution of line 2 was further increased in the 19F spectrum of CIT-13 / OH[3.56](23%), which underwent an inverse sigma transform to CIT-14 / IST( Fig. 23(c) As described in ). Others [describe] a series of STW-type germanosilicates ranging from pure silica to pure germania 19 F NMR spectra were investigated, and a shift in the major 19F signal from -7.5 ppm to -10.5 ppm was reported as a result of the decrease in the Si / Ge ratio from 5 to 0.42. Others also [reported] the Ge-rich ITQ-21 material 19 The presence of a high-field signal at -14 ppm in the F NMR spectrum was also reported. Using these results as a guide, the inventors believe that an up-field signal such as line 2 may be attributed to the high germanium content in the d4r unit.

[0239] The arrangement of germanium sites within the d4r monomer of CIT-13 / OH is related to the germanosilicate degermaninized using distilled water 1 H- 29 It was further investigated based on the Si CPMAS NMR spectrum ( Fig. 24 Using this type of treatment, it was assumed that most germanium sites are removed from the d4r unit, and consequently, adjacent silicon sites become silanol sites. Water-degermanized CIT-13 and IM-12 samples generally exhibit strong Q3 signals in addition to fully connected Q4 signals. The main difference between the samples was the intensity of the Q2-type (geminal) silanol signal. Degermanized IM-12 samples (Si / Ge = 4.89 and 4.23) showed the weakest Q2 signals among the degermanized materials studied, which is consistent with previous observations by others. These IM-12 samples were Ge-rich than IM-12 (Si / Ge = 5.3), which was confirmed to undergo inverse sigma transformation. 1 H-29 The trace of the Q2 signal in the Si CPMAS spectrum may be due to excessive degermination. Unlike the IM-12 sample, Fig. 24 The four CIT-13 samples shown provided a Q2 signal of moderate intensity. Of the four studied CIT-13 samples, only CIT-13 / OH [3.71] generated CIT-14 / IST through inverse sigma transformation, which exhibited the weakest Q2 signal among the CIT-13s. The two CIT-13 / F samples provided a stronger Q2 signal than CIT-13 / OH [4.33] regardless of the Si / Ge ratio. These CIT-13 / F samples were not transformed into CIT-14 through inverse sigma transformation as indicated above. Furthermore, their degerminate forms 1 H- 29 The Si CPMAS spectrum was similar to the spectra of ITH and IWW in terms of strong Q2 signals. This observation further supported the premise that the presence / absence of fluoride in the synthetic gel for CIT-13 affected the germanium arrangement within the d4r bridging unit.

[0240] Three exemplary types of germanium arrangements (I, II, and III) and two Ge-rich arrangements (II-2 and III-2, having 5 and 6 Ge sites, respectively) within the [Si4Ge4]-d4r unit are Fig. 25 This is exemplified in [document]. Corma et al. showed that the alternating arrangement of Si and Ge sites within the d4r unit (i.e., Type I arrangement) is the most energetically favorable among the possible [Si4Ge4]-d4r arrangements in AST-type germanosilicates based on calculation results. It was also suggested by Liu et al. that such germanium arrangements exist in the unprocessed CIT-13 / F. Types II and III are found in fluorinated and degermanized ITQ-13, ITQ-22, and IM-12 germanosilicates. 19 F MAS and 1 H-29 [Si4Ge4]-d4r arrays are proposed to exist in ITH / IWW and UTL, respectively, based on Si CPMAS spectra. 28 Most importantly, the type III arrays can explain the extraction of Ge-4 rings during the inverse sigma transformation of IM-12 and the high Si / Ge ratio of the resulting COK-14 material.

[0241] It has been noted that in CIT-13 / F, the presence of Si-O-Si bridges can hinder complete exfoliation into cfi-type layered materials under acidic media. Furthermore, CIT-13 / F was not converted to CIT-14 through strong acid treatment as described above. This result implies the absence of pure Ge-4 rings within the d4r monomers of the corresponding CIT-13 / F samples. Although very slow, CIT-13 / F was completely converted to Ge-CIT-5 when exposed to ambient moisture. This conversion is mechanically accompanied by the hydrolytic dissociation of TOT bonds parallel to the main 14MR channels within the d4r monomers. Therefore, it is unlikely that CIT-13 / F possesses Si-O-Si bonds along the main channel direction in d4r. Thus, a Type I or Type II-2 (Ge-rich) configuration can explain all the conversion behaviors exhibited by CIT-13 / F. However, according to DFT-based calculations by Camblor et al., highly clustered germanium sites such as Type II-2 are not observed in CIT-13 / F 19 It can lead to a large contribution of the line 2 signal in F NMR ( Fig. 23(a) Therefore, CIT-13 / F may have other possible arrays that can describe type I or conversion operations.

[0242] Fig. 23(b) and 23(c)As illustrated, the fluorinated form of the CIT-13 / OH sample exhibits a -8 ppm signal broader than that of IM-12,28 (Line 1) and a 16 to 23% contribution to the additional upfield signal (Line 2). These data imply the presence of highly clustered germanium sites within d4r units, such as Type II-2 and Type III-2. Ge-O-Ge bonds parallel to the main channel direction also contribute to the rapid upfield signal of CIT-13 / OH. * The conversion rate from CTH to CFI can be explained. The type III-2 arrangement is also consistent with the presence of a pure Ge-4 ring and the high germanium content within the s4r sites of the generated CIT-14 / IST. Indeed, the currently refined structural solution obtained from the synchrotron PXRD confirmed that the Si / Ge ratio of the bridging s4r unit is approximately 4, which implies the presence of one or two additional germanium substitutions on top of the pure Ge-4 ring within the d4r unit of CIT-13 / OH. Thus, the inventors suggest that the absence of fluoride in the synthetic gel for CIT-13 can result in clustered germanium sites such as type II-2 or type III-2.

[0243] As will be understood by those skilled in the art, numerous variations and modifications of the invention are possible in light of these teachings, and all such are taken into account. All references cited herein are incorporated herein by reference for their teachings, at least in the context in which they are presented.

Claims

Claim 1 A crystalline microporous germanosilicate composition designated as CIT-14 / IST having eight-membered and twelve-membered ring channels, characterized by a powder X-ray diffraction (XRD) pattern having at least five characteristic peaks at 2-θ 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 ± 0.3, 27.19 ± 0.3 and 27.69 ± 0.

3. Claim 2 A crystalline microporous germanosilicate composition having a Si:Ge molar ratio in the range of 12:1 to 20:1 in claim 1. Claim 3 A crystalline microporous germanosilicate composition comprising orthorhombic crystals, according to claim 1. Claim 4 In paragraph 3, Cmmm space group, or Cmcm A crystalline microporous germanosilicate composition characterized by a space group, or an intracrystalline mixing (disorder) of two domains. Claim 5 In paragraph 3, a crystalline microporous germanosilicate composition having monomer cell parameters according to the following: . Claim 6 A crystalline microporous germanosilicate composition according to claim 1, wherein the 8-membered ring channel has pore dimensions of 3.3 Å x 3.9 Å and the 12-membered ring channel has pore dimensions of 4.9 Å x 6.4 Å. Claim 7 A crystalline microporous germanosilicate composition that does not contain fluoride, according to claim 1. Claim 8 A crystalline microporous germanosilicate composition having micropores optionally containing an alkali metal cation salt, an alkaline earth metal salt, a transition metal, a transition metal oxide, a transition metal salt, or a combination thereof, in claim 1. Claim 9 A method for preparing a crystalline microporous germanosilicate composition of claim 1, wherein the method comprises contacting a crystalline microporous germanosilicate CIT-13 / OH with a concentrated strong aqueous mineral acid at an elevated temperature for a time sufficient to form an intermediate microporous germanosilicate "-CIT-14", and the crystalline microporous germanosilicate CIT-13 / OH is fluoride-free, has a three-dimensional framework having pores defined by 10-membered and 14-membered rings, and exhibits a powder X-ray diffraction (XRD) pattern having at least five peaks at 2-θ of 6.45 ± 0.2, 7.18 ± 0.2, 12.85 ± 0.2, 20.78 ± 0.2, 26.01 ± 0.2, and 26.68 ± 0.

2. A method in which the concentration of a strong aqueous mineral acid is in the range of 6 to 12 M; the elevated temperature is in the range of 80°C to 120°C; and the sufficient time is in the range of 4 to 24 hours. Claim 10 In paragraph 9, the method wherein the mineral acid is aqueous HCl or HNO3. Claim 11 A method according to claim 9, further comprising separating the intermediate microporous germanosilicate "-CIT-14", washing the "-CIT-14" material with water until the washing solution becomes pH neutral, and then heating the separated and washed "-CIT-14" material at a temperature in the range of 450°C to 650°C for a time in the range of 2 to 12 hours. Claim 12 In claim 8, the composition is a crystalline microporous germanosilicate composition used as a catalyst or vehicle for gas separation. Claim 13 By contacting each feedstock with the crystalline microporous germanosilicate composition of claim 8, (a) carbonylating dimethyl ether (DME) to CO; (b) reducing NOx to methane; (c) cracking, hydrocracking, or dehydrogenating hydrocarbons; (d) dewaxing hydrocarbon feedstocks; (e) converting paraffins to aromatics; (f) isomerizing or disproportionating aromatic feedstocks; (g) alkylating aromatic hydrocarbons; (h) oligomerizing alkenes; (i) aminating alcohols having 1-10 carbons, linear or branched forms; (j) separating and adsorbing alkanes having 1-10 carbons, linear or branched forms from hydrocarbon feedstocks; (k) isomerizing olefins; (l) producing high molecular weight hydrocarbons from C1-C6 hydrocarbons; (m) reforming hydrocarbons; (n) converting alcohols or other oxygenated hydrocarbons having 1-10 carbons, linear or branched forms to produce olefin products; (o) epoxidizing olefins with hydrogen peroxide; (p) reducing the content of nitrogen oxides contained in a gas stream in the presence of oxygen; (q) separating nitrogen from a nitrogen-containing gas mixture; or (r) converting a synthesis gas containing hydrogen and carbon monoxide into a hydrocarbon stream; or (s) reducing the concentration of organic halides in hydrocarbon products, comprising a method. Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete

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