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Definitions

• the germanosilicate CIT-14 was accessible by the ADOR transformation (Assembly-Disassembly-Organization-Re-assembly) of the phyllosilicate designated CIT- 13P, as described in U.S. Patent No. 10,293,33, the contents of which are incorporated by reference herein for all purposes or at least for the methods of preparing and characterization of CIT-14.
• the CIT-14/IST compositions are, in some embodiments, characterized by claims 1 to 4, wherein the crystals are orthorhombic.
• the CIT-14/IST crystals have a Cmmm space group, or a Cmcm space group, or an intracrystal mixture (disorder) of the two domains.
• the crystalline microporous germanosilicate CIT-14/IST composition have unit cell parameters according to:
• the crystalline microporous germanosilicate CIT- 14/IST are used as catalysts or adsorbents in a range of processes set forth elsewhere herein.
• This disclosure also embraces other embodiments directed to the preparation of the crystalline microporous germanosilicate CIT-14/IST, including those methods comprising contacting a crystalline microporous 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 to an as- made “-CIT-14” composition.
• This disclosure also embraces the pre-calcined, as-made CIT-14” composition.
• FIGs. 4(A-B) shows SEM images of CIT-14/IST samples derived from (a) CIT- 13/ OH[3.71 ] (FIG. 4(A)); and CIT- 13/OH[3.56] (FIG. 4(B)).
• FIGs. 11(A-E) shows structural change during the *CTH-to-CFI transformation observed based on PXRD profiles.
• the change of the d200 interlayer distances of CIT-13/OH[4.33] compared to that of CIT-13/F[4.31] (FIG. 11(E)).
• FIG. 16 shows the effects of elemental composition on intensities of PXRD peaks of CIT-14.
• the CIT-14/IST germanosilicate composition comprises a pure germanosilicate.
• the CIT-14/IST germanosilicate composition comprises a framework including one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium. These additional oxides may derive from the precursor CIT-13/OH used in the preparation of the CIT-14/IST germanosilicate compositions. Methods of incorporating these oxides in the precursor CIT- 13/OH compositions are set forth elsewhere herein.
• These crystalline microporous germanosilicate CIT-14/IST compositions may be characterized by their powder X-ray diffraction (XRD) pattern having at least five characteristic peaks 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 2-Q.
• the powder X-ray diffraction (XRD) pattern exhibits at least five characteristic peaks at five, six, seven, eight, nine, or ten of these characteristic peaks set forth above.
• the concentration of the mineral acid is in a range of from 6 to 12 M. Higher concentrations are preferred (e.g., 10 to 12 M) as these seem to improve the kinetics and yields of the reactions.
• the effective crystallization conditions include subjecting the mixture to a temperature of from about 140°C to about 180°C, and for a time of from about 4 days to about 4 weeks;
• the micropores may contain a transition metal or transition metal oxide.
• the addition of such materials may be accomplished, for example, by chemical vapor deposition or chemical precipitation.
• the transition metal or transition metal oxide comprises an element of Groups 6, 7, 8, 9, 10,
• transition metal has been defined elsewhere herein, but in certain other independent embodiments, the transition metal or transition metal oxide comprises an element of Groups 6, 7, 8, 9, 10, 11, or 12. In still 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. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.
• Such transformations / separations may 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 a hydrocarbon feedstock , MTO (methanol to olefin), isomerizing aromatics (e.g., xylenes), disproportionating aromatics (e.g., toluene), alkylating aromatic hydrocarbons, oligomerizing alkenes, aminating lower alcohols, separating and sorbing lower alkanes, hydrocracking a hydrocarbon, dewaxing a hydrocarbon feedstock, isomerizing an olefin, producing a higher molecular weight hydrocarbon from lower molecular weight hydrocarbon, reforming a hydrocarbon, converting lower alcohol or other oxygenated hydrocarbons to produce olefin products, epoxiding olefins
• Also included in the present disclosure is a process for preparing a lubricating oil which comprises hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil, and catalytically dewaxing said effluent comprising hydrocracked oil at a temperature of at least about 400°F and at a pressure of from 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 this disclosure.
• the present disclosure further provides processes for oligomerizing olefins, each process comprising contacting an olefin feed under oligomerization conditions with a catalyst comprising a crystalline microporous solid of this disclosure.
• synthesis gas containing hydrogen and carbon monoxide also referred to as syngas or synthesis gas
• a catalyst comprising any of the germanosilicates described herein, including those having CIT-13 frameworks, and Fischer-Tropsch catalysts.
• Such catalysts are described in U.S. Patent No. 9,278,344, which is incorporated by reference for its teaching of the catalysts and methods of using the catalysts.
• the Fischer-Tropsch component includes a transition metal component of groups 8-10 (i.e., Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), preferably cobalt, iron and/or ruthenium.
• the optimum amount of catalytically active metal present depends inter alia on the specific catalytically active metal.
• the amount of cobalt present in the catalyst may range from 1 to 100 parts by weight per 100 parts by weight of support material, preferably from 10 to 50 parts by weight per 100 parts by weight of support material. In one embodiment, from 15 to 45 wt % cobalt is deposited on the hybrid support as the Fischer-Tropsch component. In another embodiment from 20 to 45 wt % 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 promoters may be present as metals or as metal oxide, depending upon the particular promoter concerned. Suitable promoters include metals or oxides of transition metals, including lanthanides and/or the actinides or oxides of the lanthanides and/or the actinides.
• Still further process embodiments include those processes for increasing the octane of a hydrocarbon feedstock to produce a product having an increased aromatics content comprising contacting a hydrocarbonaceous feedstock which comprises normal and slightly branched hydrocarbons having a boiling range above about 40 C and less than about 200 C under aromatic conversion conditions with the catalyst.
• mineral acids refers to mineralizing acids conventionally used in molecular sieve zeolite syntheses, for example HC1, HBr, HF, HNCb, or H2SO4. Oxalic acid and other strong organic acids may also be employed in lieu of mineral acids. Generally, HC1 and HNO3 are preferred mineral acids. As used herein throughout, the terms “concentrated” and “dilute” with respect to mineral acids refer to concentrations in excess and less than 0.5 M, respectively.
• oxygenated hydrocarbons or “oxygenates” as known in the art of hydrocarbon processing to refer to components which include alcohols, aldehydes, carboxylic acids, ethers, and/or ketones which are known to be present in hydrocarbon streams or derived from biomass streams other sources (e.g., ethanol from fermenting sugar).
• crystalline microporous solids' or cry stalline microporous germanosilicate are crystalline structures having very regular pore structures of molecular dimensions, i.e., under 2 nm. The maximum size of the species that can enter the pores of a crystalline microporous solid is controlled by the dimensions of the channels.
• the term “pillanng” refers generally to a process that introduces stable metal oxide structures ("so-called "pillars") between substantially parallel crystalline silicate layers.
• the metal oxide structures keep the silicate layers separated, creating by interlayer spacings of molecular dimensions.
• the term is generally used in the context of clay chemistry and is well understood by those skilled in the art of clays and zeolites, especially as applied to catalysts.
• 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.
• Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.
• Embodiment 2 The crystalline microporous germanosilicate CIT-14/IST composition of Embodiment 1, characterized by a powder X-ray diffraction (XRD) pattern having at least five characteristic peaks 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 2-Q.
• XRD powder X-ray diffraction
• the CIT-14/IST germanosilicate composition comprises a pure germanosilicate.
• the CIT-14/IST germanosilicate composition comprises a framework including one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium.
• the powder X-ray diffraction (XRD) pattern exhibits at least five characteristic peaks at five, six, seven, eight, nine, or ten of these characteristic peaks set forth above.
• the uncertainties of the peak locations are independently (for each peak) ⁇ 0.5 degrees 2-Q, ⁇ 0.4 degrees 2-Q, ⁇ 0.3 degrees 2-Q, ⁇ 0.2 degrees 2-Q, ⁇ 0.15 degrees 2-Q, or ⁇ 0.15 degrees 2-Q.
• Embodiment 8 The crystalline microporous germanosilicate CIT-14/IST composition of any one of Embodiments 1 to 7 that is derived or derivable from a reaction characterized as an inverse sigma transformation of a cry stalline microporous germanosilicate, designated CIT-13/OH.
• CIT-13/OH The specific characteristics of CIT-13/OH are described in greater detail elsewhere herein and these descriptions are incorporated herein as if bodily incorporated.
• composition of this CIT-13/OH germanosilicate is considered an independent Embodiment of this disclosure, as is its use in the preparation of CIT-14/IST.
• Embodiment 11 The crystalline microporous germanosilicate CIT-14/IST composition of Embodiment 8 or 9 or the crystalline microporous germanosilicate CIT- 13/OH of Embodiment 10, wherein the crystalline microporous germanosilicate designated CIT-13/OH is prepared by a method comprising hydrothermally treating an aqueous composition derived from the admixture of:
• the at least one substituted benzyl-imidazolium organic structure-directing agent (OSDA) cation has a structure:
• the Si:Ge ratio is in a range of from 3.5 to 3.6, from 3.6 to 3.7, from 3.7 to 3.8, from 3.8 to 3.9, from 3.9 to 4.0, from 4.0 to 4.1, from 4.1 to 4.2, from 4.2 to 4.3, from 4.3 to 4.4, from 4.4 to 4.5, from 4.5 to 4.6, from 4.6 to 4.7, from 4.7 to 4.8, from 4.8 to 4.9, from 4.9 to 5.0, from 5.0 to 5.2, or in a range defined by any two or more of the foregoing ranges, for example, from 3.5 to 3.9. Each of these ranges is considered an independent Aspect within this Embodiment.
• SSRL Stanford Synchrotron Radiation Lightsource
• FIG. 8(B-E) PXRD profiles of as-prepared and calcined CIT-13/OH[3.88] and CIT- 13/OH[4.33] are displayed in FIG. 8(B-E). Other PXRD patterns are provided in FIG. 9. All PXRD profiles were obtained under ambient conditions. The positions of diffraction peaks matched well with those of a reference CIT-13/F shown in FIG. 8(F). However, there were differences between CIT-13/F and CIT-13/OH noted in peak intensities. Except for CIT- 13/OH[3.88] that was the only CIT-13/OH crystallized using ortho-methylbenzyl OSDA (FIG. 8(A) and FIG.
• CIT-13-type germanosilicates slowly transformed into CFI-type germanosili cates upon exposure to ambient moisture (*CTH-to-CFI transformation), unlike other d4r-type germanosilicate, such as UTL, IWW, and ITH, that are known not to undergo the analogous transformations.
• This transformation occurred by the re-arrangement of Ge- rich d4r units into dzc units, owing to the instability of the CIT-13 framework induced by the presence of germanium-rich d4r units and the crystallographic nature of the cfi-layers.
• CIT-13/OH transformed into the corresponding germanosilicate CIT-5 much faster than CIT-13/F having similar germanium contents.
• CIT-13/OH crystals have more germanium within its d4r units than with CIT- 13/F crystals having similar overall Si/Ge ratios.
• CIT- 13/F it was confirmed that the cfi-layers also have non-zero germanium occupancies. It is known that the formation of d4r units was promoted by the presence of fluoride anions and/or high germanium contents that can stabilize low framework T-O-T angles.
• the -8 ppm signals of the CIT-13 samples were broader than that of IM-12, indicating that the germanium arrangement within d4r units of CIT-13 appeared to be less uniform than that of fluorinated IM-12, regardless of the type of mineralizers used.
• the -8 ppm signals of CIT- 13 samples were deconvoluted into two groups of peaks: Line 1 (-7.3 to -8.3 ppm) and Line 2 (- 11.0 to -11.7 ppm).
• CIT-13/OH[4.33] (16%) gave a stronger Line 2 signal than CIT-13/F[4.33] (1%), as shown in FIGs. 23(A) and 23(B).
• the present refined structure solution obtained from the synchrotron PXRD confirmed that the Si/Ge ratio of bridging s4r units was approximately four, that implies that one or two additional germanium substitutions on the top of pure Ge-4- ring within d4r units of CIT-13/OH.
• the inventors suggest that the absence of fluoride in synthesis gels for CIT-13 can result in clustered germanium sites such as Type II-2 or Type III-2.

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