SYNTHESIS OF MORDENITE USING MULTIPLE ORGANICS

Abstract

The methods for synthesizing mordenite (MOR) zeolite crystals described herein utilize a combination of organics and produce MOR crystals with reduced size, higher Si/Al ratio, fewer stacking faults, less occluded organics in the final product, and a longer catalyst lifetime.

Claims

1. A method for forming a mordenite (MOR) material, comprising: combining N, N-trimethyl-1-1-adamantammonium (TMAda), at least one alcohol, a sodium source, an aluminum source, and a silica source at room temperature to form a synthesis mixture; maintaining the synthesis mixture for a time and at a temperature sufficient to allow mordenite (MOR) material to form; and separating the mordenite (MOR) material from the synthesis mixture.

2. The method of claim 1, wherein the at least one alcohol is 1,2-hexanediol (D6.sub.1,2).

3. The method of claim 1, wherein the N, N-trimethyl-1-1-adamantammonium (TMAda) and the at least one alcohol are combined to produce a synthesis mixture comprising an excess of the alcohol relative to the N, N-trimethyl-1-1-adamantammonium (TMAda).

4. The method of claim 3, wherein the N, N-trimethyl-1-1-adamantammonium (TMAda) and the at least one alcohol are combined at a ratio of about 1.5 to 16.0 of the alcohol to the N, N-trimethyl-1-1-adamantammonium (TMAda) in the synthesis mixture.

5. The method of claim 1 wherein the sodium source is sodium hydroxide, the aluminum source is aluminum hydroxide, and the silica source is fumed silica.

6. The method of claim 1 wherein the mordenite (MOR) material is mordenite (MOR) nanosheets.

7. The method of claim 6, wherein the mordenite (MOR) nanosheets have an average thickness of 60-80 nm.

8. The method of claim 1, wherein the synthesis mixture comprises an excess of alcohol relative to the N, N-trimethyl-1-1-adamantammonium (TMAda).

9. The method of claim 1, further comprising the step of washing the mordenite (MOR) material with a solvent after separation from the synthesis mixture.

10. The method of claim 9, wherein the solvent is water.

11. The method of claim 1, wherein crystals in the mordenite (MOR) material have dimensions of less than 100 nm.

12. The method of claim 1, wherein the mordenite (MOR) material has a Si/Al ratio of about 10.

13. The method of claim 1, further comprising one or more of the steps of heating, stirring, rotating under pressure, or centrifuging the synthesis mixture in order to allow the mordenite (MOR) material to form or to separate the mordenite (MOR) material from the synthesis mixture.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] FIG. 1A shows an electron micrograph and dihedral angle measurements of nanosheets of mordenite (MOR).

[0011] FIG. 1B shows an electron micrograph and dihedral angle measurements of nanosheets of mordenite (MOR).

[0012] FIG. 1C shows an electron micrograph and dihedral angle measurements of conventional MOR.

[0013] FIG. 1D shows an electron micrograph and dihedral angle measurements of conventional MOR.

[0014] FIG. 2A shows the crystal structures of zeolites MFI, CHA, and MOR (from left to right).

[0015] FIG. 2B shows composite building units corresponding to the three different zeolite frameworks (MFI, CHA, and MOR, respectively).

[0016] FIG. 2C shows electron scanning micrographs of the three different zeolites (MFI, CHA, and MOR respectively) obtained using three different combinations of organics.

[0017] FIG. 3A shows powder X-ray diffraction patterns of the solid precipitate obtained after 6 days of complete crystallization at 180 C., which confirms CHA (SSZ-13) (bottom line), MFI (ZSM-5) (second from bottom line), and MOR (second from top line).

[0018] FIG. 3B shows thermogravimetric analysis of washed samples where differences in mass loss are associated with the entrapment of organics within zeolite frameworks.

[0019] FIG. 3C shows an amplitude mode image of HOU-4 obtained using atomic force microscopy in air and in the inset, a height histogram obtained from the analysis of many HOU-4 crystals using height mode AFM images.

[0020] FIG. 4A shows an electron micrograph of conventional mordenite synthesized using a reported protocol.

[0021] FIG. 4B shows an electron micrograph of crystals obtained using TMAda with 1,2-pentanediol.

[0022] FIG. 4C shows an electron micrograph of crystals obtained using TMAda with 1,2-propanediol.

[0023] FIG. 4D shows an electron micrograph of MFI crystals obtained using TMAda-OH and butane-1,2-diol.

[0024] FIG. 4E shows powder X-ray diffraction pattern of the as synthesized product using TMAda-OH and butane-1,2-diol.

[0025] FIG. 5A shows an electron micrograph of conventional MOR crystals obtained using composition 1 (C1) with molar ratio of 6 Na.sub.2O:1 Al.sub.2O.sub.3:30 SiO.sub.2:780 H.sub.2O.

[0026] FIG. 5B shows an electron micrograph of MOR crystals obtained using composition 1 with D6.sub.1,2.

[0027] FIG. 5C shows a powder XRD pattern for conventional MOR synthesis with and without D6.sub.1,2.

[0028] FIG. 6 shows comparative catalytic performance of H-MOR crystals from a conventional synthesis (labeled as MOR) and HOU-4 nanosheets (labeled ns-MOR).

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0029] The present disclosure relates to methods for the synthesis of mordenite (MOR) crystals in sub-micron sizes.

[0030] Preferred embodiments described herein relate to methods for synthesizing MOR using N, N, N-trimethyl-1-1-adamantammonium (TMAda) in combination with at least one alcohol (preferably 1,2-hexandiol, D6.sub.1,2) as organic structure-directing agents (OSDAs) in a growth solution where at least one of the OSDAs has a hydrophobic alkyl tail and hydrophilic hydroxyl functional groups. In preferred embodiments, this synthetic method produces ultrathin MOR crystals (HOU-4). These crystals exhibit the typical hexagonal habit where the thickness can range from about 50 nm to about 1 m and the average length-to-width aspect ratio is 4.00.7. FIGS. 1A and 1B show electron micrographs and angle measurements of HOU-4. FIGS. 1C and 1D show electron micrographs and angle measurements of conventional MOR.

[0031] The synthesis mixture utilized in preferred embodiments may also include sodium as an inorganic structure-directing agent (SDA) that yields the zeolite ZSM-5 (MFI) in the absence of organics. Introduction of D6.sub.1,2 to this synthesis mixture does not alter the crystal structure, but does lead to changes in crystal size and morphology. The use of TMAda as a sole SDA is well documented to yield zeolite SSZ-13 (CHA). It is interesting to note that each SDA and their binary combination generate three very different zeolite frameworks. MFI is a 3-dimensional medium-pore zeolite; CHA is a 3-dimensional small-pore zeolite; and MOR is a 1-dimensional large-pore zeolite. FIG. 2A shows general representations of the crystal structures zeolites MFI, CHA, and MOR. The composite building units (CBUs) of these three structures are vastly different, with the exception of the mor oligomer being shared by both MFI and MOR. FIG. 2B shows composite building units corresponding to the three different zeolite frameworks (MFI, CHA, and MOR, respectively). There are no known reported examples of situations where three different zeolites can be prepared from the same synthesis condition using two OSDAs. Moreover, comparatively few zeolite syntheses employ alcohols as OSDAs, which is a unique aspect of HOU-4 crystallization as described herein.

[0032] All three zeolites (MFI, CHA, and MOR) have approximately the same Si/Al ratio, as shown in Table 1 below (showing the elemental analysis of various zeolite frameworks using energy-dispersive X-ray spectroscopy (EDX)), but differ with respect to crystal size and shape and the quantity of occluded OSDA. SSZ-13 crystals have a spheroidal morphology with sizes of 1-2 m and about 10 wt % occluded OSDA (1.3 TMAda per unit cell). MFI crystals are rough, lack a distinct morphology, exhibit sub-micron dimensions, and contain about 5 wt % occluded OSDA (2.65 D6.sub.1,2 per unit cell). FIG. 2C shows electron scanning micrographs of the three different zeolites (MFI, CHA, and HOU-4, respectively) obtained using three different combinations of organics.

TABLE-US-00001 TABLE 1 EDX analysis Sample Si/Al HOU-4 9.5 MOR 8.0 SSZ-13 11.6 MFI 11.7

[0033] Thermogravimetric analysis (TGA) of HOU-4 indicate much less occluded OSDA (about 4 wt %). To test this, HOU-4 samples were prepared by extracting solids from the supernatant without washing, after which occluded D6.sub.1,2 was also observed by solid-state .sup.13C MAS NMR. In washed samples, the weight loss is attributed to about 0.56 TMAda per unit cell. This is shown in Table 2 below. The facile extraction of OSDA molecules from zeolite frameworks without post-synthesis calcination is uncommon, but it provides a method of recovering and potentially recycling the OSDA(s).

TABLE-US-00002 TABLE 2 Molecular % weight wt/unit loss SDA/unit Framework Unit cell cell (TGA) cell SSZ-13 Na.sub.3Al.sub.3Si.sub.33O.sub.72 2228.52 10 1.28 MFI Na.sub.8Al.sub.8Si.sub.88O.sub.192 5942.72 5 2.65 HOU-4 Na.sub.5Al.sub.5Si.sub.43O.sub.96 2993.24 3.5 0.56

[0034] Accordingly, preferred embodiments described herein relate to methods for synthesizing zeolites having MOR framework by preparing a synthesis mixture by combining N, N, N-trimethyl-1-1-adamantammonium (TMAda), at least one alcohol (preferably 1,2-hexanediol, D6.sub.1,2), a sodium source, an aluminum source, and a silica source at room temperature, then allowing the MOR crystals to form and separating them from the remaining synthesis mixture. In certain embodiments, the synthesis mixture is heated, stirred, rotated under pressure, and/or centrifuged in order to produce the MOR crystals. Suitable sodium sources include sodium halides, sodium nitrate, and sodium hydroxide. Suitable aluminum sources include sodium aluminate, aluminum isopropoxide, alumina, aluminum sulfate, and natural sources (e.g. boehmite). Suitable silica sources include sodium silicate, colloidal silicates, fumed silica, silica glass, and tetraethylorthosilicate. In preferred embodiments the sodium source may be sodium hydroxide, the aluminum source may be aluminum hydroxide, and the silica source may be fumed silica. In further preferred embodiments, the MOR crystals are HOU-4 (ultrathin crystals). In additional preferred embodiments, after separation of the MOR crystals from the remaining synthesis mixture, the MOR crystals are washed with a solvent to remove any remaining N, N-trimethyl-1-1-adamantammonium (TMAda) or alcohol. In certain embodiments, the solvent is water. In further preferred embodiments, the N, N-trimethyl-1-1-adamantammonium (TMAda) and alcohol are combined in the synthesis mixture with an excess of alcohol (preferably D6.sub.1,2), preferably at a ratio of about 1.5 to 16.0 of alcohol to N, N-trimethyl-1-1-adamantammonium (TMAda). In another preferred embodiment, a reduction in the water content of the synthesis composition can lead to thinner HOU-4 crystals. In additional preferred embodiments, the MOR crystals obtained have dimensions of less than 100 nm, and HOU-4 may have an average thickness of 60-80 nm. In additional preferred embodiments, HOU-4 has a Si/Al ratio of about 10.

Examples

[0035] The following chemicals were used as reagents: Cab-O-Sil (M-5, Spectrum Chemical), sodium hydroxide (98% pellets, MACRON Fine Chemicals), N,N,N-trimethyl-1-1-adamantammonium hydroxide (25 wt % in water, SACHEM Inc.), 1,2-hexanediol (D6.sub.1,2, 98%) and aluminum hydroxide (80.3 wt % Al(OH).sub.3, SPI0250 hydrogel). Deionized (DI) water used in all experiments was purified with an Aqua Solutions RODI-C-12A purification system (18.2 Me). All reagents were used as received without further purification.

[0036] HOU-4 (MOR-type) crystals were synthesized with the OSDA N,N,N-trimethyl-1-1-adamantammonium hydroxide (TMAda-OH) and 1,2-hexanediol (D6.sub.1,2) using solutions with a molar composition of 0.052 Al(OH).sub.3:1.0 SiO.sub.2:0.2 NaOH:44 H.sub.2O:0.1 TMAda-OH:1.6 1,2-hexanediol. Sodium hydroxide (0.09 g, 0.0022 mol) was first dissolved in water (8.21 g, 0.4959 mol), followed by the addition of TMAda-OH (0.95 g, 0.0011 mol) and 1,2-hexanediol (2.17 g, 0.018 mol). This solution was stirred until clear (ca. 15 min). Aluminum hydroxide (0.06 g, 0.0005 mol) was added to the solution and left to stir for another 15 min at room temperature. To this clear solution was added the silica source (0.67 g, 0.0112 mol), and the resulting mixture was stirred (400 rpm) for 4 h at 80 C. (mineral oil bath). Approximately 10 g of growth solution after 4 h of heating under stirring was placed in a Teflon-lined stainless steel acid digestion bomb (Parr Instruments) and was heated under rotation (30 rpm) and autogenous pressure in a Thermo-Fisher Precision Premium 3050 Series gravity oven. The nominal time and temperature for MOR synthesis was 6 days at 180 C. The products of all syntheses were isolated as white powder (ca. 600 mg) by centrifuging the mother liquor (13,000 rpm for 45 min) for three cycles with DI water washes. Samples for microscopy were prepared by first redispersing a small amount of powder (ca. 5 mg) in DI water. An aliquot of this solution was placed on a glass slide and dried overnight. Crystals were transferred to metal sample disks for microscopy studies by contacting the glass slide with carbon tape for SEM.

[0037] Atomic force microscopy (AFM) measurements were performed in air using an Asylum Research MFP-3D-SA instrument (Santa Barbara, Calif.). An aliquot of HOU-4 crystals dispersed in water was placed on a silicon wafer and was allowed to dry at room temperature. The silicon wafer was calcined at 500 C. for 5 h, followed by cleaning under inert Ar gas flow to remove loosely-bound crystals. AFM images were collected using a Cr/Au-coated silicon nitride cantilever (Olympus RC800PB) with a spring constant of 0.82 N/m. AFM images were collected in contact mode at a scan rate of 1.2 Hz and 256 lines/scan.

[0038] Scanning electron microscopy (SEM) was performed with a FEI 235 dual-beam (focused ion-beam) system operated at 15 kV and a 5 mm working distance. All SEM samples were coated with a thin carbon layer (ca. 20 nm) prior to imaging.

[0039] Energy-dispersive X-ray spectroscopy (EDX) was performed using a JEOL JSM 6330F field emission scanning electron microscope (SEM) at working distance of 15 mm and voltage of 15 kV and 12 mA. Powder X-ray diffraction (XRD) patterns of as-made zeolite samples were collected on a Siemens D5000 X-ray diffractometer using a Cu K source (40 kV, 30 mA). The zeolite frameworks were confirmed using reference patterns provided by the International Zeolite Association Structure Database.

[0040] FIG. 3A-3D show results for the characterization of HOU-4 crystals. FIG. 3A shows powder X-ray diffraction patterns of the solid precipitate obtained after 6 days of complete crystallization at 180 C., which confirms SSZ-13 (bottom line), MFI (second from bottom line), and MOR (second from top line). The MOR framework was confirmed using a reference (top line). FIG. 3B shows thermogravimetric analysis showing the entrapment of organics within zeolite frameworks. FIG. 3C shows an amplitude mode image of HOU-4 obtained using atomic force microscopy in air and in the inset, a height histogram of HOU-4 obtained using height mode AFM images. FIG. 3D shows a transmission electron microscopy (TEM) image of HOU-4 depicting orientation of basal plane.

[0041] Atomic force microscopy measurements of HOU-4 samples (FIG. 3C) reveal distributions of crystal thickness (FIG. 3C, inset) with an average size of 80 nm. One aspect that distinguishes HOU-4 from nanocrystals reported in literature (or sold by commercial vendors) is that the former are isolated crystals, whereas the latter tend to be large aggregates comprised of small subdomains. As previously mentioned, ns-MOR prepared as described herein are formed via the cooperative action of two OSDAs.

[0042] FIG. 4A shows an electron micrograph of conventional mordenite synthesized using a reported protocol. In one example, a growth mixture that generates HOU-4 is actually one reported for SSZ-13 when TMAda is the sole OSDA. A study was previously published showing that D6.sub.1,2 is an effective modifier of SSZ-13 crystallization, and at sufficiently low concentrations (i.e., molar ratios less than 1.0 D6.sub.1,2: 1.0 SiO.sub.2) the diol reduces the size of SSZ-13 crystals by an order of magnitude. Here it is shown that increased alcohol concentration (i.e., molar ratios larger than 1.6 D6.sub.1,2: 1.0 SiO.sub.2) shifts the role of diol from that of crystal growth modifier to OSDA.

[0043] The formation of HOU-4 is also highly sensitive to diol selection. Systematic studies of HOU-4 synthesis using diols of varying carbon length reveal that deviations from C6 compromises the purity of the final product. FIG. 4B shows an electron micrograph of crystals obtained using TMAda with 1,2-pentanediol and FIG. 4C shows an electron micrograph of crystals obtained using TMAda with 1,2-propanediol. The former produces mixed phases of MOR and CHA while the latter produces pure CHA. For comparison, FIG. 4D shows an electron micrograph of MFI crystals obtained using TMAda-OH and butane-1,2-diol. FIG. 4E shows powder X-ray diffraction pattern of the as synthesized product using TMAda-OH and butane-1,2-diol. Thus, combinations of TMAda with either 1,2-pentanediol (FIG. 4B) or 1,2-butanediol (FIG. 4D) lead to SSZ-13 impurity, whereas the switch to 1,2-propanediol results in pure SSZ-13 (FIG. 4C).

[0044] The role of TMAda and D6.sub.1,2 in the formation of ultrathin crystals is seemingly unrelated to growth modification given that conventional MOR synthesis in the presence of organics does not produce thin crystals. In fact, the presence of D6.sub.1,2 tends to increase the [001] thickness of MOR crystals. FIG. 5A shows an electron micrograph of conventional MOR crystals obtained using composition 1 (C1) with molar ratio of 6 Na.sub.2O:1 Al.sub.2O.sub.3:30 SiO.sub.2:780 H.sub.2O. FIG. 5B shows an electron micrograph of MOR crystals obtained using composition 1 with D6.sub.1,2. FIG. 5C shows a powder XRD pattern for conventional MOR synthesis with and without D6.sub.1,2.

[0045] The ability to prepare ultrathin MOR crystals has significant implications for their use in applications such as catalysis. Zeolites such as MOR with low dimension (1D) channels and large (12-MR) pores are highly susceptible to rapid deactivation by coking (i.e., pore blockage due to the retention of carbon deposits). To this end, a reduction in crystal dimension can have a substantial impact on catalyst performance Proton forms of HOU-4 were prepared and their catalytic properties were compared to a conventional MOR catalyst (ca. 5 m) using cumene cracking as a model reaction to evaluate on-stream lifetime. These studies were conducted at space velocity of 2 h.sup.1 and at 350 C. in a packed-bed reactor. FIG. 6 shows comparative catalytic performance of H-MOR crystals from a conventional synthesis (labeled as MOR) and nanosheets (labeled ns-MOR). It was observed that the lifetime of nanosheets (HOU-4) is a factor of two longer (FIG. 6) and has a slower rate of deactivation compared to conventional MOR.

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