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WO2025018511A1 - Procédé de fabrication d'un catalyseur de zéolite bea pour réaction de conversion de glucose et catalyseur ainsi fabriqué - Google Patents

Procédé de fabrication d'un catalyseur de zéolite bea pour réaction de conversion de glucose et catalyseur ainsi fabriqué Download PDF

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WO2025018511A1
WO2025018511A1 PCT/KR2024/004670 KR2024004670W WO2025018511A1 WO 2025018511 A1 WO2025018511 A1 WO 2025018511A1 KR 2024004670 W KR2024004670 W KR 2024004670W WO 2025018511 A1 WO2025018511 A1 WO 2025018511A1
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bea
mww
zeolite catalyst
bea zeolite
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박민범
권성준
조윤혜
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Incheon National University INU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0081—Preparation by melting

Definitions

  • the present invention relates to a method for producing a BEA zeolite catalyst for a glucose conversion reaction and a catalyst produced thereby, and more particularly, to a method for producing a cobalt, nickel, zinc silicate BEA zeolite catalyst by a single-step structural conversion of a borosilicate MWW zeolite.
  • zeolites Since the discovery of natural stilbite (framework type STI) by the Swedish mineralogist Cronstedt in 1756, zeolites have been used as heterogeneous catalysts, solid adsorbents, and catalyst supports due to their excellent unique properties, such as large surface area and porosity, and excellent hydrothermal stability.
  • the physicochemical properties of zeolites can be controlled by substituting different framework atoms in the tetrahedral (T) coordination sites of the zeolite structure with phosphorus and transition metals to generate aluminophosphate (AlPO), silicoaluminophosphate (SAPO), metalloaluminophosphate (MAPO), and metallosilicoaluminophosphate (MAPSO).
  • metallosilicates and metalloaluminosilicates have been proposed as excellent catalysts in various industrial fields because the metal heteroatoms present in the zeolite structure exhibit excellent stability, catalytic activity, and product form selectivity.
  • titanosilicates with MFI, BEA, and MWW structures have been successfully applied as efficient catalysts for oxidation reactions such as ammonia oxidation, epoxidation, and hydroxylation.
  • Stannosilicate BEA Sn-BEA
  • metallosilicates can be prepared by two synthetic routes. One is the top-down replacement of heterometal atoms by acid and/or base treatment to remove the native framework atoms (Fig. 1a), and the other is the bottom-up hydrothermal synthesis of tetrahedrally coordinated metallosilicates via a conventional crystallization step using a metal precursor solution (Fig. 1b). In many cases, the materials synthesized using the latter method exhibit higher structural stability and catalytic activity than those synthesized using the former. Yang et al. reported excellent stability of framework Fe species in bottom-up-synthesized MFI-type iron silicate zeolites, which were not reduced at 600 °C under H 2 atmosphere, showing excellent activity in ethane dehydrogenation.
  • Fan et al. synthesized TS-1(MFI) with abundant framework Ti species without the formation of octahedrally coordinated framework Ti using (NH 4 ) 2 CO 3 precursor, which was determined by showing a UV absorption peak below 260 nm. Furthermore, this catalyst showed excellent performance in the oxidation of various reactants such as linear alkenes and alkanes, alcohols, styrene, and benzene. However, the bottom-up synthesis of metallosilicates has not been generalized due to the rate mismatch between crystallization and metal substitution, unsuitable TOT bond length and angle, easy formation of metal species outside the framework, and the formation of aggregated metal oxides.
  • metallosilicates via conventional hydrothermal bottom-up synthesis may have prolonged crystallization time due to factors such as slow diffusion, complex chemical reactions, and nucleation processes.
  • the synthesis of Sn-BEA via conventional hydrothermal crystallization takes up to about 40 days as reported in the literature.
  • the interzeolite transformation method involves the decomposition of parent zeolites into common building blocks (CBUs) with daughter zeolites, which are then reassembled into daughter zeolites with similar but different structures (Fig. 1c).
  • CBUs common building blocks
  • Fig. 1c daughter zeolites with similar but different structures
  • Co, Ni, and Zn-containing BEA structured metallosilicates via a single-step interzeolite structural transformation of borosilicate MWW (B-MWW) with respective metal precursor solutions (Fig. 1d).
  • Co, Ni, and Zn are three representative transition metals used as catalysts in various applications.
  • Co is used in the Fischer–Tropsch synthesis and reforming reaction
  • Ni is used in CO2 reforming of steam and methane, CO2 methanation, and ammonia decomposition
  • Zn is used in industrial organic synthesis and zinc-air batteries.
  • the BEA type zeolites substituted with the three transition metals are compared in terms of structural transformation and metal incorporation kinetics, framework metal coordination environment, and Lewis acidity during interzeolite structural transformation, and Lewis acid catalytic activity depending on the type of heteroatom species.
  • the present invention provides a method for preparing a BEA zeolite catalyst, comprising: a step of synthesizing a borosilicate MWW zeolite precursor [B-MWW(P)] or an aluminosilicate MWW zeolite precursor [Al-MWW(P)]; a step of dissolving the B-MWW(P) or Al-MWW(P) and dealuminated siliceous BEA seeds in a transition metal hydrate aqueous solution; a step of adding a tetraethylammonium hydroxide solution or a tetraethylammonium bromide solution to the transition metal hydrate aqueous solution; a step of adding ammonium fluoride (NH 4 F) to the transition metal hydrate aqueous solution and drying it; and a step of heating and crystallizing the powder.
  • B-MWW(P) borosilicate MWW zeolite precursor
  • the above MWW is one of the zeolite structures existing in a lamellar form, and the MWW framework structure is a three-dimensional zeolite including two independent pore systems, namely, a pore system of two-dimensional sinusoidal 10-ring (10-MR) channels having an elliptical ring cross-section of 4.1 ⁇ ⁇ 5.1 ⁇ and a pore system including a large 12-MR giant cage connected to the 10-MR window.
  • the step of synthesizing the above MWW zeolite precursor [MWW(P)] can be synthesized using an organic structure derivative (SDA), as an example, and a three-dimensional MWW can be formed by removal of the organic structure derivative and condensation by calcination during the synthesis process, but is not limited thereto and can be synthesized by a generally known method, and a detailed description thereof is omitted herein.
  • SDA organic structure derivative
  • the above B-MWW(P) is characterized in that the molar ratio of Si/B is 9-10, preferably 9.5.
  • the Si/Al molar ratio of the above Al-MWW(P) is characterized by being 12-18, preferably 15.
  • the above transition metal may be cobalt (Co), nickel (Ni) or zinc (Zn), and in this case, the transition metal hydrate aqueous solution may be a solution of cobalt (II) nitrate hexahydrate, nickel (II) nitrate hexahydrate or zinc (II) nitrate hexahydrate.
  • concentration of the transition metal hydrate aqueous solution may be 0.005-0.1 M, and preferably 0.01 M.
  • the crystallization time is characterized by being 1-168 hours, and the heating temperature of the crystallization step is 150-250°C, preferably 190°C.
  • the above BEA zeolite catalyst manufacturing method may further include a washing step and a calcination step after the crystallization step.
  • the above washing step can be performed with HF or KOH solution for 20-30 hours, and the above calcination step can be performed at a temperature of 500-600°C for 5-12 hours.
  • a BEA zeolite catalyst manufactured by the method for manufacturing the BEA zeolite catalyst is provided.
  • the BEA zeolite catalyst manufactured by the above BEA zeolite catalyst manufacturing method is characterized in that the BET surface area of the BEA zeolite increases as the molecular weight of the transition metal decreases.
  • the BEA zeolite catalyst is characterized in that it does not exhibit Bronstedt acidity but exhibits Lewis acidity, and the Lewis acidity is characterized in that it increases in the order of Zn-BEA, Co-BEA, and Ni-BEA.
  • the above BEA zeolite catalyst can be a catalyst for a glucose conversion reaction, and among the Zn-BEA, Co-BEA and Ni-BEA zeolite catalysts, the Zn-BEA zeolite catalyst is characterized by a higher 5-HMF conversion yield than the Co-BEA and Ni-BEA zeolite catalysts.
  • Figure 1 is a schematic diagram showing (a) top-down synthesis of metallosilicates using acid treatment and/or metal precursor solutions, (b) bottom-up synthesis of metallosilicates, (c) inter-zeolite structural conversion into metallosilicates, and (d) single-step inter-zeolite structural conversion using metal precursor solutions in this study.
  • FIG. 2 is a graph of crystallization; powder XRD patterns of solid products obtained from the crystallization of (a) Co-BEA (batch 1), (b) Ni-BEA (batch 2) and (c) Zn-BEA (batch 3), with powder XRD patterns of B-MWW and B-BEA added for comparison; curves of relative crystallinity ( ⁇ : MWW, ⁇ : BEA) and TEA+ content ( ⁇ ) as a function of crystallization time of (d) batches 1, (e) batches 2 and (f) batches 3; determined from powder XRD and TGA/DTA, respectively; BET surface areas of solid products obtained from (g) batches 1, (h) batches 2 and (i) batches 3 as a function of crystallization time. The BET surface area of the parent B-MWW is shown for comparison.
  • Figure 3 shows normalized IR spectra in the structural region 500-1600 cm -1 for a series of solid products obtained from the crystallization of (a) Co-BEA (batch 1 ), (b) Ni-BEA (batch 2) and (c) Zn-BEA (batch 3) at different crystallization times, respectively, with IR spectra of parent B-MWW and B-BEA added for comparison.
  • (df) TEM and (g-i) STEM-EDS images of fully zeolite structure-converted (d,g) Co-, (e,h) Ni- and (f,i) Zn-BEA obtained after crystallization times of 48, 24 and 168 h in batches 1-3 are shown.
  • Figure 4 shows the framework-metal ( ⁇ ) and boron ( ⁇ ) contents as a function of crystallization time and the Si/Me ratio curves ( ⁇ ) for solid products obtained from (a) batch 1 (Co-BEA), (b) batch 2 (Ni-BEA) and (c) batch 3 (Zn-BEA) as determined by ICP elemental analysis, with elemental analysis data for the parent B-MWW added for comparison.
  • Co, Ni, and Zn 2p XPS spectra of fully zeolite-interconverted (g) Co-, (h) Ni-, and (i) Zn-BEAs obtained after crystallization times of 48, 24, and 168 h in batches 1-3 are shown; respectively: experimental (top); simulated (middle); and resolved constituent peaks (bottom).
  • Figure 5 shows (a,b) general and (ce) enlarged views of the most stable DFT-optimized structures of polymorph A zeolite BEA with (a,b) (ac) Co2 + , (d) Ni2 + , and (e) Zn2+ atoms substituted: Si (red); O (blue); Co (violet); Ni (cyan); Zn (orange); H (white).
  • Figure 6 shows the IR spectra after pyridine adsorption at 100 °C for fully zeolite-interconverted Co-, Ni-, and Zn-BEA catalysts obtained after 48, 24, and 168 h of crystallization in batches 1-3 (a) and (b) IR spectra in the hydroxyl region, (c) glucose conversion, and (d) yields of fructose (closed) and 5-HMF (open) over Co-, Ni-, and Zn-BEA catalysts. Regions are presented using ball-and-stick and line styles, respectively, which were relaxed and fixed during optimization. Distances between substituted metals and neighboring oxygen atoms are indicated ( ⁇ ).
  • the synthetic molar compositions of B-, Al- , and Ga-MWW(P) were 2.0HMI ⁇ 0.6Na2O ⁇ 1.0B2O3 ⁇ 3.0SiO2 ⁇ 57H2O, 15HMI ⁇ 1.7Na2O ⁇ 1.0A2O3 ⁇ 30SiO2 ⁇ 1350H2O , and 10HMI ⁇ 2.0Na2O ⁇ 1.0Ga2O3 ⁇ 20SiO2 ⁇ 900H2O .
  • B -MWW(P) was prepared using 1 M cobalt(II) nitrate hexahydrate ( 98%, Junsei), nickel(II) nitrate hexahydrate (98%, Samchun), and zinc ( II) nitrate hexahydrate (98%, Samchun) solutions, respectively, according to the procedures reported in our previous study.
  • the synthetic molar composition of Me-MWW was 4.0SiO 2 ⁇ 1.0MeO ⁇ 9.4H 2 O. All synthesized MWW were calcined at 550 °C for 8 h to remove the organic SDA trapped in the structure.
  • tetraethylammonium hydroxide solution TEAOH, 35%, Aldrich
  • TEABr TEABr
  • NH 4 F 98%, Junsei
  • the final molar composition of the synthesis mixture is (0 or 1)SiO 2 (0, 0.3, or 0.9)TEA + ⁇ 0.5NH 4 F (0.03 or 0.3)Me with 0 or 10 wt% dealuminate BEA seeds relative to SiO 2 of B-MWW.
  • the dried synthesis powders denoted as 0 h, were transferred to a 23 mL Teflon-lined stainless steel autoclave and heated at 190 °C for various crystallization times (1 h to 28 days) under static conditions.
  • the Teflon lining was routinely washed with diluted HF and KOH solutions for 24 h each.
  • the solid product was thoroughly washed with deionized water (DI), recovered by filtration, and dried at room temperature.
  • DI deionized water
  • the synthesized product was calcined at 550°C for 8 h to remove the organic SDA.
  • the detailed molar compositions of each synthetic batch are summarized in [Table 1].
  • H-Me-BEA the protonated form of Me-BEA
  • 1 M ammonium nitrate (98%, Aldrich) solution at 80 °C for 8 h and then calcined at 550 °C for 2 h.
  • calcined Al- and Ga-MWW were used as silica sources instead of B-MWW.
  • B-, Co-, Ni-, and Zn-BEA were prepared from the structural transformations between zeolites, B-, Co-, Ni-, and Zn-MWW, respectively, at 190 °C for 12 h according to the following procedure.
  • Figure 2a–c shows the powder XRD patterns of the solid products obtained from the synthesis of Co-BEA (batch 1), Ni-BEA (batch 2), and Zn-BEA (batch 3) as a function of crystallization time, respectively.
  • the representative synthesis conditions and results are also summarized in Table 1.
  • the solid sample obtained at 0 h exhibited only the characteristic pattern of MWW without the peaks of BEA structure, which was due to the relatively small amount of BEA seeds compared to B-MWW and/or the dissolution of BEA seeds during the preparation of the synthetic gel.
  • the XRD patterns for the parent MWW gradually disappeared and the BEA phase gradually increased.
  • the crystallization rate under the same synthesis conditions varied depending on the metal precursor solutions used. As shown in Figures 2d–f, complete structural transformation occurred within 48, 24, and 168 h for Co-, Ni-, and Zn-BEA, respectively. Interestingly, the crystallization kinetics of the direct transformation from B-MWW to Ni-BEA using nickel nitrate solution in this study (Fig. 1d) was slower than that of the structural transformation between zeolites from Ni-MWW to Ni-BEA reported in a previous study (Fig. 1b). In the latter case, Ni-BEA was almost completely crystallized in 2 h, indicating that the structural transformation of zeolites and the substitution of framework atoms occurred separately during the crystallization process.
  • Figures 2d–f show the variation of TEA + content of the solid products as a function of crystallization time determined via TGA/DTA.
  • the organic content profiles of Co-, Ni-, and Zn-BEA versus crystallization time ( ⁇ ) are consistent with the XRD-based crystallization curves ( ⁇ ) of the BEA phase.
  • the organic contents of the solid products are about 4, 7, and 2 wt% for batches 1–3, respectively, which is proportional to the crystallization rate.
  • the organic contents of the fully crystallized Co-, Ni-, and Zn-BEA are about 15, 11, and 9 wt%, respectively, which is inversely proportional to the molecular weight of the metal species.
  • the MWW phase decreased steadily during the inter-zeolite structural transformation of synthetic batches 1–3.
  • Me-BEA After complete crystallization, Me-BEA exhibited a total surface area in the following order: Co-BEA (420 m 2 g -1 ) > Ni-BEA (394 m 2 g -1 ) > Zn-BEA (293 m 2 g -1 ), which is also inversely proportional to the molecular weight of the metals used, as explained above.
  • the lowest total surface area of Zn-BEA can be attributed to the highest molecular weight of Zn, since the metal content of the fully crystallized Me-BEA is similar (i.e., about 3 wt% in Table 2). Underestimated surface area and/or non-fully crystallized Zn-BEA structures are formed.
  • batch 1 (Co-BEA) 1 412 53 359 0.8 1.0 120.5 - - 2 418 72 346 2.0 0.8 49.5 - - 3 425 97 328 2.5 0.7 38.9 - - 6 406 35 371 2.7 0.6 37.4 - - 12 380 42 338 2.8 0.5 36.9 - - 24 420 25 395 2.6 0.5 40.2 - - 48 420 19 401 2.4 0.5 43.0 0 (0) 129 (80) batch 2 (Ni-BEA) 1 456 90 366 2.6 0.8 39.6 - - 2 474 127 347 2.8 0.7 38.6 - - 3 466 115 351 2.8 0.6 39.8 - - 6 421 58 363 3.0 0.5 38.3 - - 12 403 27 376 3.1 0.4 39.4 - - 24 394 21 373 3.1 0.4 41.9 0 (0) 302 (194) batch 3 (Zn-BEA)
  • Figure 3a–c shows IR spectra in the structural region 500–1600 cm -1 for a series of solid products synthesized by structural transformations between zeolites from B-MWW to Co-, Ni-, and Zn-BEA. All solids obtained after 1 h of crystallization exhibited characteristic IR bands of the MWW structure at 569, 611, 809, 1080, 1183, and 1243 cm -1 . The IR bands at 937 and 1403 cm -1 are assigned to the four- and three-coordinated framework B species.
  • the fully crystallized Me-BEA sample clearly showed IR bands for PBU and OTO asymmetric vibrations of the BEA structure at 1060 cm -1 without the characteristic peaks corresponding to MWW and framework B species, indicating a complete zeolite structural transformation and replacement of metal species for B species within the structure.
  • each of the final Me-BEA products showed IR peaks assigned to Si-O-Co, Si-O-Ni, and Si-O-Zn at around 1020 cm -1 , indicating that Co, Ni, and Zn atoms were introduced into the T-sites during the direct zeolite structural transformation of B-MWW.
  • the highly dispersed framework heteroatoms were confirmed by (S)TEM-EDS images (Fig. 3d–i).
  • Figure 4a–c shows the elemental composition changes of the solid products obtained from batches 1–3 as a function of crystallization time.
  • the values are also summarized in Table 2.
  • the weakly acidic (pH ⁇ 6) metal nitrate precursor solution with a concentration of 0.01 M could also induce the leaching of B atoms from the borosilicate framework in the preparation of synthetic gels.
  • the metal contents of the solid products increased rapidly, but the increasing rates varied depending on the type of metal species.
  • the Co content of the solid product obtained at 1 h of crystallization was only 0.8 wt%, while that of Ni and Zn was 2.6 wt% at the same time.
  • the metal substitution degree was the lowest in Co-BEA. This can be explained by the higher stability of Co 2+ ion than other metal cations in the aqueous synthetic gel, as shown in the potential-pH equilibrium diagram.
  • the larger size of hydrated Co cations (i.e., Co(H 2 O) 6 2+ ) than Ni and Zn during the crystallization process may induce higher diffusion restrictions for their access to the vacancies created by the extraction of B from the synthetic solution.
  • Figure 4d–f shows the UV-DRS spectra of the solid products obtained from the crystallization of Co-, Ni-, and Zn-BEA. Intense UV absorption bands below 250 nm were observed in all cases before crystallization (0 h) due to the decomposition of the corresponding metal precursors and/or the formation of metal hydroxides and/or metal silicates from the dissolution of the parent B-MWW under alkaline conditions, respectively. Since the XRD pattern for the 0 h sample shows only the MWW structure (Fig. 2a–c), it appears that the 0 h sample mainly consists of the undecomposed parent B-MWW and amorphous metal hydroxides.
  • the UV absorption band intensities of the samples obtained from batches 1–0 h were lower than the other two 0 h samples from batches 2 and 3, which can be explained by the higher stability of the Co 2+ ion discussed above (Fig. 4a–c).
  • the intensity of the UV absorption band observed in the sample before crystallization (0 h) decreased significantly upon crystallization at 190 °C due to further conversion of the metal hydroxide to metal silicate.
  • the increase in the UV absorption band centered below 260 nm corresponding to the framework Co species was prominent during the initial period of crystallization (1–3 h), whereas the increase in the band was observed later and reached a maximum at 12 h.
  • the UV absorption band around 200 nm was dominant after 1 h of crystallization, while the band around 260 nm steadily increased after 12 h of crystallization (Fig. 4f). Since the Zn species in ZnO have a UV absorption band at a higher wavelength of around 300 nm, the UV absorption band appearing in the range of 200–260 nm should come from the injected framework Zn species.
  • Zn ⁇ + exists in the actual chemical environment of Zn-BEA, since Zn has the [Ar]3d 10 4s 2 electronic configuration and thus the electrons in the filled 3d 10 shell do not participate in chemical reactions.
  • the UV absorption band at around 260 nm represents the incompletely formed framework Me 2+ species, i.e., O-Me-OH (intermediate Me, Figure 1d-iii), and the band below 210 nm represents the fully formed framework Me 2+ species, i.e., O-Me-O (isolated Me, Figure 1d-iv).
  • the intermediate Me-OH can be converted into isolated Me-O by further condensation, which is most obvious in Ni-BEA ( Figure 4e).
  • the proportion of isolated Me in the calcined Me-BEA was in the following order: Ni-BEA (82%) > Co-BEA (60%) > Zn-BEA (13%), and the intermediate Me-OH was in the reverse order.
  • Figure 4g–i shows the Co, Ni, and Zn 2p XPS spectra of three fully crystallized Me-BEA samples.
  • the Me 2p XPS spectrum can be divided into two spin-orbit doublets, namely, Co 2p 1/2 (785.0–813.0 eV) and 2p 3/2 (775.0–784.0 eV), Ni 2p 1/2 (872.0–877.0 eV) and 2p 3/2 (850.0–854.0 eV), and Zn 2p 1/2 (1045.1–1045.8 eV) and 2p 3/2 (1022.0–1022.7 eV).
  • the Co and Ni 2p XPS spectra have peaks of shake-up satellites at 786.8 and 804.6 eV for Co and at 862.0 and 880.0 eV for Ni.
  • the Me 2p 3/2 XPS spectrum can be resolved into two or three peaks.
  • the Co- and Zn-BEA can observe peaks appearing at the lowest binding energy, which are attributed to the oxidized Co and Zn species, while in Ni-BEA, almost no peaks for NiO were observed.
  • the two Me 2p 3/2 peaks present at the highest or second highest binding energies should come from the framework metal species. And these two peaks can be considered as the isolated and intermediate metal species, respectively, because the higher binding energy indicates a stronger interaction with the framework oxygen atoms.
  • the ratio of the two or three XPS peaks appearing from high to low binding energies is similar to the ratio of the UV absorption band from low to high wavelength.
  • Zn-BEA exhibited the lowest isolated Me ratio but the highest intermediate Me ratio, which was associated with the lowest crystallization rate of Zn-BEA (Fig. 2f).
  • Figure 5 shows the most stable DFT-optimized structures of polymorph A of BEA zeolite in which two Co, Ni and Zn atoms are substituted at the Si8 site.
  • Co 2+ and Ni 2+ are characterized by two protons attached to the O4 and O17 atoms, whereas Zn 2+ is characterized by two protons bridging the O6 and O10 atoms.
  • Their E sub values were estimated to follow the order Co (58.4 kJ mol -1 ) > Ni (13.8 kJ mol -1 ) > Zn (-0.5 kJ mol -1 ).
  • borosilicates are known to facilitate the substitution of heteroatoms because B has similar atomic properties to Al but a smaller atomic radius.
  • Al- and Ga-MWW were also prepared under the same conditions as B-MWW to compare their structural transformation properties. Ga also has similar atomic properties to B and Al, which belong to the same group in the periodic table, and gallosilicates can generally be prepared with the same zeolite structure as aluminosilicates.
  • Al- and Ga-MWW showed XRD patterns of pure MWW structures like B-MWW, except for the difference in relative crystallinity.
  • the strongest X-ray peak corresponding to the (311) plane of the MWW structure gradually shifted to lower angles (from 26.4° for B-MWW to 26.1° for Al-MWW and 26.0° for Ga-MWW). This was due to the expansion of the lattice volume by the larger size of the framework atoms (Ga > Al > B).
  • the UV-DRS spectrum of the Ni precursor sample (0 h) indicates Ni substitution in the structure as described above, indicating that mostly nickel silicates were formed without hydrothermal heating among the products of the batches 10-12.
  • the dissolution of siliceous BEA seeds varied with the pH value of the Me-BEA composite gel: 9.68 (Ni-BEA) > 9.55 (Co-BEA) > 9.48 (Zn-BEA) (Table 1), which may have affected the structural transformation rate of Me-BEA. Therefore, the solubility of siliceous BEA seeds appears to play a role in controlling the crystallization kinetics of Me-BEA.
  • the MWW phases were maintained for up to 28 days after hydrothermal treatment. In addition, little BEA structure was formed in the synthesis using Zn precursor. These results indicate that the decomposed BEA seeds serve as CBUs that can accelerate the growth into BEA structure. In the absence of TEAOH (batches 16-18), no BEA structure was formed in any of the syntheses under the three metal precursors even after hydrothermal heating for 28 days, and the parent MWW structure was not dissolved in the Zn precursor synthesis.
  • Pyridine adsorption IR spectroscopy can be used to analyze the acidic properties of zeolite catalysts, i.e., the Br ⁇ nsted and Lewis acid sites appearing at 1540 and 1450 cm -1 , respectively.
  • the pyridine adsorption IR spectrum of B-MWW containing 1.8 wt% of B species showed almost no acidity (Table 2), which suggests that the B species in the structure of fully crystallized Me-BEA does not affect the catalytic results.
  • Fig. 6a all the fully crystallized Me-BEA catalysts did not show Br ⁇ nsted acidity due to the compensation of proton cations, but only Lewis acidity in the order of Ni-BEA > Co-BEA > Zn-BEA (Table 2).
  • the IR spectra in the hydroxyl region show silanol groups in the order of Zn-BEA > Co-BEA > Ni-BEA, which is in good agreement with the relative ratios of intermediate Me determined by UV-DRS and XPS characterizations (Fig. 4d-i).
  • the framework heteroatoms of Me-BEA are coordinated as much as the number of positively charged atoms.
  • the Lewis acidity of Mn-doped BEA zeolites was reported to depend on the amount of isolated mononuclear Mn species. Therefore, the order of Lewis acidity can also be explained by the difference in the amount of isolated Me in Me-BEA, i.e., Ni-BEA > Co-BEA > Zn-BEA.
  • the yields of fructose decreased for all catalysts, while the yields of 5-HMF gradually increased with the increasing reaction time. This is a typical result of the cascade conversion of glucose. In particular, the yield of 5-HMF was the highest than that of Zn-BEA. Although no Br ⁇ nsted acid sites were observed in these three catalysts in the pyridine adsorption IR analysis (Fig. 6a and Table 2), this result may be attributed to the Br ⁇ nsted acidic nature of the defective silanol groups (Fig. 6b). These silanols may contribute to the production of 5-HMF by the conversion of fructose, but the pyridine adsorption IR peak was not detected due to their weak acidity.
  • Co, Ni, and Zn containing BEA-type metallosilicates were successfully prepared via a single-step interzeolite structural transformation of B-MWW.
  • the structural transformation rates were rapid in the order of Ni-BEA ( ⁇ 1 d), Co-BEA ( ⁇ 2 d), and Zn-BEA (> 7 d), and the metal substitution resulted in distinct kinetic processes in which the substitution rate of Co was slower than that of the other two metals.
  • These two separate kinetics were mainly dependent on the solubility of siliceous BEA seeds and the stability of hydrated metal ions, respectively, under the acidic–basic conditions of the aqueous synthetic gel.

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Abstract

La présente invention concerne un procédé de fabrication d'un catalyseur de zéolite BEA pour une réaction de conversion de glucose et un catalyseur ainsi fabriqué et, plus spécifiquement, un procédé de fabrication d'un catalyseur de zéolite BEA de silicate de cobalt, de nickel et/ou de zinc par conversion structurale en une seule étape de zéolite de borosilicate MWW.
PCT/KR2024/004670 2023-07-18 2024-04-08 Procédé de fabrication d'un catalyseur de zéolite bea pour réaction de conversion de glucose et catalyseur ainsi fabriqué Pending WO2025018511A1 (fr)

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