| Citation: |
ZHANG Jiakang, WANG Huan, ZHANG Senhan, et al. HZSM-5 synthesized by montmorillonite and its application for production of hydrogen via steam reforming of dimethyl ether[J]. Acta Materiae Compositae Sinica, 2025, 42(5): 2627-2635. DOI: 10.13801/j.cnki.fhclxb.20240801.005
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HZSM-5 with different texture and acidity was prepared using sub-molten salt activated montmorillonite as raw material by traditional hydrothermal method, seed-directed method, steam-assisted crystallization method and aerosol crystallization method. And the HZSM-5 used as solid acid was physically mixed with commercial Cu/ZnO/Al2O3 to obtain bifunctional catalysts for steam reforming of dimethyl ether (SRD) reaction. The samples were systematically characterized by XRD, FTIR, SEM, N2 adsorption-desorption at low temperature, and NH3-TPD techniques. The results showed that the crystal size, textural and acidity properties of HZSM-5 could be effectively regulated by the synthesis method, and then affecting the SRD performance of the corresponding bifunctional catalyst. TH-HZSM-5 synthesized by the traditional hydrothermal method exhibited suitable acid content and relatively large surface area, pore volume and pore size, and thus bifunctional catalyst composed of TH-HZSM-5 as solid acid and Cu/ZnO/Al2O3 with a mass ratio of 1∶1 showed better SRD reaction performance, and the dimethyl ether conversion and H2 yield reached 100% and 91% under the conditions of reaction temperature 300℃, pressure 0.1 MPa, space velocity
Hydrogen production via steam reforming of dimethyl ether (SRD) is a reasonable and practical way to solve the problem of hydrogen supply for proton exchange membrane fuel cells (PEMFC). SRD is a two-step sequential reaction consisting of hydrolysis of dimethyl ether (DME) to methanol and steam reforming of methanol to hydrogen. DME hydrolysis is likely to be a rate-controlled step reaction of SRD. Therefore, it is particularly important to develop low cost and high efficiency acid catalysts for hydrolysis of DME.
A series of HZSM-5 were prepared using sub-molten salt activated montmorillonite as raw material by traditional hydrothermal method, seed-directed method, steam-assisted crystallization method and aerosol crystallization method, respectively, (The obtained HZSM-5 was listed as TH-HZSM-5, SD-HZSM-5, SAC-HZSM-5, and AC-HZSM-5, respectively). And the HZSM-5 used as solid acid was physically mixed with commercial Cu/ZnO/AlO to obtain bifunctional catalysts for SRD reaction. The materials were characterized by XRD, FT-IR, SEM, N adsorption-desorption at low temperature, and NH-TPD techniques. The SRD reaction performance of the bifunctional catalyst consisting of HZSM-5 prepared by different method was investigated in detail.
HZSM-5 molecular sieve with microporous were successfully synthesized by the four methods. Although the acid strength of HZSM-5 synthesized by different methods was similar, the acid content of them was slightly different, i.e., they decreased in order of AC-HZSM-5>SAC-HZSM-5>TH-HZSM-5>SD-HZSM-5. All bifunctional catalysts exhibited the high initial DME conversion rate. The bifunctional catalysts based on AC-HZSM-5 with the highest acid content presented rapid deactivation due to inducing faster side reactions such as DTH and MTH, and the DME conversion rate decreased by 23% within reacting for 11 h, meanwhile, the H yield was the lowest (60%). TH-HZSM-5 had moderate acid content and large specific surface area, pore volume and pore size could inhibit the occurrence of carbon deposition because the reaction product could quickly diffuse out, thus it showed good stability, and the H yield was the highest (85%) at 11 h. All bifunctional catalysts exhibited low CH selectivity. The selectivity of C products of SD-HZSM-5 based bifunctional catalyst was about 4%. With the increase of acid content of HZSM-5 prepared by different methods, the side reaction of DTH and MTH was promoted, resulting in the selectivity of C products of corresponding bifunctional catalysts gradually increasing, and the increasing degree of them was positively correlated with the acid content. According to the two-step reaction mechanism of SRD, the hydrolysis rate of DME to methanol on AC-HZSM-5 with high acid content was greater than the reforming rate of methanol on Cu/ZnO/AlO, thus AC-HZSM-5 based bifunctional catalyst showed a high methanol selectivity. When the acidity of HZSM-5 prepared by other methods was weakened, the hydrolysis rate of DME was slowed down, so the methanol selectivity of other bifunctional catalyst was reduced, and the methanol selectivity was proportional to the acid content of the corresponding solid acid. Under the current reaction conditions, Cu/ZnO/AlO catalysts exhibited good catalytic activity for methanol reforming to hydrogen, and the reverse water gas shift (RWGS) reaction was greatly inhibited, thus, all catalysts showed high CO selectivity (63-89%) and low CO selectivity (<4%).Conclusions: HZSM-5 was successfully synthesized using sub-molten salt activated montmorillonite as raw material by traditional hydrothermal method, seed-directed method, steam-assisted crystallization method and aerosol crystallization method. However, the crystal size, textural and acidity properties of HZSM-5 could be effectively regulated by the synthesis method, and then affecting the SRD performance of the corresponding bifunctional catalyst. TH-HZSM-5 synthesized by the traditional hydrothermal method exhibited suitable acid content and relatively large surface area, pore volume and pore size, and thus bifunctional catalyst composed of TH-HZSM-5 as solid acid and Cu/ZnO/AlO with a mass ratio of 1:1 showed better SRD reaction performance, and the DME conversion and H yield decreased from 100% to 95%, and 91% to 85%, respectively, under the conditions of reaction temperature 300 ℃, pressure 0.1 MPa, space velocity 5000 mL/(g·h), reacting for 11 h, showing good stability.
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