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Hierarchical Zeolites as Catalysts for Biodiesel Production from Waste Frying Oils to Overcome Mass Transfer Limitations.

ABSTRACT: Hierarchical crystals with short diffusion path, conventional microcrystals and nanocrystals of ZSM-5 zeolites were used for biodiesel production from waste frying oils and were assessed for their catalytic activity in regard to their pore structure and acidic properties. Produced zeolites were characterized using XRD, nitrogen adsorption-desorption, SEM, TEM, X-ray fluorescence, and FTIR. Pore size effect on molecular diffusion limitation was assessed by Thiele modulus calculations and turnover frequencies (TOF) were used to discuss the correlation between acidic character and catalytic performance of the zeolites. Owing to the enhanced accessibility and mass transfer of triglycerides and free fatty acids to the elemental active zeolitic structure, the catalytic performance of nanosponge and nanosheet hierarchical zeolites was the highest. A maximum yield of 48.29% was reached for the transesterification of waste frying oils (WFOs) using HZSM-5 nanosheets at 12:1 methanol to WFOs molar ratio, 180 °C, 10 wt % catalyst loading, and 4 h reaction time. Although HZSM-5 nanosponges achieved high conversions, these more hydrophilic zeolites did not function according to their entire acidic strength in comparison to HZSM-5 nanosheets. NSh-HZSM5 catalytic performance was still high after 4 consecutive cycles as a result of the zeolite regeneration.

SUBMITTER: Fawaz EG

PROVIDER: S-EPMC8398946 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:In this paper, the ultrasonic-assisted desilication technique was reported as an attractive and efficient way for the preparation of hierarchical zeolites with MFI structure type. The prepared materials were used as active catalysts for the dehydration of ethanol into diethyl ether and ethylene. For all catalysts, the selectivity to diethyl ether was ca 95% or higher up to 210 °C, with catalytic activity in the range of 40-68%. In case of desilicated zeolites, at 270-290 °C, the conversion of ethanol was full with selectivity to ethylene ca 80%. MFI-type commercial zeolite was treated with a sodium and/or tetrabutylammonium hydroxide aqueous solutions (NaOH or NaOH/TBAOH) for 30 min. In the case of the application of ultrasounds, a QSonica Q700 sonicator (60 W and 20 kHz) equipped with a "1" diameter horn was used. In all cases, desilication was performed in an ice bath in order to keep the procedure conditions at low temperature. It was indicated that the use of ultrasounds during desilication procedure caused higher extraction of silicon and aluminum, which was connected with an elevated mesoporosity in relation to the samples modified in the absence of ultrasounds. Ultrasonic-assisted treatment of MFI-type zeolite caused also an apparent formation of numerous holes inside zeolite grains, resembling the look of "swiss cheese". Furthermore, it was indicated that the samples prepared using ultrasonic irradiation exhibited enhanced catalytic properties in the dehydration of ethanol. For instance, MFI-type zeolite treated with NaOH/TBAOH alkaline mixture containing 10 mol% of TBAOH in the presence of ultrasounds (M-10 s) demonstrated higher both conversion of ethanol (59% vs. 47%) and selectivity to diethyl ether (95% vs. 93%) in comparison with zeolite modified conventionally (M-10c). The best catalyst was zeolite ultrasonically desilicated with NaOH/TBAOH solution of 70 mol% of TBAOH (M-70s). Generally, this catalyst indicated the highest conversion of ethanol, very high selectivity to diethyl ether (94-100%) at 150-210 °C and the highest selectivity to ethylene among investigated catalysts (21%, 66% and 84%) at 230 °C, 250 oC and 270 °C.

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Hierarchical Zeolites as Catalysts for Biodiesel Production from Waste Frying Oils to Overcome Mass Transfer Limitations.

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