A comparative study of glycerol dehydration catalyzed by micro/mesoporous MFI zeolites

Possato, Luiz G.; Diniz, Rosiane N.; Garetto, Teresita Francisca; Pulcinelli, Sandra Helena; Santilli, Celso Valentim; Martins, Leandro

doi:10.1016/j.jcat.2013.01.003

Cited by 138 publications

(141 citation statements)

References 24 publications

Supporting

Mentioning

125

Contrasting

Unclassified

Order By: Relevance

“…Similar observations have been reported when desilicating various MFI zeolites with NaOH [31]. Melian et al desilicated ZSM5 with NaOH to prepare fully exchanged Fe-ZSM5 [32].…”

Section: Catalyst Characterisationsupporting

confidence: 76%

See 1 more Smart Citation

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Sánchez

Dlugogorski

Kennedy

et al. 2016

Applied Catalysis A: General

View full text Add to dashboard Cite

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Alkaline preparation conditions engendered the zeolite with mesoporosity;Rubidium deposition enhanced allyl alcohol yield and decreased acrolein yield;Alkali post synthesis modification reduced the concentration of acid sites. AbstractUnder most reaction conditions studied, acrolein is reported as the primary product in the conversion of glycerol over zeolites. In such processes, acrolein forms at relatively high yields, with negligible allyl alcohol selectivity. In this contribution, we report the development of ZSM5-supported iron catalysts, modified by rubidium deposition, as stable materials for production of allyl alcohol from glycerol. Our results demonstrate a reduced rate of formation of acrolein over modified catalysts. Both unmodified and modified catalysts were analysed by inductively coupled plasma optical emission spectrometry, nitrogen adsorption, scanning electron microscope, X-ray diffraction, ammonia temperature programmed desorption, X-ray photoelectron spectroscopy and ultraviolet-visible spectroscopy. These techniques revealed that differences in product distribution and catalyst performance are due to the combined effects of iron loading, catalyst acidity and changes in the porosity of the catalyst.2

show abstract

“…Similar observations have been reported when desilicating various MFI zeolites with NaOH [31]. Melian et al desilicated ZSM5 with NaOH to prepare fully exchanged Fe-ZSM5 [32].…”

Section: Catalyst Characterisationsupporting

confidence: 76%

“…For the other catalysts, iron incorporation was thought to cause substantial blocking in micropores, while for the alkaline ion exchanged catalyst, desilication is invoked to explain the reduction in microporosity, as observed previously by other authors [31].…”

Section: Catalyst Characterisationsupporting

confidence: 57%

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Sánchez

Dlugogorski

Kennedy

et al. 2016

Applied Catalysis A: General

View full text Add to dashboard Cite

show abstract

“…Dehydration of glycerol is one of the most interesting catalytic processes because of its perspective to provide a sustainable route for acrolein production for industrial and agricultural applications (Fig. 12) 51 performed a systematic study on the gaseous phase dehydration of glycerol using microporous MFI zeolites and alkaline-desilicated mesoporous ones, in which all of the samples showed rather similar catalytic performance if the Si/Al ratio is similar. A slight decrease in deactivation is found although the coke contents of different catalysts increased with mesopore volume.…”

Section: Dehydration Of Glycerol To Acroleinmentioning

confidence: 99%

“…A simplified microscopic picture ( Fig. 13) was developed by Possato et al 51 in order to explain the deactivation of the ZSM-5…”

Section: Dehydration Of Glycerol To Acroleinmentioning

confidence: 99%

Catalytic test reactions for the evaluation of hierarchical zeolites

2016

View full text Add to dashboard Cite

Catalytic test reactions for the evaluation of hierarchical zeolitesStudies on the synthesis, characterization and catalytic performance of hierarchical zeolites and related porous materials are currently revitalizing the mature field of zeolite research. This review discusses the challenges in evaluating the catalytic performance of a hierarchical zeolite catalyst compared to its parent zeolite. zeolites and the facilitated access and transport in the additional meso-or macropore system. In this tutorial review, we discuss several test reactions that have been explored to show the benefit of the hierarchical pore system with respect to their suitability to prove the positive effects of hierarchical porous zeolites. It is important to note that positive effects on activity, stability and less frequently selectivity observed for hierarchically structured catalysts not necessarily are only a consequence of the additional meso-or macropores but also the number, strength and location of active sites as well as defects and impurities. With regard to these aspects, the test reaction has to be chosen carefully and potential changes in the chemistry of the catalyst have to be considered as well. In addition to the determination of conversion, yield and selectivity, we will show that the calculation of the activation energy and the determination of the Thiele modulus and the effectiveness factor are good indicators of the presence or absence of diffusion limitations in hierarchical zeolites compared to their parent materials. Key learning pointsHierarchical zeolites are an emerging technology in the mature field of industrial catalysts. Several test reactions are suggested to prove the advantage of their hierarchical structure. In addition to an increase in activity and selectivity suppression of coke formation is often observed. Concept of the Thiele modulus and the effectiveness factor is required to judge the presence of diffusion limitations in hierarchical catalysts.

show abstract

“…[4][5][6][7] Hydrogenolysis over metal catalysts affords 1,2-and 1,3-propanediols, which can be used in the production of polymers. 8,9 Dehydration over acidic catalysts produces acrolein, [10][11][12][13] an important intermediate in the synthesis of acrylic acid and other chemicals. Synthesis gas, a mixture of CO and H 2 , can be produced from glycerol aqueous phase reforming.…”

Section: Introductionmentioning

confidence: 99%

Atmospheric Pressure Continuous Production of Solketal from the Acid-Catalyzed Reaction of Glycerol with Acetone

Oliveira¹,

Souza²,

Mota³

2016

Journal of the Brazilian Chemical Society

View full text Add to dashboard Cite

A continuous-flow process at atmospheric pressure was designed for the conversion of glycerol to solketal, an oxygenated fuel additive, through the acid-catalyzed reaction of glycerol with acetone. Process optimization was performed by checking the influence of different variables on the conversion and selectivity. The variables examined were: residence time (12, 24, 60 and 120 min), catalyst type (Amberlyst-15 and K-10 Montmorillonite), catalyst loading (7, 3, and 1 g), reaction temperature (50, 40 and 30 ºC), molar ratio of the reactants (1:2, 1:5, 1:10, 1:15 and 1:20) and solvent used to homogenize the system (dimethylsulfoxide or dimethylformamide). The highest conversion (92%) was observed with 7.0 g of Amberlyst-15, reaction temperature of 50 °C, molar ratio of glycerol to acetone of 1:20 and dimethylformamide as solvent. In all cases, solketal isomers (five and six-membered ring ketals) were the only product observed. The results of solketal formation of this study, carried out at atmospheric pressure, were similar to other studies with pressures of up to 120 bar. The utilization of higher catalyst loading and molar ratio of reactants compensate the use of atmospheric pressure to achieve high conversion levels and selectivity to the desired product.

show abstract

A comparative study of glycerol dehydration catalyzed by micro/mesoporous MFI zeolites

Cited by 138 publications

References 24 publications

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Catalytic test reactions for the evaluation of hierarchical zeolites

Atmospheric Pressure Continuous Production of Solketal from the Acid-Catalyzed Reaction of Glycerol with Acetone

Contact Info

Product

Resources

About