The effect of catalyst modification on the conversion of glycerol to allyl alcohol

Sánchez, Gizelle; Friggieri, Jarrod; Keast, C.; Drewery, Matthew; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; Stockenhuber, Michael

doi:10.1016/j.apcatb.2014.01.019

Cited by 18 publications

(51 citation statements)

References 41 publications

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“…Considering that conventional methods for allyl alcohol production use fossil fuel-based propylene as feedstock and that besides propylene high prices, environmental and fuel security aspects are important limitations of these processes, investigating bio-routes for the synthesis of allyl alcohol have recently gained significant interest in the industrial context. In a continuous flow system, the active phases for the selective formation of allyl alcohol previously reported are iron [5,7,20] and MoO3 -WO3 [21]. In this contribution, we report, for the first time, the synthesis and modification (in terms of mesoporosity and acidity) of stable exchanged iron zeolites for direct conversion of glycerol to allyl alcohol in a flow reactor configuration under relatively mild reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

“…Dimensions are reported in previously published work [5]. Experiments were conducted at atmospheric pressure and 340 °C in continuous operation with nitrogen as carrier gas and a constant supply of a 35 wt % glycerol aqueous solution.…”

Section: Catalytic Measurementsmentioning

confidence: 99%

“…The ZSM5 supported 13 % iron oxide catalyst was modified by the deposition of rubidium nitrate, as basicity has been suggested to favour the formation of allyl alcohol when reacting glycerol over iron catalysts [5,7]. Despite the vast utilization of Cs exchanged zeolites, a Rb salt was selected to conduct the ZSM5-supported iron catalysts modification based on previous investigations with alumina-supported iron catalysts [5].…”

Section: Alkali Metal Depositionmentioning

confidence: 99%

“…The presence of such compounds positions zeolites as potential catalysts for allyl alcohol production from glycerol, since the presence of well defined micropores can reduce (due to shape selectivity) the formation of those "bulky" molecules which appear to be involved with, and indeed facilitate, catalyst deactivation. Thus, zeolites have a major potential advantage over other commonly used supports (most notably alumina [5] and zirconia [6]). To the best of our knowledge, investigations aimed at the use of zeolites in the conversion of glycerol to allyl alcohol have not been reported.…”

Section: Introductionmentioning

confidence: 99%

“…Catalyst acidity has been correlated with acrolein formation, while basicity was shown to drive the reaction towards allyl alcohol formation [5,7]. Zeolite acidity can be typically reduced by dealumination [8,9], modification with phosphorus [10], alkali treatment [11], alkali metal exchange [12] amongst other methods.…”

Section: Introductionmentioning

confidence: 99%

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Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Sánchez

Dlugogorski

Kennedy

et al. 2016

Applied Catalysis A: General

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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

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Section: Introductionmentioning

confidence: 99%

Section: Catalytic Measurementsmentioning

confidence: 99%

Section: Alkali Metal Depositionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Sánchez

Dlugogorski

Kennedy

et al. 2016

Applied Catalysis A: General

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Zeolites for Sustainable Chemical Transformations

Harvey

Drewery

Kennedy

et al. 2022

Heterogeneous Catalysis for Sustainable Energy

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Enhancing allyl alcohol selectivity in the catalytic conversion of glycerol; influence of product distribution on the subsequent epoxidation step

Harvey

Sánchez

Kennedy

et al. 2015

Asia-Pacific J Chem Eng

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Conversion of glycerol to allyl alcohol in a flow reactor and subsequent conversion to glycidol in a batch reactor are discussed in this paper. To increase reaction selectivity in the glycerol to allyl alcohol reaction, the catalyst was modified with alkali metal salts. The treatment of the catalyst (Fe/Al 2 O 3 ) with potassium, caesium and rubidium salts enhanced the allyl alcohol yield when a 35 wt% glycerol solution was used as feed. Furthermore, the addition of organic reductants or hydrogen to the glycerol feed increased the allyl alcohol yield. Optimisation of allyl alcohol selectivity was achieved by a combination of alkali metal cation modifiers and the addition of reductants. The influence of acid, base and redox properties on selectivity is presented, focusing on the effect of these properties on product distribution. The effect of by-products from the conversion of glycerol to allyl alcohol on the epoxidation reaction was examined to identify the ideal reaction conditions for maximising the glycidol yield. Epoxidation of allyl alcohol by 30 wt% hydrogen peroxide was conducted in a batch reactor at 333K using titanium silicate-1 catalyst. Conversion of allyl alcohol was high for all conditions; however, hydrolysis of glycidol to glycerol reduces selectivity.

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The effect of catalyst modification on the conversion of glycerol to allyl alcohol

Cited by 18 publications

References 41 publications

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Zeolite-supported iron catalysts for allyl alcohol synthesis from glycerol

Zeolites for Sustainable Chemical Transformations

Enhancing allyl alcohol selectivity in the catalytic conversion of glycerol; influence of product distribution on the subsequent epoxidation step

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