Biomass to chemicals: Catalytic conversion of glycerol/water mixtures into acrolein, reaction network

Corma, Avelino; Huber, George W.; Sauvanaud, Laurent; O’Connor, Paul

doi:10.1016/j.jcat.2008.04.016

Cited by 427 publications

(311 citation statements)

References 27 publications

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“…On these items, MicroDowner unit was able to fit DCR data, working at same temperature, a similar (somewhat higher) catalyst to oil ratio and similar residence time in reactor. Other studies including naphtha cracking [40][41], use of coked catalyst [42] and cracking of oxygenated feeds [43] also have been carried out and will be further discussed below.…”

Section: Fixed Fluid Bed Solid Well Mixed Gas: Berty Type Reactors Rmentioning

confidence: 99%

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FCC testing at bench scale: New units, new processes, new feeds

Corma

Sauvanaud

2013

Catalysis Today

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As the FCC process has evolved over decades, several laboratory scale equipment have appeared to maintain a proper assessment of catalysts activity. Several laboratory equipments are available for simulating the FCC process, from the well known fixed bed, MicroActivity Test to newer, fluid bed or transported bed units. As well, a number of units have been created to simulate other parts of the process such as regenerator or stripper, The increased pressure for treating non-conventional feeds, from reprocessing gasoline to extra-heavy feeds or oils produced from biomass containing large amounts of heteroatoms, increase the needs to have a laboratory test which is as close as possible to the process so that data extraction from the laboratory test are simplified, thus less prone to errors or misunderstanding. KeywordsLaboratory testing, catalytic cracking, naphtha cracking, coked catalyst, biooil cracking Highlights• FCC process is adapting to new feeds and new processes• Heavy resid feeds and biomass-derived feeds are being extensively tested • Significant operation and process changes are contemplated to squeeze maximum value from feeds: naphtha reprocessing, use of partially coked catalysts, several independent risers. 3

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Section: Fixed Fluid Bed Solid Well Mixed Gas: Berty Type Reactors Rmentioning

confidence: 99%

“…More instaurations gave slightly more gasoline with significantly higher aromatic content. Glycerol moiety from triglyceride cracking may be transformed into a range of oxygenated products, including high yields of acrolein [43].…”

Section: Oils From Biomass and Opportunity Stocksmentioning

confidence: 99%

FCC testing at bench scale: New units, new processes, new feeds

Corma

Sauvanaud

2013

Catalysis Today

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“…Conversion of glycerol into useful chemicals is widely studied [6][7][8][9][10][11][12][13][14][15][16]. Most of the works report on converting glycerol into acrolein [6][7][8], acetol [9], or 1,2-and 1,3-propanediol [10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Conversion of glycerol into allyl alcohol over potassium-supported zirconia–iron oxide catalyst

Konaka¹,

Tago²,

Yoshikawa³

et al. 2014

Applied Catalysis B: Environmental

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The catalytic conversion of glycerol was performed with iron oxide-based catalysts for production of allyl alcohol using a fixed-bed flow reactor at 623 K under atmospheric pressure.The glycerol dehydration proceeds on acid sites of catalysts while the allyl alcohol production is assumed to be catalyzed by non-acidic sites of catalysts through a hydrogen transfer mechanism.Different alkali metals, including Na, K, Rb, and Cs were supported on ZrO 2 -FeO X and all of them gave impressively higher allyl alcohol yield and suppressed glycerol dehydration due to the reduced catalyst acidic property. K-supported ZrO 2 -FeO X (K/ZrO 2 -FeO X ) was chosen for further studies, and allyl alcohol yield remarkably increased up to 27 mol%-C at the K content of 3-5 mol%. Since no external hydrogen gas is supplied to the system, the hydrogen transfer mechanism should take place between the reaction of glycerol and either hydrogen atoms derived from formic acid forming during the reaction, or active hydrogen species produced from the decomposition of H 2 O by ZrO 2 .Addition of Al 2 O 3 to K/ZrO 2 -FeO X (K/Al 2 O 3 -ZrO 2 -FeO X ) was examined in order to improve structure stability during the glycerol conversion. Al 2 O 3 addition to the catalyst was effective to achieve higher structure stability, leading to high glycerol conversion with stable allyl alcohol yield of above 25 mol%-C. Moreover, K/Al 2 O 3 -ZrO 2 -FeO X can be applicable to the conversion of crude glycerol which is the waste solution obtained from biodiesel production.3

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“…Conventional gas-phase catalytic processes have been studied for the conversion of glycerol into acrolein [7,8] and a wide variety of glycerol-derived chemicals, as reviewed recently by Zhou and co-workers in a comprehensive paper [9]. Hydrothermal chemistry in sub-or supercritical water (SCW), either non-catalytic or with the addition of homogeneous and heterogeneous catalysts, has received considerable attention in recent years.…”

Section: Introductionmentioning

confidence: 99%

Catalytic gasification of glycerol in supercritical water

May

Salvadó

Torras

et al. 2010

Chemical Engineering Journal

100

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The conversion of glycerol in supercritical water (SCW) was studied at 510 -550°C and a pressure of 350 bars using both a bed of inert and non-porous ZrO 2 particles (hydrothermal experiments), and a bed of 1 % Ru/ZrO 2 catalyst particles. Experiments were conducted with a glycerol concentration of 5 wt% in a continuous isothermal fixed-bed reactor at a residence time between 2 and 10 s. Hydrothermolysis of glycerol formed water-soluble products such as acetaldehyde, acetic acid, hydroxyacetone and acrolein, and also gases like H 2 , CO and CO 2 .The catalyst enhanced the formation of acetic acid, inhibited the formation of acrolein, and promoted the gasification of the glycerol decomposition products. Hydrogen and carbon oxides were the main gases produced in the catalytic experiments, with only minor amounts of methane and ethylene. Complete glycerol conversion was achieved at a residence time of 8.5 s at 510 °C, and at around 5 s at 550 °C with a 1 wt% Ru/ZrO 2 catalyst. The catalyst was not active enough to achieve complete gasification, since high yields of primary products like acetic acid and acetaldehyde were still present. Carbon balances were between 80 and 60 % in the catalytic experiments, decreasing continuously as the residence time was increased. This was attributed partially to the formation of methanol and acetaldehyde, which were not recovered and analyzed efficiently in our set-up, but also to the formation of carbon deposits. Carbon deposition was not observed on the catalyst particles but on the surface of the inert zirconia particles, especially at high residence time. This was related to the higher concentration of acetic acid and other acidic species in the catalytic experiments, which may polymerize to form tar-like carbon precursors. Because of carbon deposition, hydrogen yields were significantly lower than expected; for instance at 550 ºC the hydrogen yield potential was only 50 % of the stoichiometric value.

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Biomass to chemicals: Catalytic conversion of glycerol/water mixtures into acrolein, reaction network

Cited by 427 publications

References 27 publications

FCC testing at bench scale: New units, new processes, new feeds

FCC testing at bench scale: New units, new processes, new feeds

Conversion of glycerol into allyl alcohol over potassium-supported zirconia–iron oxide catalyst

Catalytic gasification of glycerol in supercritical water

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