A review of catalytic upgrading of bio-oil to engine fuels

Mortensen, Peter Mølgaard; Grunwaldt, Jan‐Dierk; Jensen, Peter Arendt; Knudsen, Kim; Jensen, Anker Degn

doi:10.1016/j.apcata.2011.08.046

Cited by 1,542 publications

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“…The total surface oxygen content of NanoMgO remained largely unaffected by dosing even for water exposure up to 1x10 6 L ( temperature. [59][60][61][62][63][64][65][66][67][68] In contrast, the surface oxygen concentration of NanoMgO-700 increased monotonically with water exposure, equating to a 2 % rise following 1x10 6 L. This corroborates the hypothesis that NanoMgO-700 is the more reactive surface reflecting its higher proportion of (111) facets and low coordination defects. [27,28] Further evidence for changes in surface oxygen species upon H2O adsorption was apparent from the corresponding high resolution O 1s spectra.…”

Section: Auger Parameter () = Ke (Auger E -From Photoelectron) + Besupporting

confidence: 74%

“…[3,4] Biomass, derived from non-edible sources of lignocellulose, sugars, and triglycerides offer the only sustainable and low cost solutions to alternative low carbon/carbon neutral transportation fuels. Thermal processing of lignocellulosic biomass to alkanes via pyrolysis and 2 hydrodeoxygenation (HDO) [5,6] or the conversion of plant or algae oil lipids via transesterification [7,8] to biodiesel are the subject of many investigations targeting low cost renewable transportation fuel. [9] While biodiesel production via the transesterification of C14-C20 triglyceride (TAG) components of lipids with C1-C2 alcohols [10][11][12][13] into fatty acid methyl esters (FAMEs) routes offer an energetically economical route to biofuels, [14] , [15] the use of soluble base catalysts results in fuel contamination and accompanying reactors and engine manifold corrosion.…”

Section: Introductionmentioning

confidence: 99%

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The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

et al. 2016

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An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O 2-sites to OH -and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C-H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects.Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

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Section: Auger Parameter () = Ke (Auger E -From Photoelectron) + Besupporting

confidence: 74%

Section: Introductionmentioning

confidence: 99%

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

et al. 2016

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“…This makes transport expensive and constrains its utilization [5]. Hence, it has been suggested to convert biomass into bio-oil by flash pyrolysis and subsequently upgrade this to fuel by hydrodeoxygenation, which is applicable with practically any type of biomass [6].…”

Section: Introductionmentioning

confidence: 99%

“…This is a high pressure catalytic upgrading process where hydrogen is used for exclusion of oxygen [6].…”

Section: Introductionmentioning

confidence: 99%

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Mortensen

Gardini

Damsgaard

et al. 2016

Applied Catalysis A: General

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Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol, Applied Catalysis A, General http://dx.doi.org/10. 1016/j.apcata.2016.06.002 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. Graphical abstractHighlights  Impurities as Cl, S, and K found in bio-oil will deactivate or inhibit MoS2-type catalyst by competing for the active sites  MoS2-based catalysts will produce sulfur containing hydrocarbons during HDO, but these can be removed again if a sufficiently high residence time is used enabling desulfurization of the product  Chlorine binds more strongly to the active sites of MoS2 based catalysts compared to H2O and H2S, while K irreversibly deactivates the catalyst 3 AbstractThe stability of Ni-MoS2/ZrO2 toward water, potassium, and chlorine containing compounds during hydrodeoxygenation (HDO) of a mixture of phenol and 1-octanol was investigated in a high pressure gas and liquid continuous flow fixed bed setup at 280°C and 100 bar. To maintain the stability of the catalyst, sufficient co-feeding of a sulfur source was necessary to avoid oxidation of the sulfide phase by oxygen replacement of the edge sulfur atoms in the MoS2 structure. However, the addition of sulfur to the feed gas resulted in the formation of sulfur containing compounds, mainly thiols, in the oil product if the residence time was too low. At a weight hourly space velocity (WHSV) of 4.9 h -1 the sulfur content in the liquid product was 980 ppm by weight, but this could be decreased to 5 ppm at a WHSV of 1.4 h -1 . A high co-feed of sulfur was needed when water was present in the feed and the H2O/H2S molar ratio should be below ca. 10 to maintain a decent stability of the catalyst. Chlorine containing compounds caused a reversible deactivation of the catalyst when co-fed to the reactor, where the catalytic activity could be completely regained when removing it from the feed. Commonly, chlorine, H2O, and H2S all inhibited the activity of the catalyst by competing for the active sites, with chlorine being by far the strongest inhibitor and H2S and H2O of roughly the same strength. Dissimilar, potassium was a severe poison and irreversibly deactivated the catalyst to <5% degree of deoxygenation when impregnated on the catalyst in a stoichiometric ratio relative to the active metal. This deactivation was a result of adsorption of potassium on the edge vacancy sites of the MoS2 slabs.

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“…In this sense, all major industrially-operated production processes have to be preceded by thorough studies on their equilibrium conditions. Recent examples of this fact, from several disciplines, would be the synthesis of graphene 1,2 , pharmaceutical drugs design 3,4 or novel biofuels production [5][6][7] .…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Analysis of the Experimental Equilibria for the Liquid-Phase Etherification of Isobutene with C₁ to C₄ Linear Primary Alcohols

et al. 2016

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The chemical equilibrium of the liquid-phase syntheses of 2-methoxy-2-methylpropane (MTBE), 2-ethoxy-2-methylpropane (ETBE), 2-methyl-2-propoxypropane (PTBE), and 1-tertbutoxybutane (BTBE) by reaction of isobutene with methanol, ethanol, 1-propanol, and 1-butanol, respectively, has been studied. Four different ion exchange resins as the catalysts, and two different reactor systems, namely a batch reactor and a setup of tubular reactors, were used.

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A review of catalytic upgrading of bio-oil to engine fuels

Cited by 1,542 publications

References 159 publications

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Thermodynamic Analysis of the Experimental Equilibria for the Liquid-Phase Etherification of Isobutene with C₁ to C₄ Linear Primary Alcohols

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A review of catalytic upgrading of bio-oil to engine fuels

Cited by 1,542 publications

References 159 publications

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

Thermodynamic Analysis of the Experimental Equilibria for the Liquid-Phase Etherification of Isobutene with C1 to C4 Linear Primary Alcohols

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Thermodynamic Analysis of the Experimental Equilibria for the Liquid-Phase Etherification of Isobutene with C₁ to C₄ Linear Primary Alcohols