Comparison of Lignin, Macroalgae, Wood, and Straw Fast Pyrolysis

Trinh, Trung Ngoc; Jensen, Peter Arendt; Dam‐Johansen, Kim; Knudsen, Niels Ole; Sørensen, Henrik Rokkjær; Hvilsted, Søren

doi:10.1021/ef301927y

Cited by 135 publications

(139 citation statements)

References 41 publications

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“…The first case with thiols is representative of the type of sulfur containing components which can be present in bio-oil (thiols are present in naturally occurring proteins [52]) and concentration that could be expected in bio-oil [53]. The second case was an attempt to improve the catalyst stability.…”

Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

“…For testing the influence of chlorine containing components on the stability of the catalyst, 0.3 vol% 1-chlorooctane (corresponding to 0.05 wt% Cl) was added to a feed of 50 g/l and 2 vol% DMDS in 1-octanol, simulating a typical chlorine concentration in bio-oil [53]. 1-chlorooctane is as such not a typically occurring molecule in bio-oil, but it was chosen to be comparable to the thiol addition investigated in Section 3.3.…”

Section: The Effect Of Chlorine Containing Componentsmentioning

confidence: 99%

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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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Section: The Effect Of Sulfur Containing Componentsmentioning

confidence: 99%

Section: The Effect Of Chlorine Containing Componentsmentioning

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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“…By contrast fast pyrolysis of macroalgae has been reported to produce a lower yield of bio-oil equivalent to ~76% of the energy content of the biomass [49,67]. Importantly, the lipid content of microalgae is believed to influence the energy balance of pyrolysis with higher lipid content microalgae having an improved energy balance [62], therefore the energy balance of pyrolysis of microalgae may be more favourable than for macroalgae.…”

Section: Pyrolysismentioning

confidence: 99%

Macroalgae-Derived Biofuel: A Review of Methods of Energy Extraction from Seaweed Biomass

et al. 2014

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Abstract:The potential of algal biomass as a source of liquid and gaseous biofuels is a highly topical theme, but as yet there is no successful economically viable commercial system producing biofuel. However, the majority of the research has focused on producing fuels from microalgae rather than from macroalgae. This article briefly reviews the methods by which useful energy may be extracted from macroalgae biomass including: direct combustion, pyrolysis, gasification, trans-esterification to biodiesel, hydrothermal liquefaction, fermentation to bioethanol, fermentation to biobutanol and anaerobic digestion, and explores technical and engineering difficulties that remain to be resolved.

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“…This impurity of sulfur is representative of what can be present in bio-oil. 25 Fig . 6(a) shows the development in the conversion of guaiacol and 1-octanol and the DOD as a function of TOS.…”

Section: Effect Of Sulfurmentioning

confidence: 99%

“…This corresponds to the quantity of organic bound chlorine, which can be found in bio-oil. 25 In Fig. 6(a) the development in the conversion of guaiacol and 1-octanol and the DOD is seen as a function of TOS.…”

Section: Effect Of Chlorinementioning

confidence: 99%

Stability and resistance of nickel catalysts for hydrodeoxygenation: carbon deposition and effects of sulfur, potassium, and chlorine in the feed

Mortensen

Gardini

Carvalho

et al. 2014

Catal. Sci. Technol.

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aThe long term stability and resistance toward carbon deposition, sulfur, chlorine, and potassium of Ni/ZrO 2 as a catalyst for the hydrodeoxygenation (HDO) of guaiacol in 1-octanol (as a model compound system for bio-oil) has been investigated at 250°C and 100 bar in a trickle bed reactor setup. Without impurities in the feed good stability of the Ni/ZrO 2 catalyst could be achieved over more than 100 h of operation, particularly for a sample prepared with small Ni particles, which minimized carbon deposition.Exposing the catalyst to 0.05 wt% sulfur in the feed resulted in rapid deactivation with complete loss of activity due to the formation of nickel sulfide. Exposing Ni/ZrO 2 to chlorine-containing compounds (at a concentration of 0.05 wt% Cl) on-stream led to a steady decrease in activity over 40 h of exposure.Removal of the chlorine species from the feed led to the regaining of activity. Analysis of the spent catalyst revealed that the adsorption of chlorine on the catalyst was completely reversible, but chlorine had caused sintering of nickel particles. In two experiments, potassium, as either KCl or KNO 3 , was impregnated on the catalyst prior to testing. In both cases deactivation was persistent over more than 20 h of testing and severely decreased the deoxygenation activity while the hydrogenation of guaiacol was unaffected. Overall, sulfur was found to be the worst poison, followed by potassium and then chlorine. Thus, removal/limitation of these species from bio-oil is a requirement before long term operation can be achieved with this catalyst.

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Comparison of Lignin, Macroalgae, Wood, and Straw Fast Pyrolysis

Cited by 135 publications

References 41 publications

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

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

Macroalgae-Derived Biofuel: A Review of Methods of Energy Extraction from Seaweed Biomass

Stability and resistance of nickel catalysts for hydrodeoxygenation: carbon deposition and effects of sulfur, potassium, and chlorine in the feed

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