A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis

Bu, Qian; Lei, Hanwu; Zacher, Alan H.; Wang, Lu; Ren, Shoujie; Liang, Jing; Wei, Yi; Liu, Yupeng; Tang, Juming; Zhang, Qin; Ruan, Roger

doi:10.1016/j.biortech.2012.08.089

Cited by 494 publications

(265 citation statements)

References 64 publications

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“…HDO of phenol can take place by two paths as summarized in Figure 5: a direct deoxygenation of phenol to benzene, followed by hydrogenation to cyclohexane, or an initial hydrogenation of phenol to cyclohexanol followed by dehydration to cyclohexene and then hydrogenation to cyclohexane. The preferred reaction path depends on the catalyst and reaction conditions [45][46][47][48][49][50][51].…”

Section: The Effect Of Residence Timementioning

confidence: 99%

“…For this purpose, a biooil model system of phenol in 1-octanol was used. Phenol and phenolic derivatives are a fairly abundant part of bio-oil constituting up to 15 wt% [6], which are quite persistent oxycompounds to deoxygenate [29]. 1-octanol was chosen partly as a solvent for the phenol, but also to simulate some of the more easily accessible oxygen functionalities which are also found in bio-oil [30], as simple alcohols may constitute up to 4 wt% of the bio-oil [6].…”

Section: Introductionmentioning

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 Residence Timementioning

confidence: 99%

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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“…As petroleum is playing a major role in world economy, rapid growing consumption of fossil fuels and depletion of total crude-oil reservations lead to global energy crisis [1]- [3]. Meanwhile, fossil fuel causes huge negative impact on environment and public health due to its pollutant gas emission [3] [4].…”

Section: Introductionmentioning

confidence: 99%

Renewable Hydrogen Produced from Different Renewable Feedstock by Aqueous-Phase Reforming Process

Wei¹,

Lei²,

Liu³

et al. 2014

JSBS

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Aqueous phase reforming (APR) of biomass derived feedstock producing hydrogen was reviewed. The APR process was discussed based on different feedstock categories such as sugars, polyols and ethanol. The mechanism of APR was analyzed referring to different structures of feedstock. The reaction pathways of APR were investigated. The usage of catalysts should be judged by feedstock on the requirement including C-C bond cleavage, water-gas shift (WGS) reaction, and catalyst maintenance. The prospects were concluded based on the recent works from bimetallic catalysts and high efficient supports. Examples of significant challenges of reducing catalyst cost and increasing catalyst stability have been discussed. The modification and utilization of alkane selectivity of APR processes for liquid fuel production was also investigated.

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“…15-30 MJ/kg) and chemical composition they are an attractive platform feedstock in the bioeconomy [1]. The main problems in use and handling of pyrolysis oils are their high viscosity, high acidity, lower heating value than fossil fuels and low phase stability [2][3][4][5][6][7][8]. These negative properties are mainly caused by the high oxygen content present in the organic components.…”

Section: Introductionmentioning

confidence: 99%

“…First studies on catalytic HDO were contributed by Elliott et al in the eighties [7]. Nowadays the research in this field is very Open Access *Correspondence: wolfgang.olbrich@student.kit.edu 1 Karlsruhe Institute of Technology, Institute of Catalysis Research and Technology, Hermann-von-Helmholtz-Platz 1, 76344 EggensteinLeopoldshafen, Germany Full list of author information is available at the end of the article intense and widespread, as it can be indicated by the numerous publications reporting different catalysts, reaction conditions and reactor types [2][3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Catalytic hydrodeoxygenation of pyrolysis oil over nickel-based catalysts under H2/CO2 atmosphere

Olbrich

Boscagli

Raffelt

et al. 2016

Sustain Chem Process

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Background: Renewable feedstocks and bio-refinery concepts are the key to a successful transition to a sustainable chemical industry. One conceivable refinery concept is based on pyrolysis oils from biomass, though these oils are quite difficult to handle. A well investigated approach to upgrade pyrolysis oil and turn it into a valuable products is catalytic hydrodeoxygenation (HDO). However, this process has to be optimized and new ideas are needed to make the hydrodeoxygenation process attractive sustainable and economically competitive. With regard to the many successful applications of gas-expanded liquids in heterogeneous catalysis, the expansion of pyrolysis oil with carbon dioxide was applied in the context of a hydrodeoxygenation reaction. The catalyst used for HDO was Ni/Al 2 O 3 (nickel loading 20 %wt). Results:The influence of CO 2 on the viscosity was found to be quite strong at low temperature. At 52 °C and a CO 2 pressure of 0.5 MPa the viscosity is reduced by 30 %. With 4.0 MPa of CO 2 the viscosity decreases by 60 %. With supercritical CO 2 a volume expansion of 5 % was observed. The hydrodeoxygenation showed best results at 340 °C and autogenous pressure. The experiments were started at a total pressure of 8.0 MPa at room temperature (H 2 + CO 2 ), with a respective partial pressure of CO 2 of 0 MPa, 2.0 MPa or 4.0 MPa. A deoxygenation degree of around 70 % could be reached (dry basis) under each atmosphere. The analysis of the upgraded products by different techniques indicated a slight decrease of hydrogenation with increasing the pressure of CO 2 .Conclusions: Despite we observed a change in the physical properties when expanding the pyrolysis oil with CO 2 , no real improvement of the catalytic hydrodeoxygenation reaction (e.g. deoxygenation degree) could be found yet. Possible reasons for the absence of gas-expanded liquid effects could be the polar nature of the used pyrolysis oil and the high temperature. We assume that a viscous and more tar-like, but less polar pyrolysis oil will be more influenced. Gas-expansion with CO 2 tends to be less effective with polar liquids due to the unpolar nature of CO 2 . The only observed effect in our actual system was a decrease of the hydrogenation with decreasing partial pressure of hydrogen.

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A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis

Cited by 494 publications

References 64 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

Renewable Hydrogen Produced from Different Renewable Feedstock by Aqueous-Phase Reforming Process

Catalytic hydrodeoxygenation of pyrolysis oil over nickel-based catalysts under H2/CO2 atmosphere

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