Development of new catalytic systems for upgraded bio-fuels production from bio-crude-oil and biodiesel

Yakovlev, V. А.; Хромова, С. А.; Sherstyuk, O. V.; Dundich, V. O.; Ermakov, D. Yu.; Novopashina, V. M.; Лебедев, М. В.; Булавченко, О. А.; Parmon, Valentin N.

doi:10.1016/j.cattod.2009.03.002

Cited by 344 publications

(194 citation statements)

References 14 publications

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“…Ni-MoS2/ZrO2 was chosen as catalyst, as promotion by nickel previously has been shown to be slightly superior to cobalt promotion for HDO purposes [9,25] and ZrO2 was previously found as a suitable support for HDO [31][32][33][34][35] and does apparently not suffer from the instability in high concentration of water, as reported for the conventionally used -Al2O3 support for hydrotreating catalysts [9,36,37].…”

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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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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“…Particularly, long term stability is challenging due to the formation of carbon species on the catalysts or due to impurities in the feed. 1,[6][7][8][9][10] Previous work has primarily focused on the traditional hydrotreating catalysts such as Ni-MoS 2 and Co-MoS 2 , 1,11,12 noble metal catalysts based on Pd or Ru, [13][14][15][16] or nickel based catalysts [17][18][19][20][21] for HDO. However, little work on these catalytic systems has been devoted to evaluate long term stability or resistance toward impurities during HDO.…”

Section: Introductionmentioning

confidence: 99%

“…The stability of Ni based catalysts is interesting since much research currently is investigating nickel based catalysts intended for use in HDO of bio-oil [17][18][19][20] or lignin and lignosulfonate upgrading. 26,27 It is very well known that nickel based catalysts are particularly prone to sulphur deactivation.…”

Section: Introductionmentioning

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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“…Due to the fact that metallic nickel on activated carbon is nearly inactive, but on metal oxide supports such as ZrO 2 , SiO 2 , TiO 2 or Al 2 O 3 show a very high activity, a mechanism is proposed, in which the carrier is involved in the activation of the molecules for the hydrogenation and deoxygenation. Yakovlev et al [26] already came to similar results and also pointed out the crucial role of the carrier in the reaction mechanism. The essential step may be the activation of phenol by a heterolytic cleavage of H-O bond induced by a lewis-acid site on the oxidic carrier.…”

Section: Introductionmentioning

confidence: 67%

“…However, only few groups tested their catalysts with raw pyrolysis oil [23,26,27]. For this reason the systematic testing of nickel-based catalysts on raw pyrolysis oil was the objective of a previous work conduced in our institute [28].…”

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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Development of new catalytic systems for upgraded bio-fuels production from bio-crude-oil and biodiesel

Cited by 344 publications

References 14 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

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

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

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