Ni-based sol–gel catalysts as promising systems for crude bio-oil upgrading: Guaiacol hydrodeoxygenation study

Alekseeva, M. S.; Ermakov, D. Yu.; Каичев, В. В.; Булавченко, О. А.; Saraev, Аndrey А.; Лебедев, М. В.; Yakovlev, V. А.

doi:10.1016/j.apcatb.2011.11.051

Cited by 381 publications

(231 citation statements)

References 64 publications

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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%

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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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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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“…For example Bykova et al [22] investigated the HDO reaction of guaiacol over Ni/ZrO 2 and Ni/SiO 2 . Here the deep deoxygenation was carried out at 320 °C and 17.0 MPa of hydrogen pressure.…”

Section: Introductionmentioning

confidence: 99%

“…Bykova et al [22] also investigated the effect of temperature in the deoxygenation of guaiacol over nickel catalysts. The studied temperature range was 280-360 °C.…”

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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“…Guaiacol is produced through the non-oxidative decarboxylation of vanillic acid, the oxidation product of vanillin, a derivative of ferulic acid 34 . Many recent studies are dedicated to the investigation of the properties of guaiacol [35][36][37] and it has been shown that the phenolic aromatic C-O bond is stronger than that the O-CH 3 bond of the guaiacol methoxy group 37 . Therefore, its cleavage requires more severe conditions, such as high temperature and high pressure 38 .…”

Section: Introductionmentioning

confidence: 99%

Carbonic anhydrase inhibitors: guaiacol and catechol derivatives effectively inhibit certain human carbonic anhydrase isoenzymes (hCA I, II, IX and XII)

Scozzafava

Passaponti

Supuran

et al. 2014

Journal of Enzyme Inhibition and Medicinal Chemistry

124

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Carbonic anhydrases (CAs) are widespread metalloenzymes in higher vertebrates including humans. A series of phenolic compounds, including guaiacol, 4-methylguaiacol, 4-propylguaiacol, eugenol, isoeugenol, vanillin, syringaldehyde, catechol, 3-methyl catechol, 4-methyl catechol and 3-methoxy catechol were investigated for their inhibition of all the catalytically active mammalian isozymes of the Zn 2+ -containing CA (EC 4.2.1.1). All the phenolic compounds effectively inhibited human carbonic anhydrase isoenzymes (hCA I, II, IX and XII), with K i s in the range of 2.20-515.98 lM. The various isozymes showed diverse inhibition profiles. Among the tested phenolic derivatives, compounds 4-methyl catechol and 3-methoxy catechol showed potent activity as inhibitors of the tumour-associated transmembrane isoforms (hCA IX and XII) in the submicromolar range, with high selectivity. The results obtained from this research may lead to the design of more effective carbonic anhydrase isoenzyme inhibitors (CAIs) based on such phenolic compound scaffolds.

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Ni-based sol–gel catalysts as promising systems for crude bio-oil upgrading: Guaiacol hydrodeoxygenation study

Cited by 381 publications

References 64 publications

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

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

Carbonic anhydrase inhibitors: guaiacol and catechol derivatives effectively inhibit certain human carbonic anhydrase isoenzymes (hCA I, II, IX and XII)

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