Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes

Zhao, Chen; He, Jiayue; Lemonidou, Angeliki A.; Li, Xuebing; Lercher, Johannes A.

doi:10.1016/j.jcat.2011.02.001

Cited by 472 publications

(312 citation statements)

References 35 publications

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“…Both alcohols can subsequently undergo hydrodeoxygenation to produce, respectively, cyclohexane and methane. The same reaction scheme has been observed for the HDO of guaiacol over noble metal catalysts, [43][44][45] indicating that this is a general reaction path over transition metal catalysts. Heptane was the primary product from 1-octanol (as shown in Fig.…”

Section: Kinetic Modelsupporting

confidence: 64%

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: Kinetic Modelsupporting

confidence: 64%

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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“…Five different temperatures, 40, 50, 60, 70 and 80°C, were studied, all much lower than those used in conventional catalytic conversion of phenol. 9,10 As Figs. 3A and 3B shows, increasing the reaction temperature from 40°C to 60°C led to cyclohexane yields increasing from 53.2% to 63.7% over Pt/Graphite catalysts in 0.2 mol/L HClO 4 (selectivity of cyclohexane increased from 54.3% to 63.7%).…”

Section: Temperature Effectmentioning

confidence: 99%

“…However, this approach requires high reaction temperatures and pressurized hydrogen. [8][9][10][11] Furthermore, the addition of an acid catalyst is necessary and the recovery of the acid from the reaction mixture is difficult.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Hydrogenation of Lignin-Derived Phenol into Alkanes by Using Platinum Supported on Graphite

Zhao

Guo

2014

Electrochemistry

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In this work, electrocatalytic hydrogenation (ECH) of phenol to cyclohexane and cyclohexanol was studied. Experiments were run in a H-type cell with a Pt sheet as anode. The cathode material and structure were found to have a large effect on the ECH of phenol. Among the cathodes studied, the 1.5% Pt supported on graphite gave the highest product yield and current efficiency. Temperature was another important variable, the yield of cyclohexane increased from 44.1% at 20°C to 63.7% at 60°C, but then dropped back to 50.3% at 80°C. Effects of electrolyte composition on ECH of phenol were also investigated. The yield of cyclohexane was highest when 0.2 mol/L HClO 4 as electrolyte. Variable current studies in the range of 10-90 mA showed an increase in product yields with increasing current from 10-30 mA, but yields decreased when current above 70 mA. The suitable starting concentration of phenol was 50 mmol/L.

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“…So, both of Pd/C and HZSM-5 were indispensable components for eugenol hydrodeoxygenation. According to Refs [24,25], the main reaction pathways of eugenol hydrodeoxygenation can be deduced as Fig. 3 shows.…”

Section: Catalytic Performancementioning

confidence: 99%

“…Generally, the products can be divided into three categories, including 4-propyl guaiacol, oxygenated hydrocarbons and hydrocarbons. Considering that the turnover frequency of the acid-catalyzed reaction is at least two orders of magnitude lower than the rate of metal-catalyzed hydrogenation [24], thus the acid-catalyzed reactions are the rate-determining step in the reaction network. Moreover, the HZSM-5 with smaller crystallite size possesses larger pore volume, more secondary pores and shorter channels, which can obviously reduce diffusion path length obviously [26].…”

Section: Catalytic Performancementioning

confidence: 99%

Influence of crystal size of HZSM-5 on hydrodeoxygenation of eugenol in aqueous phase

Xing

Zhou

et al. 2014

Catalysis Communications

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a b s t r a c t a r t i c l e i n f oHydrodeoxygenation of eugenol to hydrocarbons in aqueous phase can be catalyzed by the combination of Pd/C and HZSM-5. In this paper, micro-, submicro-and nano-sized HZSM-5 samples were chosen as catalysts to investigate the influence of crystal size of HZSM-5 on the hydrolysis and dehydration. It was found that the formation rates of hydrocarbons were correlated with the total acidic sites of the submicro-and nano-sized HZSM-5 samples; while for the micro-sized sample, a much lower hydrocarbon formation rate was observed. Meanwhile, HZSM-5 with larger crystal size showed a lower hydrocarbon formation rate even with higher acid density.

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Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes

Cited by 472 publications

References 35 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

Electrocatalytic Hydrogenation of Lignin-Derived Phenol into Alkanes by Using Platinum Supported on Graphite

Influence of crystal size of HZSM-5 on hydrodeoxygenation of eugenol in aqueous phase

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