Hydrodeoxygenation Of Bio-oil Research Articles

Controlled Design of Phase- and Size-Tunable Monodisperse Ni2P Nanoparticles in a Phosphonium-Based Ionic Liquid through Response Surface Methodology

Nanoparticles of nickel phosphide are finding wide ranging utility as catalysts for hydrodesulfurization, hydrogen evolution reaction, and hydrodeoxygenation of bio-oils. Herein, we present a methodology to tailor monodisperse nickel phosphide nanoparticles in terms of size and phase through the use of a statistical response surface methodology. Colloidal nickel phosphide nanoparticles were synthesized by replacing octadecene (ODE), a commonly used organic solvent, by a more sustainable phosphonium-based ionic liquid (IL). The replacement of ODE with the phosphonium-based IL resulted in faster crystallization at lower temperatures to yield phase-pure, monodisperse Ni2P nanoparticles. Using a first-order design, the PPh3/Ni precursor ratio was identified as the most critical factor influencing the resulting size and phase of the nanoparticles. Optimization using a Doehlert matrix for second-order design yielded a second-degree polynomial equation used to predict the mean diameter of the nanoparticles (over...

Role of copper- or cerium-promoters on NiMo/γ-Al2O3 catalysts in hydrodeoxygenation of guaiacol and bio-oil

Effect of copper (Cu) or cerium (Ce) as promoters for nickel-molybdenum/γ-alumina (NiMo/γ-Al2O3) catalyst on the hydrodeoxygenation (HDO) of guaiacol (GUA), a model oxygenated compound found in a bio-oil derived from woody biomass, was comparatively investigated. The addition of Cu- or Ce-promoters affected the physicochemical properties of the NiMo catalyst. The NiMo catalyst promoted by Cu showed the higher reducibility, whilst the Ce-promoter (2–8 wt% based on γ-Al2O3 content) provided the NiMo catalyst with a higher distribution of active metals and induced a greater difficulty in the reduction under hydrogen (H2) atmosphere. For the HDO of GUA at a mild reaction condition (10 bar initial H2 pressure and 300 °C) in the absence of solvent, the Cu-promoter enhanced the hydrogenation activity of the NiMo catalyst to convert GUA to phenol and methylphenols, one-atomic oxygen species. Whereas, the addition of Ce obviously inhibited the formation of coke on the catalyst surface after a long reaction period (6 h) and gave a higher GUA conversion level with increasing yield of phenols. For the HDO of real bio-oil obtained from the fast pyrolysis of cassava rhizome, the NiMo catalysts promoted by Cu or Ce at 4 wt% based on the γ-Al2O3 content showed a higher performance at eliminating the oxygenated compounds in the bio-oil, reducing the oxygen/carbon (O/C) molar ratio by over seven-fold from 1.75 to 0.24–0.25. Moreover, the gross heating value of the bio-oil was improved from 21.5 to ca. 29.0 MJ/kg after the HDO process. However, the addition of the Cu or Ce promoter did not inhibit coke deposition, possibly due to the acidic properties of the bio-oil that deteriorated the catalyst performance by metal leaching.

Hydrodeoxygenation of guaiacol as a model compound of lignin-derived pyrolysis bio-oil over zirconia-supported Rh catalyst: Process optimization and reaction kinetics

To explore the mechanism for hydrodeoxygenation (HDO) of bio-oil, which contains large compounds that share similar molecular structures of phenyl ring with oxygen-containing functional groups, guaiacol as a typical model compound of lignin-derived bio-oil was hydrotreated at 150–350 °C under 3–7 MPa (H2) using the synthesized zirconia-supported Rh catalyst in a batch reactor. With Rh/ZrO2 catalyst, guaiacol can be completely converted where reaction temperature plays a decisive role and significantly affects the degree of hydrogenation. HDO Process was optimized with insight into effects of different reaction parameters, including H2 pressure, reactant concentration, reaction time and temperature, on the whole process of HDO and formation of undesired oxygen-contained products. The optimum reaction conditions were 5 wt. % guaiacol, 300 °C and 7 MPa in which guaiacol could be completely deoxygenated with 87. 7 mol% oxygen-free product of cyclohexane in 3 h and the desired O/C and H/C ratios of products were obtained. A specific reaction network including three main steps: “guaiacol → 1-methyl-1,2-cyclohexanediol → cyclohexanone and cyclohexanol → completely deoxygenated compounds of cycloalkanes”, was deduced by a comprehensive study on different reaction parameters and a typical key reaction network for HDO of lignin-derived bio-oil is proposed based on model compounds studies. Kinetic model for HDO of guiaacol with the Rh/ZrO2 catalyst was proposed based on the credible pathway and it fits well to a pseudo-first-order kinetic model that the R2 values obtained for the fittings were all above 0.98 at four temperatures. At low temperature of 150 °C, the kinetically relevant step is hydrogenation of the aromatic ring, yielding 90 mol% 1-methyl-1,2-cyclohexanediol, while at high temperature (≥300 °C), the kinetically relevant step is the complete deoxygenation of oxygen-containing functional groups which mainly yields cyclohexane. These results would be helpful to further understand the HDO mechanism of lignin-derived bio-oil, and the excellent performance of Rh/ZrO2 demonstrated its potential application in bio-oil hydrodeoxygenative upgrading process.

Upgrading phenolic compounds and bio-oil through hydrodeoxygenation using highly dispersed Pt/TiO2 catalyst

Noble metal catalyst has an outstanding catalytic activity on the hydrodeoxygenation (HDO) process, but its high cost limits large-scale application. Herein, we put forward a novel photochemical method to prepare the highly dispersed Pt/TiO2 catalyst with a low metal loading. And it presented an efficient performance on the HDO of phenolic compounds and real bio-oil. Guaiacol could be converted into cyclohexane with 95.1% selectivity at 280 °C under 1 MPa H2 atmosphere. Characterization results revealed that the high Pt dispersion was the critical factor for the high catalytic activity. And the photochemical method preferred to achieve high metal dispersion due to the room temperature condition. Other typical phenolic monomers and dimers were able to transform into hydrocarbons with most yield above 80%, wherein not only the deoxygenation step, but also the cleavage of ether bonds can be realized in one pot. This catalytic system was also effective on the upgrade of bio-oil derived from the pyrolysis of cotton straw. Hydrocarbon content increased to 33.80% from 11.33%. Alkylphenols content increased to 51.38% from 27.86%. These two products can be used as value-added fuels and chemicals, respectively. Guaiacols and syringols were completely converted into alkylphenols and hydrocarbon. The amount of other oxygenated compounds also decreased significantly. This simple and active catalytic system is potential to apply widely for the upgrade of raw bio-oil.

Hydrodeoxygenation of crude bio-oil in situ in the bio-oil aqueous phase with addition of zero-valent aluminum

This study investigated the influence of the ratios of zero-valent aluminum (ZV-Al) to bio-oil aqueous phase (1/25, 1.5/25, and 2/25 g/mL) on hydrodeoxygenation (HDO) of crude bio-oil (CBO) with in situ hydrogen generated via the reaction of ZV-Al and the aqueous phase. The reaction of ZV-Al and the aqueous phase produced more hydrogen than the reaction of ZV-Al and water due to the aqueous phase reforming reactions. ZV-Al to the aqueous phase ratio had a positive impact on the in situ HDO of CBO. When the ratio of ZV-Al to the aqueous phase was 2/25 g/mL, the UBO yield was 39.03 wt% with a higher heating value of 38.53 MJ/kg. The highest degree of deoxygenation (76.38%) and the minimum of O/C molar ratio (0.07) were also obtained at the ratio of 2/25 g/mL. The reaction of ZV-Al and the aqueous phase for in situ HDO can significantly promote deoxygenation reactions.

Catalytic hydrodeoxygenation of bio-oil using in situ generated hydrogen in plasma reactor: Effects of allumina supported catalysts and plasma parameters

Abstract In this study, hydrodeoxygenation of guaiacol, a lignin derived model compound, has been studied experimentally via a combination of dielectric barrier discharge plasma and catalyst. Cracking of methyl groups in the chemical structure of bio-oil is used to provide the hydrogen which is required for hydrodeoxygenation reaction. In order to maximize the degree of deoxygenation and guaiacol conversion, the effects of operating and plasma parameters including applied voltage, guaiacol and argon flow rate have been examined. Furthermore, performance of plasma alone and catalytic plasma has been compared by filling the active volume of the discharge with different commercial catalysts including Ni, Co–Mo, Ni–Mo, Pt–Re and Pt–Cl supported on Al2O3. The highest guaiacol conversion of 92% and deoxygenation degree of 65% are achieved in the presence of Pt–Cl/Al2O3 and Pt–Re/Al2O3 catalysts, respectively. According to the results, the main products were BTX, phenol, methylphenols and dimethylphenols. Unlike previous studies in which catechol was produced as a major product, in our plasma system phenol can be produced selectively through direct demethoxylation rather than demethylation reaction. It is also evident from the results that the hydrogen challenges of hydrodeoxygenation reaction can be overcome by catalytic DBD plasma reactor.

Synthesis and Regeneration of Nickel-Based Catalysts for Hydrodeoxygenation of Beech Wood Fast Pyrolysis Bio-Oil

Four nickel-based catalysts are synthesized by wet impregnation and evaluated for the hydrotreatment/hydrodeoxygenation of beech wood fast-pyrolysis bio-oil. Parameters such as elemental analysis, pH value, and water content, as well as the heating value of the upgraded bio-oils are considered for the evaluation of the catalysts’ activity and catalyst reuse in cycles of hydrodeoxygenation after regeneration. The reduction temperature, selectivity and hydrogen consumption are distinct among them, although all catalysts tested produce upgraded bio-oils with reduced oxygen concentration, lower water content and higher energy density. Ni/SiO2, in particular, can remove more than 50% of the oxygen content and reduce the water content by more than 80%, with low coke and gas formation. The evaluation over four consecutive hydrotreatment reactions and catalyst regeneration shows a slightly reduced hydrodeoxygenation activity of Ni/SiO2, mainly due to deactivation caused by sintering and adsorption of poisoning substances, such as sulfur. Following the fourth catalyst reuse, the upgraded bio-oil shows 43% less oxygen in comparison to the feedstock and properties comparable to the upgraded bio-oil obtained with the fresh catalyst. Hence, nickel-based catalysts are promising for improving hardwood fast-pyrolysis bio-oil properties, especially monometallic nickel catalysts supported on silica.

Revealing the pathways of catalyst deactivation by coke during the hydrodeoxygenation of raw bio-oil

Virtually all processes aiming for fuels and chemicals from biomass entail no less than one step for removing oxygen by hydrodeoxygenation (HDO). The bottleneck of HDO is the formation of deactivating carbonaceous species on the catalyst surface. In this work, we have studied the deactivation pathways of catalysts based on noble metal nanoparticles (Pt-Pd) supported on mildly acid supports during the HDO of raw bio-oil. At conditions of accelerated deactivation, monitoring the evolution with time on stream of hydrocarbon and oxygenated compounds in the reaction medium, the intermediates on the catalyst surface and the nature-location of deactivating species, two parallel deactivation routes have been revealed: the deposition of (i) thermal or pyrolytic lignin from alkylmethoxy phenols, on the catalyst mesopores and favored at low temperature, and; of (ii) aromatic coke from polycyclic aromatic hydrocarbons, starting on the catalyst micropores through condensation reactions and promoted by acidic sites and high temperature. Nevertheless, catalyst deactivation can be controlled within limits at harsh temperature conditions (450 °C) due to the preferential HDO of alkyl(methoxy) phenols into aromatics and the formation-hydrocracking steady state of the aromatic precursors of coke.

Influence of feedstock, catalyst, pyrolysis and hydrotreatment temperature on the composition of upgraded oils from intermediate pyrolysis

Hydrodeoxygenation (HDO) of bio-oils obtained from intermediate pyrolysis with hot vapor filtration was investigated over Ru/C and NiCu/Al2O3 catalysts as a function of several parameters: feedstock (beech wood, wheat straw), pyrolysis temperature, catalyst and hydrotreatment temperature. Beech wood was found to be a suitable feedstock for HDO due to its low heteroatom content, whereas the high sulfur content in the wheat straw bio-oil caused irreversible poisoning of the catalysts. Ru/C generally consumed more hydrogen than NiCu/Al2O3, showing higher hydrogenation/HDO activity with higher selectivity towards alcohols and hydrocarbons, whereas NiCu/Al2O3 resulted in a higher concentration of ketones. The pyrolysis temperature affected the fragmentation degree; higher temperatures resulted in a higher quality pyrolysis oil with low oxygen mass fraction, but with decreased mass yield. By varying the hydrotreatment temperature (80, 150, 250, 350 °C), different classes of compounds were converted and different deoxygenation degrees were achieved. Overall the results indicate that intermediate pyrolysis with hot vapor filtration is a valid alternative to the more commonly used fast pyrolysis for decentralized (or small-scale) applications, especially for heterogeneous feedstocks with high ash content.

Quantifying the exergetic performance of bio-fuel production process including fast pyrolysis and bio-oil hydrodeoxygenation

Fast pyrolysis of biomass in a dual fluidized bed and bio-oil hydrodeoxygenation are simulated by Aspen plus. The process includes the following unit operations: drying, pyrolysis, char combustion, bio-oil vapor condensation, mild hydrodeoxygenation, and depth hydrodeoxygenation. Based on the simulative results, exergetic analysis of the whole process is performed to optimize the overall exergetic efficiency. The overall exergetic efficiency of the process is 57%. The exergetic efficiencies of the fast pyrolysis process and the bio-oil hydrodeoxygenation process are 68% and 78%, respectively. The results indicate that the exergetic efficiency is improved slightly with a decrement in the system pressure drop. Moreover, the exergetic efficiency of pyrolysis is improved from 69% to 76% when the percentage of the pyrolysis char combusted is reduced from 100% to 65%. Compared to other conversion technologies, biomass to liquid fuel conversion via fast pyrolysis and subsequent hydrodeoxygenation has higher exergetic efficiency.

Catalytic hydrodeoxygenation of crude bio-oil in supercritical methanol using supported nickel catalysts

Pyrolysis oil (bio-oil) consists of high water content and vast variety of oxygenates (acids, alcohols, aldehydes, esters, ketones, sugars and phenols), causing some undesirable properties that prevent the direct use of bio-oil as a transportation fuel. Bio-oil upgrading to decrease its oxygen content provides a sustainable fuel that can be considered a valuable substitution for depleting fossil fuels. Catalytic hydrodeoxygenation (HDO) is an efficient method for bio-oil upgrading. This paper presents the HDO of crude bio-oil in supercritical fluid (ethanol, methanol, and 2-propanol) using a batch high pressure reactor. Supercritical fluids have unique physicochemical properties of liquid-like density and gas-like high diffusivity and low viscosity. The upgrading efficiency was evaluated by measuring the elemental composition (CHNSO), water content, carbon residue, and high heating value (HHV) of the bio-oil upgraded over Ni/HBeta catalyst. Compared to ethanol and 2-propanol, supercritical methanol resulted in a higher decrease in the oxygen content of bio-oil. The activity of Ni/HBeta was examined by varying the Ni loading (5–20 wt%), initial hydrogen pressure (10–30 bar), and reaction time (2–6 h). Meanwhile, effects of support materials (HZSM-5, HBeta, HY, Al-SBA-15, and silylated HBeta) on the performance of nickel catalyst in bio-oil upgrading were investigated using supercritical methanol.

Measurement of HDO Products Using GC-TCD: Towards Obtaining Reliable Analytical Data

Abstract This paper reported the method development and validation of a gas chromatography with thermal conductivity detector (GC-TCD) method for the measurement of the gaseous products of hydrodeoxygenation (HDO). The method validation parameters include selectivity, precision (repeatability and reproducibility), accuracy, linearity, limit of detection (LoD), limit of quantitation (LoQ), and robustness. The results showed that the developed method was able to separate the target components (H2, CO2, CH4 and CO) from their mixtures without any special sample treatment. The validated method was selective, precise, accurate, and robust. Application of the developed and validated GC-TCD method to the measurement of by-product components of HDO of bio-oil revealed a good performance with relative standard deviation (RSD) less than 1.0% for all target components, implying that the process of method development and validation provides a trustworthy way of obtaining reliable analytical data.

Hydrodeoxygenation of Pyrolysis Bio-Oil Over Ni Impregnated Mesoporous Materials.

The catalytic hydrodeoxygenation (HDO) of bio-oil over Ni-supported mesoporous materials was performed using a high pressure autoclave reactor. The actual pyrolysis oil of cork oak wood was used as a sample, and Ni/Al-SBA-15 and Ni/Al-MSU-F were used as catalysts. In addition, supercritical ethanol was added as solvent. Both Ni-supported mesoporous catalysts showed efficient HDO reaction ability. A higher heating value and pH of bio-oil were achieved by the HDO reaction over both catalysts and upgraded bio-oil had a lower viscosity. Compared to Ni/Al-MSU-F, Ni/Al- SBA-15 produced more upgraded bio-oil with a lower oxygen content and higher heating value via a catalytic HDO process.

Hydrodeoxygenation of fast pyrolysis oil with novel activated carbon-supported NiP and CoP catalysts

Catalytic hydrodeoxygenation (HDO) has been considered as a promising technical route to upgrade fast pyrolysis oil to liquid transportation fuels. In this work, a series of active and inexpensive catalysts were synthesized for bio-oil HDO, i.e., activated carbon (AC)-supported nickel phosphide and cobalt phosphide catalysts, with a metal/P molar ratio varying from 5/2, 3/2, 1/1, 1/2, 1/3. For comparison, AC-support pure metal catalysts without P were also prepared. Effects of phosphorus content on HDO performance of the catalysts were investigated on a 100 mL bench-scale reactor system using a wood-derived pyrolysis oil at 300 °C and initial hydrogen pressure of 50 bar for 3 h. The results showed that the properties of the upgraded bio-oils were greatly affected by the phosphorus content in both Ni and Co catalysts. The best performance seemed to be achieved with the catalysts at a metal/P molar ratio of about 3/2. Moreover, 0.5 wt% of Ru was further added to the catalysts at a metal/P molar ratio of 3/2 and to the pure metal catalysts. The addition of a small amount of Ru was found to markedly decrease the relative molecular weight of the upgraded bio-oils, and achieved high quality bio-oil products similar to that obtained with an expensive commercially available 5 wt% Ru/C catalyst.

Upgrading of pinyon-juniper catalytic pyrolysis oil via hydrodeoxygenation

Abstract In this study we discuss hydrodeoxygenation (HDO) of pinyon juniper (PJ) catalytic pyrolysis oil over Ni/SiO2 Al2O3 catalyst in a batch reactor to improve the physicochemical properties of the oil. The influence of temperature (350–500 °C), reaction time (15–90 min), and initial hydrogen pressure (3.5–10 MPa), on hydrodeoxygenation of PJ pyrolysis oil was investigated. After hydrogenation was completed, gas, coke, and a liquid product of two immiscible phases (aqueous and organic), were obtained. Maximum HDO of bio-oil was achieved at 450° C while the initial hydrogen pressure was 7 MPa and the reaction time was 30 min. Under these conditions, the H/C and O/C atomic ratios changed from 1.29 to 0.29 respectively for bio-oil to 2.36 and 0 for HDO oil respectively. The higher heating value increased from 27.64 MJ/kg of bio-oil to 45.58 MJ/kg of upgraded oil. The water content of organic liquid product was less than 0.05 wt% while it was 1.63 wt% in the feed. The viscosity of upgraded oil was 1.26 cP compared to119 cP for the crude bio-oil.

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd\u2013Mo catalyst

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.

Hydrodeoxygenation of Lignin-Derived Phenols: From Fundamental Studies towards Industrial Applications

Hydrodeoxygenation (HDO) of bio-oils, lignin and their model compounds is summarized in this review. The main emphasis is put on elucidating the reaction network, catalyst stability and time-on-stream behavior, in order to better understand the prerequisite for industrial utilization of biomass in HDO to produce fuels and chemicals. The results have shown that more oxygenated feedstock, selection of temperature and pressure as well as presence of certain catalyst poisons or co-feed have a prominent role in the HDO of real biomass. Theoretical considerations, such as density function theory (DFT) calculations, were also considered, giving scientific background for the further development of HDO of real biomass.

Upgrading pyrolysis bio-oil through hydrodeoxygenation (HDO) using non-sulfided Fe-Co/SiO2 catalyst

Hydrodeoxygenation (HDO) is an effective route to upgrade bio-oil to hydrocarbon bio-oil, but the development of efficient catalysts for bio-oil HDO still remains a challenge. In this study, non-sulfided Fe-Co/SiO2catalysts were used to upgrade bio-oil using HDO. A series of Fe-Co/SiO2 catalysts with different Fe/Co mole ratios were prepared, characterized and evaluated. The Fe and/or Co loading did not change SiO2 crystalline structure. The Fe and/or Co metals increased the amount and strength of Fe-Co/SiO2 catalyst acidity. Physicochemical properties of upgraded bio-oils produced using Fe-Co/SiO2 catalysts such as water content, total acid number, viscosity and higher heating values improved in comparison to raw bio-oil. Bimetallic Fe-Co/SiO2 catalysts resulted in better HDO performance than monometallic Fe/SiO2 or Co/SiO2 catalysts. This was due to the synergistic effect of Fe and Co occurring on the SiO2 support. Fe-Co/SiO2 catalyst having medium amount of acidity was more effective for bio-oil upgrading. The highest hydrocarbons content produced using Fe-Co(1)/SiO2 catalyst was 22.44%. The mechanism of bio-oil HDO on Fe-Co/SiO2 catalysts is proposed.

Synergistic effects of Ru and Fe on titania-supported catalyst for enhanced anisole hydrodeoxygenation selectivity

The hydrodeoxygenation (HDO) of bio-oil is considered among the most promising techniques for upgrading pyrolysis bio-oils to biofuels. However, its commercial application is challenging because of the complexity of the reaction. In particular, minimizing the hydrogen consumption in HDO is a main concern. In this study, ruthenium supported on mesoporous TiO2 (Ru/meso-TiO2) catalysts were prepared with various Fe loadings for this reaction, using anisole as a model substrate. Analytical techniques, such as transmission electron microscopy, CO chemisorption, and X-ray photoelectron spectroscopy, revealed that the addition of Fe increased the number of oxygen vacancies, reaching a maximum when the Fe loading was 1wt.%. H2 consumption can be reduced by performing HDO reaction at high temperatures. The Ru/meso-TiO2 without Fe converted anisole mainly to methoxycyclohexane, indicating that hydrogenation (HYD) is the dominant reaction pathway. The addition of Fe remarkably promotes the conversion and selectivity of the catalyst. The reaction path could be drastically changed from HYD to direct deoxygenation (DDO) by the addition of a proper amount of Fe. This change can be assigned to the synergism between Ru particles and Fe species on the surface of meso-TiO2 support. The catalyst with 1wt.% Fe exhibited the highest conversion and benzene selectivity due to its largest number of oxygen vacancies, indicating that it utilized a minimum amount of H2.

Enhanced Phenol Hydrodeoxygenation Over a Ni Catalyst Supported on a Mixed Mesoporous ZSM-5 Zeolite and Al2O3

Developing highly active catalysts for bio-oil hydrodeoxygenation is of great importance in the low cost production of conventional transport alkane fuels. Toward this goal, a Ni catalyst supported on mesoporous ZSM-5 zeolite mixed with 25 wt% γ-Al2O3 (Ni/Al-HMZSM-5) was designed for hydrodeoxygenation of phenol as model compound. For comparison, the catalytic activities of Ni catalysts on conventional microporous ZSM-5, mesoporous ZSM-5 and γ-Al2O3 were also investigated. It was found that almost complete phenol conversion (99.6%) was achieved over the Ni/Al-HMZSM-5 catalyst along with a high cyclohexane selectivity (98.3%) under a relatively mild condition (170 °C, 4 MPa H2). The open mesopores, stronger acid sites and synergism effect of Bronsted and Lewis acidities are jointly responsible for the excellent hydrodeoxygenation performance. In addition, it was shown that the catalyst was recycled several times with little loss of activity and selectivity.