Catalytic hydrotreatment of fast pyrolysis oil using bimetallic Ni–Cu catalysts on various supports

Ardiyanti, A. R.; Хромова, С. А.; Venderbosch, R. H.; Yakovlev, V. А.; Melián‐Cabrera, Ignacio; Heeres, Hero J.

doi:10.1016/j.apcata.2012.09.016

Cited by 125 publications

(58 citation statements)

References 34 publications

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“…The experimentally determined hydrogen consumption is a good measure for catalytic activity [17,27]. However, in the case of extensive methane formation, the activity for liquid phase reactions (hydrogenation, hydrodeoxygenation, and hydrocracking) is overestimated when using this procedure.…”

Section: Activity Of the Catalystsmentioning

confidence: 99%

“…The amount of gas phase after reaction was determined by the pressure difference in the reactor before and after reaction at room temperature using the ideal gas law, assuming that the volume of the gas hold-up in the reactor before and after reaction was constant. A detailed procedure for the latter is given in previous studies [17,27].…”

Section: Catalytic Hydrotreatment Of Pyrolysis Liquids In a Batch Autmentioning

confidence: 99%

“…These conditions were selected based on earlier catalyst screening studies by our group [23,[25][26][27][28]. Both biand tri-metallic catalyst Ni-based catalysts were prepared and tested with Mo, Cu, and Pd as promoters.…”

Section: Introductionmentioning

confidence: 99%

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Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

Wang

Venderbosch

et al. 2017

Biomass Conv. Bioref.

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Catalytic hydrotreatment is a promising technology to convert pyrolysis liquids into intermediates with improved properties. Here, we report a catalyst screening study on the catalytic hydrotreatment of pyrolysis liquids using bi-and tri-metallic nickel-based catalysts in a batch autoclave (initial hydrogen pressure of 140 bar, 350°C, 4 h). The catalysts are characterized by a high nickel metal loading (41 to 57 wt%), promoted by Cu, Pd, Mo, and/or combination thereof, in a SiO 2 , SiO 2 -ZrO 2 , or SiO 2 -Al 2 O 3 matrix. The hydrotreatment results were compared with a benchmark Ru/C catalyst. The results revealed that the monometallic Ni catalyst is the least active and that particularly the use of Mo as the promoter is favored when considering activity and product properties. For Mo promotion, a product oil with improved properties viz. the highest H/C molar ratio and the lowest coking tendency was obtained. A drawback when using Mo as the promoter is the relatively high methane yield, which is close to that for Ru/C. 1 H, 13 C-NMR, heteronuclear single quantum coherence (HSQC), and two-dimensional gas chromatography (GC × GC) of the product oils reveal that representative component classes of the sugar fraction of pyrolysis liquids like carbonyl compounds (aldehydes and ketones and carbohydrates) are converted to a large extent. The pyrolytic lignin fraction is less reactive, though some degree of hydrocracking is observed.

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Section: Activity Of the Catalystsmentioning

confidence: 99%

Section: Catalytic Hydrotreatment Of Pyrolysis Liquids In a Batch Autmentioning

confidence: 99%

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Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

Wang

Venderbosch

et al. 2017

Biomass Conv. Bioref.

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“…Several nickel-based catalysts were used to lower the oxygen content and increase the H/C ratio. [38][39][40] Although no product compositions were reported, HDO of these pyrolysis oils over nickel catalysts has been shown to result in the formation of mainly ring-hydrogenated products. 41 For the production of BTX and phenol from lignin a two-step process is desired, however, which combines a high depolymerization activity with a HDO catalyst that does not show ring-hydrogenation activity.…”

Section: Reaction Optimizationmentioning

confidence: 99%

Liquid-phase reforming and hydrodeoxygenation as a two-step route to aromatics from lignin

2013

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A two-step approach to the conversion of organosolv, kraft and sugarcane bagasse lignin to monoaromatic compounds of low oxygen content is presented. The first step consists of lignin depolymerization in a liquid phase reforming (LPR) reaction over a 1 wt% Pt/γ-Al 2 O 3 catalyst at 225°C in alkaline ethanolwater. The first LPR step resulted in a decrease in lignin molecular weight of 32%, 57% and 27% for organosolv, kraft and bagasse lignin, respectively. GC analysis of the depolymerized lignin reaction mixture furthermore showed the formation of alkylated phenol, guaiacol and syringol-type products in 11%, 9% and 5% yields from organosolv, kraft and bagasse lignin, respectively. The lignin-oil that was isolated by extraction of the ethanol-water solution was subjected to a subsequent hydrodeoxygenation (HDO) reaction in the second conversion step. HDO of the lignin-oil was performed in dodecane at 300°C under 50 bar hydrogen pressure over CoMo/Al 2 O 3 and Mo 2 C/CNF catalysts. GC analysis of the product mixture obtained after the two-step LPR-HDO process revealed the formation of, amongst others, benzene, toluene, xylenes and ethylmethylbenzenes. Of the total observed monomeric products (9%), 25% consisted of these oxygen-free products. Notably, such products cannot be obtained by direct HDO of lignin. HDO of the lignin-oil at 350°C resulted in the conversion of all tris-oxygenated products, with 57% of the observed monomeric products now identified as mono-oxygenated phenolics.

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“…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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Catalytic hydrotreatment of fast pyrolysis oil using bimetallic Ni–Cu catalysts on various supports

Cited by 125 publications

References 34 publications

Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

Liquid-phase reforming and hydrodeoxygenation as a two-step route to aromatics from lignin

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

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