Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose

Hernando, Héctor; Hernández-Giménez, Ana M.; Ochoa‐Hernández, Cristina; Bruijnincx, Pieter C. A.; Houben, Klaartje; Baldus, Marc; Pizarro, Patricia; Coronado, Juan M.; Fermoso, Javier; Čejka, Jiřı́; Weckhuysen, Bert M.; Serrano, David

doi:10.1039/c8gc01722k

Cited by 111 publications

(73 citation statements)

References 60 publications

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“…[10,26] The performance of the ZrO 2 /n-ZSM-5-ATP material in the catalytic pyrolysis of de-ashed wheat straww as tested by using six C/B ratios (0.1, 0.2, 0.3, 0.4, 0.5, and 0.7 gg À1 )t o obtain insights about the progression of the pyrolysis vapors upgrading as af unction of the catalystl oading. In line with previouss tudies, [10,35] the presence of the catalyst caused strong changesi nt he yield of the different fractions compared with the pure thermal test. The char yield was approximately 19 wt %f or all experiments,i ndependent of the C/B ratio.…”

Section: Laboratory-scale Testssupporting

confidence: 90%

“…Figure S1 in the Supporting Information). [35] The attapulgite phase is evidentf rom the XRD of the ZrO 2 /n-ZSM-5-ATP catalystb yt he presence of a small amount of quartz phase, ac ommon impurity of this clay also detected by TEM (Figure 1d), at 2q = 31.18 ( Figure S2 ci n the Supporting Information). Figure S2 (in the Supporting Information) shows the XRD pattern of the ZrO 2 /n-ZSM-5-ATP catalyst, compared with the parentm aterials, the pure zeolite n-ZSM-5, and impregnated ZrO 2 /n-ZSM-5.…”

Section: Catalyst Propertiesmentioning

confidence: 95%

“…Incorporation of ZrO 2 into zeolite n-ZSM-5 increased the overall acidity owing to the generation of an ew type of acidic sites, whicha lso had an enhancement effect on the concentration of basic sites. The binder-free n-ZSM-5 and ZrO 2 /n-ZSM-5 samples are formed of nanocrystallites of approximately 40-60 nm, aggregated into 20-50 mmp articles, [35] whereas attapulgite shows its characteristic needle-like morphology [37,38] as well as some impuritiesa ssociated with quartz (highlighted in the image). [36] Accordingly,t he technical ZrO 2 /n-ZSM-5-ATPc atalyst exhibits singular acid-base properties, showingacombination of Brønsted and Lewis acidity as well as basic sites.…”

Section: Catalyst Propertiesmentioning

confidence: 99%

“…[35] We showed in af urther work that the use of clay bindersf or the agglomeration of pyrolysis catalysts also has anoticeableinfluence on their behavior in biomass catalytic pyrolysis. [35] We showed in af urther work that the use of clay bindersf or the agglomeration of pyrolysis catalysts also has anoticeableinfluence on their behavior in biomass catalytic pyrolysis.…”

Section: Introductionmentioning

confidence: 99%

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Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO₂/ZSM‐5‐Attapulgite

et al. 2019

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Ex situ catalytic biomass pyrolysis was investigated at both laboratory and bench scale by using a zeolite ZSM‐5‐based catalyst for selectively upgrading the bio‐oil vapors. The catalyst consisted of nanocrystalline ZSM‐5, modified by incorporation of ZrO2 and agglomerated with attapulgite (ZrO2/n‐ZSM‐5‐ATP). Characterization of this material by means of different techniques, including CO2 and NH3 temperature‐programmed desorption (TPD), NMR spectroscopy, UV/Vis microspectroscopy, and fluorescence microscopy, showed that it possessed the right combination of accessibility and acid–base properties for promoting the conversion of the bulky molecules formed by lignocellulose pyrolysis and their subsequent deoxygenation to upgraded liquid organic fractions (bio‐oil). The results obtained at the laboratory scale by varying the catalyst‐to‐biomass ratio (C/B) indicated that the ZrO2/n‐ZSM‐5‐ATP catalyst was more efficient for bio‐oil deoxygenation than the parent zeolite n‐ZSM‐5, producing upgraded bio‐oils with better combinations of mass and energy yields with respect to the oxygen content. The excellent performance of the ZrO2/n‐ZSM‐5‐ATP system was confirmed by working with a continuous bench‐scale plant. The scale‐up of the process, even with different raw biomasses as the feedstock, reaction conditions, and operation modes, was in line with the laboratory‐scale results, leading to deoxygenation degrees of approximately 60 % with energy yields of approximately 70 % with respect to those of the thermal bio‐oil.

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Section: Laboratory-scale Testssupporting

confidence: 90%

Section: Catalyst Propertiesmentioning

confidence: 95%

Section: Catalyst Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO₂/ZSM‐5‐Attapulgite

et al. 2019

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“…As expected, the elemental analysis of the FP oil shows oxygen composition similar to its biomass precursor, i. e. 38.7 % versus 42.8 %, respectively. This implies the inefficacy of a pure thermal degradation to effectively deoxygenate the intermediate volatiles that eventually condenses into the organic liquid product . When spinel oxides were used as catalysts for the upgrade of the fast pyrolysis reaction vapours the degree of deoxygenation was improved (Figure ‐a).…”

Section: Resultsmentioning

confidence: 99%

Hybridization of ZSM‐5 with Spinel Oxides for Biomass Vapour Upgrading

et al. 2020

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In this study, we report catalytic fast pyrolysis of biomass using multifunctional hybrid spinel‐oxide@zeolite catalysts prepared by using the steam‐assisted crystallization (SAC) method to create the mesoporous zeolite followed by urea hydrolysis of metal nitrates to deposit spinel‐oxides. This hybrid catalyst was quite effective in the deoxygenation of pinewood sawdust pyrolysis vapours, while avoiding over cracking of the lignin precursors, which are already ideal as chemical and fuel precursors. In the first step, multiple spinel oxides MgB2O4 (where B=Fe, Al, Ce, Ga, Cr) were screened as catalysts for the pyrolysis of pinewood sawdust and the resultant bio‐oil (bio‐oil on the water‐free basis) was assessed in terms of carbon efficiency, oxygen content and chemical composition. While all the tested spinel oxides deoxygenated the pyrolysis vapour, MgAl2O4 and MgFe2O4 were found to provide a well‐balanced deoxygenation degree and producing bio‐oil with acceptable carbon efficiency. Catalytic activity and product distribution were affected by the density and strength of the acid sites of the spinel oxides. Subsequently, CFP over MgFe2O4@ZSM5 and MgAl2O4@ZSM5 was investigated under similar condition. The better performance of the hybrid catalyst was attributed to the deposition of small particles of MgFe2O4 in the external surface of the zeolite. The presence of this spinel oxide on the external surface depolymerized bulky oxygenates to lighter fractions that could easily access the active sites within the mesoporous structure of the zeolite, thus providing the catalytic function needed for the oxygen removal after aromatic ring saturation.

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Carbon Deposit Analysis in Catalyst Deactivation, Regeneration, and Rejuvenation

Vogt

Weckhuysen

2023

Angewandte Chemie

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Hydrocarbon conversion catalysts suffer from deactivation by deposition or formation of carbon deposits. Carbon deposit formation is thermodynamically favored above 350 °C, even in some hydrogen-rich environments. We discuss four basic mechanisms: a carbenium-ion based mechanism taking place on acid sites of zeolites or bifunctional catalysts, a metal-induced formation of soft coke (i.e., oligomers of small olefins) on bifunctional catalysts, a radicalmediated mechanism in higher-temperature processes, and fast-growing carbon filament formation. Catalysts deactivate because carbon deposits block pores at different length scales, or directly block active sites. Some deactivated catalysts can be re-used, others can be regenerated or have to be discarded. Catalyst and process design can mitigate the effects of deactivation. New analytical tools allow for the direct observation (in some cases even under in situ or operando conditions) of the 3D-distribution of coke-type species as a function of catalyst structure and lifetime.

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Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose

Abstract: Zeolite ZSM-5 properties have been optimised for catalytic bio-oil upgrading.

Cited by 111 publications

References 60 publications

Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO₂/ZSM‐5‐Attapulgite

Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO₂/ZSM‐5‐Attapulgite

Hybridization of ZSM‐5 with Spinel Oxides for Biomass Vapour Upgrading

Carbon Deposit Analysis in Catalyst Deactivation, Regeneration, and Rejuvenation

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Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose

Abstract: Zeolite ZSM-5 properties have been optimised for catalytic bio-oil upgrading.

Cited by 111 publications

References 60 publications

Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO2/ZSM‐5‐Attapulgite

Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO2/ZSM‐5‐Attapulgite

Hybridization of ZSM‐5 with Spinel Oxides for Biomass Vapour Upgrading

Carbon Deposit Analysis in Catalyst Deactivation, Regeneration, and Rejuvenation

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Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO₂/ZSM‐5‐Attapulgite

Scaling‐Up of Bio‐Oil Upgrading during Biomass Pyrolysis over ZrO₂/ZSM‐5‐Attapulgite