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

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

doi:10.1039/c8gc01722k

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

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

^*Corresponding author for this work

IMDEA Institute
Czech Academy of Sciences
Max Planck Institute for Coal Research
Universidad Rey Juan Carlos

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The properties of the zeolite ZSM-5 have been optimised for the production and deoxygenation of the bio-oil∗ (bio-oil on water-free basis) fraction by lignocellulose catalytic pyrolysis. Two ZSM-5 supports possessing high mesopore/external surface area, and therefore enhanced accessibility, have been employed to promote the conversion of the bulky compounds formed in the primary cracking of lignocellulose. These supports are a nanocrystalline material (n-ZSM-5) and a hierarchical sample (h-ZSM-5) of different Si/Al ratios and acid site concentrations. Acidic features of both zeolites have been modified and adjusted by incorporation of ZrO₂, which has a significant effect on the concentration and distribution of both Brønsted and Lewis acid sites. These materials have been tested in the catalytic pyrolysis of acid-washed wheat straw (WS-ac) using a two-step (thermal/catalytic) reaction system at different catalyst/biomass ratios. The results obtained have been assessed in terms of oxygen content, energy yield and composition of the produced bio-oil∗, taking also into account the selectivity towards the different deoxygenation pathways. The ZrO₂/n-ZSM-5 sample showed remarkable performance in the biomass catalytic pyrolysis, as a result of the appropriate combination of accessibility and acidic properties. In particular, modification of the zeolitic support acidity by incorporation of highly dispersed ZrO₂ effectively decreased the extent of secondary reactions, such as severe cracking and coke formation, as well as promoted the conversion of the oligomers formed initially by lignocellulose pyrolysis, thus sharply decreasing the proportion of the components not detected by GC-MS in the upgraded bio-oil∗.

Original language	English
Pages (from-to)	3499-3511
Number of pages	13
Journal	Green Chemistry
Volume	20
Issue number	15
DOIs	https://doi.org/10.1039/c8gc01722k
Publication status	Published - 1 Jan 2018

Funding

The authors gratefully acknowledge the financial support from: the European Union Seventh Framework Programme (FP7/2007–2013) under grant agreement no 604307 (CASCATBEL project), and from the Spanish Ministry of Economy and Competitiveness through CATPLASBIO project (Ref: CTQ2014-602209-R). J. Čejka thanks the Czech Science Foundation for the financial support (P106/12/G015). Likewise, the authors thank SILKEM company for the preparation and supply of the hierarchical ZSM-5 sample. The NMR studies were supported by NWO (Middelgroot program, grant number 700.58.102 to MB).

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c8gc01722kFinal published version, 5.2 MBLicence: Taverne

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Hernando, H., Hernández-Giménez, A. M., Ochoa-Hernández, C., Bruijnincx, P. C. A., Houben, K., Baldus, M., Pizarro, P., Coronado, J. M., Fermoso, J., Čejka, J., Weckhuysen, B. M., & Serrano, D. P. (2018). Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose. Green Chemistry, 20(15), 3499-3511. https://doi.org/10.1039/c8gc01722k

@article{e4a59573753148e39711ba5565b8e94b,

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

abstract = "The properties of the zeolite ZSM-5 have been optimised for the production and deoxygenation of the bio-oil∗ (bio-oil on water-free basis) fraction by lignocellulose catalytic pyrolysis. Two ZSM-5 supports possessing high mesopore/external surface area, and therefore enhanced accessibility, have been employed to promote the conversion of the bulky compounds formed in the primary cracking of lignocellulose. These supports are a nanocrystalline material (n-ZSM-5) and a hierarchical sample (h-ZSM-5) of different Si/Al ratios and acid site concentrations. Acidic features of both zeolites have been modified and adjusted by incorporation of ZrO2, which has a significant effect on the concentration and distribution of both Br{\o}nsted and Lewis acid sites. These materials have been tested in the catalytic pyrolysis of acid-washed wheat straw (WS-ac) using a two-step (thermal/catalytic) reaction system at different catalyst/biomass ratios. The results obtained have been assessed in terms of oxygen content, energy yield and composition of the produced bio-oil∗, taking also into account the selectivity towards the different deoxygenation pathways. The ZrO2/n-ZSM-5 sample showed remarkable performance in the biomass catalytic pyrolysis, as a result of the appropriate combination of accessibility and acidic properties. In particular, modification of the zeolitic support acidity by incorporation of highly dispersed ZrO2 effectively decreased the extent of secondary reactions, such as severe cracking and coke formation, as well as promoted the conversion of the oligomers formed initially by lignocellulose pyrolysis, thus sharply decreasing the proportion of the components not detected by GC-MS in the upgraded bio-oil∗.",

author = "H{\'e}ctor Hernando and Hern{\'a}ndez-Gim{\'e}nez, \{Ana M.\} and Cristina Ochoa-Hern{\'a}ndez and Bruijnincx, \{Pieter C.A.\} and Klaartje Houben and Marc Baldus and Patricia Pizarro and Coronado, \{Juan M.\} and Javier Fermoso and Ji{\v r}{\'i} {\v C}ejka and Weckhuysen, \{Bert M.\} and Serrano, \{David P.\}",

year = "2018",

month = jan,

day = "1",

doi = "10.1039/c8gc01722k",

language = "English",

volume = "20",

pages = "3499--3511",

journal = "Green Chemistry",

issn = "1463-9262",

publisher = "Royal Society of Chemistry",

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Hernando, H, Hernández-Giménez, AM, Ochoa-Hernández, C, Bruijnincx, PCA, Houben, K, Baldus, M, Pizarro, P, Coronado, JM, Fermoso, J, Čejka, J, Weckhuysen, BM & Serrano, DP 2018, 'Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose', Green Chemistry, vol. 20, no. 15, pp. 3499-3511. https://doi.org/10.1039/c8gc01722k

TY - JOUR

T1 - Engineering the acidity and accessibility of the zeolite ZSM-5 for efficient bio-oil upgrading in catalytic pyrolysis of lignocellulose

AU - Hernando, Héctor

AU - Hernández-Giménez, Ana M.

AU - Ochoa-Hernández, Cristina

AU - Bruijnincx, Pieter C.A.

AU - Houben, Klaartje

AU - Baldus, Marc

AU - Pizarro, Patricia

AU - Coronado, Juan M.

AU - Fermoso, Javier

AU - Čejka, Jiří

AU - Weckhuysen, Bert M.

AU - Serrano, David P.

PY - 2018/1/1

Y1 - 2018/1/1

N2 - The properties of the zeolite ZSM-5 have been optimised for the production and deoxygenation of the bio-oil∗ (bio-oil on water-free basis) fraction by lignocellulose catalytic pyrolysis. Two ZSM-5 supports possessing high mesopore/external surface area, and therefore enhanced accessibility, have been employed to promote the conversion of the bulky compounds formed in the primary cracking of lignocellulose. These supports are a nanocrystalline material (n-ZSM-5) and a hierarchical sample (h-ZSM-5) of different Si/Al ratios and acid site concentrations. Acidic features of both zeolites have been modified and adjusted by incorporation of ZrO2, which has a significant effect on the concentration and distribution of both Brønsted and Lewis acid sites. These materials have been tested in the catalytic pyrolysis of acid-washed wheat straw (WS-ac) using a two-step (thermal/catalytic) reaction system at different catalyst/biomass ratios. The results obtained have been assessed in terms of oxygen content, energy yield and composition of the produced bio-oil∗, taking also into account the selectivity towards the different deoxygenation pathways. The ZrO2/n-ZSM-5 sample showed remarkable performance in the biomass catalytic pyrolysis, as a result of the appropriate combination of accessibility and acidic properties. In particular, modification of the zeolitic support acidity by incorporation of highly dispersed ZrO2 effectively decreased the extent of secondary reactions, such as severe cracking and coke formation, as well as promoted the conversion of the oligomers formed initially by lignocellulose pyrolysis, thus sharply decreasing the proportion of the components not detected by GC-MS in the upgraded bio-oil∗.

AB - The properties of the zeolite ZSM-5 have been optimised for the production and deoxygenation of the bio-oil∗ (bio-oil on water-free basis) fraction by lignocellulose catalytic pyrolysis. Two ZSM-5 supports possessing high mesopore/external surface area, and therefore enhanced accessibility, have been employed to promote the conversion of the bulky compounds formed in the primary cracking of lignocellulose. These supports are a nanocrystalline material (n-ZSM-5) and a hierarchical sample (h-ZSM-5) of different Si/Al ratios and acid site concentrations. Acidic features of both zeolites have been modified and adjusted by incorporation of ZrO2, which has a significant effect on the concentration and distribution of both Brønsted and Lewis acid sites. These materials have been tested in the catalytic pyrolysis of acid-washed wheat straw (WS-ac) using a two-step (thermal/catalytic) reaction system at different catalyst/biomass ratios. The results obtained have been assessed in terms of oxygen content, energy yield and composition of the produced bio-oil∗, taking also into account the selectivity towards the different deoxygenation pathways. The ZrO2/n-ZSM-5 sample showed remarkable performance in the biomass catalytic pyrolysis, as a result of the appropriate combination of accessibility and acidic properties. In particular, modification of the zeolitic support acidity by incorporation of highly dispersed ZrO2 effectively decreased the extent of secondary reactions, such as severe cracking and coke formation, as well as promoted the conversion of the oligomers formed initially by lignocellulose pyrolysis, thus sharply decreasing the proportion of the components not detected by GC-MS in the upgraded bio-oil∗.

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DO - 10.1039/c8gc01722k

M3 - Article

AN - SCOPUS:85051128136

SN - 1463-9262

VL - 20

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EP - 3511

JO - Green Chemistry

JF - Green Chemistry

IS - 15

ER -

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

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