5588 Chem. Soc. Rev., 2011, 40, 5588–5617 This journal is c The Royal Society of Chemistry 2011 Cite this: Chem. Soc. Rev., 2011, 40, 5588–5617 Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels Chun-Hui Zhou,* a Xi Xia, a Chun-Xiang Lin, b Dong-Shen Tong a and Jorge Beltramini b Received 5th May 2011 DOI: 10.1039/c1cs15124j Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references). 1 Introduction The depletion of fossil fuel resources and the resulting adverse effects on the global environment and climate are of major academic, economic and political concern worldwide. 1–3 As supplies of fossil fuels and related petrochemicals may soon be limited, alternative solutions are sought. One alternative is to a Research Group for Advanced Materials & Sustainable Catalysis (AMSC), Breeding Base of State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou, 310032, China. E-mail: [email protected], [email protected]b The School of Chemical Engineering, ARC Centre of Excellence for Functional Nanomaterials, AIBN, The University of Queensland, St. Lucia, QLD 4072, Australia Chun-Hui Zhou Dr Chun-Hui (Clayton) Zhou is a Professor of Chemical Engineering and Group Leader of the Research Group for Advanced Materials and Sustainable Catalysis (AMSC) at Zhejiang Univer- sity of Technology as well as a Member of the Editorial Board of Applied Clay Science (Elsevier). He worked as a visiting Academic at the ARC Center of Excellence for Func- tional Nanomaterials, AIBN, the University of Queensland in 2006–2007 and as Visiting Professor at the Centre for Strategic Nano-fabrication, the University of Western Australia in 2010. His research interests include clay-based materials for miscellaneous applications, sustainable catalysis for fuels and chemicals from biorenewable resources, process intensification and advanced biomaterials. Xi Xia Xi Xia has been a postgradu- ate under the supervision of Prof. Chun-Hui Zhou in the Research Group for Advanced Materials & Sustainable Catalysis, Zhejiang University of Technology (ZJUT) since September, 2008. He obtained his Bachelor’s Degree in Chemistry from Nanyang Normal University in 2008 and his Master’s degree of Industrial Catalysis at ZJUT in 2011. His research interests are in advanced clay-based materials, catalysts and their potential for the catalytic conversion of biomass into liquid fuels and chemicals. Chem Soc Rev Dynamic Article Links www.rsc.org/csr CRITICAL REVIEW Downloaded by University of Oxford on 21 October 2011 Published on 24 August 2011 on http://pubs.rsc.org | doi:10.1039/C1CS15124J View Online
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5588 Chem. Soc. Rev., 2011, 40, 5588–5617 This journal is c The Royal Society of Chemistry 2011
Cite this: Chem. Soc. Rev., 2011, 40, 5588–5617
Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels
Chun-Hui Zhou,*aXi Xia,
aChun-Xiang Lin,
bDong-Shen Tong
aand Jorge Beltramini
b
Received 5th May 2011
DOI: 10.1039/c1cs15124j
Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for
sustainable production of chemicals and fuels. This critical review provides insights into the state-of
the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals
from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis,
solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes
presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and
various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast
pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is
typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are
the prime factors that affect the yield and composition of the target products. Most of processes yield a
complex mixture, leading to problematic upgrading and separation. An emerging technique is to
integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to
convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the
promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still
exist technological barriers that need to be overcome (229 references).
1 Introduction
The depletion of fossil fuel resources and the resulting adverse
effects on the global environment and climate are of major
academic, economic and political concern worldwide.1–3
As supplies of fossil fuels and related petrochemicals may soon
be limited, alternative solutions are sought. One alternative is to
a Research Group for Advanced Materials & Sustainable Catalysis(AMSC), Breeding Base of State Key Laboratory of GreenChemistry Synthesis Technology, College of Chemical Engineeringand Materials Science, Zhejiang University of Technology,Hangzhou, 310032, China. E-mail: [email protected],[email protected]
b The School of Chemical Engineering, ARC Centre of Excellence forFunctional Nanomaterials, AIBN, The University of Queensland,St. Lucia, QLD 4072, Australia
Chun-Hui Zhou
Dr Chun-Hui (Clayton) Zhouis a Professor of ChemicalEngineering and GroupLeader of the Research Groupfor Advanced Materialsand Sustainable Catalysis(AMSC) at Zhejiang Univer-sity of Technology as well as aMember of the EditorialBoard of Applied Clay Science(Elsevier). He worked as avisiting Academic at the ARCCenter of Excellence for Func-tional Nanomaterials, AIBN,the University of Queenslandin 2006–2007 and as Visiting
Professor at the Centre for Strategic Nano-fabrication, theUniversity of Western Australia in 2010. His research interestsinclude clay-based materials for miscellaneous applications,sustainable catalysis for fuels and chemicals from biorenewableresources, process intensification and advanced biomaterials.
Xi Xia
Xi Xia has been a postgradu-ate under the supervision ofProf. Chun-Hui Zhou in theResearch Group for AdvancedMaterials & SustainableCatalysis, Zhejiang Universityof Technology (ZJUT) sinceSeptember, 2008. He obtainedhis Bachelor’s Degree inChemistry from NanyangNormal University in 2008and his Master’s degree ofIndustrial Catalysis at ZJUTin 2011. His research interestsare in advanced clay-basedmaterials, catalysts and their
potential for the catalytic conversion of biomass into liquid fuelsand chemicals.
CrCl3�6H2O+ [C4MIM]Cl Pine wood MW (400 W) 5-HMF 52.0 Zhang et al./2010 1053 min, 0.1 MPa Furfural 31.0
CuCl2/CrCl2 + EMIM]Cl Cellulose 393 K, 8 min 5-HMF 57.5 Su et al./2010 107— Sorbitol 1.27
CrCl3 (0.02 M) Cellulose 473 K, 3 h Levulinic acid 67.0 Peng et al./2011 104—
K2CO3 (0.5 wt%) Cellulose 608 K, 4.7 s bio-oil N/a Kumar et al./2008 12427.6 MPa
K2CO3 (1.0 M) Empty palmfruit bunch
543 K, 20 min Phenolic compounds N/a Akhtar et al./2008 1192 MPa (H2O)
Na2CO3 (1.0 wt%) Corn stalk 647 K bio-oil 47.2 (wt%) Song et al./2004 12325 MPa (H2O)
Na2CO3 Woody biomass 653 K, 16–20 min Heavy oil 53.3 Qian et al./2007 1228 MPa (H2)
Ca(OH)2 (0.0243 M) Sawdust 553 K, 15 min Oil 9.3 (wt%) Karagoz et al./2004 115KOH (0.5 M) Walnut shells 523 K, 430 min, Phenolic compounds N/a Liu et al./2006 59
1.5–8.6 MPaBa(OH)2 or Rb2CO3 Lignin 573 K, 1 h Phenolic compounds
and oilsB53 Tymchyshyn et al./2010 126
2 MPa, H2
Ba(OH)2 or Rb2CO3 Sawdust/cornstalks 573 K, 1 h Phenolic compoundsand oils
5612 Chem. Soc. Rev., 2011, 40, 5588–5617 This journal is c The Royal Society of Chemistry 2011
still less investigated. Moreover, the most workable and
economical way could be to use lignocellulosic biomass
directly, rather than pure cellulose. It might be right to say
that the technology of catalytic conversion of lignocellulosic
biomass to fuels and chemicals remains in its infancy. Recent
advances have shown an exciting prospect of putting catalytic
conversion of lignocellulosic biomass to good use. The next
decades will certainly witness the use and growth of catalytic
production of fuels and chemicals from lignocellulosic
biomass with continual technological innovations.
Acknowledgements
We thank anonymous reviewers for thoroughly reading the
manuscript, providing thoughtful, valuable suggestions and
comments on the early version of this manuscript, which
almost lead to a new version. We would like to thank the
Publishers for granting permissions to reproduce copyright
materials cited or adapted in this manuscript. The results and
illustrations are credited to the original researchers to whom
we would like to express our gratitude. The authors wish to
acknowledge the financial support from the Distinguished
Young Scholar Grants from the Natural Scientific Foundation
of Zhejiang Province (R4100436), the National Natural
Scientific Foundation of China (20773110, 20541002), Zhejiang
‘‘151’’ talents project, and Project (2009C14G2020021) from
Science and Technology Department of Zhejiang Provincial
Government for the related research and development. The
authors wish to acknowledge the support of the School
of Chemical Engineering and ARC Centre of Excellence
for Functional Nanomaterials, AIBN in the University of
Queensland during the preparation of this work.
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