Catalytic upgrading of carboxylic acids as bio-oil models over hierarchical ZSM-5 obtained via an organosilane approach

Biomass is an interesting renewable energy resource as it is widespread in nature and low cost. The development of bio-oil derived from biomass as a fuel is still a scientific and industrial challenge. In this context, we demonstrate the synthetic method of bio-oil upgrading catalysts based on hierarchical zeolites and open up interesting perspectives for bio-oil upgrading processes. The hierarchical ZSM-5 zeolite has been successfully prepared via a direct hydrothermal synthesis with the aid of a commercial organosilane surfactant (TPOAC). The influences of TPOAC content and Si/Al ratio on hierarchical structures were also systematically studied. To illustrate their catalytic performances, an esterification reaction of various organic acids such as (acetic acid and levulinic acid) and alcohols was performed as the model reaction representing the bio-oil upgrading application. The synergic effect of acidity and the hierarchical structure of catalysts can greatly enhance the catalytic performance in terms of activity, product yield, coke formation, and reusability of the catalysts. For example, they can convert almost 100% of reactant in 8 h in the esterification of acetic acid and alcohols, whereas the conventional zeolite reveals significantly lower activity (<20%). Interestingly, the hierarchical zeolite can also greatly improve the catalytic activity of the esterification of levulinic acid and ethanol to produce ethyl levulinate that can be used as a diesel miscible biofuel (DMB). In addition, the efficiency of hierarchical catalysts obtained by different synthesis methods is also discussed. This first example demonstrates that the hierarchical zeolite obtained via a direct synthesis approach can benefit bio-oil upgrading applications via the esterification of various carboxylic acids.

[1]  Atsushi Tsutsumi,et al.  Upgrading of bio-oil from biomass pyrolysis over Cu-modified β-zeolite catalyst with high selectivity and stability , 2016 .

[2]  B. Puértolas,et al.  Hierarchical NaY Zeolites for Lactic Acid Dehydration to Acrylic Acid , 2016 .

[3]  M. Krishnamurthy,et al.  Hierarchically structured MFI zeolite monolith prepared using agricultural waste as solid template , 2016 .

[4]  J. Limtrakul,et al.  One-pot synthesis of novel hierarchical bifunctional Ga/HZSM-5 nanosheets for propane aromatization , 2016 .

[5]  B. Weckhuysen,et al.  Recent advances in zeolite chemistry and catalysis. , 2015, Chemical Society reviews.

[6]  J. Leahy,et al.  Catalytically Upgrading Bio-oil via Esterification , 2015 .

[7]  Prashant Kumar,et al.  Quantification of thickness and wrinkling of exfoliated two-dimensional zeolite nanosheets , 2015, Nature Communications.

[8]  K. Wilson,et al.  Catalytic upgrading of bio-oils by esterification. , 2015 .

[9]  Hyun-Seog Roh,et al.  Study on coke formation over Ni/γ-Al2O3, Co-Ni/γ-Al2O3, and Mg-Co-Ni/γ-Al2O3 catalysts for carbon dioxide reforming of methane , 2014 .

[10]  Sharon Mitchell,et al.  Prospectives for bio-oil upgrading via esterification over zeolite catalysts , 2014 .

[11]  Tatsuya Suzuki,et al.  Formation of hierarchically organized zeolites by sequential intergrowth. , 2013, Angewandte Chemie.

[12]  E. Hensen,et al.  Mesoporous SSZ-13 zeolite prepared by a dual-template method with improved performance in the methanol-to-olefins reaction , 2013 .

[13]  T. Tatsumi,et al.  Effect of desilication of H-ZSM-5 by alkali treatment on catalytic performance in hexane cracking , 2012 .

[14]  J. Limtrakul,et al.  The versatile synthesis method for hierarchical micro‐ and mesoporous zeolite: An embedded nanocarbon cluster approach , 2012 .

[15]  O. Terasaki,et al.  Zeolite Synthesis Using Hierarchical Structure-Directing Surfactants: Retaining Porous Structure of Initial Synthesis Gel and Precursors , 2012 .

[16]  J. Limtrakul,et al.  Skeletal Isomerization of 1-Butene over Ferrierite Zeolite: A Quantum Chemical Analysis of Structures and Reaction Mechanisms , 2012 .

[17]  L. Schmidt,et al.  Kinetics and mechanism of acetic acid esterification with ethanol on zeolites , 2011 .

[18]  Kyungsu Na,et al.  Hierarchically Structure-Directing Effect of Multi-Ammonium Surfactants for the Generation of MFI Zeolite Nanosheets , 2011 .

[19]  Peter Arendt Jensen,et al.  A review of catalytic upgrading of bio-oil to engine fuels , 2011 .

[20]  Arjan J. J. Koekkoek,et al.  Hierarchically structured Fe/ZSM-5 as catalysts for the oxidation of benzene to phenol , 2011 .

[21]  D. Verboekend,et al.  Design of hierarchical zeolite catalysts by desilication , 2011 .

[22]  S. Mitchell,et al.  Full Compositional Flexibility in the Preparation of Mesoporous MFI Zeolites by Desilication , 2011 .

[23]  K. Domen,et al.  A comparative IR characterization of acidic sites on HY zeolite by pyridine and CO probes with silica-alumina and γ-alumina references. , 2010, Physical chemistry chemical physics : PCCP.

[24]  B. Shanks,et al.  Aldol Condensations Using Bio-oil Model Compounds: The Role of Acid–Base Bi-functionality , 2010 .

[25]  J. Dumesic,et al.  Catalytic upgrading of bio-oils by ketonization. , 2009, ChemSusChem.

[26]  Xuefeng Guo,et al.  The hydrophilic/hydrophobic effect of porous solid acid catalysts on mixed liquid phase reaction of esterification , 2009 .

[27]  Xiaohong Li,et al.  Hydrothermal synthesis of mesoporous zirconosilicate with enhanced textural and catalytic properties with the aid of amphiphilic organosilane , 2009 .

[28]  Byung-Geon Park,et al.  Esterification of oleic acid in soybean oil on zeolite catalysts with different acidity , 2009 .

[29]  Zhicheng Liu,et al.  Synthesis of ZSM-5 with intracrystal or intercrystal mesopores by polyvinyl butyral templating method. , 2009, Journal of colloid and interface science.

[30]  Michael Stöcker,et al.  Biofuels and biomass-to-liquid fuels in the biorefinery: catalytic conversion of lignocellulosic biomass using porous materials. , 2008, Angewandte Chemie.

[31]  Jeongnam Kim,et al.  Assessment of the mesopore wall catalytic activities of MFI zeolite with mesoporous/microporous hierarchical structures , 2008 .

[32]  R. Saxena,et al.  Bio-fuels from thermochemical conversion of renewable resources: A review , 2008 .

[33]  Xiaoming Zheng,et al.  The deposition of coke from methane on a Ni/MgAl2O4 catalyst , 2007 .

[34]  Rajendra Srivastava,et al.  Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity , 2006, Nature materials.

[35]  Toshiyuki Yokoi,et al.  Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. , 2006, Angewandte Chemie.

[36]  K. Chary,et al.  Esterification of alcohols with acetic acid over zeolites Hβ, HY and HZSM5 , 2006 .

[37]  J. Moulijn,et al.  Decoupling mesoporosity formation and acidity modification in ZSM-5 zeolites by sequential desilication–dealumination , 2005 .

[38]  Javier Pérez-Ramírez,et al.  Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals. , 2005, Journal of the American Chemical Society.

[39]  S. Furuta,et al.  Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure , 2004 .

[40]  J. Moulijn,et al.  Optimal Aluminum-Assisted Mesoporosity Development in MFI Zeolites by Desilication , 2004 .

[41]  C. Christensen,et al.  Mesoporous MEL – Type Zeolite Single Crystal Catalysts , 2004 .

[42]  A. Bridgwater,et al.  Overview of Applications of Biomass Fast Pyrolysis Oil , 2004 .

[43]  A. Koster,et al.  Exploratory study of mesopore templating with carbon during zeolite synthesis , 2003 .

[44]  Iver Schmidt,et al.  Catalytic benzene alkylation over mesoporous zeolite single crystals: improving activity and selectivity with a new family of porous materials. , 2003, Journal of the American Chemical Society.

[45]  J. Fierro,et al.  Acid-Functionalized Amorphous Silica by Chemical Grafting−Quantitative Oxidation of Thiol Groups , 2003 .

[46]  Astrid Boisen,et al.  Carbon Nanotube Templated Growth of Mesoporous Zeolite Single Crystals , 2001 .

[47]  C. Jacobsen,et al.  Zeolites by confined space synthesis – characterization of the acid sites in nanosized ZSM-5 by ammonia desorption and 27Al/29Si-MAS NMR spectroscopy , 2000 .

[48]  P. Cañizares,et al.  Effect of zeolite pore geometry on isomerization of n-butane , 2000 .

[49]  A. Corma,et al.  Modified faujasite zeolites as catalysts in organic reactions: Esterification of carboxylic acids in the presence of HY zeolites , 1989 .

[50]  J. H. de Boer,et al.  Studies on pore systems in catalysts: V. The t method , 1965 .

[51]  E. Teller,et al.  ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS , 1938 .

[52]  J. Limtrakul,et al.  Direct synthesis of hierarchical ferrierite nanosheet assemblies via an organosilane template approach and determination of their catalytic activity , 2016 .

[53]  K. Góra-Marek,et al.  Porosity and accessibility of acid sites in desilicated ZSM-5 zeolites studied using adsorption of probe molecules , 2014 .

[54]  V. Caps,et al.  Synthesis and catalytic properties of TS-1 with mesoporous/microporous hierarchical structures obtained in the presence of amphiphilic organosilanes , 2010 .

[55]  E. Barrett,et al.  (CONTRIBUTION FROM THE MULTIPLE FELLOWSHIP OF BAUGH AND SONS COMPANY, MELLOX INSTITUTE) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms , 1951 .