Stable Sulfonic MCM-41 Catalyst for Furfural Production from Renewable Resources in a Biphasic System

An MCM-41-SO3H catalyst with 14 wt% S was successfully synthesized to be used in furfural production from xylose and hemicellulose in a biphasic n-butanol/water system. The precursor MCM-41 and the acid-functionalized MCM-41-SO3H catalyst were characterized by XRD, FTIR, TEM, N2 physisorption, ICP-MS, TPD-NH3, and XPS. The characterization results indicated that the sulfonic process partially decreased the ordered mesoporous structure and increased the acid strength of the initial MCM-41. The catalytic performance of the xylose conversion was evaluated in a batch-type reactor using different biphasic ecological and renewable n-butanol/water ratios (1:1, 1.5:1, 2:1, and 2.5:1) as dissolvent at 170 ◦C. The effect of the dissolvent mixture was clearly seen from the larger initial reaction rate and TOF values for the 1.5:1 ratio. This catalytic behavior indicated that a proper proportion of n-butanol/water dissolvent mixture enhanced the solubility of the substrate in the n-butanol-rich mixture and prevented the deactivation of acidic sulfonated surface groups. To achieve transformation of lignocellulosic raw material to value-added products, the MCM-41-SO3H catalyst was also used for the production of furfural. The recycling evaluation tests indicated that for the recovered catalyst submitted to a sulfonation process, the yield of furfural was closer to the fresh catalyst.

[1]  Xuebing Zhao,et al.  Lignocellulosic biomass as sustainable feedstock and materials for power generation and energy storage , 2021 .

[2]  C. Parra,et al.  Effects on Lignin Redistribution in Eucalyptus globulus Fibres Pre-Treated by Steam Explosion: A Microscale Study to Cellulose Accessibility , 2021, Biomolecules.

[3]  M. F. Qaseem,et al.  Characterization of hemicelluloses in sugarcane (Saccharum spp. hybrids) culm during xylogenesis. , 2020, International journal of biological macromolecules.

[4]  Dibyajyoti Haldar,et al.  A review on the environment-friendly emerging techniques for pretreatment of lignocellulosic biomass: Mechanistic insight and advancements. , 2020, Chemosphere.

[5]  N. Escalona,et al.  Selective conversion of biomass-derived furfural to cyclopentanone over carbon nanotube-supported Ni catalyst in Pickering emulsions , 2020, Catalysis Communications.

[6]  Junming Xu,et al.  Selective conversion of hemicellulose into furfural over low-cost metal salts in a γ-valerolactone/water solution , 2020 .

[7]  Q. Peng,et al.  Preparation of Self-Assembled Composite Films Constructed by Chemically-Modified MXene and Dyes with Surface-Enhanced Raman Scattering Characterization , 2019, Nanomaterials.

[8]  E. Vasile,et al.  Heteroatom modified MCM-41-silica carriers for Lomefloxacin delivery systems , 2019, Microporous and Mesoporous Materials.

[9]  Hern Kim,et al.  Efficient Dehydration of Glucose, Sucrose, and Fructose to 5-Hydroxymethylfurfural Using Tri-cationic Ionic Liquids , 2019, Catalysis Letters.

[10]  S. Tangestaninejad,et al.  SO3H-functionalized MCM-41 as an efficient catalyst for the combinatorial synthesis of 1H-pyrazolo-[3,4-b]pyridines and spiro-pyrazolo-[3,4-b]pyridines , 2017, Journal of the Iranian Chemical Society.

[11]  Suwadee Kongparakul,et al.  Highly efficient sulfonic MCM-41 catalyst for furfural production: Furan-based biofuel agent , 2016 .

[12]  M. Ojeda,et al.  Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels , 2016 .

[13]  Suwadee Kongparakul,et al.  Biodiesel production from Hevea brasiliensis oil using SO 3 H-MCM-41 catalyst , 2016 .

[14]  Y. Sarrafi,et al.  MCM-41-SO3H: an efficient, reusable, heterogeneous catalyst for the one-pot, three-component synthesis of pyrano[3,2-b]pyrans , 2015, Research on Chemical Intermediates.

[15]  Heather L. Trajano,et al.  Review of hemicellulose hydrolysis in softwoods and bamboo , 2014 .

[16]  Iker Agirrezabal-Telleria,et al.  Heterogeneous acid-catalysts for the production of furan-derived compounds (furfural and hydroxymethylfurfural) from renewable carbohydrates: A review , 2014 .

[17]  I. Vankelecom,et al.  SPEEK and functionalized mesoporous MCM-41 mixed matrix membranes for CO2 separations , 2012 .

[18]  Juan Carlos Serrano-Ruiz,et al.  Efficient microwave-assisted production of furfural from C5 sugars in aqueous media catalysed by Brönsted acidic ionic liquids , 2012 .

[19]  Shengping Wang,et al.  Microwave synthesis, characterization and transesterification activities of Ti-MCM-41 , 2012 .

[20]  Shijie Liu,et al.  Conversion of D-xylose into furfural with mesoporous molecular sieve MCM-41 as catalyst and butanol as the extraction phase , 2012 .

[21]  A. Mohamed,et al.  Synthesis of monoglyceride through glycerol esterification with lauric acid over propyl sulfonic acid post-synthesis functionalized SBA-15 mesoporous catalyst , 2011 .

[22]  Saet-Byul Kim,et al.  Fabrication of sulfonic acid modified mesoporous silica shells and their catalytic performance with dehydration reaction of d-xylose into furfural , 2011 .

[23]  Liang Han,et al.  One-pot synthesis of tryptophols with mesoporous MCM-41 silica catalyst functionalized with sulfonic acid groups , 2011 .

[24]  Panpan Li,et al.  Selective Preparation of Furfural from Xylose over Sulfonic Acid Functionalized Mesoporous Sba-15 Materials , 2011 .

[25]  A. Bumajdad,et al.  Characterization of mesoporous VOx/MCM-41 composite materials obtained via post-synthesis impregnation , 2010 .

[26]  Joseph J. Bozell,et al.  Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited , 2010 .

[27]  A. Amani,et al.  Ultrasound promoted rapid and green synthesis of 1,8-dioxo-octahydroxanthenes derivatives using nanosized MCM-41-SO(3)H as a nanoreactor, nanocatalyst in aqueous media. , 2010, Ultrasonics sonochemistry.

[28]  V. Meynen,et al.  Verified syntheses of mesoporous materials , 2009 .

[29]  Martyn Pillinger,et al.  Conversion of mono/di/polysaccharides into furan compounds using 1-alkyl-3-methylimidazolium ionic liquids , 2009 .

[30]  M. Pillinger,et al.  Dehydration of d-xylose into furfural catalysed by solid acids derived from the layered zeolite Nu-6(1) , 2008 .

[31]  V. S. Kumar,et al.  Sulfonic acid functionalized mesoporous SBA-15 for selective synthesis of 4-phenyl-1,3-dioxane , 2007 .

[32]  H. Matsuhashi,et al.  The surface structure of sulfated zirconia : Studies of XPS and thermal analysis , 2006 .

[33]  P. Reyes,et al.  Ordered mesoporous silicates of MCM-41 type as support of pt catalysts for the enantioselective hydrogenation of 1-phenyl-1,2-propanedione , 2005 .

[34]  Martyn Pillinger,et al.  Dehydration of xylose into furfural over micro-mesoporous sulfonic acid catalysts , 2005 .

[35]  Johnathan E. Holladay,et al.  Top Value Added Chemicals From Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas , 2004 .

[36]  C. Moreau,et al.  Development of a continuous catalytic heterogeneous column reactor with simultaneous extraction of an intermediate product by an organic solvent circulating in countercurrent manner with the aqueous phase , 1995 .

[37]  J. B. Higgins,et al.  A new family of mesoporous molecular sieves prepared with liquid crystal templates , 1992 .

[38]  J. S. Beck,et al.  Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism , 1992, Nature.

[39]  M. Boudart,et al.  Experimental criterion for the absence of artifacts in the measurement of rates of heterogeneous catalytic reactions , 1982 .

[40]  C. Moreau,et al.  Selective preparation of furfural from xylose over microporous solid acid catalysts , 1998 .

[41]  M Ratner,et al.  Heterogeneous Catalysis: Fundamentals and Applications , 2011 .