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2,2,5,5-tetramethyloxolane (TMO) has recently been identified and demonstrated as a safer solvent to replace toluene, THF, and hydrocarbons in a handful of applications. Herein, several bio-based routes to TMO are presented and assessed for greenness, assisted by the CHEM21 Metrics Toolkit and BioLogicTool plots. Using glucose as a common starting point, two chemocatalytic routes and two biochemical routes to TMO were identified and the pathways compared using the aforementioned tools. In addition, bio-based TMO was synthesised via one of these routes; from methyl levulinate supplied by Avantium, a by-product of the sugar dehydration step during the production of 2,5-furandicarboxylic acid. First, methyl levulinate underwent triple methylation using methyl magnesium chloride (MeMgCl) to yield 2,5-dimethylhexane-2,5-diol (DHL) in high yields of 89.7%. Then DHL was converted to high purity TMO (>98.5%) by cyclodehydration using H-BEA zeolites based on the previously reported approach. Bio-based content of this TMO was confirmed by ASTM D6866-20 Method B and found to have 64% bio-based carbon, well above the threshold of 25% set by CEN/TC 411 standards and matching the anticipated content. This study represents the first demonstration of a bio-based synthesis of TMO and confirmation of bio-content by accepted standards.
Fergal Byrne; James Clark; Carlo Angelici; Ed de Jong; Thomas Farmer. Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO). Sustainable Chemistry 2021, 2, 392 -406.
AMA StyleFergal Byrne, James Clark, Carlo Angelici, Ed de Jong, Thomas Farmer. Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO). Sustainable Chemistry. 2021; 2 (3):392-406.
Chicago/Turabian StyleFergal Byrne; James Clark; Carlo Angelici; Ed de Jong; Thomas Farmer. 2021. "Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO)." Sustainable Chemistry 2, no. 3: 392-406.
The use of a biorefinery co-product, such as humins, in combination with an iron precursor in a solvent-free method yields a catalytic material with potential use in selective oxidative cleavage reactions. In particular, this catalyst was found active in the hydrogen-peroxide assisted oxidation of a naturally extracted molecule, isoeugenol, to high added-value flavouring agent, vanillin. By carrying out the reaction in continuous flow, not only a better understanding of the reaction mechanism and of the catalyst deactivation can be achieved, but also important insights for optimised conditions can be developed. The findings of this paper could pave the way to a more sustainable process for the production of a valuable food and perfume additive, vanillin.
Layla Filiciotto; María Dolores Márquez-Medina; Antonio Pineda; Alina M. Balu; Antonio A. Romero; Carlo Angelici; Ed de Jong; Jan C. van der Waal; Rafael Luque. Continuous flow study of isoeugenol to vanillin: A bio-based iron oxide catalyst. Catalysis Today 2019, 368, 281 -290.
AMA StyleLayla Filiciotto, María Dolores Márquez-Medina, Antonio Pineda, Alina M. Balu, Antonio A. Romero, Carlo Angelici, Ed de Jong, Jan C. van der Waal, Rafael Luque. Continuous flow study of isoeugenol to vanillin: A bio-based iron oxide catalyst. Catalysis Today. 2019; 368 ():281-290.
Chicago/Turabian StyleLayla Filiciotto; María Dolores Márquez-Medina; Antonio Pineda; Alina M. Balu; Antonio A. Romero; Carlo Angelici; Ed de Jong; Jan C. van der Waal; Rafael Luque. 2019. "Continuous flow study of isoeugenol to vanillin: A bio-based iron oxide catalyst." Catalysis Today 368, no. : 281-290.
Humins is a biomass-derived material, co-product of the acid-catalyzed conversion of cellulose and hemicellulose to platform chemicals. This work presents a thorough study concerning the crosslinking kinetics of humins by chemorheological analysis and model-free kinetics under isothermal and non-isothermal curing. Humins can auto-crosslink under the effect of temperature, and the reaction can be fastener when adding an acidic initiator. Thus, the effect of P-Toluenesulfonic acid monohydrate (pTSA) on the crosslinking kinetics was also studied. The dependencies of the effective activation energy (Eα-dependencies) were determined by an advanced isoconversional method and correlated with the variation of complex viscosity during curing. It is shown that humins curing involves multi-step complex reactions and that the use of an acidic initiator allows faster crosslinking at lower temperatures, involving lower Eα. The shift from chemical to diffusion control was also estimated.
Anna Sangregorio; Nathanaël Guigo; Ed De Jong; Nicolas Sbirrazzuoli; Jong. Kinetics and Chemorheological Analysis of Cross-Linking Reactions in Humins. Polymers 2019, 11, 1804 .
AMA StyleAnna Sangregorio, Nathanaël Guigo, Ed De Jong, Nicolas Sbirrazzuoli, Jong. Kinetics and Chemorheological Analysis of Cross-Linking Reactions in Humins. Polymers. 2019; 11 (11):1804.
Chicago/Turabian StyleAnna Sangregorio; Nathanaël Guigo; Ed De Jong; Nicolas Sbirrazzuoli; Jong. 2019. "Kinetics and Chemorheological Analysis of Cross-Linking Reactions in Humins." Polymers 11, no. 11: 1804.
The concept of circular economy is aiming at promoting innovative use of wastes, residues or by-products into marketable chemicals and intermediates, while enhancing process economics and environmental sustainability. Within biorefineries, the focus has now shifted towards “humins”, polymeric condensation by-products far less investigated than lignins. Humins are produced in many bio-based value chains that start from polysaccharides pre-treatment, targeting access to C6 and C5 sugars and further conversion to furanics or levulinics based platform chemicals. They are complex and versatile substrates, and combustible since of organic nature. A first insight on safety issues of humins is therefore proposed in this paper, considering the growing interest on humins as new bio-based feedstocks for various applications. The current study provides characterization details necessary to establish safety information on a global context. This first attempt has brought in preliminary safety data mainly focusing on thermal and fire hazards of humins, to ensure safe storage, handling, transportation and processing. The obtained results show that, overall fire risk of humins so far is similar to the conventional cellulosic fuels such as woody materials. Further consolidation of safety information shall be done with scenario-based risk assessment approach for conditioning safe use of humins in further innovative applications.
Anitha Muralidhara; Pierluigi Tosi; Alice Mija; Nicolas Sbirrazzuoli; Christophe Len; Victor Engelen; Ed De Jong; Guy Marlair. Insights on Thermal and Fire Hazards of Humins in Support of Their Sustainable Use in Advanced Biorefineries. ACS Sustainable Chemistry & Engineering 2018, 6, 16692 -16701.
AMA StyleAnitha Muralidhara, Pierluigi Tosi, Alice Mija, Nicolas Sbirrazzuoli, Christophe Len, Victor Engelen, Ed De Jong, Guy Marlair. Insights on Thermal and Fire Hazards of Humins in Support of Their Sustainable Use in Advanced Biorefineries. ACS Sustainable Chemistry & Engineering. 2018; 6 (12):16692-16701.
Chicago/Turabian StyleAnitha Muralidhara; Pierluigi Tosi; Alice Mija; Nicolas Sbirrazzuoli; Christophe Len; Victor Engelen; Ed De Jong; Guy Marlair. 2018. "Insights on Thermal and Fire Hazards of Humins in Support of Their Sustainable Use in Advanced Biorefineries." ACS Sustainable Chemistry & Engineering 6, no. 12: 16692-16701.
A new macroporous foam‐like material is presented based on autocross‐linking humins, an industrial biorefinery byproduct. Humins foams are obtained by a simple heating process, without any pretreatment and with high control of morphology, porosity, and carbon content. Untreated humins have been characterized by GC, ultra‐performance liquid chromatography (UPLC), elemental analysis, and FTIR, whereas the mechanism of foaming was elucidated by a combination of thermal and rheological analyses. A preliminary screening of conditions was conducted to identify the parameters controlling this foaming process. A foam was produced in a controlled way with open and/or closed cells with cell diameters between 0.2 and 3.5 mm. Humins foams were characterized by Raman spectroscopy, FTIR, SEM, nitrogen adsorption, pycnometry, and mechanical tests. The results show that, based on humins, it is possible to obtain porous materials with controlled architectures and a range of parameters that can be tailored, depending on the foreseen applications.
Pierluigi Tosi; Gerard P. M. Van Klink; Alain Celzard; Vanessa Fierro; Luc Vincent; Ed de Jong; Alice Mija. Auto‐Crosslinked Rigid Foams Derived from Biorefinery Byproducts. ChemSusChem 2018, 11, 2797 -2809.
AMA StylePierluigi Tosi, Gerard P. M. Van Klink, Alain Celzard, Vanessa Fierro, Luc Vincent, Ed de Jong, Alice Mija. Auto‐Crosslinked Rigid Foams Derived from Biorefinery Byproducts. ChemSusChem. 2018; 11 (16):2797-2809.
Chicago/Turabian StylePierluigi Tosi; Gerard P. M. Van Klink; Alain Celzard; Vanessa Fierro; Luc Vincent; Ed de Jong; Alice Mija. 2018. "Auto‐Crosslinked Rigid Foams Derived from Biorefinery Byproducts." ChemSusChem 11, no. 16: 2797-2809.
Ilona van Zandvoort; Gerard P.M. van Klink; Ed de Jong; Jan C. van der Waal. Selectivity and stability of zeolites [Ca]A and [Ag]A towards ethylene adsorption and desorption from complex gas mixtures. Microporous and Mesoporous Materials 2018, 263, 142 -149.
AMA StyleIlona van Zandvoort, Gerard P.M. van Klink, Ed de Jong, Jan C. van der Waal. Selectivity and stability of zeolites [Ca]A and [Ag]A towards ethylene adsorption and desorption from complex gas mixtures. Microporous and Mesoporous Materials. 2018; 263 ():142-149.
Chicago/Turabian StyleIlona van Zandvoort; Gerard P.M. van Klink; Ed de Jong; Jan C. van der Waal. 2018. "Selectivity and stability of zeolites [Ca]A and [Ag]A towards ethylene adsorption and desorption from complex gas mixtures." Microporous and Mesoporous Materials 263, no. : 142-149.
The effect of nanocrystalline cellulose dispersion on the nonisothermal crystallization of poly(ethylene 2,5-furandicarboxylate) (PEF) has been investigated by means of solvent casting. The cellulose dispersion plays a significant role on the crystallization temperature, thus dispersive equipments of increasing energies were employed to improve the cellulose particles disaggregation. Therefore, ultra-sonic bath, ultra-sonication, and ultra-turrax were used to disperse cellulose nanocrystals in 1,1,1,3,3,3-hexafluoro-2-propanol. Dissolved separately in the same solvent, PEF was then poured into the cellulose suspension before casting. The cellulose whiskers were inspected by transmission electron microscopy. Differential scanning calorimetry was used to measure the crystallization temperature, while scanning electron microscopy visualized the cellulose dispersion at the fracture surface. After investigation on the interaction of cellulose/PEF via Fourier transform infrared spectroscopy, the thermal stability of the blends was measured by means of thermogravimetric analysis.
Amandine Codou; Nathanaël Guigo; Jesper Gabriël Van Berkel; Ed De Jong; Nicolas Sbirrazzuoli. Preparation and characterization of poly(ethylene 2,5-furandicarboxylate/nanocrystalline cellulose composites via solvent casting. nano Online 2018, 1 .
AMA StyleAmandine Codou, Nathanaël Guigo, Jesper Gabriël Van Berkel, Ed De Jong, Nicolas Sbirrazzuoli. Preparation and characterization of poly(ethylene 2,5-furandicarboxylate/nanocrystalline cellulose composites via solvent casting. nano Online. 2018; ():1.
Chicago/Turabian StyleAmandine Codou; Nathanaël Guigo; Jesper Gabriël Van Berkel; Ed De Jong; Nicolas Sbirrazzuoli. 2018. "Preparation and characterization of poly(ethylene 2,5-furandicarboxylate/nanocrystalline cellulose composites via solvent casting." nano Online , no. : 1.
Poly(ethylene 2,5-furandicarboxylate) (PEF), an emerging biobased polyester, was compounded with cellulose via twin-screw extrusion. Different extrusion parameters such as mixing time, screw speed and temperature were employed. Composite thin films containing 1, 2 and 4% cellulose w/w were prepared and compared with neat PEF films. The morphology of PEF/cellulose composites was examined by scanning electron microscopy (SEM) and the molecular weight after extrusion was controlled by means of size exclusion chromatography (SEC). The influence of the cellulose on both isothermal and non-isothermal crystallizations of PEF was investigated by differential scanning calorimetry (DSC). Crystallization is faster in presence of cellulose and the nucleating effect increases with the cellulose concentration.
Amandine Codou; Nathanaël Guigo; Jesper Gabriël van Berkel; Ed de Jong; Nicolas Sbirrazzuoli. Preparation and crystallization behavior of poly(ethylene 2,5-furandicarboxylate)/cellulose composites by twin screw extrusion. Carbohydrate Polymers 2017, 174, 1026 -1033.
AMA StyleAmandine Codou, Nathanaël Guigo, Jesper Gabriël van Berkel, Ed de Jong, Nicolas Sbirrazzuoli. Preparation and crystallization behavior of poly(ethylene 2,5-furandicarboxylate)/cellulose composites by twin screw extrusion. Carbohydrate Polymers. 2017; 174 ():1026-1033.
Chicago/Turabian StyleAmandine Codou; Nathanaël Guigo; Jesper Gabriël van Berkel; Ed de Jong; Nicolas Sbirrazzuoli. 2017. "Preparation and crystallization behavior of poly(ethylene 2,5-furandicarboxylate)/cellulose composites by twin screw extrusion." Carbohydrate Polymers 174, no. : 1026-1033.
Jos Feijen; Gerard Klink; Ed de Jong; Andreas Schmid; Niels G. Deen; Michael Boot. Spray Combustion Analysis of Humins. SAE Technical Paper Series 2017, 1, 1 .
AMA StyleJos Feijen, Gerard Klink, Ed de Jong, Andreas Schmid, Niels G. Deen, Michael Boot. Spray Combustion Analysis of Humins. SAE Technical Paper Series. 2017; 1 ():1.
Chicago/Turabian StyleJos Feijen; Gerard Klink; Ed de Jong; Andreas Schmid; Niels G. Deen; Michael Boot. 2017. "Spray Combustion Analysis of Humins." SAE Technical Paper Series 1, no. : 1.
The effect of nanocrystalline cellulose dispersion on the nonisothermal crystallization of poly(ethylene 2,5-furandicarboxylate) (PEF) has been investigated by means of solvent casting. The cellulose dispersion plays a significant role on the crystallization temperature, thus dispersive equipments of increasing energies were employed to improve the cellulose particles disaggregation. Therefore, ultra-sonic bath, ultra-sonication, and ultra-turrax were used to disperse cellulose nanocrystals in 1,1,1,3,3,3-hexafluoro-2-propanol. Dissolved separately in the same solvent, PEF was then poured into the cellulose suspension before casting. The cellulose whiskers were inspected by transmission electron microscopy. Differential scanning calorimetry was used to measure the crystallization temperature, while scanning electron microscopy visualized the cellulose dispersion at the fracture surface. After investigation on the interaction of cellulose/PEF via Fourier transform infrared spectroscopy, the thermal stability of the blends was measured by means of thermogravimetric analysis.
Amandine Codou; Nathanaël Guigo; Jesper Van Berkel; Ed de Jong; Nicolas Sbirrazzuoli. Preparation and characterization of poly(ethylene 2,5-furandicarboxylate/nanocrystalline cellulose composites via solvent casting. Journal of Polymer Engineering 2017, 37, 869 -878.
AMA StyleAmandine Codou, Nathanaël Guigo, Jesper Van Berkel, Ed de Jong, Nicolas Sbirrazzuoli. Preparation and characterization of poly(ethylene 2,5-furandicarboxylate/nanocrystalline cellulose composites via solvent casting. Journal of Polymer Engineering. 2017; 37 (9):869-878.
Chicago/Turabian StyleAmandine Codou; Nathanaël Guigo; Jesper Van Berkel; Ed de Jong; Nicolas Sbirrazzuoli. 2017. "Preparation and characterization of poly(ethylene 2,5-furandicarboxylate/nanocrystalline cellulose composites via solvent casting." Journal of Polymer Engineering 37, no. 9: 869-878.
Miao Tian; Robert McCormick; Jon Luecke; Ed de Jong; Jan Cornelis van der Waal; Gerard P.M. van Klink; Michael D. Boot. Anti-knock quality of sugar derived levulinic esters and cyclic ethers. Fuel 2017, 202, 414 -425.
AMA StyleMiao Tian, Robert McCormick, Jon Luecke, Ed de Jong, Jan Cornelis van der Waal, Gerard P.M. van Klink, Michael D. Boot. Anti-knock quality of sugar derived levulinic esters and cyclic ethers. Fuel. 2017; 202 ():414-425.
Chicago/Turabian StyleMiao Tian; Robert McCormick; Jon Luecke; Ed de Jong; Jan Cornelis van der Waal; Gerard P.M. van Klink; Michael D. Boot. 2017. "Anti-knock quality of sugar derived levulinic esters and cyclic ethers." Fuel 202, no. : 414-425.
The conversion of the four possible ketohexoses (fructose, tagatose, sorbose and psicose) into 5-hydroxymethylfurfural (HMF) was explored in water using sulphuric acid as the catalyst (33 mM HSO, 120 °C). Significant differences in reactivity were observed and tagatose (48% conversion after 75 min) and psicose (35% conversion after 75 min) were clearly more reactive than fructose and sorbose (around 20% conversion after 75 min). The selectivity to HMF was found to be higher for fructose and psicose than for tagatose and sorbose. 2-Hydroxyacetylfuran (HAF) was shown to be a by-product for mainly sorbose and tagatose (as high as 2% yield). The results indicate that the relative orientation of the hydroxyl groups on C3 and C4 has a major effect on the reactivity and selectivity. This suggests that the dehydration towards HMF takes place via a mechanism with cyclic intermediates in which the C3C4 bond is fixed in a ring structure. A reaction mechanism involving a bicyclic structure is proposed to explain the formation of HAF. The reactivity of the sugars was significantly lower in water than previously observed in methanol.
Robert-Jan van Putten; Jan C. van der Waal; Ed de Jong; Hero J. Heeres. Reactivity studies in water on the acid-catalysed dehydration of psicose compared to other ketohexoses into 5-hydroxymethylfurfural. Carbohydrate Research 2017, 446-447, 1 -6.
AMA StyleRobert-Jan van Putten, Jan C. van der Waal, Ed de Jong, Hero J. Heeres. Reactivity studies in water on the acid-catalysed dehydration of psicose compared to other ketohexoses into 5-hydroxymethylfurfural. Carbohydrate Research. 2017; 446-447 ():1-6.
Chicago/Turabian StyleRobert-Jan van Putten; Jan C. van der Waal; Ed de Jong; Hero J. Heeres. 2017. "Reactivity studies in water on the acid-catalysed dehydration of psicose compared to other ketohexoses into 5-hydroxymethylfurfural." Carbohydrate Research 446-447, no. : 1-6.
Nowadays biobased building materials are used in various fields and for a wide range of applications such as polymers, fillers, coatings, adhesives, impregnation materials or high performance composites. This work focuses on humins, a biomacromolecular by-product of a HydroxyMethylFurfural/FuranDiCarboxylic Acid biorefinery. Humins are obtained by acidic treatment of polysaccharides and show very interesting potential as a reactive, semi-ductile thermoset matrix to impregnate cellulosic fibres. Therefore, humins have the essential characteristics to develop a new class of thermoset materials and composites, offering excellent possibilities to increase the renewable carbon content of the final products and improve its properties. A proper characterization of the neat humins in terms of solubility, flow behaviour and thermal resistance is essential in order to find the optimal parameters of processing humins solutions as well as co-reactive mixtures for impregnations or to prepare composites. In addition the study further indicates that humins enhance the modulus and the tensile strength of pure polyfurfurylalcohol resins. It was also shown that there is a difference in behaviour when sulfuric acid or maleic anhydride is used as initiator. The most optimal initiator will depend on application and preferred processing conditions. These encouraging results assure an important future for humins as economic green matrix for the production of composites and wood impregnation.
Alice Mija; Jan C. van der Waal; Jean-Mathieu Pin; Nathanael Guigo; Ed de Jong. Humins as promising material for producing sustainable carbohydrate-derived building materials. Construction and Building Materials 2017, 139, 594 -601.
AMA StyleAlice Mija, Jan C. van der Waal, Jean-Mathieu Pin, Nathanael Guigo, Ed de Jong. Humins as promising material for producing sustainable carbohydrate-derived building materials. Construction and Building Materials. 2017; 139 ():594-601.
Chicago/Turabian StyleAlice Mija; Jan C. van der Waal; Jean-Mathieu Pin; Nathanael Guigo; Ed de Jong. 2017. "Humins as promising material for producing sustainable carbohydrate-derived building materials." Construction and Building Materials 139, no. : 594-601.
International audienceSeveral equations have been compared for the modelling of semi-cristalline polymer crystallization on cooling from the melt and on heating from the glass. The temperature dependence was described with the Hoffman–Lauritzen (HL) equation, where U* and Kg were first determined by fitting the activation energy (Eα) dependency with temperature computed with an advanced isoconversional method (AIC) from DSC data. Several models were used to describe the extent of crystallization dependence, such as Sestak-Berggren and Avrami models. Simulations using Ozawa and AIC methods were performed for comparisons. It was shown that the model-free approach is able to take into account additional crystallization phenomena that are not considered in the classical HL or Avrami equations. Then, a new equation has been proposed to simulate additional phenomena occurring at the end of crystallization on heating from the glass, which are not described by the Hoffman–Lauritzen theory. The experimental finding that application of an isoconversional method to crystallization data following a HL mechanism, should lead to positive decreasing values for crystallization from the glass and to negative increasing values for crystallization from the melt was confirmed by simulations
Nathanael Guigo; Jesper van Berkel; Ed de Jong; Nicolas Sbirrazzuoli. Modelling the non-isothermal crystallization of polymers: Application to poly(ethylene 2,5-furandicarboxylate). Thermochimica Acta 2017, 650, 66 -75.
AMA StyleNathanael Guigo, Jesper van Berkel, Ed de Jong, Nicolas Sbirrazzuoli. Modelling the non-isothermal crystallization of polymers: Application to poly(ethylene 2,5-furandicarboxylate). Thermochimica Acta. 2017; 650 ():66-75.
Chicago/Turabian StyleNathanael Guigo; Jesper van Berkel; Ed de Jong; Nicolas Sbirrazzuoli. 2017. "Modelling the non-isothermal crystallization of polymers: Application to poly(ethylene 2,5-furandicarboxylate)." Thermochimica Acta 650, no. : 66-75.
The electrocatalytic conversion of furanic compounds, i.e. mainly furfural and 5-hydroxymethylfurfural, has recently emerged as a potentially scalable technology for both oxidation and hydrogenation processes because of its highly valuable products. However, its practical application in industry is currently limited by low catalytic activity and product selectivity. Thus, a better understanding of the catalytic reactions as well as a strategy for the catalyst design can bring solutions for a complete and selective conversion into desired products. In this perspective, we review the status and challenges of electrocatalytic oxidation and hydrogenation of furanic compounds, including thermodynamics, voltammetric studies, and bulk electrolysis with important reaction parameters (i.e., catalyst, electrolyte, temperature, etc.) and reaction mechanisms. In addition, we introduce methods of energy-efficient electrocatalytic furanic synthesis by combining yields of anodic and cathodic reactions in a paired reactor or a reactor powered by a renewable energy source (i.e., solar energy). Current challenges and future opportunities are also discussed, aiming at industrial applications.
Youngkook Kwon; Klaas Jan P. Schouten; Jan C. Van Der Waal; Ed de Jong; Marc T. M. Koper. Electrocatalytic Conversion of Furanic Compounds. ACS Catalysis 2016, 6, 6704 -6717.
AMA StyleYoungkook Kwon, Klaas Jan P. Schouten, Jan C. Van Der Waal, Ed de Jong, Marc T. M. Koper. Electrocatalytic Conversion of Furanic Compounds. ACS Catalysis. 2016; 6 (10):6704-6717.
Chicago/Turabian StyleYoungkook Kwon; Klaas Jan P. Schouten; Jan C. Van Der Waal; Ed de Jong; Marc T. M. Koper. 2016. "Electrocatalytic Conversion of Furanic Compounds." ACS Catalysis 6, no. 10: 6704-6717.
Bio‐based furanics can be aromatized efficiently by sequential Diels–Alder (DA) addition and hydrogenation steps followed by tandem catalytic aromatization. With a combination of zeolite H‐Y and Pd/C, the hydrogenated DA adduct of 2‐methylfuran and maleic anhydride can thus be aromatized in the liquid phase and, to a certain extent, decarboxylated to give high yields of the aromatic products 3‐methylphthalic anhydride and o‐ and m‐toluic acid. Here, it is shown that a variation in the acidity and textural properties of the solid acid as well as bifunctionality offers a handle on selectivity toward aromatic products. The zeolite component was found to dominate selectivity. Indeed, a linear correlation is found between 3‐methylphthalic anhydride yield and the product of (strong acid/total acidity) and mesopore volume of H‐Y, highlighting the need for balanced catalyst acidity and porosity. The efficient coupling of the dehydration and dehydrogenation steps by varying the zeolite‐to‐Pd/C ratio allowed the competitive decarboxylation reaction to be effectively suppressed, which led to an improved 3‐methylphthalic anhydride/total aromatics selectivity ratio of 80 % (89 % total aromatics yield). The incorporation of Pd nanoparticles in close proximity to the acid sites in bifunctional Pd/H‐Y catalysts also afforded a flexible means to control aromatic products selectivity, as further demonstrated in the aromatization of hydrogenated DA adducts from other diene/dienophile combinations.
Homer C. Genuino; Shanmugam Thiyagarajan; Jan C. Van Der Waal; Ed De Jong; Jacco Van Haveren; Daan S. Van Es; Dr. Bert M. Weckhuysen; Pieter C. A. Bruijnincx. Selectivity Control in the Tandem Aromatization of Bio-Based Furanics Catalyzed by Solid Acids and Palladium. ChemSusChem 2016, 10, 277 -286.
AMA StyleHomer C. Genuino, Shanmugam Thiyagarajan, Jan C. Van Der Waal, Ed De Jong, Jacco Van Haveren, Daan S. Van Es, Dr. Bert M. Weckhuysen, Pieter C. A. Bruijnincx. Selectivity Control in the Tandem Aromatization of Bio-Based Furanics Catalyzed by Solid Acids and Palladium. ChemSusChem. 2016; 10 (1):277-286.
Chicago/Turabian StyleHomer C. Genuino; Shanmugam Thiyagarajan; Jan C. Van Der Waal; Ed De Jong; Jacco Van Haveren; Daan S. Van Es; Dr. Bert M. Weckhuysen; Pieter C. A. Bruijnincx. 2016. "Selectivity Control in the Tandem Aromatization of Bio-Based Furanics Catalyzed by Solid Acids and Palladium." ChemSusChem 10, no. 1: 277-286.
The acid‐catalysed dehydration of the four 2‐ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 g L−1 substrate concentration, 17 and 34 mm sulfuric acid, 100 °C) with Avantium high‐throughput technology. Significant differences in the reactivities of the hexoses and yields of 5‐hydroxymethylfurfural (HMF) and its methyl ether (MMF) were observed. Psicose and tagatose were the most reactive, and psicose also afforded the highest combined yield of MMF and HMF of approximately 55 % at 96 % sugar conversion. Hydroxyacetylfuran and its corresponding methyl ether were formed as byproducts, particularly for sorbose and tagatose, with a maximum combined yield of 8 % for sorbose. The formation of hydroxyacetylfuran was studied through 13C NMR spectroscopy with labelled sorbose, which provided new insights into the reaction mechanism.
Robert-Jan Van Putten; Jan C. Van Der Waal; Martin Harmse; Henk H. Van De Bovenkamp; Ed de Jong; Dr. Hero J. Heeres. A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol. ChemSusChem 2016, 9, 1827 -1834.
AMA StyleRobert-Jan Van Putten, Jan C. Van Der Waal, Martin Harmse, Henk H. Van De Bovenkamp, Ed de Jong, Dr. Hero J. Heeres. A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol. ChemSusChem. 2016; 9 (14):1827-1834.
Chicago/Turabian StyleRobert-Jan Van Putten; Jan C. Van Der Waal; Martin Harmse; Henk H. Van De Bovenkamp; Ed de Jong; Dr. Hero J. Heeres. 2016. "A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol." ChemSusChem 9, no. 14: 1827-1834.
Levulinic acid (LA) is readily available from sugars and known to mankind long before the onset of the petrochemical revolution. This chapter gives a full overview of levulinic synthesis routes, its market players, and its versatility in many chemical outlets. All of this shows the high potential of levulinates in future applications. The synthesis of levulinic acid is industrially possible via several routes based on the feedstock employed. The currently employed industrial process uses petrochemical-derived maleic anhydride. The emerging bio-based technologies, however, can either use C6 sugars or C5 sugars as the starting point. Since the levulinate esters are often the more preferred starting point for further conversions, an important reaction at this point is the interconversion of levulinic acid and levulinate esters. Currently levulinic acid is used as specialty chemical in pharmaceutical, cosmetic, and food applications.
Jan C. Van Der Waal; Ed de Jong. Avantium Chemicals: The High Potential for the Levulinic Product Tree. Industrial Biorenewables 2016, 97 -120.
AMA StyleJan C. Van Der Waal, Ed de Jong. Avantium Chemicals: The High Potential for the Levulinic Product Tree. Industrial Biorenewables. 2016; ():97-120.
Chicago/Turabian StyleJan C. Van Der Waal; Ed de Jong. 2016. "Avantium Chemicals: The High Potential for the Levulinic Product Tree." Industrial Biorenewables , no. : 97-120.
Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination.
Shanmugam Thiyagarajan; Homer C. Genuino; Jan C. Van Der Waal; Ed De Jong; Bert M. Weckhuysen; Jacco Van Haveren; Pieter C. A. Bruijnincx; Daan S. Van Es. A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics. Angewandte Chemie 2015, 128, 1390 -1393.
AMA StyleShanmugam Thiyagarajan, Homer C. Genuino, Jan C. Van Der Waal, Ed De Jong, Bert M. Weckhuysen, Jacco Van Haveren, Pieter C. A. Bruijnincx, Daan S. Van Es. A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics. Angewandte Chemie. 2015; 128 (4):1390-1393.
Chicago/Turabian StyleShanmugam Thiyagarajan; Homer C. Genuino; Jan C. Van Der Waal; Ed De Jong; Bert M. Weckhuysen; Jacco Van Haveren; Pieter C. A. Bruijnincx; Daan S. Van Es. 2015. "A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics." Angewandte Chemie 128, no. 4: 1390-1393.
Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination.
Shanmugam Thiyagarajan; Homer C. Genuino; Jan C. Van Der Waal; Ed De Jong; Dr. Bert M. Weckhuysen; Jacco Van Haveren; Pieter C. A. Bruijnincx; Daan S. Van Es. A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics. Angewandte Chemie International Edition 2015, 55, 1368 -1371.
AMA StyleShanmugam Thiyagarajan, Homer C. Genuino, Jan C. Van Der Waal, Ed De Jong, Dr. Bert M. Weckhuysen, Jacco Van Haveren, Pieter C. A. Bruijnincx, Daan S. Van Es. A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics. Angewandte Chemie International Edition. 2015; 55 (4):1368-1371.
Chicago/Turabian StyleShanmugam Thiyagarajan; Homer C. Genuino; Jan C. Van Der Waal; Ed De Jong; Dr. Bert M. Weckhuysen; Jacco Van Haveren; Pieter C. A. Bruijnincx; Daan S. Van Es. 2015. "A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics." Angewandte Chemie International Edition 55, no. 4: 1368-1371.