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Publication YXY 2015

Isothermal Crystallization Kinetics of Poly(Ethylene 2,5-Furandicarboxylate)

Jesper G. van Berkel, Nathanaël Guigo, Jeffrey J. Kolstad, Laszlo Sipos, Bing Wang, Matheus A. Dam and Nicolas Sbirrazzuoli, Macromol. Mater. Eng., 2015Vol. 300 (4), p. 466–474

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Poly(ethylene 2,5-furandicarboxylate) (PEF) is a polyester from ethylene glycol and 2,5-Furandicarboxylic acid which has gained increasing interest due to its excellent properties compared to chemically similar PET. This paper presents an estimation of the crystallization enthalpy, the crystalline and amorphous density and the crystallization kinetics of PEF. Using Avrami and the Hoffman-Lauritzen theory, Hoffman-Lauritzen parameters are proposed that relate crystal growth rate of catalyst-free PEF to temperature and molecular weight. Characteristic is a higher activation energy for chain diffusion (U*) for PEF compared PET, which can be attributed to more restricted chain conformational changes. Finally, the crystallization rate of PEF is shown to be significantly affected by catalyst type.

DOI: 10.1002/mame.201400376


Publication Catalysis 2015

Oxidative Coupling of Methane in Small Scale Parallel Reactors

Erik-Jan Ras, Santiago Gomez-Quero, Top. Catal. 2014Vol. 57, p.1392

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In this work the testing of high temperature reactions in small scale parallel reactors is explored using the oxidative coupling of methane as an example. The advantages of small scale reactors for this very exothermic and complex reaction are discussed. The data generated in this study is explored making use of response surface models derived from statistically designed experiments. Methane conversion has been explored over a Mn-promoted Na2WO4/SiO2 catalyst over the temperature range 755–875 °C, pressure range 0.2–8.4 barg and GHSV range 4,000–36,000 h−1 using air as oxidant. Methane to oxygen stoichiometries of 4–8 have been explored. The highest C2 yield (16 %) is obtained at at low pressure.

DOI 10.1007/s11244-014-0310-8


Publication YXY 2014

Experimental and Modeling Studies on the Solubility of d-Arabinose, d-Fructose, d-Glucose, d-Mannose, Sucrose and d-Xylose in Methanol and Methanol–Water Mixtures

Robert-Jan van Putten, Jozef G. M. Winkelman, Farhad Keihan, Jan C. van der Waal, Ed de Jong, and Hero J. Heeres, Ind. Eng. Chem. Res. 201453 (19), 8285

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The solubilities of d-glucose, d-arabinose, d-xylose, d-fructose, d-mannose, and sucrose in methanol and methanol–water mixtures (less than 25 wt % water) were determined at temperatures between 295 and 353 K using a unique high-throughput screening technique. The data were modeled with a UNIQUAC framework with an average error between calculated and experimental data of 3.7%. The results provide input for the design of efficient chemical processes for the conversion of these sugars into valuable biobased building blocks in methanol–water mixtures.







Publication YXY 2014

Non-isothermal Crystallization Kinetics of Biobased Poly(ethylene 2,5-furandicarboxylate) Synthesized via the Direct Esterification Process

Amandine Codou, Nathanael Guigo, Jesper van Berkel, Ed de Jong, and Nicolas Sbirrazzuoli, Macromol. Chem. Phys 2014, Vol 215, issue 21, p. 2065

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Poly(ethylene 2,5-furandicarboxylate) (PEF) is an emergent biobased polyester whose chemical structure is analogous to poly(ethylene terephthalate). Pilot-scale PEF is synthesized through the direct esterification process from 2,5-furandicarboxylic acid and bio-ethylene glycol. Wide-angle X-ray diffraction (WAXD) measurements reveal similar crystallinities and unit cell structures for melt-crystallized and glass-crystallized samples. The non-isothermal crystallization of PEF sample is investigated by means of DSC experiments both from the glass and the melt. The temperature dependence of the effective activation energy of the growth rate is obtained from these data, and the results show that the glass and early stage of the melt crystallization share common dynamics. Hoffman–Lauritzen parameters and the temperature at maximum crystallization rate are evaluated. It is found that the melt-crystallization kinetics undergo a transition from regime I to II; however, the crystal growth rate from the melt shows an atypical depression at T < 171 °C compared with the predicted Hoffman–Lauritzen theory.



Publication YXY 2014

Valorization of bio-refinery side stream products: combination of humins with polyfurfuryl alcohol for composite elaboration

J-M. Pin, N. Guigo, A. Mija, L. Vinzent, N. Sbirrazzuoli, J.C. van der Waal, E. de Jong, ACS Sustainable Chem. Eng. 2014, 2 (9), 2182–2190.

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A challenge of today’s industry is to transform low-value side products into more value-added materials. Humins, a byproduct derived from sugar conversion processes, can be transformed into high value-added products. Thermosetting furanic composites were elaborated with cellulose filters. Large quantities of humins were included into a polyfuranic thermosetting network. Comparisons were made with composites generated with polyfurfuryl alcohol (PFA) and with PFA/lignin. It was concluded that new chemical interactions were created between the side-chain oxygen groups of the humins and the PFA network. Analysis of the fracture surface of the composites containing humins lead to the conclusion that higher interfacial bonding and more efficient stress transfer between the matrix and the fibers is present. The higher ductility of the humins-based matrix allows for a two-fold higher tensile strength in comparison with other composites tested. Incorporation of humins decreases the brittleness of the furanic composites, which is one major drawback of the pure PFA composites.

DOI 10.1021/sc5003769


Publication Catalysis 2014

Evaluation of MoS2 based catalysts for the conversion of syngas into alcohols: A combinatorial approach

Arthur José Gerbasi da Silva, Paula Claassens-Dekker, Antônio Carlos Sallarès de Mattos Carvalho, Antônio Manzolillo Sanseverino, Cristina Pontes Bittencourt Quitete, Alexandre Szklo, Eduardo Falabella Sousa-Aguiar, J. Env. Chem. Eng. 2014, 2, 2148.

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72 MoS2 catalysts were tested in the conversion of syngas to alcohols, using a high-throughput catalyst evaluation unit, to identify the best catalyst, based on CO conversion, both ethanol and higher alcohols and total alcohols selectivity. Catalysts prepared by thermal decomposition of (NH4)2MoS4 at low temperature showed a higher selectivity to total alcohols. The highest selectivity to ethanol and higher alcohols was obtained at 300 °C by a catalyst prepared by reacting Mo(CO)6 with sulphur. Catalysts prepared by thermal decomposition of (NH4)2MoS4 at high temperature showed very low activity. Catalysts prepared by thermal decomposition of (NH4)2MoS4 in tridecane/water with hydrogen atmosphere showed low activity and selectivity. There was no significant difference among the alkaline metal promoters K, Cs and Rb regarding total alcohols selectivities. Incorporation of Co and Ni led to catalysts with activity levels equivalent to catalysts that contain Rh.

DOI 10.1016/j.jece.2014.09.006


Publication YXY 2014

Acid catalysed alcoholysis of wheat straw: towards second generation furan-derivatives

R.J.H. Grisel, J.C. van der Waal, E. de Jong, W.J.J. Huijgen, Catalysis Today 2014, 223, 3.

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The acid-catalysed alcoholysis of wheat straw has been studied in 95% methanol and 94% ethanol (w/w) in the presence of various amounts of H2SO4 and compared to the alcoholysis of wheat straw-derived organosolv pulp and commercially available celluloses. Substrate liquefaction and the product distribution were found to depend mainly on the temperature and the amount of H2SO4 added compared to the acid neutralisation capacity (ANC) of the substrate. The process was optimised for the one-step conversion of wheat straw into methyl glucosides, defined as the sum of α and β anomers. The maximum total methyl glucosides yield from wheat straw was 56 mol-% based on initial glucan after 120 min methanolysis at 175 °C and 40 mM H2SO4. Concurrently, furfural was formed at 40 mol-% yield based on initial xylan. The solid residue consisted of mainly acid insoluble (pseudo)lignin, humins and minerals. Switching to ethanol resulted in a shift from glycosides to furfural, 5-(alkoxymethyl)-2-furfural and levulinates. Addition of MgCl2, as well as substituting H2SO4 by HCl led to poorer biomass liquefaction and lower glucosides yield presumably due to consumption of protons under the typical reaction conditions. Alcoholysis of delignified, cellulose-enriched pulp obtained via organosolv fractionation resulted in higher glucosides yields and more concentrated product streams, as higher glucan loadings are possible and undesired side-reactions are minimised. Furthermore, organosolv fractionation prior to alcoholysis allows for the separation and valorisation of the lignin fraction. The glucosides can be separated, e.g. by means of chromatography, and may be converted into furan building blocks, for example for the production of plastic precursors, such as 2,5-furandicarboxylic acid.

DOI 10.1016/j.cattod.2013.07.008




Publication Catalysis 2013

Catalytic process development for renewable materials

eds. Pieter Imhof, Jan Cornelis van der Waal, John Wiley & Sons 2013, 370 p.

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Green, clean and renewable are the hottest keywords for catalysis and industry. This handbook and ready reference is the first to combine the fields of advanced experimentation and catalytic process development for biobased materials in industry. It describes the entire workflow from idea, approach, research, and process development, right up to commercialization. A large part of the book is devoted to the use of advanced technologies and methodologies like high throughput experimentation, as well as reactor and process design models, with a wide selection of real-life examples included at each stage. The contributions are from authors at leading companies and institutes, providing firsthand information and knowledge that is hard to find elsewhere. This work is aimed at decision makers, engineers and chemists in industry, chemists and engineers working with/on renewables, chemists in the field of catalysis, and chemical engineers.

ISBN 3527656669, 9783527656660


Publication YXY 2013

Hydroxymethylfurfural, a versatile platform chemical made from renewable resources

R-J. van Putten, J.C. van der Waal, E. de Jong, C.B. Rasrendra, H.J. Heeres, J.G. de Vries, Chem. Rev. 2013, 113, 1499.

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1. Introduction 2. Nutritional and Toxicological Aspects of HMF and Its Derivatives2.1. HMF Occurrence in Our Diet 2.2. Metabolic Breakdown of HMF and Its Derivatives 2.3. Toxicological Effects of HMF and Its Derivatives 3. Dehydration Chemistry3.1. Neutral Monomeric Sugars3.1.1. Mechanistic Aspects 3.1.2. Byproducts 3.1.3. Computational Studies 3.2. Disaccharides and Polysaccharides 3.3. Sugar Acids 3.4. Conclusion 4. Process Chemistry4.1. HMF Formation in Single-Phase Systems4.1.1. Fructose Dehydration in Single-Phase Systems 4.1.2. Glucose Dehydration in Single-Phase Systems 4.1.3. Dehydration of Disaccharides, Trisaccharides, and Polysaccharides and Biomass Feedstock in Single-Phase Systems 4.2. HMF Formation in Biphasic Solvent Systems4.2.1. Fructose Dehydration in Biphasic Solvent Systems 4.2.2. Glucose Dehydration in Biphasic Solvent Systems 4.2.3. Dehydration of Oligo- and Polysaccharides in Biphasic Solvent Systems 4.3. HMF Formation in Ionic Liquids4.3.1. Definition of Ionic Liquids 4.3.2. Dehydration of Carbohydrates to HMF in Ionic Liquids 4.3.3. Conclusion on HMF Production in Ionic Liquids 5. Process Technology5.1. Introduction5.1.1. Aqueous Reaction Systems 5.1.2. Nonaqueous Reaction Systems 5.1.3. Mixed Solvent Reaction Systems 5.2. Kinetic Studies on HMF Formation5.2.1. Kinetic Studies on the Formation of HMF from Fructose 5.2.2. Kinetic Studies on the Formation HMF from Glucose 5.2.3. Kinetic Studies on the Formation of HMF from Cellulose, Lignocellulosic Biomass, and Fructan-Based Biomass 5.2.4. Kinetic Studies on the Decomposition of HMF 5.3. Reactor Concepts5.3.1. Reactions in Water 5.3.2. Reactions in Nonaqueous and Mixed Solvent Systems 5.4. Separation and Purification Strategies5.4.1. Separation and Purification Strategies for Aqueous Systems 5.4.2. Separation and Purification Strategies for Nonaqueous Systems 5.5. Pilot Scale Production of HMF5.5.1. Pilot Scale Studies of Aqueous HMF Processes 5.5.2. Pilot Scale Production Using Nonaqueous Solvents 5.5.3. Pilot Scale Production Using Mixed Solvent Systems 5.5.4. Pilot Scale Production of HMF Involving an HMF Derivative 5.6. Technoeconomic Evaluations of Different Modes of HMF Production 6. Relevance of 5-Hydroxymethylfurfural as a Platform Chemical6.1. Conversion of HMF to Monomers for Polymers6.1.1. HMF-Based Diols 6.1.2. 2,5-Diformylfuran 6.1.3. 2,5-Furandicarboxylic Acid (FDCA), Adipic Acid, and 5-Hydroxymethyl-2-furan Carboxylic Acid 6.1.4. Conversion of HMF into Other Monomers 6.2. Fine Chemicals6.2.1. Pharmaceuticals 6.2.2. Agrochemicals 6.2.3. Flavors and Fragrances 6.2.4. Natural Products 6.2.5. Macrocycles 6.2.6. Heterocycles 6.2.7. Sugar Derivatives 6.2.8. Spiroketals 6.2.9. Other Synthetic Conversions 6.3. HMF as Precursor of Fuel Components 7. Conclusions

DOI 10.1021/cr300182k


Publication YXY 2013

Electrocatalytic hydrogenation of 5-hydroxymethylfurfural in the absence and presence of glucose

Y. Kwon, E. de Jong, S. Raoufmoghaddam, M.T.M. Koper, Chem. Sus. Chem. 2013, 6, 1659.

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Electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) or other species, such as 2,5-dimethylfuran, on solid metal electrodes in neutral media is addressed, both in the absence and in the presence of glucose. The reaction is studied by combining voltammetry with on-line product analysis by using HPLC, which provides both qualitative and quantitative information about the reaction products as a function of electrode potential. Three groups of catalysts show different selectivity towards: (1) DHMF (Fe, Ni, Ag, Zn, Cd, and In), (2) DHMF and other products (Pd, Al, Bi, and Pb), depending on the applied potential, and (3) other products (Co, Au, Cu, Sn, and Sb) through HMF hydrogenolysis. The rate of electrocatalytic HMF hydrogenation is not strongly catalyst-dependent because all catalysts show similar onset potentials (−0.5±0.2 V) in the presence of HMF. However, the intrinsic properties of the catalysts determine the reaction pathway towards DHMF or other products. Ag showed the highest activity towards DHMF formation (up to 13.1 mM cm−2 with high selectivity> 85 %). HMF hydrogenation is faster than glucose hydrogenation on all metals. For transition metals, the presence of glucose enhances the formation of DHMF and suppresses the hydrogenolysis of HMF. On poor metals such as Zn, Cd, and In, glucose enhances DHMF formation; however, its contribution in the presence of Bi, Pb, Sn, and Sb is limited. Remarkably, in the presence of HMF, glucose hydrogenation itself is largely suppressed or even absent. The first electron-transfer step during HMF reduction is not metal-dependent, suggesting a non-catalytic reaction with proton transfer directly from water in the electrolyte.

DOI 10.1002/cssc.201300443



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