University of Groningen Experimental and modelling studies on the synthesis of 5-hydroxymethylfurfural from sugars van Putten, Robert-Jan IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2015 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): van Putten, R-J. (2015). Experimental and modelling studies on the synthesis of 5-hydroxymethylfurfural from sugars. [S.n.]. Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license. More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne- amendment. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 04-10-2021 Experimental and modelling studies on the synthesis of 5-hydroxymethylfurfural from sugars Robert-Jan van Putten ISBN 978-94-6259-502-6 ISBN 978-94-6259-504-0 (electronic version) Experimental and modelling studies on the synthesis of 5-hydroxymethylfurfural from sugars PhD thesis to obtain the degree of PhD at the University of Groningen on the authority of the Rector Magnificus Prof. E. Sterken and in accordance with the decision by the College of Deans. This thesis will be defended in public on Friday 16 January 2015 at 16.15 hours by Robert-Jan van Putten born on 18 August 1981 in Hilversum Supervisor Prof. H.J. Heeres Co-supervisors Dr. E. de Jong Dr. ir. J.C. van der Waal Assessment committee Prof. A.A. Broekhuis Prof. R. Palkovits Prof. G. Centi Table of contents 1 Preface 1 1.1 Biomass as source for energy, transportation fuels and materials 1 1.2 This thesis 3 1.3 References 5 2 Hydroxymethylfurfural, a versatile platform chemical made from 7 renewable resources 2.1 Introduction 7 2.2 Nutritional and toxicological aspects of HMF and its derivatives 11 2.2.1 HMF occurrence in our diet 11 2.2.2 Metabolic breakdown of HMF and derivatives 16 2.2.3 Toxicological effects of HMF and its derivatives 18 2.3 Dehydration chemistry 20 2.3.1 Neutral monomeric sugars 20 2.3.2 Disaccharides and polysaccharides 42 2.3.3 Sugar acids 44 2.3.4 Conclusion 46 2.4 Process chemistry 47 2.4.1 HMF formation in single-phase systems 47 2.4.2 HMF formation in biphasic solvent systems 100 2.4.3 HMF formation in ionic liquids 123 2.5 Process technology 155 2.5.1 Introduction 155 2.5.2 Kinetic studies on HMF formation 159 2.5.3 Reactor concepts 201 2.5.4 Separation and purification strategies 206 2.5.5 Pilot scale production of HMF 212 2.5.6 Technoeconomic evaluations of different modes of HMF 216 production 2.6 Relevance of 5-hydroxymethylfurfural as a platform chemical 220 2.6.1 Conversion of HMF to monomers for polymers 220 2.6.2 Fine chemicals 233 2.6.3 HMF as precursor of fuel components 259 2.7 Conclusions 261 2.8 References 264 3 The dehydration of different ketoses and aldoses to 5- 281 hydroxymethylfurfural 3.1 Introduction 282 3.2 Experimental section 285 3.2.1 High-throughput screening 285 3.2.2 Kinetic experiments 285 3.2.3 Determination of the kinetic parameters 286 3.2.4 DFT calculations 286 3.3 Results and discussion 286 3.3.1 High-throughput screening 286 3.3.2 Kinetic study 291 3.3.3 DFT calculations 293 3.3.4 Mechanistic aspect 295 3.4 Conclusions 298 3.5 References 299 4 A comparative study on the reactivity of various ketohexoses to furanics in 301 methanol 4.1 Introduction 302 4.2 Experimental section 305 4.2.1 Chemicals 305 4.2.2 High-throughput experimentation 305 4.2.3 Synthesis of 2-methoxyacetylfuran 306 4.2.4 Chromatographic analysis 306 4.2.5 Experiments with L-[6-13C]sorbose 307 4.3 Results and discussion 307 4.3.1 High-throughput experimentation 308 4.3.2 Mechanistic considerations and 13C labelling experiments with 320 sorbose 4.4 Conclusions 326 4.5 References 328 5 Reactivity studies on the acid-catalysed dehydration of ketohexoses to 5- 329 hydroxymethylfurfural in water 5.1 Introduction 330 5.2 Experimental section 332 5.3 Results and discussion 332 5.3.1 Sugar reactivity 332 5.3.2 HMF yield 334 5.3.3 Product selectivity 337 5.4 Conclusions 338 5.5 References 339 6 Experimental and modelling studies on the solubility of D-arabinose, D- 341 fructose, D-glucose, D-mannose, sucrose and D-xylose in methanol and methanol-water mixtures 6.1 Introduction 342 6.2 Experimental section 345 6.2.1 Chemicals 345 6.2.2 Solubility measurements 345 6.2.3 UNIQUAC modeling 346 6.3 Results and discussion 348 6.3.1 Experimental studies 348 6.3.2 Modelling studies 351 6.3.3 Literature comparison 352 6.4 Conclusions 355 6.5 Symbols 355 6.6 References 356 7 Concluding remarks and recommendations 359 Summary 363 Samenvatting 367 Acknowledgements 371 Publications 373 |1 1 Preface 1.1 Biomass as resource for energy, transportation fuels and biobased chemicals Our world is completely dependent on fossil resources for materials and energy production. Almost everything we use and consume in everyday life has a significant input of oil, coal and natural gas, including the production of food. The earth’s population is still growing, mainly in developing countries, and combined with economic development and the accompanying increase in consumption in countries like India and China creates an enormous pressure on earth’s resources. This is not a sustainable situation and it is of critical importance to develop alternatives for fossil resources for energy and bulk materials production. For energy generation, renewables like solar and wind energy are available. For bulk materials production, though, sources of fixed carbon are required. This leads to biomass as the obvious solution, since it is the largest sustainable global source of fixed carbon. There are however major differences in the chemical composition of fossil carbon sources and biomass. Fossil feedstocks generally have a very high carbon and hydrogen content and are very low in heteroatoms like oxygen, sulphur and nitrogen. On the contrary, biomass generally has a very high oxygen content and also a higher nitrogen content than fossil feeds. Especially the amount of oxygen in the molecular structure of the biomass has to be reduced before it can be used in any potential application. Apart from water, biomass mainly consists of carbohydrates, lignin, fatty acids, lipids and proteins of which the carbohydrates are the most abundant. This makes carbohydrates a very appropriate feed stock for a biobased economy. The conversion of carbohydrates into suitable building block molecules for the petrochemical industry in most cases requires the removal of the majority of the oxygen from the molecular structure. There are three main methods for oxygen removal: (i) removing small, highly oxidised molecules such as CO2, CO, formaldehyde and formic acid; (ii) hydrogenolysis, typically removing water at the cost of hydrogen; and (iii) dehydration. The removal of highly oxygenated compounds like CO2 2| Chapter 1 comes at the cost of carbon loss, a significant disadvantage when the carbohydrate acts as a carbon source. Hydrogenolysis requires at least one molecule of hydrogen for each oxygen atom that is removed. This is only applicable in bulk application when a sustainable source of hydrogen can be used. Dehydration, when possible, is very appealing as it retains all the carbon atoms from the carbohydrate by removing water exclusively. Avantium Chemicals B.V., founded in 2000, is a spin-off from Royal Dutch Shell and based in Amsterdam, the Netherlands. Its core business revolves around advanced catalysis research, selling both services and high-end equipment to a broad customer base, consisting of some of the world’s largest chemical companies. Advanced catalysis research deals with high-throughput experimentation on a small scale and an infrastructure of experimental design and analytics, which allows the generation of large amounts of data at the cost of relatively little resources (time, material). In 2006 Avantium started the development of its own process for the production of biobased plastics by applying their advanced technology to biomass conversion. This YXY project deals with the production of a polyethylene terephtalate (PET) replacement named polyethylene furanoate (PEF). PET is one of the most used plastics on the planet with a global production of around 65 million tons per year. Replacing it with PEF would result in a significant reduction of non-renewable energy use and thus increasing sustainability.1 PEF is synthesised by polymerising 2,5-furandicarboxylic acid (FDCA), which replaces terephtalic acid used in PET, and ethylene glycol (Scheme 1). PEF is not just favourable compared to PET from an environmental point of view, but it also has strongly improved material properties.2,3 The barrier properties, for instance, are better than for PET and show much lower permeability for most gases, especially CO2 and oxygen.