Molecular structure and composition elucidation of an industrial humin and its fractions
Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydr...
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| Veröffentlicht in: | Green chemistry : an international journal and green chemistry resource : GC Jg. 26; H. 13; S. 7739 |
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| Sprache: | Englisch |
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01.07.2024
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| ISSN: | 1463-9262 |
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| Abstract | Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities. |
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| AbstractList | Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities. Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities.Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities. |
| Author | de Peinder, Peter Baldus, Marc Vogelzang, Willem van Es, Daan S Bruijnincx, Pieter C A Constant, Sandra Frissen, Augustinus E Pazhavelikkakath Purushothaman, Rajeesh Kumar Lancefield, Christopher S Weckhuysen, Bert M Houben, Klaartje |
| Author_xml | – sequence: 1 givenname: Sandra orcidid: 0000-0001-9843-156X surname: Constant fullname: Constant, Sandra email: p.c.a.bruijnincx@uu.nl organization: Avantium Renewable Polymers B.V. Zekeringstraat 29 1014 BV Amsterdam The Netherlands – sequence: 2 givenname: Christopher S orcidid: 0000-0001-9134-5589 surname: Lancefield fullname: Lancefield, Christopher S email: p.c.a.bruijnincx@uu.nl organization: Inorganic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Faculty of Science, Utrecht University Universiteitsweg 99 3584 CG Utrecht The Netherlands p.c.a.bruijnincx@uu.nl – sequence: 3 givenname: Willem orcidid: 0009-0003-6841-7611 surname: Vogelzang fullname: Vogelzang, Willem email: daan.vanes@wur.nl organization: Wageningen Food & Biobased Research Bornse Weilanden 9 6708 WG Wageningen The Netherlands daan.vanes@wur.nl – sequence: 4 givenname: Rajeesh Kumar orcidid: 0000-0003-0811-2261 surname: Pazhavelikkakath Purushothaman fullname: Pazhavelikkakath Purushothaman, Rajeesh Kumar email: daan.vanes@wur.nl organization: Wageningen Food & Biobased Research Bornse Weilanden 9 6708 WG Wageningen The Netherlands daan.vanes@wur.nl – sequence: 5 givenname: Augustinus E surname: Frissen fullname: Frissen, Augustinus E email: daan.vanes@wur.nl organization: Wageningen Food & Biobased Research Bornse Weilanden 9 6708 WG Wageningen The Netherlands daan.vanes@wur.nl – sequence: 6 givenname: Klaartje surname: Houben fullname: Houben, Klaartje organization: NMR Spectroscopy Research Group, Bijvoet Center for Biomolecular Research, Utrecht University Padualaan 8 3584 CH Utrecht The Netherlands – sequence: 7 givenname: Peter surname: de Peinder fullname: de Peinder, Peter organization: VibSpec Haaftenlaan 28 4006 XL Tiel The Netherlands – sequence: 8 givenname: Marc orcidid: 0000-0001-7068-5613 surname: Baldus fullname: Baldus, Marc organization: NMR Spectroscopy Research Group, Bijvoet Center for Biomolecular Research, Utrecht University Padualaan 8 3584 CH Utrecht The Netherlands – sequence: 9 givenname: Bert M orcidid: 0000-0001-5245-1426 surname: Weckhuysen fullname: Weckhuysen, Bert M email: p.c.a.bruijnincx@uu.nl organization: Inorganic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Faculty of Science, Utrecht University Universiteitsweg 99 3584 CG Utrecht The Netherlands p.c.a.bruijnincx@uu.nl – sequence: 10 givenname: Daan S orcidid: 0000-0001-7476-5813 surname: van Es fullname: van Es, Daan S email: daan.vanes@wur.nl organization: Wageningen Food & Biobased Research Bornse Weilanden 9 6708 WG Wageningen The Netherlands daan.vanes@wur.nl – sequence: 11 givenname: Pieter C A orcidid: 0000-0001-8134-0530 surname: Bruijnincx fullname: Bruijnincx, Pieter C A email: p.c.a.bruijnincx@uu.nl organization: Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Utrecht University, Faculty of Science Universiteitsweg 99 3584 CG Utrecht The Netherlands |
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| Title | Molecular structure and composition elucidation of an industrial humin and its fractions |
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