Molecular structure and composition elucidation of an industrial humin and its fractions

S Constant; CS Lancefield; W Vogelzang; RKP Purushothaman; AE Frissen; K Houben; P de Peinder; M Baldus; BM Weckhuysen; DS van Es; PCA Bruijnincx

doi:10.1039/d4gc00429a

Molecular structure and composition elucidation of an industrial humin and its fractions

S Constant, CS Lancefield, W Vogelzang, RKP Purushothaman, AE Frissen, K Houben, P de Peinder, M Baldus, BM Weckhuysen, DS van Es^*, PCA Bruijnincx^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

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.

Original language	English
Pages (from-to)	7739-7751
Number of pages	13
Journal	Green Chemistry
Volume	26
Issue number	13
Early online date	21 Mar 2024
DOIs	https://doi.org/10.1039/d4gc00429a
Publication status	Published - Jul 2024

Bibliographical note

Publisher Copyright:
© 2024 The Royal Society of Chemistry.

Funding

This project has been performed within the framework of the CatchBio program. The authors gratefully acknowledge the financial support of the Smart Mix Program of the Netherlands Ministry of Economic Affairs and the Netherlands Ministry of Education, Culture and Science. The authors acknowledge contribution of PEFerence project that has received funding from the Bio-based Industries Joint Undertaking (JU) under the European Union's Horizon 2020 research and innovation programme under grant agreement no. 744409. The JU received support from the European Union's Horizon 2020 research and innovation programme and the Bio-based Industries Consortium. We also acknowledge the financial support of uNMR-NL, an NWO-funded National Roadmap Large-Scale Facility for the Netherlands (No. 184.032.207). Dr Hans L. J. Wienk and Prof. Rolf Boelens, are acknowledged for technical support and access to the Utrecht NMR facility. Dr Johann Jastrzebski, Dr Andrei Gurinov, Marjan Versluijs-Helder and Pascal Wijten (Utrecht University) are thanked for technical support with the NMR, SEM and GPC measurements. We also thank Dr Ed de Jong, Dr Gerard van Klink and Tom Claessen (Avantium) for the insightful discussions on the humin material. Finally, we thank Prof. Erik Heeres (Rijksuniversiteit Groningen) for providing the purified synthetic humin sample (PSH).

Funders	Funder number
Ministerie van Economische Zaken
Smart Mix Program of the Netherlands Ministry of Economic Affairs and the Netherlands Ministry of Education, Culture and Science	744409
Bio-based Industries Joint Undertaking (JU) under the European Union
European Union's Horizon 2020 Research and Innovation Programme	184.032.207
NWO-funded National Roadmap Large-Scale Facility for the Netherlands

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Cite this

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title = "Molecular structure and composition elucidation of an industrial humin and its fractions",

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{\textregistered} 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 = "S Constant and CS Lancefield and W Vogelzang and RKP Purushothaman and AE Frissen and K Houben and {de Peinder}, P and M Baldus and BM Weckhuysen and {van Es}, DS and PCA Bruijnincx",

note = "Publisher Copyright: {\textcopyright} 2024 The Royal Society of Chemistry.",

year = "2024",

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doi = "10.1039/d4gc00429a",

language = "English",

volume = "26",

pages = "7739--7751",

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T1 - Molecular structure and composition elucidation of an industrial humin and its fractions

AU - Constant, S

AU - Lancefield, CS

AU - Vogelzang, W

AU - Purushothaman, RKP

AU - Frissen, AE

AU - Houben, K

AU - de Peinder, P

AU - Baldus, M

AU - Weckhuysen, BM

AU - van Es, DS

AU - Bruijnincx, PCA

PY - 2024/7

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N2 - 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.

AB - 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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DO - 10.1039/d4gc00429a

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SP - 7739

EP - 7751

JO - Green Chemistry

JF - Green Chemistry

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ER -

Molecular structure and composition elucidation of an industrial humin and its fractions

Abstract

Bibliographical note

Funding

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