Abstract
Humins are undesired solids formed during the hydrothermal degradation of carbohydrates. In order to reveal the mechanism of formation of humins, we studied the degradation behavior of 11 model compounds including carbohydrates and furfural derivatives, within water and various pure organic solvents as reaction media. All the studied carbohydrates could generate solid humins in both water and studied organic solvents except ethanol, while the furfural derivatives could generate solid humins in only water. The results could be explained by regarding the formed α-carbonyl aldehydes and α,β-unsaturated aldehydes as primary precursors for formation of humins. Furfural derivatives could generate chain α-carbonyl aldehydes (for example, 6-hydroxy-2,5-dioxohexanal from 5-hydroxymethylfurfural and 2-oxopentanedial from furfural) through hydrolytic ring opening reaction; thus, water is essential for these furfural derivatives to generate humins. As for carbohydrates, they could generate α-carbonyl aldehydes and α,β-unsaturated aldehydes through simple step of β-elimination in all solvents; thus, they could form humins in both water and studied organic solvents except ethanol. Ethanol could react with α-carbonyl aldehydes by acetalization; thus, the condensation between α-carbonyl aldehydes was suppressed in ethanol, leading to few humins formation from carbohydrates. Based on the above analysis, we proposed that the formed α-carbonyl aldehydes and α,β-unsaturated aldehydes should be the primary precursor of humins.
Similar content being viewed by others
References
Mika LT, Csefalvay E, Nemeth A (2018) Catalytic conversion of carbohydrates to initial platform chemicals: chemistry and sustainability. Chem Rev 118(2):505–613
Huang YB, Fu Y (2013) Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chem 15(5):1095–1111
Verendel JJ, Church TL, Andersson PG (2011) Catalytic one-pot production of small organics from polysaccharides. Synthesis-Stuttgart 11:1649–1677
Shi N, Liu QY, He X, Cen H, Ju RM, Zhang YL, Ma LL (2019) Production of lactic acid from cellulose catalyzed by easily prepared solid Al2(WO4)3. Bioresource Technol Rep 5:66–73
Shi N, Liu QY, Zhang Q, Wang TJ, Ma LL (2013) High yield production of 5-hydroxymethylfurfural from cellulose by high concentration of sulfates in biphasic system. Green Chem 15(7):1967–1974
Shi N, Liu QY, Wang TJ, Ma LL, Zhang Q, Zhang Q (2014) One-pot degradation of cellulose into furfural compounds in hot compressed steam with dihydric phosphates. ACS Sustain Chem Eng 2(4):637–642
Kang SM, Fu JX, Zhang G (2018) From lignocellulosic biomass to levulinic acid: a review on acid-catalyzed hydrolysis. J Renew Sustain Energy Rev 94:340–362
Van Zandvoort I, Wang YH, Rasrendra CB, Van Eck ERH, Bruijnincx PCA, Heeres HJ, Weckhuysen BM (2013) Formation, molecular structure, and morphology of humins in biomass conversion: influence of feedstock and processing conditions. ChemSusChem 6(9):1745–1758
Van Zandvoort I, Koers EJ, Weingarth M, Bruijnincx PCA, Baldus M, Weckhuysen BM (2015) Structural characterization of 13C-enriched humins and alkali-treated 13C humins by 2D solid-state NMR. Green Chem 17(8):4383–4392
Sangregorio A, Guigo N, Van Der Waal JC, Sbirrazzuoli N (2018) Humins from biorefineries as thermoreactive macromolecular systems. ChemSusChem 11(24):4246–4255
Filiciotto L, Balu AM, Van Der Waal JC, Luque R (2018) Catalytic insights into the production of biomass-derived side products methyl levulinate, furfural and humins. Catal Today 302:2–15
Muralidhara A, Tosi P, Mija A, Sbirrazzuoli N, Len C, Engelen V, De Jong E, Marlair G (2018) Insights on thermal and fire hazards of humins in support of their sustainable use in advanced biorefineries. ACS Sustain Chem Eng 6(12):16692–16701
Hoang TM, Lefferts L, Seshan K (2013) Valorization of humin-based byproducts from biomass processing-a route to sustainable hydrogen. ChemSusChem 6(9):1651–1658
Hoang TMC, Van Eck ERH, Bula WP, Gardeniers JGE, Lefferts L, Seshan K (2015) Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production. Green Chem 17(2):959–972
Wang K, Jiang J, Liang X, Wu H, Xu J (2018) Direct conversion of cellulose to levulinic acid over multifunctional sulfonated humins in sulfolane–water solution. ACS Sustain Chem Eng 6(11):15092–15099
Björnerbäck F, Hedin N (2018) Microporous humins prepared from sugars and bio-based polymers in concentrated sulfuric acid. ACS Sustain Chem Eng 7(1):1018–1027
Kang S, Fu J, Deng Z, Jiang S, Zhong G, Xu Y, Guo J, Zhou J (2018) Valorization of biomass hydrolysis waste: activated carbon from humins as exceptional sorbent for wastewater treatment. Sustainability 10(6):1795
Kang S, Jiang S, Peng Z, Lu Y, Guo J, Li J, Zeng W, Lin X (2018) Valorization of humins by phosphoric acid activation for activated carbon production. Biomass Convers Bior 8(4):889–897
Kang S, Fu J, Zhang G, Zhang W, Yin H, Xu Y (2017) Synthesis of humin-phenol-formaldehyde adhesive. Polymers 9(8):373–382
Sangregorio A, Guigo N, Van Der Waal JC, Sbirrazzuoli N (2019) All ‘green’ composites comprising flax fibres and humins’ resins. Compos Sci Technol 171:70–77
Dee SJ, Bell AT (2011) A study of the acid-catalyzed hydrolysis of cellulose dissolved in ionic liquids and the factors influencing the dehydration of glucose and the formation of humins. ChemSusChem 4(8):1166–1173
Cheng BG, Wang XH, Lin QX, Zhang X, Meng L, Sun RC, Xin FX, Ren JL (2018) New understandings of the relationship and initial formation mechanism for pseudo-lignin, humins, and acid-induced hydrothermal carbon. J Agric Food Chem 66(45):11981–11989
Sumerskii IV, Krutov SM, Zarubin MY (2010) Humin-like substances formed under the conditions of industrial hydrolysis of wood. Russ J Appl Chem 83(2):320–327
Patil SKR, Lund CRF (2011) Formation and growth of humins via aldol addition and condensation during acid-catalyzed conversion of 5-hydroxymethylfurfural. EnergyFuel 25(10):4745–4755
Patil SKR, Heltzel J, Lund CRF (2012) Comparison of structural features of humins formed catalytically from glucose, fructose, and 5-hydroxymethylfurfuraldehyde. Energy Fuel 26(8):5281–5293
Krystof M, Perez-Sanchez M, De Maria PD (2013) Lipase-catalyzed (trans)esterification of 5-hydroxymethylfurfural and separation from HMF esters using deep-eutectic solvents. ChemSusChem 6(4):630–634
Shi N, Liu QY, Wang TJ, Zhang Q, Tu JL, Ma LL (2014) Conversion of cellulose to 5-hydroxymethylfurfural in water-tetrahydrofuran and byproducts identification. Chin J Chem Phys 27(6):711–717
Wang H, Wang Y, Deng T, Chen C, Zhu Y, Hou X (2015) Carbocatalyst in biorefinery: selective etherification of 5-hydroxymethylfurfural to 5,5’(oxy-bis(methylene))bis-2-furfural over graphene oxide. Catal Commun 59:127–130
Horvat J, Klaic B, Metelko B, Sunjic V (1985) Mechanism of levulinic acid formation. Tetrahedron Lett 26(17):2111–2114
Akien GR, Qi L, Horvath IT (2012) Molecular mapping of the acid catalysed dehydration of fructose. Chem Commun 48(47):5850–5852
Yong G, Zhang YG, Ying JY (2008) Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose. Angew Chem Int Ed 47(48):9345–9348
Zhao HB, Holladay JE, Brown H, Zhang ZC (2007) Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science 316(5831):1597–1600
Tsilomelekis G, Orella MJ, Lin Z, Cheng Z, Zheng W, Nikolakis V, Vlachos DG (2016) Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins. Green Chem 18(7):1983–1993
Tolborg S, Meier S, Sadaba I, Elliot SG, Kristensen SK, Saravanamurugan S, Riisager A, Fristrup P, Skrydstrup T, Taarning E (2016) Tin-containing silicates: identification of a glycolytic pathway via 3-deoxyglucosone. Green Chem 18(11):3360–3369
Chen HS, Wang A, Sorek H, Lewis JD, Roman-Leshkov Y, Bell AT (2016) Production of hydroxyl-rich acids from xylose and glucose using Sn-BEA zeolite. Chemistryselect 1(14):4167–4172
Elliot SG, Andersen C, Tolborg S, Meier S, Sádaba I, Daugaard AE, Taarning E (2017) Synthesis of a novel polyester building block from pentoses by tin-containing silicates. RSC Adv 7(2):985–996
Sølvhøj A, Taarning E, Madsen R (2016) Methyl vinyl glycolate as a diverse platform molecule. Green Chem 18(20):5448–5455
Holm MS, Saravanamurugan S, Taarning E (2010) Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts. Science 328(5978):602–605
Holm MS, Pagán-Torres YJ, Saravanamurugan S, Riisager A, Dumesic JA, Taarning E (2012) Sn-Beta catalysed conversion of hemicellulosic sugars. Green Chem 14:702
Dusselier M, Van Wouwe P, De Clippel F, Dijkmans J, Gammon DW, Sels BF (2013) Mechanistic insight into the conversion of tetrose sugars to novel α-hydroxy acid platform molecules. Chemcatchem 5(2):569–575
Dusselier M, De Clercq R, Cornelis R, Sels BF (2017) Tin triflate-catalyzed conversion of cellulose to valuable (alpha-hydroxy-)esters. Catal Today 279:339–344
Clercq RD, Dusselier M, Christiaens C, Dijkmans J, Iacobescu RI, Pontikes Y, Sels BF (2015) Confinement effects in Lewis acid-catalyzed sugar conversion: steering toward functional polyester building blocks. ACS Catal 5(10):5803–5811
Nikolla E, Roman-Leshkov Y, Moliner M, Davis ME (2011) “One-pot” synthesis of 5-(hydroxymethyl)furfural from carbohydrates using tin-Beta zeolite. ACS Catal 1(4):408–410
Roman-Leshkov Y, Chheda JN, Dumesic JA (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312(5782):1933–1937
Herzfeld J, Rand D, Matsuki Y, Daviso E, Mak-Jurkauskas M, Mamajanov I (2011) Molecular structure of humin and melanoidin via solid state NMR. J Phys Chem B 115(19):5741–5745
Wondrak GT, Tressl R (1997) Maillard reaction of free and nucleic acid-bound 2-deoxy-D-ribose and D-ribose with ö-amino acids. J Agric Food Chem 45:321–327
Hu X, Li CZ (2011) Levulinic esters from the acid-catalysed reactions of sugars and alcohols as part of a bio-refinery. Green Chem 13(7):1676–1679
Hu X, Lievens C, Larcher A, Li CZ (2011) Reaction pathways of glucose during esterification: effects of reaction parameters on the formation of humin type polymers. Bioresour Technol 102(21):10104–10113
Huang YB, Yang T, Lin YT, Zhu YZ, Li LC, Pan H (2018) Facile and high-yield synthesis of methyl levulinate from cellulose. Green Chem 20:1323–1334
Funding
This research received support from the Guizhou province science and technology plan project ([2017]5789-08), the National Natural Science Foundation of China (51576199), and the Natural Science Foundation of Guangdong Province (2017A030308010).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 8197 kb)
Rights and permissions
About this article
Cite this article
Shi, N., Liu, Q., Cen, H. et al. Formation of humins during degradation of carbohydrates and furfural derivatives in various solvents. Biomass Conv. Bioref. 10, 277–287 (2020). https://doi.org/10.1007/s13399-019-00414-4
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13399-019-00414-4