Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej; Nikolakis, Vladimiros; Vlachos, Dionisios G.

doi:10.1039/c5gc01257k

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

Journal Article · Sat Jul 25 00:00:00 UTC 2015 · Green Chemistry

DOI:https://doi.org/10.1039/c5gc01257k· OSTI ID:1370906

Swift, T. Dallas ^[1]; Nguyen, Hannah ^[1]; Anderko, Andrzej ^[2]; Nikolakis, Vladimiros ^[1]; Vlachos, Dionisios G. ^[1]

Univ. of Delaware, Newark, DE (United States)
OLI Systems Inc., Cedar Knolls, NJ (United States)

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl₃–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl₃ concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl₃ concentration. This is attributed to the interactions between HCl and CrCl₃ speciation in solution that leads to HMF yield being maximized at moderate HCl concentrations for each CrCl₃ concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001004

OSTI ID:: 1370906

Journal Information:: Green Chemistry, Journal Name: Green Chemistry Journal Issue: 10 Vol. 17; ISSN 1463-9262

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Aromatics from Lignocellulosic Biomass: Economic Analysis of the Production of p-Xylene from 5-Hydroxymethylfurfural Lin, Zhaojia; Ierapetritou, Marianthi; Nikolakis, Vladimiros AIChE Journal, Vol. 59, Issue 6 https://doi.org/10.1002/aic.13969	journal	February 2013
Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water Román-Leshkov, Yuriy; Moliner, Manuel; Labinger, Jay A. Angewandte Chemie International Edition, Vol. 49, Issue 47, p. 8954-8957 https://doi.org/10.1002/anie.201004689	journal	October 2010
The Role of Salts and Brønsted Acids in Lewis Acid-Catalyzed Aqueous-Phase Glucose Dehydration to 5-Hydroxymethylfurfural Wrigstedt, Pauli; Keskiväli, Juha; Leskelä, Markku ChemCatChem, Vol. 7, Issue 3 https://doi.org/10.1002/cctc.201402941	journal	December 2014
Reactivity of Metal Catalysts in Glucose-Fructose Conversion Loerbroks, Claudia; van Rijn, Jeaphianne; Ruby, Marc-Philipp Chemistry - A European Journal, Vol. 20, Issue 38 https://doi.org/10.1002/chem.201402437	journal	August 2014
Kinetics and Reaction Engineering of Levulinic Acid Production from Aqueous Glucose Solutions Weingarten, Ronen; Cho, Joungmo; Xing, Rong ChemSusChem, Vol. 5, Issue 7 https://doi.org/10.1002/cssc.201100717	journal	June 2012
Integrated Chemo-Enzymatic Production of 5-Hydroxymethylfurfural from Glucose Simeonov, Svilen P.; Coelho, Jaime A. S.; Afonso, Carlos A. M. ChemSusChem, Vol. 6, Issue 6 https://doi.org/10.1002/cssc.201300176	journal	April 2013
Dehydration of Different Ketoses and Aldoses to 5-Hydroxymethylfurfural van Putten, Robert-Jan; Soetedjo, Jenny N. M.; Pidko, Evgeny A. ChemSusChem, Vol. 6, Issue 9 https://doi.org/10.1002/cssc.201300345	journal	August 2013
Efficient Solid Acid Catalyst Containing Lewis and Brønsted Acid Sites for the Production of Furfurals Mazzotta, Michael G.; Gupta, Dinesh; Saha, Basudeb ChemSusChem, Vol. 7, Issue 8 https://doi.org/10.1002/cssc.201402007	journal	May 2014
Mechanism of Brønsted Acid-Catalyzed Glucose Dehydration Yang, Liu; Tsilomelekis, George; Caratzoulas, Stavros ChemSusChem, Vol. 8, Issue 8 https://doi.org/10.1002/cssc.201403264	journal	January 2015
Current Technologies, Economics, and Perspectives for 2,5-Dimethylfuran Production from Biomass-Derived Intermediates Saha, Basudeb; Abu-Omar, Mahdi M. ChemSusChem, Vol. 8, Issue 7 https://doi.org/10.1002/cssc.201403329	journal	February 2015
The Catalytic Conversion of d-Glucose to 5-Hydroxymethylfurfural in DMSO Using Metal Salts Rasrendra, C. B.; Soetedjo, J. N. M.; Makertihartha, I. G. B. N. Topics in Catalysis, Vol. 55, Issue 7-10 https://doi.org/10.1007/s11244-012-9826-y	journal	June 2012
Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C Shock, Everett L.; Helgeson, Harold C. Geochimica et Cosmochimica Acta, Vol. 52, Issue 8 https://doi.org/10.1016/0016-7037(88)90181-0	journal	August 1988
Revised pourbaix diagrams for chromium at 25–300 °C Beverskog, B.; Puigdomenech, I. Corrosion Science, Vol. 39, Issue 1 https://doi.org/10.1016/S0010-938X(97)89244-X	journal	January 1997
Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes Shock, Everett L.; Sassani, David C.; Willis, Marc Geochimica et Cosmochimica Acta, Vol. 61, Issue 5 https://doi.org/10.1016/S0016-7037(96)00339-0	journal	March 1997
A speciation-based model for mixed-solvent electrolyte systems Wang, Peiming; Anderko, Andrzej; Young, Robert D. Fluid Phase Equilibria, Vol. 203, Issue 1-2 https://doi.org/10.1016/S0378-3812(02)00178-4	journal	December 2002
Dealuminated Beta zeolite as effective bifunctional catalyst for direct transformation of glucose to 5-hydroxymethylfurfural Otomo, Ryoichi; Yokoi, Toshiyuki; Kondo, Junko N. Applied Catalysis A: General, Vol. 470 https://doi.org/10.1016/j.apcata.2013.11.012	journal	January 2014
Reaction media dominated product selectivity in the isomerization of glucose by chromium trichloride: From aqueous to non-aqueous systems Jia, Songyan; Liu, Kairui; Xu, Zhanwei Catalysis Today, Vol. 234 https://doi.org/10.1016/j.cattod.2014.02.038	journal	October 2014
On the kinetics of the isomerization of glucose to fructose using Sn-Beta Rajabbeigi, Nafiseh; Torres, Ana I.; Lew, Christopher M. Chemical Engineering Science, Vol. 116 https://doi.org/10.1016/j.ces.2014.04.031	journal	September 2014
Chemicals from biomass: Etherification of 5-hydroxymethyl-2-furfural (HMF) into 5,5′(oxy-bis(methylene))bis-2-furfural (OBMF) with solid catalysts Casanova, O.; Iborra, S.; Corma, A. Journal of Catalysis, Vol. 275, Issue 2 https://doi.org/10.1016/j.jcat.2010.08.002	journal	October 2010
Conversion of glucose into levulinic acid with solid metal(IV) phosphate catalysts Weingarten, Ronen; Kim, Yong Tae; Tompsett, Geoffrey A. Journal of Catalysis, Vol. 304 https://doi.org/10.1016/j.jcat.2013.03.023	journal	August 2013
Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources van Putten, Robert-Jan; van der Waal, Jan C.; de Jong, Ed Chemical Reviews, Vol. 113, Issue 3 https://doi.org/10.1021/cr300182k	journal	February 2013
“One-Pot” Synthesis of 5-(Hydroxymethyl)furfural from Carbohydrates using Tin-Beta Zeolite Nikolla, Eranda; Román-Leshkov, Yuriy; Moliner, Manuel ACS Catalysis, Vol. 1, Issue 4, p. 408-410 https://doi.org/10.1021/cs2000544	journal	April 2011
Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p -Xylene Williams, C. Luke; Chang, Chun-Chih; Do, Phuong ACS Catalysis, Vol. 2, Issue 6 https://doi.org/10.1021/cs300011a	journal	April 2012
Production of 5-Hydroxymethylfurfural from Glucose Using a Combination of Lewis and Brønsted Acid Catalysts in Water in a Biphasic Reactor with an Alkylphenol Solvent Pagán-Torres, Yomaira J.; Wang, Tianfu; Gallo, Jean Marcel R. ACS Catalysis, Vol. 2, Issue 6, p. 930-934 https://doi.org/10.1021/cs300192z	journal	April 2012
Framework and Extraframework Tin Sites in Zeolite Beta React Glucose Differently Bermejo-Deval, Ricardo; Gounder, Rajamani; Davis, Mark E. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300474x	journal	November 2012
Kinetics of Homogeneous Brønsted Acid Catalyzed Fructose Dehydration and 5-Hydroxymethyl Furfural Rehydration: A Combined Experimental and Computational Study Swift, T. Dallas; Bagia, Christina; Choudhary, Vinit ACS Catalysis, Vol. 4, Issue 1 https://doi.org/10.1021/cs4009495	journal	December 2013
Correction to Kinetics of Homogeneous Brønsted Acid Catalyzed Fructose Dehydration and 5-Hydroxymethyl Furfural Rehydration: A Combined Experimental and Computational Study Swift, T. Dallas; Bagia, Christina; Choudhary, Vinit ACS Catalysis, Vol. 4, Issue 5 https://doi.org/10.1021/cs500313w	journal	April 2014
Active Sites in Sn-Beta for Glucose Isomerization to Fructose and Epimerization to Mannose Bermejo-Deval, Ricardo; Orazov, Marat; Gounder, Rajamani ACS Catalysis, Vol. 4, Issue 7, p. 2288-2297 https://doi.org/10.1021/cs500466j	journal	May 2014
Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels–Alder Products Patet, Ryan E.; Nikbin, Nima; Williams, C. Luke ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/cs5020783	journal	March 2015
Chromium(III) hydrolysis constants and solubility of chromium(III) hydroxide Rai, Dhanpat; Sass, Bruce M.; Moore, Dean A. Inorganic Chemistry, Vol. 26, Issue 3 https://doi.org/10.1021/ic00250a002	journal	February 1987
Life Cycle Assessment of Biobased p -Xylene Production Lin, Zhaojia; Nikolakis, Vladimiros; Ierapetritou, Marianthi Industrial & Engineering Chemistry Research, Vol. 54, Issue 8 https://doi.org/10.1021/ie5037287	journal	February 2015
Insights into the Interplay of Lewis and Brønsted Acid Catalysts in Glucose and Fructose Conversion to 5-(Hydroxymethyl)furfural and Levulinic Acid in Aqueous Media Choudhary, Vinit; Mushrif, Samir H.; Ho, Christopher Journal of the American Chemical Society, Vol. 135, Issue 10 https://doi.org/10.1021/ja3122763	journal	March 2013
Challenges of and Insights into Acid-Catalyzed Transformations of Sugars Caratzoulas, Stavros; Davis, Mark E.; Gorte, Raymond J. The Journal of Physical Chemistry C, Vol. 118, Issue 40 https://doi.org/10.1021/jp504358d	journal	August 2014
Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates Román-Leshkov, Yuriy; Barrett, Christopher J.; Liu, Zhen Y. Nature, Vol. 447, Issue 7147, p. 982-985 https://doi.org/10.1038/nature05923	journal	June 2007
Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents Saha, Basudeb; Abu-Omar, Mahdi M. Green Chem., Vol. 16, Issue 1 https://doi.org/10.1039/C3GC41324A	journal	January 2014
Insights into the Cr( iii ) catalyzed isomerization mechanism of glucose to fructose in the presence of water using ab initio molecular dynamics Mushrif, Samir H.; Varghese, Jithin J.; Vlachos, Dionisios G. Phys. Chem. Chem. Phys., Vol. 16, Issue 36 https://doi.org/10.1039/C4CP02095B	journal	January 2014
Solvation dynamics and energetics of intramolecular hydride transfer reactions in biomass conversion Mushrif, Samir H.; Varghese, Jithin J.; Krishnamurthy, Chethana B. Physical Chemistry Chemical Physics, Vol. 17, Issue 7 https://doi.org/10.1039/C4CP05063K	journal	January 2015
Catalytic conversion of biomass using solvents derived from lignin Azadi, Pooya; Carrasquillo-Flores, Ronald; Pagán-Torres, Yomaira J. Green Chemistry, Vol. 14, Issue 6 https://doi.org/10.1039/c2gc35203f	journal	January 2012
Industrial use of immobilized enzymes DiCosimo, Robert; McAuliffe, Joseph; Poulose, Ayrookaran J. Chemical Society Reviews, Vol. 42, Issue 15 https://doi.org/10.1039/c3cs35506c	journal	January 2013
Thermodynamics of Enzyme‐Catalyzed Reactions: Part 5. Isomerases and Ligases Goldberg, Robert N.; Tewari, Yadu B. Journal of Physical and Chemical Reference Data, Vol. 24, Issue 6 https://doi.org/10.1063/1.555970	journal	November 1995
Summary of the Apparent Standard Partial Molal Gibbs Free Energies of Formation of Aqueous Species, Minerals, and Gases at Pressures 1 to 5000 Bars and Temperatures 25 to 1000 °C Oelkers, Eric H.; Helgeson, Harold C.; Shock, Everett L. Journal of Physical and Chemical Reference Data, Vol. 24, Issue 4 https://doi.org/10.1063/1.555976	journal	July 1995
Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water Moliner, M.; Roman-Leshkov, Y.; Davis, M. E. Proceedings of the National Academy of Sciences, Vol. 107, Issue 14, p. 6164-6168 https://doi.org/10.1073/pnas.1002358107	journal	March 2010
Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites Bermejo-Deval, R.; Assary, R. S.; Nikolla, E. Proceedings of the National Academy of Sciences, Vol. 109, Issue 25 https://doi.org/10.1073/pnas.1206708109	journal	June 2012
Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose Roman-Leshkov, Yuriy; Chheda, Juben N.; Dumesic, James A. Science, Vol. 312, Issue 5782, p. 1933-1937 https://doi.org/10.1126/science.1126337	journal	June 2006
Green Chemicals Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J. Chemical Engineering Research and Design, Vol. 84, Issue 5 https://doi.org/10.1205/cherd05038	journal	May 2006
Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin Holladay, John E.; White, James F.; Bozell, Joseph J. https://doi.org/10.2172/921839	report	October 2007
Thermodynamic properties of aqueous species and the solubilities of minerals at high pressures and temperatures; the system Al 2 O 3 -H 2 O-NaCl Pokrovskii, V. A.; Helgeson, H. C. American Journal of Science, Vol. 295, Issue 10 https://doi.org/10.2475/ajs.295.10.1255	journal	December 1995

Cited By (14)

Conversion of carbohydrates into 5-hydroxymethylfurfural in a green reaction system of CO ₂ -water-isopropanol Lin, Haizhou; Xiong, Qingang; Zhao, Yuan AIChE Journal, Vol. 63, Issue 1 https://doi.org/10.1002/aic.15550	journal	November 2016
Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors Hommes, Arne; Heeres, Hero Jan; Yue, Jun ChemCatChem, Vol. 11, Issue 19 https://doi.org/10.1002/cctc.201900807	journal	August 2019
Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts Cheng, Ziwei; Saha, Basudeb; Vlachos, Dionisios G. ChemSusChem, Vol. 11, Issue 20 https://doi.org/10.1002/cssc.201801535	journal	September 2018
Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts Cheng, Ziwei; Saha, Basudeb; Vlachos, Dionisios G. ChemSusChem, Vol. 11, Issue 20 https://doi.org/10.1002/cssc.201802326	journal	September 2018
Solvent Effects on Degradative Condensation Side Reactions of Fructose in Its Initial Conversion to 5‐Hydroxymethylfurfural Fu, Xing; Hu, Yexin; Zhang, Yanru ChemSusChem, Vol. 13, Issue 3 https://doi.org/10.1002/cssc.201902309	journal	October 2019
Solvent Effects on Degradative Condensation Side Reactions of Fructose in Its Initial Conversion to 5‐Hydroxymethylfurfural Fu, Xing; Hu, Yexin; Zhang, Yanru ChemSusChem, Vol. 13, Issue 3 https://doi.org/10.1002/cssc.201903479	journal	January 2020
High yield conversion of cellulosic biomass into 5-hydroxymethylfurfural and a study of the reaction kinetics of cellulose to HMF conversion in a biphasic system Atanda, Luqman; Konarova, Muxina; Ma, Qing Catalysis Science & Technology, Vol. 6, Issue 16 https://doi.org/10.1039/c6cy00820h	journal	January 2016
Pt catalysts for efficient aerobic oxidation of glucose to glucaric acid in water Lee, Jechan; Saha, Basudeb; Vlachos, Dionisios G. Green Chemistry, Vol. 18, Issue 13 https://doi.org/10.1039/c6gc00460a	journal	January 2016
Sulfonated polyaniline as a solid organocatalyst for dehydration of fructose into 5-hydroxymethylfurfural Dai, Jinhang; Zhu, Liangfang; Tang, Dianyong Green Chemistry, Vol. 19, Issue 8 https://doi.org/10.1039/c6gc03604j	journal	January 2017
Structural analysis of humins formed in the Brønsted acid catalyzed dehydration of fructose Cheng, Ziwei; Everhart, Jeffrey L.; Tsilomelekis, George Green Chemistry, Vol. 20, Issue 5 https://doi.org/10.1039/c7gc03054a	journal	January 2018
Propylene carbonate and γ-valerolactone as green solvents enhance Sn( iv )-catalysed hydroxymethylfurfural (HMF) production from bread waste Yu, Iris K. M.; Tsang, Daniel C. W.; Yip, Alex C. K. Green Chemistry, Vol. 20, Issue 9 https://doi.org/10.1039/c8gc00358k	journal	January 2018
Direct speciation methods to quantify catalytically active species of AlCl ₃ in glucose isomerization Norton, Angela M.; Nguyen, Hannah; Xiao, Nicholas L. RSC Advances, Vol. 8, Issue 31 https://doi.org/10.1039/c8ra03088j	journal	January 2018
Ultrafast flow chemistry for the acid-catalyzed conversion of fructose Desir, Pierre; Saha, Basudeb; Vlachos, Dionisios G. Energy & Environmental Science, Vol. 12, Issue 8 https://doi.org/10.1039/c9ee01189g	journal	January 2019
Replacement of Chromium by Non-Toxic Metals in Lewis-Acid MOFs: Assessment of Stability as Glucose Conversion Catalysts Pertiwi, Ralentri; Oozeerally, Ryan; Burnett, David L. Catalysts, Vol. 9, Issue 5 https://doi.org/10.3390/catal9050437	journal	May 2019

Similar Records

Cooperative Brønsted-Lewis acid sites created by phosphotungstic acid encapsulated metal–organic frameworks for selective glucose conversion to 5-hydroxymethylfurfural

Journal Article · Fri Nov 12 00:00:00 UTC 2021 · Fuel · OSTI ID:1958749

Alcohol fermentation of sweet potato - 1. Acid hydrolysis and factors involved

Journal Article · Wed Apr 01 04:00:00 UTC 1981 · Biotechnol. Bioeng.; (United States) · OSTI ID:5167434

Alcohol fermentation of sweet potato. 1. Acid hydrolysis and factors involved

Journal Article · Wed Apr 01 04:00:00 UTC 1981 · Biotechnol. Bioeng.; (United States) · OSTI ID:5392692

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bio-inspired
biofuels (including algae and biomass)
catalysis (heterogeneous)
catalysis (homogeneous)
hydrogen and fuel cells
materials and chemistry by design
synthesis (novel materials)
synthesis (scalable processing)
synthesis (self-assembly)

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

Citation Formats

References (47)

Cited By (14)

Similar Records

Related Subjects