Microwave-assisted catalyst-free hydrolysis of fibrous cellulose for deriving sugars and biochemicals

Abstract

Microwave (MW) assisted catalyst-free hydrolysis of fibrous cellulose (FC, cellulolysis) at 200°C promoted a cellulose conversion of ca . 37.2% and quantitative production of valuable C5/C6 sugars (e.g ., glucose) and the according platform biochemicals (e.g ., 5-hydroxymethylfurfural), corresponding to an overall selectivity of 96.5%. Conversely, conventional hydrothermal cellulolysis under similar conditions was not effective, even after 24 h, carbonising the FC. Based on the systematic study of MW-assisted cellulolysis, the specific interaction between water molecules and macroscopic FC under the MW irradiation was proposed, accounting for the interpretation of the experimental observation. The kinetic energy of water molecules under the MW irradiation facilitated the C–C (in the non-hindered surface –CH ₂OH groups) and C–O–C bond breaking (inside the cellulose cavities) in FC, producing primary cellulolysis products of xylose, glucose and cellobiose.

Graphical abstract

Keywords

microwave / fibrous cellulose / hydrolysis / sugars / mechanism

References

[1] Jérôme F, Chatel G, Vigier K D O. Depolymerization of cellulose to processable glucans by non-thermal technologies. Green Chemistry, 2016, 18(14): 3903–3913

[2] Hamelinck C N, Van Hooijdonk G, Faaij A P. Ethanol from lignocellulosic biomass: Techno-economic performance in short-, middle-and long-term. Biomass and Bioenergy, 2005, 28(4): 384–410

[3] Chimentão R J, Lorente E, Gispert-Guirado F, Medina F, López F. Hydrolysis of dilute acid-pretreated cellulose under mild hydrothermal conditions. Carbohydrate Polymers, 2014, 111: 116–124

[4] Zhou L, Yang X, Xu J, Shi M, Wang F, Chen C, Xu J. Depolymerization of cellulose to glucose by oxidation-hydrolysis. Green Chemistry, 2015, 17(3): 1519–1524

[5] Sun B, Duan L, Peng G, Li X, Xu A. Efficient production of glucose by microwave-assisted acid hydrolysis of cellulose hydrogel. Bioresource Technology, 2015, 192: 253–256

[6] Mission E G, Quitain A T, Sasaki M, Kida T. Synergizing graphene oxide with microwave irradiation for efficient cellulose depolymerization into glucose. Green Chemistry, 2017, 19(16): 3831–3843

[7] Sweygers N, Alewaters N, Dewil R, Appels L. Microwave effects in the dilute acid hydrolysis of cellulose to 5-hydroxymethylfurfural. Scientific Reports, 2018, 8(1): 7719

[8] Wu Y, Fu Z, Yin D, Xu Q, Liu F, Lu C, Mao L. Microwave-assisted hydrolysis of crystalline cellulose catalyzed by biomass char sulfonic acids. Green Chemistry, 2010, 12(4): 696–700

[9] Mok W S, Antal M J Jr, Varhegyi G. Productive and parasitic pathways in dilute acid-catalyzed hydrolysis of cellulose. Industrial & Engineering Chemistry Research, 1992, 31(1): 94–100

[10] Chakraborty S, Singh P K, Paramashetti P. Microreactor-based mixing strategy suppresses product inhibition to enhance sugar yields in enzymatic hydrolysis for cellulosic biofuel production. Bioresource Technology, 2017, 237(suppl C): 99–107

[11] Dutta S, Wu K C W. Enzymatic breakdown of biomass: Enzyme active sites, immobilization, and biofuel production. Green Chemistry, 2014, 16(11): 4615–4626

[12] Wang J, Xi J, Wang Y. Recent advances in the catalytic production of glucose from lignocellulosic biomass. Green Chemistry, 2015, 17(2): 737–751

[13] Fan J, De Bruyn M, Budarin V L, Gronnow M J, Shuttleworth P S, Breeden S, Macquarrie D J, Clark J H. Direct microwave-assisted hydrothermal depolymerization of cellulose. Journal of the American Chemical Society, 2013, 135(32): 11728–11731

[14] Li H, Li J, Fan X, Li X, Gao X. Insights into the synergetic effect for co-pyrolysis of oil sands and biomass using microwave irradiation. Fuel, 2019, 239: 219–229

[15] Li H, Shi P, Fan X, Gao X. Understanding the influence of microwave on the relative volatility used in the pyrolysis of Indonesia oil sands. Chinese Journal of Chemical Engineering, 2018, 26(7): 1485–1492

[16] Ou X, Xu S, Warnett J M, Holmes S M, Zaheer A, Garforth A A, Williams M A, Jiao J, Fan X. Creating hierarchies promptly: Microwave-accelerated synthesis of ZSM-5 zeolites on macrocellular silicon carbide (SiC) foams. Chemical Engineering Journal, 2017, 312: 1–9

[17] Budarin V L, Clark J H, Lanigan B A, Shuttleworth P, Macquarrie D J. Microwave assisted decomposition of cellulose: A new thermochemical route for biomass exploitation. Bioresource Technology, 2010, 101(10): 3776–3779

[18] Benoit M, Rodrigues A, Zhang Q, Fourré E, De Oliveira Vigier K, Tatibouët J M, Jérôme F. Depolymerization of cellulose assisted by a nonthermal atmospheric plasma. Angewandte Chemie International Edition, 2011, 50(38): 8964–8967

[19] Zhang Z, Zhao Z K. Solid acid and microwave-assisted hydrolysis of cellulose in ionic liquid. Carbohydrate Research, 2009, 344(15): 2069–2072

[20] Ma H Y, Zhao Z P, Lu P. Cellulose hydrolysis by acidic Ionic liquids enhanced with microwave heating. Advanced Materials Research, 2018, 1145(8): 75–79

[21] Nasution H. Yurnaliza, Veronicha, Irmadani, Sitompul S. Preparation and characterization of cellulose microcrystalline (MCC) from fiber of empty fruit bunch palm oil. In: IOP Conference Series: Materials Science and Engineering, 1st Annual Applied Science and Engineering Conference. Bandung: IOP Publishing, 2017, 180: 012007

[22] Ciolacu D, Ciolacu F, Popa V I. Amorphous cellulose-structure and characterization. Cellulose Chemistry and Technology, 2011, 45(1–2): 13–21

[23] Kappe C O. Unraveling the mysteries of microwave chemistry using silicon carbide reactor technology. Accounts of Chemical Research, 2013, 46(7): 1579–1587

[24] Gabriel C, Gabriel S, Grant E H, Grant E H, Halstead B S J, Michael P, Mingos D. Dielectric parameters relevant to microwave dielectric heating. Chemical Society Reviews, 1998, 27(3): 213–224

[25] Kappe C O, Stadler A, Dallinger D. Microwaves in Organic and Medicinal Chemistry. Weinheim: John Wiley & Sons, 2012

[26] Xiouras C, Radacsi N, Sturm G, Stefanidis G D. Furfural synthesis from D-xylose in the presence of sodium chloride: Microwave versus conventional heating. ChemSusChem, 2016, 9(16): 2159–2166

[27] Cao F, Schwartz T J, McClelland D J, Krishna S H, Dumesic J A, Huber G W. Dehydration of cellulose to levoglucosenone using polar aprotic solvents. Energy & Environmental Science, 2015, 8(6): 1808–1815