A multi-component reaction kinetics model for the hydrothermal liquefaction of carbohydrates and co-liquefaction to produce 5-ethoxymethyl furfural

Chacón-Parra, Andrés; Lewis, David M.; Glasius, Marianne; Eyk, Philip J. van

doi:10.1016/j.fuel.2021.122499

Cited by 5 publications

(8 citation statements)

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“…The gaseous product yields were calculated by the weight difference between the precharged nitrogen and the total mass of gases released after the reaction was completed and cooled down. ,, Solid- and liquid-phase products were collected by pouring and pushing the reactor content into separation tubes, centrifuged at 3500 rpm for 10 min to separate solid, aqueous, and crude phases; then, 1 mL of the aqueous phase was pipetted and filtered (0.22 μm cellulose acetate) into a 2 mL chromatography vial for analysis. Two aqueous samples (50 μL each) were taken and diluted 200 and 1000 times in 10 and 50 mL volumetric flasks, respectively, for colorimetric nitrogen tests and nonpurgeable organic carbon (NPOC) as total organic carbon (TOC).…”

Section: Methodsmentioning

confidence: 99%

“…The mass spectrometer (5977B MSD) was scanned from m / z 40–500. The compounds were tentatively identified using the NIST14 Spectral Library database using the ChemStation MS data analysis module (Agilent software). , …”

Section: Methodsmentioning

confidence: 99%

“…The compounds were tentatively identified using the NIST14 Spectral Library database using the ChemStation MS data analysis module (Agilent software). 12,34 Elemental analysis (EA) of HTL renewable biocrude was conducted using a PerkinElmer 2400 Series II Elemental Analyzer in the CHN configuration. The analysis was carried out with a sample weight of 4 ± 1 mg (AD 6000 ultramicrobalance) combusted at 925 °C.…”

Section: Design Of Experiments and The Reactor Systemmentioning

confidence: 99%

“…Using TGA as one-to-one fuel oil contrasting based on boiling point distribution might not be a correct indicator of renewable crude quality due to thermal decomposition. 12,58 However, the relevance of the hydrocarbon breaking/ fractionation via a reduction in boiling point should be further investigated with more specific analytical methods. 54,58−60 Another commonly used thermochemical analysis of biocrude is elemental composition (CHN/CHNS).…”

Section: Bulk Product Phase Yields and The Primarymentioning

confidence: 99%

“…Proteins and carbohydrates are two of the major components of all biological organisms and represent a significant portion of biomass and biowaste. , Rich protein biomass such as soy protein produces on average a 25% mass yield of water-insoluble biocrude and around 60% nitrogen recovery in the aqueous phase. ,− The HTL conversion of carbohydrates generates high solid yields and acidic aqueous phases with relatively high concentrations of 5-hydroxymethyl furfural (HMF) and levulinic acid (LA) among other water-soluble intermediates. ,,,,− The Maillard interaction between carbohydrate and protein intermediates might boost the renewable biocrude yields. ,− , Despite the Maillard reaction pathway being well known in the food industry, it is scarcely understood throughout the thermochemical conversion of biomass and its impact on current kinetic models is negligible. ,− …”

Section: Introductionmentioning

confidence: 99%

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Elucidating the Maillard Reaction Mechanism in the Hydrothermal Liquefaction of Binary Model Compound Mixtures and Spirulina

Chacón-Parra

Hall

Lewis

et al. 2022

ACS Sustainable Chem. Eng.

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Hydrothermal liquefaction (HTL) transforms wet biomass and biowaste feedstock into water-insoluble biocrude and valuable water-soluble organic products. HTL takes advantage of the exceptional properties of water near the critical point to break bio-macromolecule linkages, and as a reaction medium, subcritical water ions allow the reaction and recondensation of intermediates into various structures and product phases. Among the different reaction mechanisms involved in the hydrothermal conversion, the synergetic interaction between protein and carbohydrate intermediates, known as the Maillard reactions, can boost the renewable biocrude yield up to 25% higher than solely free fatty acid hydrolysis from lipids. However, the reaction mechanisms and the effect of biomass composition are not fully understood. In this study, the Maillard reactions have been investigated with a central composite design to validate the impact of mass ratio (carbohydrate/protein) over temperature and residence time, via product response analysis, including product yields, boiling point distribution, aqueous tests, elemental, and chemical compositions. Then, the gas chromatography−mass spectrometry data is used to propose a potential pathway, followed by levulinic acid from carbohydrates as a candidate, to produce proline via Maillard interactions before amino acid condensation into piperazinediones and reduction into pyrazines among other complex degradations. The understanding of Maillard interactions under HTL conditions could lead to more robust compositional models, and the present results showed that a protein-to-carbohydrate mass ratio 2:1 would maximize the volatile fraction, elemental carbon, and higher heating value in the renewable crude, with a 90−95% of the maximum crude yield being obtained. The HTL experiments were run with glucose and soy protein as model compounds and spirulina in a batch reactor at 300 °C temperature, 20 min residence time, and 50% mass ratio as a central point, with an alpha (α) of 20 °C, at 10 min, and a 25% mass ratio.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Design Of Experiments and The Reactor Systemmentioning

confidence: 99%

Section: Bulk Product Phase Yields and The Primarymentioning

confidence: 99%