The purpose of this paper is to give a comprehensive description of the construction and commissioning of a continuous reactor system for hydrothermal liquefaction of biomass. The basis is a newly established facility at Aarhus University. It is capable of handling viscous biomass slurries and features a novel induction-based heating method that facilitates well-defined reaction environments. Carbon balance closure is obtained as all product fractions are recovered and positively quantified. The paper includes a residence time distribution measurement and a 24 h proof-of-concept experiment conducted at 350°C, 250 bar, and 15 min reaction time. It is based on the biomass dried distillers grains with solubles, a waste product of the bioethanol industry. The experiment seeks to determine the steady-state characteristics of the continuous reactor system for use in future experimental studies. It was found that steady state occurs within 6 h. Furthermore, data sampling windows of 2.1 h were found to mask the intrinsic variations of the system while still exposing trends. At steady state, the oil mass yield was found to be 38.9 ± 3.2% and the higher heating value was 35.3 ± 0.28 MJ kg −1 .

Hydrothermal liquefaction is a promising technique for the production of bio-oil. The process produces an oil phase, a gas phase, a solid residue, and an aqueous phase. Gas chromatography coupled with mass spectrometry is used to analyze the complex aqueous phase. Especially small organic acids and nitrogen-containing compounds are of interest. The efficient derivatization reagent methyl chloroformate was used to make analysis of the complex aqueous phase from hydrothermal liquefaction of dried distillers grains with solubles possible. A circumscribed central composite design was used to optimize the responses of both derivatized and nonderivatized analytes, which included small organic acids, pyrazines, phenol, and cyclic ketones. Response surface methodology was used to visualize significant factors and identify optimized derivatization conditions (volumes of methyl chloroformate, NaOH solution, methanol, and pyridine). Twenty-nine analytes of small organic acids, pyrazines, phenol, and cyclic ketones were quantified. An additional three analytes were pseudoquantified with use of standards with similar mass spectra. Calibration curves with high correlation coefficients were obtained, in most cases R (2) > 0.991. Method validation was evaluated with repeatability, and spike recoveries of all 29 analytes were obtained. The 32 analytes were quantified in samples from the commissioning of a continuous flow reactor and in samples from recirculation experiments involving the aqueous phase. The results indicated when the steady-state condition of the flow reactor was obtained and the effects of recirculation. The validated method will be especially useful for investigations of the effect of small organic acids on the hydrothermal liquefaction process.

The effect of the reaction temperature on hydrothermal liquefaction of dried distillers grains with solubles (DDGS) was investigated using a novel stop-flow reactor system at varying temperatures (300−400°C), fixed pressure (250 bar), and fixed reaction time (15 min). The stop-flow reactor provides rapid heating of biomass feeds and the option of performing multiple sequential repetitions. This bypasses long, uncontrollable temperature gradients and unintended changes in the reaction chemistry. The product, a crude bio-oil, was characterized in terms of yield, elemental composition, and chemical composition. Higher reaction temperatures resulted in improved bio-oil yields, less char formation, and higher heating values of the bio-oil. A supercritical reaction temperature of 400°C was found to produce bio-oil in the highest yields and of the best quality.

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The effect of recycling the aqueous phase in a continuous hydrothermal liquefaction process was investigated in terms of product yield distribution, carbon balance, and composition of all main fractions. Using a custom-built continuous reactor system, a long-term experiment was conducted at 350 °C and 250 bar with a feedstock of dried distiller’s grains with solubles. In two consecutive recycle experiments, the aqueous phase of the preceding experiment was used as dispersion medium for the feedstock preparation. In these recycle-experiments a significant increase in biocrude yields was observed with a maximum increase in the first recycle experiment. However, the recycling of the aqueous phase also resulted in lower heating values and higher water contents in the oil fraction. Based on these findings, recycling the aqueous phase is a trade-off between improved yields and reduced burn qualities of the biocrude. That said, recycling also lowers carbon discharge to the aqueous fraction, which may contribute significantly to reducing the environmental footprint of an industrial HTL plant.

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