https://par.nsf.gov/servlets/purl/10172004

Valorization of hydrothermal liquefaction aqueous phase: pathways towards commercial viability

The potential application of bio-oil production from nitrogen-containing biomass via hydrothermal liquefaction (HTL) may be limited due to high nitrogen content, making this product oil unsuitable for fuel-related uses. The Maillard reaction is expected to play a most significant role in the interaction between proteins and carbohydrates during the hydrothermal treatment. To evaluate the Maillard reaction network in this process, lactose, maltose, and lysine were employed as model substances and tested individually and in binary mixtures. HTL experiments were conducted at temperatures between 250 and 350 °C and at 20 min reaction time. When treated individually, conversion of lysine leads to higher bio-oil yields (5–17 wt.%) than the model carbohydrates (6–10 wt.%) during HTL. In mixtures with carbohydrates, the measured bio-oil yields exceeded those obtained from conversion of the single substances (10–39 wt.%). Both yields and the relative nitrogen content of the bio-oil, increase with rising reaction temperature. The composition of the bio-oils obtained through HTL experiments was investigated in more detail: cyclopentenes and furfurals were obtained from disaccharide decomposition, piperidines and quinolines in the bio-oil originate from lysine, pyrazine and its derivatives are obtained from the mixture of lysine and disaccharides. A reaction scheme based on key chemical compounds accompanied with functional groups identified by FT-IR and NMR was developed to provide a better understanding of the Maillard reaction and its impact during HTL of protein-containing biomass.

Hydrothermal liquefaction of protein-containing biomass: study of model compounds for Maillard reactions

Microalgae to biofuels through hydrothermal liquefaction: Open-source techno-economic analysis and life cycle assessment

Hydrothermal liquefaction (HTL) process is a wet-thermochemical conversion technology that was used to convert biomass into bio-crude oil. Commercialization of the HTL technology faces drawbacks due to product stability, by-products generation and working area. In order to overcome these challenges, this review especially focuses on possible pathways to valorise and recover nutrients from post-hydrothermal liquefaction wastewater (PHWW) that was obtained during the HTL process. Numerous studies were reported on bio-oil production from biomasses like algae, forest and agriculture residues, etc at a temperature range of 240–320 °C at time of 30–60 min. Apart from bio-oil, nearly 25 to 50 wt% of aqueous phase was generated, disposal of this aqueous phase is hectic since it comprised of low molecular weight acid compounds. In this study, the composition of PHWW and possible routes (biological and thermochemical pathways) to valorise it were discussed in detail. In addition, recycle and reutilization of PHWW were reviewed with recent findings. From the review, the use of anaerobic digestion as a detoxify step prior to microalgae cultivation resulted in decreasing the fresh water dilution from 20 × to 4 × and improved the energy output from 3.44 to 20.7 kJ g⁻1 COD. This review will provide new insights towards closed circular approach opportunities in thermochemical pathways during sustainable energy production.

Insights into valuing the aqueous phase derived from hydrothermal liquefaction

An economic analysis was conducted for an algae hydrothermal liquefaction (HTL) and biocrude upgrading system with alternative aqueous phase treatment methods. Using experimental data, three different methods were modeled and compared: 1) direct recycle of HTL aqueous phase to the algae farm, 2) catalytic hydrothermal gasification (CHG), and 3) anaerobic digestion (AD). Direct recycle consumes the most natural gas because unlike AD and CHG, no methane is generated from the aqueous phase organics conversion. However, direct recycle has the lowest cost compared to other two cases because it only requires the addition of pumps and buffer tankage related to the aqueous phase recycle. The CHG and AD cases require significant capital and operating costs for aqueous phase treatment, which increase the minimum fuel selling price (MFSP) over the direct recycle case by 11% and 2.9%, respectively. The CHG and AD respectively increase the conversion cost only (excludes the cost to grow, harvest, and dewater algae) by 75% and 21%. Sensitivity analysis suggests that the key factors affecting the total cost of fuel production are the feedstock cost, the biocrude yield, the plant scale, and the method of aqueous phase treatment.

Techno-economic analysis of alternative aqueous phase treatment methods for microalgae hydrothermal liquefaction and biocrude upgrading system

Phosphorus and nitrogen are essential components of microalgal growth media. Critical to a wide range of biochemical processes, they commonly limit primary productivity. Recycling elemental phosphorus and fixed nitrogen after fuel conversion via hydrothermal liquefaction (HTL) of algae biomass reduces the need for mined phosphorus and synthetic nitrogen resources. Scenedesmus obliquus DOE 0152.Z and Chlorella sorokiniana DOE1412 were used as test organisms in assessing nutrient recycle of phosphorus from filtered solids collected downstream of the HTL reactor and nitrogen collected from the aqueous phase after gravimetric biocrude separation. Maximum specific growth rates were measured in growth media using HTL waste as the sole source of either phosphorus or nitrogen and were compared to an algal growth medium control (BG-11). The maximum specific growth rate of both organisms in the recycled phosphorus medium were nearly identical to rates observed in the control medium. Both organisms showed significantly reduced growth rates in the recycled nitrogen medium. C. sorokiniana DOE1412 adapted after several days of exposure whereas S. obliquus DOE0152.Z exhibited poor adaptability to the recycled nitrogen medium. After adaptation, growth rates observed with C. sorokiniana DOE1412 in the recycled nitrogen medium were 3.02 (± 0.13) day − 1 , 89% of the control medium (3.40 ± 0.21). We further tested maximum specific growth rates of C. sorokiniana DOE1412 in a medium derived entirely from HTL byproducts, completely replacing all components including nitrogen and phosphorus. In this medium we observed rates of 2.70 ± 0.05 day − 1 , 79% of the control. Adding trace metals to this recycled medium improved growth rates significantly to 3.10 ± 0.10, 91% of the control, indicating a critical element is lost in the conversion process. Recycling elemental resources such as phosphorus and nitrogen from the HTL biofuel conversion process can provide a significant reduction in media cost and improves the prospects for industrial scale, algae-based biofuels.

Phosphorus and nitrogen recycle following algal bio-crude production via continuous hydrothermal liquefaction

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Phosphorus and nitrogen recycle following algal bio-crude production via continuous hydrothermal liquefaction