Roles of Co-solvents in hydrothermal liquefaction of low-lipid, high-protein algae.

Valorization of algal biomass is often limited by its low lipid content. Here, different alcohols: ethanol, isopropanol, and glycerol, were studied as co-solvents to improve the conversion efficiency of a lipid-poor microalgae, Galdieria sulphuraria, by hydrothermal liquefaction. Bio-crude oil yield increases, from 13 to 73 wt% (on dry algae basis), were attributed to the alcohols facilitating the transfer of algal protein-derived fragments from the aqueous phase into the oil phase. A series of characterization results showed that bio-crude oil formation was mainly the result of alcohols reacting with algal fragments via Maillard reactions, alkylation, and esterification, respectively. Insights into the synergistic effect of low-lipid feed and alcohol provide mechanistic support for choosing an alcohol-rich waste, crude glycerol, to improve bio-crude oil production from HTL of wastewater-grown G. sulphuraria. Promising improvements in yield and energy recovery indicates competitive economics for a low-lipid biomass waste-to-biofuel conversion technique.

Modification of a pilot-scale continuous flow reactor for hydrothermal liquefaction of wet biomass.

A pilot-scale continuous flow reactor (CFR) was modified for hydrothermal liquefaction (HTL) of algae slurry under subcritical conditions to investigate the feasibility of scaling up from batch to continuous processing. Modifications included a novel dual filter system that can remove solids at system pressure and temperature, and undergo in-situ cleaning. Commissioning was carried out to address potential particle settling and clogging problems, and to estimate reactor transport characteristics. CFR performance was evaluated by running 31.4 L algae slurry with solids loadings of 3-5 wt.% under 325-350 °C and 18 MPa for 7 h. C and N elemental yields in HTL aqueous phase reached 39.0 wt.% and 61.8 wt.%, respectively. Future improvements to the CFR system will focus on higher solids loading and addition of in-line HTL liquid upgrading capabilities following the filtration system. •A high-temperature, high-pressure filtration system was designed to remove solids from HTL liquid/gaseous products at near reaction conditions to keep heavy oils in the liquid phase.•Uninterrupted reactor operation was achieved by cycling between the dual filter systems and performing in-situ filter cleaning.•Measured reactor residence time distributions were narrow and close to the calculated theoretical mean time.

Bio-crude oil from hydrothermal liquefaction of wastewater microalgae in a pilot-scale continuous flow reactor.

To explore the feasibility of scaling up hydrothermal liquefaction (HTL) of algal biomass, a pilot-scale continuous flow reactor (CFR) was operated to produce bio-crude oil from algal biomass cultivated in urban wastewater. The CFR system ran algal slurry (5 wt.% solids loading) at 350 °C and 17 MPa for 4 h without any clogging issues. Bio-crude oil chemistry was characterized by high-resolution Fourier transform mass spectroscopy (FT-MS), proton nuclear magnetic resonance spectroscopy (1H NMR), bomb calorimetry, and elemental analysis. Bio-crude oil yield of 28.1 wt% was obtained with higher heating values of 38-39 MJ/kg. The quality of light bio-crude oil produced from the CFR system was comparable in terms of molecular structures to bio-crude oil produced in a batch reactor.

Hydrothermal liquefaction of Galdieria sulphuraria grown on municipal wastewater.

Two strains of Galdieria sulphuraria algae, 5587.1 and SOOS, were grown on municipal wastewater to develop energy-positive treatment systems. Hydrothermal liquefaction (HTL) of 5-10 wt% algal biomass solids was conducted at 310-350 °C for 5-60 min to produce bio-crude oil. HTL product yields and energy recovery were compared to those from previous studies using G. sulphuraria grown on a modified Cyanidium medium. Total bio-crude oil yields were lower (11.2-23.0 wt%) and char yields were higher (22.6-36.4 wt%) for HTL of algae grown on actual wastewater compared with that grown on media (31.4 wt% and 4.8 wt%, respectively), indicating a potential limitation for using yields from media-based studies. High-resolution mass spectroscopy of bio-crude oil provides new insights into differences in composition based on growth media. Energy recovery in total bio-crude oil and char at 350 °C was 17-28% and 14-19%, respectively, for the 5587.1 strain, and 23-27% and 14-25%, respectively, for the SOOS strain.

Laboratory Conversion of Cultivated Oleaginous Organisms into Biocrude for Biofuel Applications.

Hydrothermal liquefaction (HTL) is a thermochemical process for the wet conversion of oleaginous microorganisms and other biomass and carbon rich feedstocks to biofuels under subcritical conditions. It is a novel green process that produces biocrude as a primary product along with other by-products which include gases, aqueous phase coproduct (ACP) and solid residues. Here we describe in detail the protocols for the conversion of biomass to biocrude through HTL and separation, quantification and analyses of HTL products.

Evaluation of three cultivars of sweet sorghum as feedstocks for ethanol production in the Southeast United States.

Sweet sorghum has become a promising alternative feedstock for biofuel production because it can be grown under reduced inputs, responds to stress more efficiently than traditional crops, and has large biomass production potential. A three-year field study was conducted to evaluate three cultivars of sweet sorghum as bioenergy crops in the Southeast United States (Fort Valley, Georgia): Dale, M81 E and Theis. Parameters evaluated were: plant density, stalk height, and diameter, number of nodes, biomass yield, juice yield, °Bx, sugar production, and theoretical ethanol yields. Yields were measured at 85, 99, and 113 days after planting. Plant fresh weight was the highest for Theis (1096 g) and the lowest for Dale (896 g). M81 E reported the highest stalk dry weight (27 Mg ha-1) and Theis reported the lowest (21 Mg ha-1). Theis ranked the highest °Bx (14.9), whereas M81 E was the lowest (13.2). Juice yield was the greatest for M81 E (10915 L ha-1) and the lowest for Dale (6724 L ha-1). Theoretical conservative sugar yield was the greatest for Theis (13 Mg ha-1) and the lowest for Dale (9 Mg ha-1). Theoretical ethanol yield was the greatest for Theis (7619 L ha-1) and the lowest for Dale (5077 L ha-1).

Oleaginous yeast platform for producing biofuels via co-solvent hydrothermal liquefaction.

BACKGROUND: Oleaginous microorganisms are attractive feedstock for production of liquid biofuels. Direct hydrothermal liquefaction (HTL) is an efficient route that converts whole, wet biomass into an energy-dense liquid fuel precursor, called 'biocrude'. HTL represents a promising alternative to conventional lipid extraction methods as it does not require a dry feedstock or additional steps for lipid extraction. However, high operating pressure in HTL can pose challenges in reactor sizing and overall operating costs. Through the use of co-solvents the HTL operating pressure can be reduced. The present study investigates low-temperature co-solvent HTL of oleaginous yeast, Cryptococcus curvatus, using laboratory batch reactors. RESULTS: In this study, we report the co-solvent HTL of microbial yeast biomass in an isopropanol-water binary system in the presence or absence of Na2CO3 catalyst. This novel approach proved to be effective and resulted in significantly higher yield of biocrude (56.4 ± 0.1 %) than that of HTL performed without a co-solvent (49.1 ± 0.4 %)(p = 0.001). Addition of Na2CO3 as a catalyst marginally improved the biocrude yield. The energy content of the resulting biocrude (~37 MJ kg(-1)) was only slightly lower than that of petroleum crude (42 MJ kg(-1)). The HTL process was successful in removing carboxyl groups from fatty acids and creating their associated straight-chain alkanes (C17-C21). Experimental results were leveraged to inform techno-economic analysis (TEA) of the baseline HTL conversion pathway to evaluate the commercial feasibility of this process. TEA results showed a renewable diesel fuel price of $5.09 per gallon, with the HTL-processing step accounting for approximately 23 % of the total cost for the baseline pathway. CONCLUSIONS: This study shows the feasibility of co-solvent HTL of oleaginous yeast biomass in producing an energy-dense biocrude, and hence provides a platform for adding value to the current dairy industry. Co-solvents can be used to lower the HTL temperature and hence the operating pressure. This process results in a higher biocrude yield at a lower HTL temperature. A conceptual yeast HTL biofuel platform suggests the use of a dairy waste stream for increasing the productivity and sustainability of rural areas while providing a new feedstock (yeast) for generating biofuels.

Techno-economic feasibility and life cycle assessment of dairy effluent to renewable diesel via hydrothermal liquefaction.

The economic feasibility and environmental impact is investigated for the conversion of agricultural waste, delactosed whey permeate, through yeast fermentation to a renewable diesel via hydrothermal liquefaction. Process feasibility was demonstrated at laboratory-scale with data leveraged to validate systems models used to perform industrial-scale economic and environmental impact analyses. Results show a minimum fuel selling price of $4.78 per gallon of renewable diesel, a net energy ratio of 0.81, and greenhouse gas emissions of 30.0g-CO2-eqMJ(-1). High production costs and greenhouse gas emissions can be attributed to operational temperatures and durations of both fermentation and hydrothermal liquefaction. However, high lipid yields of the yeast counter these operational demands, resulting in a favorable net energy ratio. Results are presented on the optimization of the process based on economy of scale and a sensitivity analysis highlights improvements in conversion efficiency, yeast biomass productivity and hydrotreating efficiency can dramatically improve commercial feasibility.

Effect of operating conditions of thermochemical liquefaction on biocrude production from Spirulina platensis.

This study investigated the optimum thermochemical liquefaction (TCL) operating conditions for producing biocrude from Spirulina platensis. TCL experiments were performed at various temperatures (200-380°C), holding times (0-120 min), and solids concentrations (10-50%). TCL conversion at 350°C, 60 min holding time and 20% solids concentration produced the highest biocrude yield of 39.9% representing 98.3% carbon conversion efficiency. Light fraction biocrude (B(1)) appeared at 300°C or higher temperatures and represented 50-63% of the total biocrude. Biocrude obtained at 350-380°C had similar fuel properties to that of petroleum crude with energy density of 34.7-39.9 MJ kg(-1) compared to 42.9 MJ kg(-1) for petroleum crude. Biocrude from conversion at 300°C or above had 71-77% elemental carbon, and 0.6-11.6% elemental oxygen and viscosities in the range 40-68 cP. GC/MS of biocrude reported higher hydrocarbons (C(16)-C(17)), phenolics, carboxylic acids, esters, aldehydes, amines, and amides.

Evaluation of microalgae cultivation using recovered aqueous co-product from thermochemical liquefaction of algal biomass.

This study characterized the ACP stream from the TCL of Spirulina and evaluated its potential as a nutrient source for cultivation of microalgae. TCL of 100 g of dry Spirulina resulted in 40% BioOil and 429.80% ACP. The ACP was found to have high nitrogen (16,200 mg L(-1)), phosphorus (795 mg L(-1)), potassium (11,260 mg L(-1)) and secondary and micronutrients. Growth media were prepared using ACP as sole nutrient source in deionized water at 0.2%, 0.33%, 1%, and 10% v/v concentration and compared with a standard growth medium (BG 11) for algal cultivation. Chlorella minutissima was grown in these media for 12 days and monitored for biomass concentration, total chlorophyll and lipids. Biomass productivities with the ACP added media at 0.2% and 0.1% concentration were 0.035 and 0.027 g L(-1) d(-1), respectively, compared to 0.07 g L(-1) d(-1) in BG 11.