Dichloromethane (DCM) is a solvent commonly used in laboratories for microalgae hydrothermal liquefaction (HTL) product separation. The addition of DCM would lead to an "overestimation effect" of biocrude yield and diminish biocrude quality. However, it is currently not clear to what extent this overestimation effect will impact a continuous HTL process. In this study, Chlorella vulgaris microalgae was processed in a continuous stirred tank reactor at different temperatures (300, 325, 350, 375, and 400 °C) at 24 MPa for 15 min holding time. Two separation methods were applied to investigate the effect of using DCM in a cHTL product separation procedure in terms of product yield, biocrude elemental content, and aqueous product (AP) composition. Subsequently, the feasibility of reusing AP for algae cultivation has been evaluated. Results suggest that 350 °C is the optimal temperature for cHTL operation, leading to the highest biocrude yield, and an average increase in biocrude yield of 9 wt % was achieved when using DCM in cHTL product separation. Within the temperature range investigated, an average biocrude yield estimation can be proposed by yield non-DCM ≈ 0.818 × yield DCM . The AP has been characterized by total organic carbon and total nitrogen, high-performance liquid chromatography, and inductively coupled plasma optical emission spectroscopy. Results show that at 350−375 °C more nitrogen and other ions were directed into the AP, which could be advantageous in nutrient recovery. With the help of optical density testing, algae was shown to exhibit a better growth using AP with activated carbon absorption purification treatment as compared to the standard medium. The recovery of water and nutrients from the HTL-AP could improve the economics of a microalgae biorefinery process.
In the past decade, microalgae biomass has been attracting considerable interest in valuable biocomponents and biofuel production. Meanwhile, plastic waste handling has become one of the most pressing global environmental concerns. Coprocessing of plastic waste and biomass has previously been reported to produce good quality fuel oil and high-value chemicals. In this study, we examined a coliquefaction process (co-HTL) of 2 microalgae, Chlorella vulgaris (Cv) and Nannochloropsis gaditana (Ng), with nine types of common plastics. In a first step, the co-HTL process was conducted in microautoclave reactors with a fixed algae/plastic mass ratio (50:50) at a temperature of 350 °C and a pressure of 16 MPa for a holding time of 15 min. Among the different types of plastics, positive synergistic effects between polycarbonate (PC), polystyrene (PS), and microalgae have been observed: (1) Plastics showed greater decomposition. (2) HTL crude oil yields were increased. Ng algae exhibits a higher interaction ability with plastics. Then, PC and PS were coprocessed with Ng algae using the response surface methodology to optimize the effects of temperature (300−400 °C), algae/plastic mass ratio (20:80−80:20), and holding time (5−45 min) on HTL crude oil yield. Software-based data analysis of the co-HTL experiments were conducted, and the optimal parameters were proposed, which were verified by the experiment results; Ng+PC (20:80 wt %) exhibits the highest crude oil yield of 67.2% at 300 °C with a 5 min holding time, while Ng+PS (80:20 wt %) generates 51.4 wt % crude oil yield at 400 °C and a 25 min holding time. Finally, the analytical results of elemental analysis, FTIR, 1 H NMR, GPC, GC-MS, and TGA on the crude oil produced from pure microalgae HTL and co-HTL were compared, indicating that Ng+PC crude oil is more suitable for aromatic chemicals production and Ng+PS crude oil could be more favorable for biofuel applications.
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