• Energy Research

Although lignin is one of the most abundant renewable organic materials in the world, it is principally a waste product of the paper industry which is used for the production of heat and power. Hydrothermal lignin depolymerisation aids in facilitating the valorization of lignin in aqueous solutions or suspensions. For the recovery of valuable phenolic products from lignin it is crucial to understand the main reaction pathways of lignin degradation and the reaction kinetics. Batch experiments were carried out for studying the depolymerisation of an enzymatic hydrolysis lignin from spruce wood in near critical water. Phenolic products were extracted from the aqueous phase and quantified via gas chromatography. The main reaction products were grouped (lumped), the main reaction pathways of hydrothermal lignin depolymerisation were discovered and formal kinetic rate coefficients were determined. Optimization of these formal kinetic parameters yielded a satisfying approximation of the experimental yields of phenolic products and describes the most important tendencies over temperature and residence time of solid residue and gas. The model is validated by the comparison with other kinetic studies of the degradation of lignin as well as the decomposition of intermediate phenolics, such as catechols and methoxyphenols.

Abstract The removal of nitrogen (N) and sulphur (S) from biocrude oil produced using hydrothermal liquefaction (HTL), is important for the production of high quality renewable fuels. Here the effect of co-liquefaction of bagasse and algae was analysed. Algae (Chlorella vulgaris and Cyanobacteria) were mixed with bagasse (1:1) subjected to HTL at 250–350 °C for 10–60 min. Higher HTL temperatures had a positive effect in increasing the biocrude yield and slightly reduced N content; S did not show a consistent trend. Most of the nitrogen (~66%) and sulphur (~80%) were recovered in the aqueous phase rather than in the biocrude phase, opening the opportunity to recycle these nutrients for algae cultivation. Co-liquefying bagasse with algae improved the biocrude yield (54 wt%) compared to pure Cyanobacteria (47.5 wt%). It also reduced N content from 7 wt% (Cyanobacteria biocrude) to 4.2 wt% (Cyanobacteria: Bagasse) and S from 0.7 wt% to 0.4 wt%. Principal Component Analysis (PCA) analysis identified that biocrude yield is positively correlated with the initial lipid content and anti-correlated with the carbohydrates fraction. Biocrude N content is closely related to the initial amount of proteins in the algae. The Preference Ranking Organization METHod for Enrichment of Evaluations and its descriptive complement Geometrical Analysis for Interactive Aid (PROMETHEE and GAIA) analysis ranked the co-liquefaction of Chlorella vulgaris and bagasse (1:1) at 350 °C and 60 min as one of the best overall combination in terms of biocrude yield, N and S content.

Hydrothermal liquefaction (HTL) can be considered a promising route for the energy valorisation of waste sewage sludge (SS). However, not much information is available on continuous flow processing. In this study, the mixed SS was subjected to HTL at 350°C for 8 min in a continuous reactor with loadings of 10 wt% in the feed flow. The results show that the mass recovery reached 88%, with a biocrude yield of 30.8 wt% (3.9 wt% N content). The recovered biocrude yields are highly dependent on the selection of the recovery solvent for extraction, and dichloromethane can contribute an additional 3.1 wt% biocrude from aqueous phase, acetone can extract some pyrrole derivatives into the trapped phases. Comparable results were also achieved by performing batch reactions under the same conditions: a slightly higher biocrude yield (33.1 wt%) with an N content of 4.3 wt%. The higher N content observed in the biocrude from the batch process indicates that interactions and chelation between intermediates are enhanced during heating up and cooling period, which lead to more N-containing compounds.

The interest in third generation biofuels from microalgae has been rising during the past years. Meanwhile, it seems not economically feasible to grow algae just for biofuels. Co-products with a higher value should be produced by extracting a particular algae fraction to improve the economics of an algae biorefinery. The present study aims at analyzing the influence of two main microalgae components (lipids and proteins) on the composition and quantity of biocrude oil obtained via hydrothermal liquefaction of two strains (Nannochloropsis gaditana and Scenedesmus almeriensis). The algae were liquefied as raw biomass, after extracting lipids and after extracting proteins in microautoclave experiments at different temperatures (300-375°C) for 5 and 15min. The results indicate that extracting the proteins from the microalgae prior to HTL may be interesting to improve the economics of the process while at the same time reducing the nitrogen content of the biocrude oil.

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, 1H 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.

In this study, the fate of nitrogen during catalytic hydrothermal liquefaction (HTL) of sewage sludge (SS) is investigated using three different catalysts (CuNi/SiO$_2$, HCOOH, CuSO$_4$) with 5 wt% loading. The bio-crude yields obtained from HTL experiments catalyzed with CuNi/SiO$_2$ are similar to those obtained through non-catalyzed experiments. HCOOH slightly increases the bio-crude yields, while maximum yields of 24.5 wt% is obtained in the presence of CuSO$_4$, which also reduces the nitrogen content by 15 % and enhances the hydrocarbons compared to the non-catalyzed HTL. Mechanistic investigations regarding the interaction of amino acids and carbohydrates by Maillard reactions are carried out using model compounds, namely lysine and lactose. CuSO$_4$ effectively increases the yield with 50 % and reduces the nitrogen content by 24 % in the bio-crude during HTL of lysine alone. In the case of the model mixtures, bio-crude yields, nitrogen content, and Maillard reactions products behaved similarly both for catalytic and non-catalytic HTL, a slight reduction of amines was found in the presence of CuSO$_4$. Hydro-char and some organic compounds are assumed to act highly reductant during catalytic HTL. Coke deposition and adsorbed poisoning by Maillard reaction products are proposed as the main reasons for the deactivation of catalysts.

Abstract Hydrothermal liquefaction (HTL) biocrude is a promising source of energy with potential for co-processing with conventional fuels or as a drop-in fuel. However, it needs upgrading to reduce heteroatoms (e.g., N, S, O), improve physical properties, stability, and miscibility with hydrocarbons. Distillation is a conventional physical upgrading method that has not been studied extensively for biocrude using an industry-accepted procedure on a large scale. In this study, an algae-based biocrude was distilled into four fractions using ASTM D2892 standard method: Fraction 1 (