Thermodynamic Model for Hydrogen Production from Rice Straw Supercritical Water Gasification.

Supercritical water gasification (SCWG) technology is highly promising for its ability to cleanly and efficiently convert biomass to hydrogen. This paper developed a model for the gasification of rice straw in supercritical water (SCW) to predict the direction and limit of the reaction based on the Gibbs free energy minimization principle. The equilibrium distribution of rice straw gasification products was analyzed under a wide range of parameters including temperatures of 400-1200 °C, pressures of 20-50 MPa, and rice straw concentrations of 5-40 wt%. Coke may not be produced due to the excellent properties of supercritical water under thermodynamic constraints. Higher temperatures, lower pressures, and biomass concentrations facilitated the movement of the chemical equilibrium towards hydrogen production. The hydrogen yield was 47.17 mol/kg at a temperature of 650 °C, a pressure of 25 MPa, and a rice straw concentration of 5 wt%. Meanwhile, there is an absorptive process in the rice straw SCWG process for high-calorific value hydrogen production. Energy self-sufficiency of the SCWG process can be maintained by adding small amounts of oxygen (ER < 0.2). This work would be of great value in guiding rice straw SCWG experiments.

Prediction of Individual Gas Yields of Supercritical Water Gasification of Lignocellulosic Biomass by Machine Learning Models.

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.

Mechanistic insights and catalytic enhancement of phenolic wastewater supercritical water gasification: A combined experiment and density functional theory study.

Supercritical water gasification technology provides a favorable technology to achieve pollution elimination and resource utilization of phenolic wastewater. In this study, the reaction mechanism of phenolic wastewater supercritical water gasification was investigated using a combination of experimental and computational methods. Five reaction channels were identified to elucidate the underlying pathway of phenol decomposition. Importantly, the rate-determining step was found to be the dearomatization reaction. By integrating computational and experimental analyses, it was found that phenol decomposition via the path with the lowest energy barrier generates cyclopentadiene, featuring a dearomatization barrier of 70.97 kcal/mol. Additionally, supercritical water plays a catalytic role in the dearomatization process by facilitating proton transfer. Based on the obtained reaction pathway, alkali salts (Na2CO3 and K2CO3) are employed as a catalyst to diminish the energy barrier of the rate-determining step to 40.00 kcal/mol and 37.14 kcal/mol. Alkali salts catalysis significantly improved carbon conversion and pollutant removal from phenolic wastewater, increasing CGE from 58.44% to 93.55% and COD removal efficiency from 94.11% to 99.79%. Overall, this study provides a comprehensive understanding of the decomposition mechanism of phenolic wastewater in supercritical water.

Catalytic Supercritical Water Gasification of Canola Straw with Promoted and Supported Nickel-Based Catalysts.

Lignocellulosic biomass such as canola straw is produced as low-value residue from the canola processing industry. Its high cellulose and hemicellulose content makes it a suitable candidate for the production of hydrogen via supercritical water gasification. However, supercritical water gasification of lignocellulosic biomass such as canola straw suffers from low hydrogen yield, hydrogen selectivity, and conversion efficiencies. Cost-effective and sustainable catalysts with high catalytic activity for supercritical water gasification are increasingly becoming a focal point of interest. In this research study, novel wet-impregnated nickel-based catalysts supported on carbon-negative hydrochar obtained from hydrothermal liquefaction (HTL-HC) and hydrothermal carbonization (HTC-HC) of canola straw, along with other nickel-supported catalysts such as Ni/Al2O3, Ni/ZrO2, Ni/CNT, and Ni/AC, were synthesized for gasification of canola straw on previously optimized reaction conditions of 500 °C, 60 min, 10 wt%, and 23-25 MPa. The order of hydrogen yield for the six supports was (10.5 mmol/g) Ni/ZrO2 > (9.9 mmol/g) Ni/Al2O3 > (9.1 mmol/g) Ni/HTL-HC > (8.8 mmol/g) Ni/HTC-HC > (7.7 mmol/g) Ni/AC > (6.8 mmol/g) Ni/CNT, compared to 8.1 mmol/g for the non-catalytic run. The most suitable Ni/ZrO2 catalyst was further modified using promotors such as K, Zn, and Ce, and the performance of the promoted Ni/ZrO2 catalysts was evaluated. Ni-Ce/ZrO2 showed the highest hydrogen yield of 12.9 mmol/g, followed by 12.0 mmol/g for Ni-Zn/ZrO2 and 11.6 mmol/g for Ni-K/ZrO2. The most suitable Ni-Ce/ZrO2 catalysts also demonstrated high stability over their repeated use. The superior performance of the Ni-Ce/ZrO2 was due to its high nickel dispersion, resilience to sintering, high thermal stability, and oxygen storage capabilities to minimize coke deposition.

Hydrogen-rich gas production via supercritical water gasification (SCWG) of oily sludge over waste tire-derived activated carbon impregnated with Ni: Characterization and optimization of activated carbon production.

In this study, the production of activated carbon (AC) through the chemical activation of waste tire (WT) using H3PO4 and KOH for H2 production by SCWG of oily sludge (OS) donated by Persian Gulf Star Oil Company was investigated. H3PO4 was the best activating agent based on some pretests results, and then the synthesis of AC was optimized using Response Surface Methodology. Based on BET surface area of synthesized ACs, thirty combinations of the four variables namely; activation temperature (350-550 °C); activation time (1-4 h); H3PO4 to WT ratio (1-3 w.w-1); and H3PO4 concentration (20-40 wt%) were optimized. CHNS, TGA, FE-SEM, and EDS-mapping analyses were used to characterize the AC and catalyst synthesized in optimum condition (activation temperature: 450 °C; activation time: 2.5 h; H3PO4 to WT ratio: 2 w.w-1; and H3PO4 concentration: 40 wt%), which presented a surface area of 170 m2 g-1. Finally, Ni was impregnated on the optimized AC with different loadings (5-15 wt%) to evaluate its performance in H2 production by SCWG of OS. Although H2 yield in catalytic experiments was higher than that observed in non-catalytic experiment, results showed that the maximum H2 selectivity was 66% in SCWG of OS using AC impregnated with 10 wt% Ni.

Directional transformation and migration pathways of nitrogen during pig manure supercritical water gasification.

Nitrogen is a valuable nutrient element in pig manure. This work focuses on investigating the distribution, directional transformation, and migration pathways to facilitate the recovery of nitrogen from supercritical water gasification products. Results indicated that no nitrogen-containing gas was detected and 12.65 % of nitrogen remained in solid products. 82.49 % of nitrogen migrated into liquid products, which are predominated by ammonia. Catalysts were employed to promote the conversion of solid nitrogen to liquid nitrogen and organic nitrogen to ammonia. Finally, 85 % of nitrogen is enriched into liquid products and ammonia predominated the liquid nitrogen. The percentage of ammonia increased to 97.51 % at 620 °C in the presence of potassium carbonate. The migration pathways indicated that nitrogen was transformed into ammonia by various intermediates such as indole. The rest of the nitrogen remained in solid products with stable quaternary-nitrogen. These findings provide valuable insights into nitrogen management and recovery.

An experimental and thermodynamic equilibrium investigation of heavy metals transformation in supercritical water gasification of oily sludge.

Supercritical water gasification (SCWG) is an advanced and highly efficient method for treating oily sludge. However, it is crucial to consider the transformation characteristics of heavy metals (HMs) during the SCWG process to prevent potential secondary pollution. This work studied the transformation and distribution characteristics of Cu, Cr and Zn after SCWG of oily sludge in a batch reactor at temperatures ranging from 550 to 700 °C. Additionally, thermodynamic equilibrium analysis was conducted to assess the distribution of HMs based on the minimization of Gibbs free energy. Experimental results indicated that higher temperatures led to the conversion of HMs into more stable forms, effectively immobilizing them within solid products. Furthermore, the addition of Na2CO3 enhanced this process and contributed to a reduction in HMs pollution in the effluent. Thermodynamic equilibrium results were consistent with our experimental data, indicating that the molar fraction of stable HMs forms followed the order: Cr > Cu > Zn. Besides, it is worth noting that Na2CO3 had a limited impact on the distribution of Cu and Cr. However, it played a significant role in inhibiting the formation of silicate Zn at lower temperatures, promoting the decomposition of ZnO*Al2O3 into unstable Zn. This may explain the higher presence of unstable Zn when Na2CO3 was introduced. In summary, this study offers valuable insights into the transformation characteristics of heavy metals and strategies for pollution control during SCWG of oily sludge.

Experimental study on supercritical water gasification of oily sludge using a continuous two-step method.

Supercritical water gasification (SCWG) technology can convert oily sludge into hydrogen-rich gas. To achieve high gasification efficiency of oily sludge with a high oil concentration under mild conditions, a two-step method involving a desorption process and a catalytic gasification process using Raney-Ni catalyst was investigated. High oil removal efficiency (99.57%) and carbon gasification efficiency (93.87%) were achieved. The lowest wastewater total organic carbon, oil content, and carbon content in the solid residues were 4.88 ppm, 0.08% and 0.88%, respectively, using a gasification temperature of 600 °C, treatment concentration of 1.11 wt%, gasification time of 70.7 s, and the optimal desorption temperature of 390 °C. The main organic carbon component in the solid residues was cellulose, which is environmentally safe. As the treatment concentration increased, the two-step method outperformed the single-step method. The mechanism for the two-step SCWG of oily sludge was revealed. In the first step, supercritical water is used in the desorption unit to achieve a high oil removal efficiency with few liquid products generated. In the second step, the Raney-Ni catalyst promotes efficient gasification of high-concentration oil at a low temperature. This research provides valuable insights into the effective SCWG of oily sludge at a low temperature.

Evolution of phosphorus with the promotion of KOH in supercritical water gasification of dewatered cyanobacteria from ion perspective.

Phosphorus is a very important resource, and dewatered cyanobacteria contains a large amount of it. Basic additives, such as KOH, are often used to promote hydrogen production during supercritical water gasification (SCWG) of biomass, but their effects phosphorus transformation have rarely been investigated. In this study, SCWG of dewatered cyanobacteria with potassium salt and KOH was conducted in autoclave at 400 °C for 10 min, to investigate the effect of K+ on the transformation of phosphorus under neutral and alkaline conditions. Results showed that K+ increased the proportion of phosphorus in the solid phase from 88.4% to 90.8-98.3%. Furthermore, K+ could promote the transformation of iron-combined phosphorus to calcium-combined phosphorus and occluded phosphate. Only when the reaction environment was alkaline, the proportion of phosphorus in the solid phase was significantly reduced to a minimum of 26.1%. When the amount of OH- was sufficient, can this part of phosphorus and organic phosphorus, which was decomposed and transformed by the promotion of OH-, be transferred to the liquid products. Results from this study laid a foundation simultaneously for hydrogen production and phosphorus recovery more environmentally and high-effectively.

Technological advancements in valorisation of industrial effluents employing hydrothermal liquefaction of biomass: Strategic innovations, barriers and perspectives.

Hydrothermal liquefaction (HTL) is identified as a promising thermochemical technique to recover biofuels and bioenergy from waste biomass containing low energy and high moisture content. The wastewater generated during the HTL process (HTWW) are rich in nutrients and organics. The release of the nutrients and organics enriched HTWW would not only contaminate the water bodies but also lead to the loss of valued bioenergy sources, especially in the present time of the energy crisis. Thus, biotechnological as well as physicochemical treatment of HTWW for simultaneous extraction of valuable resources along with reduction in polluting substances has gained significant attention in recent times. Therefore, the treatment of wastewater generated during the HTL of biomass for reduced environmental emission and possible bioenergy recovery is highlighted in this paper. Various technologies for treatment and valorisation of HTWW are reviewed, including anaerobic digestion, microbial fuel cells (MFC), microbial electrolysis cell (MEC), and supercritical water gasification (SCWG). This review paper illustrates that the characteristics of biomass play a pivotal role in the selection process of appropriate technology for the treatment of HTWW. Several HTWW treatment technologies are weighed in terms of their benefits and drawbacks and are thoroughly examined. The integration of these technologies is also discussed. Overall, this study suggests that integrating different methods, techno-economic analysis, and nutrient recovery approaches would be advantageous to researchers in finding way for maximising HTWW valorisation along with reduced environmental pollution.

Experimental study on alkali catalytic gasification of oily sludge in supercritical water with a continuous reactor.

Realizing the harmless resource utilization of oily sludge is urgent for petroleum industry and of great significance for environmental management. The treatment of oily sludge was investigated using supercritical water gasification (SCWG) with a continuous fluidized bed reactor. The effect of operating parameters on gasification efficiency and gas yield without catalyst was tested, and then the influences of catalyst type (K2CO3 and Na2CO3) and concentrations (1-8 wt%) were systematically studied. The results indicated that a medium mass flow ratio and low feedstock concentration were beneficial for gas production. Alkali catalyst improved carbon gasification efficiency (CE) prominently, and Na2CO3 showed better performance due to its better stability. A maximum CE of 95.87% was achieved when 5 wt% Na2CO3 was added at 650 °C, 23 MPa with 5 wt% oily sludge concentration. Besides, according to XRD patterns of solid residues, Na2CO3 was more stable than K2CO3 during SCWG. SEM-EDX results also revealed that more K was migrated into solid residues than Na. The analysis of pore structure demonstrated that alkali catalyst promoted the evolution of pore structure, resulting in higher specific surface areas and total pore volumes. Na2CO3 has a more substantial destructive effect on solid matrix, causing the matrix structure to collapse and inhibiting pore structure development. The FTIR spectra of solid products exhibited a lower content of carbohydrates and aromatic structures than the initial oily sludge. NH4-N results demonstrated that SCWG was a potential green treatment process for oily sludge. This work can not only give an insight into the reaction mechanism of alkali catalytic gasification of oily sludge, but also help to guide the optimal design of reactor and the regulation of operating parameters.

Characteristics and mechanisms of nitrogen transformation during chicken manure gasification in supercritical water.

Supercritical water gasification (SCWG) is a clean and efficient method for the energy utilization of biomass waste. Studying the behavior of nitrogen in feedstock during the SCWG process is essential because of its significant potential impact on the environment. In this study, the characteristics and mechanisms of nitrogen transformation during chicken manure gasification in supercritical water were investigated in autoclave reactors. The results revealed that temperature plays an important role in raw material conversion and product distribution, especially for nitrogenous components. In particular, the carbon gasification efficiency was 92.66 % at 700 °C, 10 wt%, and K2CO3 as catalysts, implying that the chicken manure was nearly completely converted. NOx was not identified in the gaseous products. As the temperature increased, nitrogen in the raw material was mainly transferred to the liquid. This process is accompanied by the conversion of organic nitrogen to inorganic nitrogen, which is mainly present as NH3-N in liquids. Finally, the migration pathways of nitrogenous intermediates were investigated. The hydrolysis of proteins and amino acids in the initial phases creates conditions for the Maillard reaction, forming nitrogenous heterocyclic compounds (NHCs). Most NHCs gradually ring-opened and eventually converted to CO2, H2, NH3, and other gases. Only a small number of NHCs undergo a series of polymerization reactions at lower temperatures to form nitrogenous carbon precursors that are challenging to gasify. This study provides a theoretical foundation for the targeted removal of nitrogen components during the SCWG of high-nitrogenous biomass.

Supercritical water gasification of hyperaccumulators for hydrogen production and heavy metal immobilization with alkali metal catalysts.

The high moisture content and heavy metal concentration of hyperaccumulator are the main bottlenecks of resource utilization. Supercritical water gasification technology was used to convert Sedum plumbizincicola (a hyperaccumulator of Zn and Cd) into hydrogen gas and to immobilize HMs into biochar. Homogeneous alkali metal catalysts such as NaOH, Na2CO3 and Ca(OH)2 were added to optimize the experimental conditions. The results showed that NaOH was effective in capturing CO2in-situ, thereby shifting the water-gas shift reaction equilibrium in the forward direction. And the increase of NaOH concentration had a significant promotion effect on hydrogen production. In the non-catalytic gasification of Sedum plumbizincicola, the highest hydrogen (1.5 mol/kg) and H2 selectivity (22.9%) with greater carbon gasification efficiency (19.3%) and lower H2 gasification efficiency (8.7%) of the gas products were obtained at 400 °C with 6 wt% material concentration for 20 min. However, NaOH at 5% mass fraction maximized hydrogen and H2 selectivity up to 7.5 and 98.2%, respectively. Alkali catalyst not only promoted the generation of hydrogen-rich bio-gas but also enhanced the immobilization efficiency of heavy metals. Compared to non-catalytic, when the addition amount of NaOH was 1 wt%, the Zn、Mn、Cd、Pb、Cr accumulated in biochar increased significantly for 76.8, 42.5, 80.8, 75.6 and 80.0%, respectively. This study highlights the remarkable ability of SCWG with alkali catalyst for hydrogen production and heavy metal stabilization.

Influence of reaction parameters on the fate of nitrogen during the supercritical water gasification of dewatered sewage sludge.

This study investigated the effects of different parameters on the fate of nitrogen (N) in products after supercritical water gasification (SCWG) of dewatered sewage sludge (DSS). N distribution and morphology were most affected by temperature, followed by reaction time and heating rate, while reaction pressure had little effect on them. In terms of specific performance, higher temperature, longer reaction time, and slower heating rate were beneficial to the increase of NH4+-N content in the liquid phase. Compared with raw sludge, after SCWG, the solid phase contained more inorganic-N and less protein-N, a certain proportion of quaternary-N and nitrile-N. The proportion of N-containing compounds in the biocrude phase was between 0.26%-20.34%, suggesting the importance of more research on N in the biocrude phase. The recovery rate of N in all samples was between 64.34%-93.82%. The major proportion of N (42.27%-60.91%) was transformed into the liquid phase, while the remaining entered the solid phase (10.54%-21.45%) and the biocrude phase (6.18%-15.78%). These findings are helpful to better understand the principle of N distribution in products of DSS after SCWG and provide some new ideas for reducing N-containing by-product formation in the future.

Assessment of black liquor hydrothermal treatment under sub- and supercritical conditions: Products distribution and economic perspectives.

This study reports an alternative method for black liquor treatment with potential for energy and process savings in the paper and pulp industry. Gasification of black liquor was carried out under sub- and supercritical conditions, varying the black liquor feed composition (0.10, 2.55 and 5.00 wb%) and temperature (350, 425 and 500 °C). Liquid products were identified by high resolution mass spectrometry (FT-Orbitrap MS) and compounds belonging to classes O3 and O4 were found to be the most representative in the products of reactions performed at 500 °C. The mass spectra results also revealed the overall selectivity of reactions, where decarboxylation and demethoxylation reactions were favored under subcritical and supercritical conditions, respectively. Among the gaseous products, hydrogen and methane were produced with maximum of 69.04 and 28.75 mol%, respectively, at 2.55 wb% and 425 °C. The proposed thermodynamic modelling of the reaction system satisfactorily predicted the gas phase behavior of the system. In the economic analysis, the simulated conditions indicated that the main energy requirements for a scaled-up black liquor gasification process are related to the necessary heat exchangers and pressurizing of the black liquor solution. Furthermore, the cost of the black liquor gasification is around 0.06 US$ per kg of feed stream. Liquid and gaseous products from gasification could be obtained at a cost of 56.64 US$ and 3.35 US$ per tonne of stream, respectively. Therefore, black liquor gasification is an interesting route for obtaining combustible gases and value-added bioproducts.

Effect of alkali additives on desulfurization of syngas during supercritical water gasification of sewage sludge.

Amount of H2S and SO2 were generated during the SCWG of sewage sludge. It is essential to reduce the sulfur concentration in syngas for depth utilization of syngas from SCWG of sewage sludge. The syngas desulfurization ability of five additives (KOH, K2CO3, NaOH, Na2CO3, AC) were tested and the result indicated that K2CO3 had the best syngas desulfurization effect while KOH could significantly promote the yield of syngas at 450 °C and 4% loading. Increasing KOH and K2CO3 loading to 12% could reduce around 90% of sulfur in syngas comparing to no additives. The XPS analysis results indicated that alkali additives promoted the cyclization and oxidation of unstable sulfur compounds in raw sludge, which can convert it into stable sulfur compounds such as thiophene, sulfone and sulfate. The sulfur in liquid was mainly in the forms of sulfate, and the effect of alkali and AC additive on sulfur in liquid was relatively weak.

Microplastic degradation as a sustainable concurrent approach for producing biofuel and obliterating hazardous environmental effects: A state-of-the-art review.

As plastics have been omnipresent in society ever since their introduction in 1907, global plastic production has ballooned in the 20th century or the Plasticene Era (Plastic Age). After their useful life span, they deliberately or accidentally, are disposed of in the environment. Influenced by different factors, plastics undergo fragmentation into microplastics (MPs) and present hazardous risks in all life forms including humans. Obliterating MPs from the environment has been a global challenge for the attainment of sustainable development goals (SDGs). This review aims to present MP degradation routes with a great focus on the thermodegradation and biodegradation routes as sustainable routes of MP degradation. These routes can achieve the reduction and obliteration of MPs in the environment, thus reducing their hazardous effects. Moreover, the thermodegradation of MPs can produce fuels that help solve the dilemma of energy security. Overall, continued research and development are still needed, however, these novel approaches and the increased awareness of the microplastics' hazards give us hope that we can achieve sustainable development in the near future.

Experimental investigation on gasification of cationic ion exchange resin used in nuclear power plants by supercritical water.

Spent ion exchange resins produced by nuclear power plants are radioactive organic waste. Until now, there is no satisfactory industrial treatment. Supercritical water gasification (SCWG) of cationic ion exchange resin (CIER) used in nuclear power plants was carried out in a batch reactor in this study. Results showed that the gasification efficiency increased with the growth of temperature (550-750 °C), addition of alkali homogeneous catalyst (K2CO3), proper ratio loading of catalyst to CIER (1:1), decrease of feed concentration (2-10 wt%) and extension of residence time (10-60 min). Carbon gasification efficiency was up to 97.98% with K2CO3 added and 30 min at 750 °C in the batch reactor. The gaseous products mainly consist of H2, CO, CO2 and CH4. The GC-MS analysis showed that the organic component in liquid products was mainly composed of benzene, monocycle arenes, phenol group and polycyclic aromatic hydrocarbons. Based on the experimental results, the formation and gasification pathways of CIER in SCW were proposed.

Supercritical water gasification (SCWG) as a potential tool for the valorization of phycoremediation-derived waste algal biomass for biofuel generation.

Phycoremediation is an emerging technology, where algae-based processes were used to effectively remove nutrients, organic wastes, and toxic heavy metals from the polluted environment. The waste algal biomass obtained after phycoremediation, which may contain residual hazardous materials, could still be used as feedstock to produce biofuels/bioenergy preferably through thermochemical conversion technology. This review proposes a synergistic approach by utilizing the phycoremediation-derived algal biomass (PCDA) as feedstock for efficient hazardous waste treatment and clean energy generation via supercritical water gasification (SCWG). The review provides an in-depth study of catalytic, non-catalytic, and continuous SCWG of algal biomass, aiming to lay out the foundations for future study. In addition, the concepts of heat integration as well as water, nutrient, and CO2 recycling were introduced for a sustainable algae-to-biofuel process, which significantly enhances the overall energy and material efficiency of SCWG. The production of biofuel from algal biomass via other advanced gasification technologies, such as integration with other thermochemical conversion techniques, co-gasification, chemical looping gasification (CLG), and integrated gasification and combined cycle (IGCC) were also discussed. Furthermore, the discussion of kinetics and thermodynamics models, as well as life cycle and techno-economic assessments, appear to provide insights for future commercial applications.

Char derived from sewage sludge of hydrothermal carbonization and supercritical water gasification: Comparison of the properties of two chars.

Supercritical water gasification (SCWG) is considered a promising technology for sewage sludge (SS) treatment and utilization; however, char produced by a side reaction has become a bottleneck in SCWG. In this study, SS and its model compound (10% humic acid) were treated in an autoclave by SCWG at 400 °C for 30 min and by hydrothermal carbonization (HTC) at 250 °C for 300 min. The char yield was 15.4% in SCWG and 41.3% in HTC. The chars were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller (BET) analysis, and elemental analysis. By comparing the properties the char produced by SCWG and the hydrochar produced by HTC, which has been considered a valuable product, the feasibility of using char as an additional product in SCWG was explored. Compared with the char produced by HTC, the char generated in SCWG exhibits a lower BET specific surface area (8.257 and 15.782 m2/g) and combustion activity, a higher proportion of small pores (with pore sizes of 1-2 nm), and greater thermal stability. The formation pathway of the two types of chars is related to both dehydration and aromatization; decarboxylation also occurs in char formation during SCWG. Humus was proved to be related to char formation during the SCWG of SS based on experimental results obtained with the model compound. This work provides insights needed to guide follow-up treatments or utilization of the char produced during the SCWG of SS.