Supercritical Water Gasification Research Articles

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.

Hydrogen-rich syngas upgrading via CO2 adsorption by amine-functionalized Cu-BTC: the effect of different amines.

Syngas produced from supercritical water gasification typically contain a high amount of CO2 along with H2. In order to improve the quality of syngas, amine-functionalized copper benzene-1,3,5-tricarboxylate (Cu-BTC) was synthesized as an effective adsorbent for selective removal of CO2 from syngas to increase the concentration of H2. The amines used in this study included monoethanolamine (MEA), ethylenediamine (EDA), and polyethyleneimine (PEI). The fundamental physicochemical character of adsorbents, CO2 adsorption capacity, and CO2/H2 selectivity were analyzed. The physicochemical characterization indicated that the structure of amine-functionalized Cu-BTC was partially damaged, which resulted in a decrease in specific surface area and pore volume. On the other hand, the enlarged pore size was beneficial for the mass transfer of gas in the adsorbent. Among these adsorbents, Cu-BTC/PEI exhibited the maximum CO2 adsorption capacity of 3.83mmol/g and the highest CO2/H2 selectivity of 19.74. It was found that the adsorption pressure is the most significant factor for the CO2 adsorption capacity. Lower temperature and higher pressure were favored for CO2 adsorption capacity and CO2/H2 selectivity, so physical adsorption by Cu-BTC played a dominant role. Moreover, Cu-BTC/PEI can be well-regenerated with stable adsorption efficiency after five consecutive cycles. These findings suggested that Cu-BTC/PEI could be a promising alternative adsorbent for CO2 capture from syngas.

Thermodynamic and environmental analysis of integrated supercritical water gasification of sewage sludge for power and hydrogen production

Supercritical water gasification is a promising process for treating sewage sludge (SS) to obtain hydrogen and electrical energy. Here, a novel thermodynamic equilibrium model for supercritical water gasification of sewage sludge was developed and the thermodynamic and environmental effects of operating parameters on the system were investigated. The sensitivity analysis revealed that the optimum reaction condition for the system was: reaction temperature of 750 °C, preheated water to SS ratio of 1, and SS concentration of 25 %. Under this condition, the system energy efficiency and exergy efficiency were 44.74 % and 46.51 %, respectively, with H2 production of 103.19 kg/h and power generation of 2526.2 kW. The energy and exergy efficiencies could be improved by reducing the preheated water to SS ratio and increasing the reaction temperature and SS concentration. The heat exchangers and the heater were the key units causing exergy losses, accounting for 40.3 % and 19.5 % of the total exergy losses, respectively. When utilizing carbon capture and storage (CCS), the global warming potential (GWP) value was only 0.31 kg CO2-eq under the optimal operating parameters, which was 61.44 % less than without CCS.

Investigating Salt Precipitation in Continuous Supercritical Water Gasification of Biomass

The formation of solid deposits in the process of supercritical water gasification (SCWG) is one of the main problems hindering the commercial application of the process. Seven experiments were conducted with the grass Reed Canary Grass with different preheating temperatures, but all ended early due to the formation of solid deposits (maximum operation of 3.8 h). The position of solid deposits in the lab plant changed with the variation in the temperature profile. Since the formation of solid deposits consisting of salts, coke, and corrosion products is a severe issue that needs to be resolved in order to enable long-time operation, inner temperature measurements were conducted to determine the temperature range that corresponds with the zone of solid formation. The temperature range was found to be 400 to 440 °C. Wherever this temperature was first reached solid deposits occurred in the system that led to blockage of the flow. Additional to the influence of the temperature, the influence of the flow direction (up-flow or down-flow) on the operation of the continuous SCWG plant was examined. If salts are not separated from the system sufficiently, up-flow reactors should be avoided because they amplify the accumulation of solid deposits leading to a shortened operation time. The heating concept coupled with the salt separation needs to be redesigned in order to separate the salts before entering the gasification reactors. Outside of the determined temperature zone no deposition was visible. Thus, even though the gasification efficiency was low it could be shown that the operation was limited to the deposits forming in the heating section and not by incomplete gasification in the reactor where T > 600 °C.

Experiment evaluation and thermodynamic analysis of pulping modification on ordered conversion of bark in supercritical water

Major obstacles of supercritical water gasification (SCWG) of lignocellulosic biomass, including ineffective pulping for energy self-sufficiency and a high conversion barrier significantly inhibited its large-scale development. In this study, the pulping effect of alkaline and salt pulping for high concentration bark slurry were compared systematically. The SCWG performances of bark (non-catalytic/catalytic) and bark slurry were evaluated. Based on energy self-sufficiency, a novel SCWG process of 50 wt% bark slurry was designated with a multistage reactor configuration and pulping process. The findings suggest that alkaline pulping had a wider applicability (reaching 50 wt%) and better rheological properties than salt pulping. Only 30 wt% bark slurry was capable for applying salt pulping because of solid residue with the excessive salt addition. Alkaline pulping resulted in an ordered conversion of 5 wt% and 10 wt% bark slurries during SCWG, with complete gasification of 5 wt% bark slurries prepared by KOH and NaOH at 650 and 680 °C, respectively. Besides, alkaline and salt pulping reduced the 26 % and 33 % carbon emissions, respectively. In the novel process, the optimal ratio of preheated water to bark slurry was 4 (water diversion to the primary and secondary gasification reactors of 1:3), which exhibits in energy and exergy efficiencies of 47.47 % and 48.63 %, respectively. This configuration reduces exergy losses in the gasification reactor and heat exchanger, aiding in the large-scale industrial output of SCWG.

Hydrogen Production from Supercritical Water Gasification of Lignosulfonate over CuO-ZnO: Sulfur Transport and Catalyst Regeneration

In this study, sodium lignosulfonate was gasified in supercritical water over CuO-ZnO, and the gasification performance and sulfur transport and fate were investigated experimentally. The products and catalysts were characterized with GC-MS, IC, FTIR, XRD and XPS. It was found that the presence of CuO-ZnO improved the gasification efficiency, and the H2 yield peaked at 9.35mol/kg with 1.5g CuO-ZnO. The sulfur element was mainly distributed as H2S and CH3SH in the gas product owing to the reducing reaction atmosphere and SO42- in the liquid product. The presence of CuO-ZnO facilitated the conversion of sulfur from H2S and CH3SH in the gas product to SO42- in the liquid product. And the CuO component was converted into Cu2S, which fixed some sulfur in the solid residues. Three regenerating methods were tested for the sulfur-poisoned CuO-ZnO, and calcination showed superiorities over SCW and SubCW treatment. The calcination eliminated the sulfur and carbon deposited on the catalyst, and also converted Cu2S into CuO by oxidation. The calcined catalyst showed relatively high catalytic activity as the fresh catalyst. With further optimization, CuO-ZnO can be a promising catalyst for SCWG of sulfur-containing organic wastes.

A review on hydrothermal treatments for solid, liquid and gaseous fuel production from biomass

The rise in the population and rapid industrialization has resulted in a rise in the global energy consumption. In order to minimize the load on the conventional energy sources, various studies are being conducted for the production of biofuels by hydrothermal operations. Unlike conventional processes of biofuel production, wet biomass can be directly utilised without drying in turn reducing the energy consumption. Feedstocks such as agricultural residue, forest residue, energy crops, algae, sludge, litter and food waste can be utilised for the production of biofuels. The operation intensities (temperature and pressure) can be varied from pressurized hot water to supercritical water. Hydrothermal operations depending on the operating parameters are further subcategorised into four types namely wet torrefaction (WT), hydrothermal carbonization (HTC), hydrothermal liquefaction (HTL) and hydrothermal gasification (HTG). Even though the operating conditions of wet torrefaction and hydrothermal carbonization lie in similar categories, the difference is clearly visible in the level of carbonization. Due to the wide range of operating temperature and pressure, mainly three different products are produced through hydrothermal operations. The temperature range for wet torrefaction can be limited between 150 and 220 °C, whereas the HTC process can be between 200 and 260 °C. At higher temperatures (260 – 370 °C) in hydrothermal liquefaction (HTL), increased isomerization, depolymerization and repolymerization of organic compounds within the biomass occurred, causing liquid product (bio-oil) to be formed as the major product. Hydrothermal gasification can be further subcategorised into three types: namely aqueous phase refining, near critical water gasification and supercritical water gasification (SCWG). This paper has reviewed different hydrothermal operations based on biofuel production from different biomass.

ReaxFF reactive molecular dynamic and density functional theory study on supercritical water gasification of waste hydrofluorocarbons to fuels

Hydrofluorocarbon (HFC) working fluid with high global warming potential are step out of the stage of history due to the intensifying global greenhouse effect. Supercritical water gasification (SCWG), an effective and clean waste disposal method, may have better potential for the conversion of waste HFCs working fluid. ReaxFF reactive molecular dynamic and density functional theory method are used in this work to investigate the SCWG mechanism of HFC-245fa. The results indicate that the main products of HFC-245fa SCWG are high value-added chemicals and fuels such as CO, CO2, H2, and HF. During the gasification process, almost 100 % of the F atoms in HFC-245fa have the potential to become HF, which means that the SCWG method has a strong defluorination effect. The generation of H2 molecules is promoted and the formation of CO molecule is inhibited in the presence of H2O molecules. More importantly, hydrogen bonds are formed between HFC-245fa and H2O molecules, which results in the dissociation of HFC-245fa is improved by the SCWG environment. This work provides an available and environmentally friendly route for the efficient conversion of waste HFCs to fuels.

Study on mechanism of supercritical water gasification of hemicellulose for hydrogen-rich syngas based on experiments and reaction molecular dynamics simulations

Hydrogen-rich syngas from supercritical water gasification (SCWG) of renewable biomass is a promising technology. However, the mechanistic studies related to experiments and simulations on hemicellulose, an important component of biomass, are still limited. Therefore, in this study, the SCWG mechanism of hemicellulose was investigated using a batch reactor and via ReaxFF molecular dynamics simulations. The results indicated that the long chains of xylan broke to short chains during the heating process, which was accompanied by the occurrence of ring-opening reactions. SCWG occurred more completely with increasing temperature or decreasing concentration, when hydrogen was more selective and methane was produced mainly by gas reforming reactions. At 600 °C and 5 g/100 g water, the total gas yield of xylan SCWG was 38.65 mmol g−1, and the hydrogen yield could reach 14.48 mmol g−1. The liquid products mainly included furfural and phenol. The solid products consisted of a high C content, which could reach more than 90 % at 500 °C, and were dominated by polycyclic aromatic hydrocarbons, and at 600 °C by benzene and naphthalene. Xylan formed carbon balls on the surface of the solid products, while hemicellulose exhibited the formation of a dense porous structure.

Developing a hybridized thermodynamic and data-driven model for catalytic supercritical water gasification of biomass for hydrogen production

Supercritical water gasification (SCWG) of biomass offers a promising pathway for sustainable energy production. This study presents a novel approach that combines an artificial intelligence (AI) technique with the Gibbs minimization (GM) method to enhance the GM approach by involving the catalyst effect on the gasified yield. The proposed strategy incorporates a modified Gibbs energy calculation, incorporating a delta term that quantifies the influence of the catalyst’s properties on the Gibbs free energy. The delta term is determined using experimental data, including characteristics of biomass and the employed catalysts. An artificial neural network (ANN) model is developed to predict the delta value and is integrated with the GM method to improve the estimation of gasified product yields in the presence of a catalyst. The ANN model establishes correlations between the catalyst specifications such as pore volume, specific surface area, and pore diameter, and delta value. The trained model can predict the delta term, allowing the catalyst’s role to be considered within the GM technique. This integration addresses a limitation of the conventional thermodynamic model, which typically ignores the catalyst’s influence. The developed ANN model exhibits high accuracy, with an R2 value of 0.92 and a mean squared error (MSE) of 0.042. The hybridized GM approach substantially improves the hydrogen yield prediction compared to the basic model, enhancing (reducing) the MSE and mean absolute error by 98% and 93%, respectively. Furthermore, sensitivity analysis reveals that increasing temperature and reducing pressure contribute to improved hydrogen production. Additionally, lower biomass concentrations are shown to be beneficial for enhancing the hydrogen yield.

Numerical simulation of fluid-particle flow of jet in supercritical water environment

Supercritical water gasification provides a new approach to the green transformation of coal. Nevertheless, the flow characteristics of fluids and particles injected into the reactor through the nozzle still need to be further investigated. In this paper, a three-dimensional numerical simulation of the particle jet in supercritical water environment is carried out coupling Large Eddy Simulation (LES) with Discrete Phase Model (DPM). The simulation focuses on the effects of particle size, Stokes number, mass flux ratio and initial fluid velocity on the flow characteristic of the fluid-particle flow, especially on the vortex structure evolution, particle distribution and velocity profile. The findings are that as the particle size decreases and the initial fluid velocity increases, the evolution of vortex structures become increasingly fierce, such as the destruction of large-scale coherent structures, the disappearance of vortex ribs, and the lateral expansion of vortices in the development section. Particle distribution exhibits characteristics similar to the vortex structure, as particles adhere closely to the carrier fluid at low Stokes number (St < 1). On the contrary, with increasing of Stokes number (St > 1), the particles are freer from fluid interference and keep their original motion state moving forward. The fluid velocity at the center of the transverse interface jet decrease with increased mass flow ratio. For higher initial fluid velocities, particle distribution is more uniform, and more particles are carried to areas with larger radial distances.

System development and thermodynamic performance analysis of a system integrating supercritical water gasification of black liquor with direct-reduced iron process

Hydrogen metallurgy is an effective way to decarbonize the steel industry. In this study, a new system integrating biomass supercritical water gasification (SCWG) with hydrogen generation-shaft furnace-electric arc furnace (HSE) was proposed. The thermodynamic performance of SCWG-HSE system were analyzed and optimized. The results show that the gasification and energy efficiency of SCWG system increase with an increase in the gasification temperature. The carbon emission of the SCWG-HSE system are effectively reduced, and the product yield and energy efficiency of the system are improved by increasing gasification temperature and recovering furnace top gas. The energy and exergy efficiency of the SCWG-HSE system are 46.66% and 40.17%, respectively. The exergy destruction of SCWG gasifier and electric arc furnace are the major exergy damage sources of the SCWG-HSE system. The exergy efficiency of the ironmaking system reaches 51.60%, and the energy consumption and carbon emission per unit product are 18.49 GJ/t and 902.40 kg/t, respectively. Compared with the traditional Coking-Blast furnace ironmaking process, the energy consumption and carbon emission of this system are reduced by 7.32% and 40.84% respectively. This work is expected to open a new way for the application of biomass in the low-carbon steel industry.

Kinetics study of total organic carbon destruction during supercritical water gasification of glucose

AbstractThe kinetics of total organic carbon (TOC) destruction during supercritical water gasification (SCWG) of glucose were studied at 400–500°C and 25 MPa in a 600 mL batch reactor. Both TOC and water concentrations are critical for the conversion of TOC in supercritical water, especially at longer residence times. Initially, it was assumed that the TOC destruction reaction followed first‐order kinetics ignoring the water concentration. However, experimental results showed that the feed‐to‐water ratio had a significant effect on TOC decomposition. Considering the water concentration in the reaction, the reaction orders of TOC (2.35) and water (1.45) were calculated using nonlinear regression analysis (the Runge‐Kutta method). The estimated pre‐exponential factor (k’) and activation energy (E) were calculated to be 8.1 ± 2/min and 90.37 ± 9.38 kJ/mol respectively.

Understanding the conversion mechanisms in supercritical water conditions of PET as a model compound of plastic wastes

In this work, polyethylene terephthalate (PET) was used as a model compound for understanding the conversion mechanism of plastic wastes through supercritical water gasification (SCWG) for producing: i) a gas rich in methane/hydrogen; and ii) for obtaining valuable molecules to be recycled in chemical processes (e.g., benzoic and acetic acids).The experiments were conducted at two different temperatures (above the critical point of water): 450 °C and 600 °C, in order to study the influence of this parameter on the conversion yield. The holding time in the reactor was set at 30 min for all trials. The experimental data were compared to the thermodynamic equilibrium calculations and the results showed that increasing the temperature from 450 °C to 600 °C, the total gas yield is highly improved (from 8.6 mol gas/kg of dried feedstock to 22 mol gas/kg of dried feedstock). The experiments with Raney-nickel catalyst indicated a significant improvement of the carbon conversion yield, which led to a higher gas production from mild to higher temperatures. The maximum total gas yield obtained with this catalyst was 63.4 mol gas/kg of dried feedstock at 600 °C, which is almost 3 times higher than that obtained at the same operating conditions without catalyst. The HHV of the obtained gas at 600 °C with the catalyst was 64.7 MJ/kg gas and 57.9 MJ/kg gas at 450 °C. Additionally at mild operating temperatures (450 °C), the obtained performance with the catalyst was even higher than that obtained at 600 °C without catalyst (50 mol gas/kg dried feedstock and 22 mol gas/kg dried feedstock, respectively), which is the major contribution of this work. At mild temperatures (450 °C) the methane production is highly favored, meanwhile at 600 °C the hydrogen production is enhanced. The methane yield obtained at 450 °C was 21.3 mol CH4/kg dried feedstock and the hydrogen yield obtained at 600 °C was 20.6 mol H2/kg dried feedstock. In the aqueous phases obtained from the experiments performed without catalyst at 450 °C, it was found valuable intermediate species such as benzoic and acetic acids (at a concentration of 4462 mg/L and 946 mg/L, respectively). This study represents a sustainable approach for valorizing plastic wastes by catalytic SCWG process.

Molecular dynamics simulation on interaction effect of complex contents on supercritical water gasification of pig breeding wastewater for hydrogen production

The scale of pig breeding in China is the largest in the world, and the pollution problem of breeding wastewater is serious. Supercritical water gasification (SCWG) process is a clean and efficient treatment technology for breeding wastewater. This paper involved constructing the molecular model of the primary organic components in pig breeding wastewater. The effects of time, temperature and mass concentration, and the interactions of different components on the SCWG characteristics of pig breeding wastewater were studied by molecular dynamics (MD) simulation, and the decomposition process of lignin and lipid molecules in the SCWG process were analyzed, and the possible intermediates were explored. The results showed that the effect of parameters on carbon gasification efficiency (CE) and H2 production follows the order of temperature > time > mass concentration. During the gasification of lignin and lipid molecules, the C–O–C bond was broken first, and the gasification rate of lignin molecules was slow due to the benzene ring. Interactions among different organic decompositions hindered the gasification process. This paper will provide theoretical guidance for the selection of operation parameters and the control of products in the actual pig breeding wastewater treatment process.

Effect of Fe and its oxides on steam gasification mechanism of lignin using ReaxFF molecular dynamics simulations

Lignin is an important biomass component and its gasification process has been extensively studied. Iron is widely found in nature, and the corresponding iron-based catalysts have been heavily used in the study of various systems. The advantages are that it is inexpensive and not easy to pollute the environment, and it can also be extracted from the system and reused. However, studies on the effect of iron and its oxides on the steam gasification of lignin are limited, most studies have focused on supercritical water gasification. In this study, the effects of Fe and its oxides on the steam gasification process of lignin dimers were simulated using reactive force field (Reaxff) molecular dynamics (MD). By analyzing the gas products and the evolution of the structures. It was found that low valence Fe greatly improved the efficiency of lignin steam gasification, while higher valence iron oxides were significantly less effective. There were also significant differences in the distribution of gas products for different valence states of Fe. Low-valent Fe greatly improves the yield of combustible gases such as H2 and CO, while high-valent Fe is better at generating CO2. Carbon accumulation occurs on the surface of the catalyst, which reduces the catalytic effect. By comparing the effects of different temperatures on the steam gasification of lignin, it was found that increasing the temperature accelerates the decomposition process of lignin, and that the steam gasification of lignin has a critical temperature at which the yield of the main gaseous products of lignin is the highest.

Experimental Investigation of the Effects of Inorganic Components on the Supercritical Water Gasification of Semi-Coke

Experimental Investigation of the Effects of Inorganic Components on the Supercritical Water Gasification of Semi-Coke

Catalyzed hydrothermal treatment of oily sludge: A review

Oily sludge is a common by-product of the petroleum exploration industry, which is rich in resources and has strong toxicity. It is categorized as hazardous waste in many nations worldwide. Owing to the distinct physical and chemical characteristics of sub/supercritical water, the application of hydrothermal conversion technology, which uses sub/supercritical water as a medium, has been growing in the utilization of resources and the safe disposal of oily sludge. In this article, the research on the oxygen-free hydrothermal transformation of oil sludge, including hydrothermal carbonization, hydrothermal liquefaction, hydrothermal upgrading, and supercritical water gasification, is reviewed. Due to the significant impact of nitrogenous and sulfurous compounds in sludge on hydrothermal conversion products, the hydrogenation conversion, reaction path, and kinetics for these two compounds were discussed. Finally, a summary and comparison of the studies conducted on carriers and catalysts in hydrothermal processes are provided. This review can offer recommendations for future studies, as well as guidance for the hydrothermal catalytic treatment of oily sludge.

Alkaline pulping catalyzed ordered conversion of bark in supercritical water

The hydrophilicity of lignocellulosic biomass hinders the application of a high concentration slurry for supercritical water gasification, thereby reducing the gasification efficiency and energy self-sufficiency. A pretreatment method of alkaline pulping with KOH and NaOH was proposed to achieve the high feed concentration for continuous reactor and macromolecular simplification for barrier reduction of conversion. In this study, bark as an example of lignocellulosic biomass, whose 30 wt% and 40 wt% slurries with favorable rheology and stability, was prepared by alkaline pulping successfully. The minimum alkali consumption of NaOH and KOH pulping for 30 wt% and 40 wt% were 11%–14%, 16%–20%, and 16%–21%, 23%–28%, respectively. The most economical conditions were 180 °C and 24% KOH addition. All slurries prepared by NaOH and KOH at 180 and 200 °C could satisfy the industrial standard of coal-water slurry, and only 3–5 times higher than water viscosity. The bark macromolecules were restructured due to the hydrolysis of cellulose and lignin by breaking down the hydrogen bond and ether bond with trivial hydrocarbon matrix loss. The scattered crystal growth facilitated the uniform premixing of bark and water. Meanwhile, a surface particle charges potential increase leading to a heightened repulsive force by alkaline pulping furtherly enhanced the premixing effect. Additionally, metal ions could be deposited onto the bark surface during alkaline pulping. The chemical modification leading by alkaline pulping achieved the premixing of feedstock and water to form bark slurry. The conversion barrier was decreased to fulfill the ordered conversion, and 95.66% gasification efficiency for 40 wt% bark slurry was displayed at 600 °C with a preheated water of 6. Phenolic compounds and hydrocarbons were the most dominant components in liquid products. Polycyclic aromatic hydrocarbons in liquid products were detected at 620 °C with a preheated water of 4. The functional groups of organic matter in the slurry were significantly converted into the gas phase, and lattice oxygen was produced in the solid product. The alkali recovery was 65% at the optimal gasification condition, and achieved the maximum of 80% at 580 °C. The successful completion of this research affirms the dominance of the pulping-alkali recovery-gasification method for expanding the application of SCWG of lignocellulosic biomass in large engineering projects.

Combining thermal–alkaline hydrolysis pretreatment with catalytic supercritical water gasification for hydrogen production from sewage sludge

An integrated process consisting of a thermal–alkaline hydrolysis pretreatment (TAHP) combined with catalytic supercritical water gasification (CSCWG) was developed to treat sewage sludge to produce H2. TAHP facilitated the transfer of organics from sludge into liquid products for subsequent CSCWG to produce H2. Upon increasing the hydrolysis temperature, time, and alkali dosage, the continuous transfer of organics to liquid products was observed, wherein the hydrolysis temperature had the greatest effect. Under the optimal pretreatment conditions (180 °C, 1 h, and mNaOH/mOM = 25 %), approximately 70 % of proteins, carbohydrates, and 50 % of humus in sludge, i.e., easily gasified organic species, were transferred. Using this process, the TOC concentration in the liquid products reached about 17,000 mg/L, and the polysaccharide and soluble protein concentrations reached 2400 and 15,000 mg/L, respectively. With this integrated process, the H2 yield and selectivity increased by 3.7–7.6 times and 5.94–52.92 times, respectively, compared with the directly catalyzed gasification of sludge. This improvement occurred because TAHP promoted the transfer of easily gasified organic species into the liquid products, while the difficult-to-gasify organics and inorganics in ash remained in the solid phase, which prevented them from inhibiting the catalyst.