K2CO3-catalyzed gasification of coal of different ranks in supercritical water for hydrogen production: A general kinetic model with good coal adaptability

Supercritical water gasification (SCWG) of coal provides a new solution for the green transformation and upgrading of traditional coal industry. Considering the good coal adaptability of SCWG and the excellent catalytic performance of K₂CO₃, a new kinetic model was developed in this work for predicting the catalytic gasification characteristics of coal of different ranks in supercritical water (SCW). In this model, various ranks of coal are characterized by the combination of three types of primary coal in different proportions, and the proportions can be obtained based on elemental analysis data and matrix computation. The SCWG of various ranks of coal can be considered as a combination of reactions of three types of primary coal in SCW. The model contains a total of 18 reactions, and various intermediates are represented by phenol and a high-carbon hydrocarbon. K₂CO₃-catalyzed SCWG experimental data of three different coal samples obtained in an improved quartz tube reactor system were used for the determination of model kinetic parameters. Then the experimental results of catalytic SCWG of other coal samples were used for the model validation, and it was found that the model can effectively predict the variations of gaseous products within an acceptable error. Afterward, the model was used to predict carbon gasification efficiency and gas compositions for coal of different ranks and to analyze carbon distribution and reaction rates for specific coal. The proposed kinetic model fits well with the good coal adaptability of SCWG technology, and it has great significance for the promotion of SCWG technology.     

Hydrogen production by coal gasification in supercritical water with a fluidized bed reactor

The technology of supercritical water gasification of coal can converse coal to hydrogen-rich gaseous products effectively and cleanly. However, the slugging problem in the tubular reactor is the bottleneck of the development of continuous large-scale hydrogen production from coal. The reaction of coal gasification in supercritical water was analyzed from the point of view of thermodynamics. A chemical equilibrium model based on Gibbs free energy minimization was adopted to predict the yield of gaseous products and their fractions. The gasification reaction was calculated to be complete. A supercritical water gasification system with a fluidized bed reactor was applied to investigate the gasification of coal in supercritical water. 24 wt% coal-water-slurry was continuously transported and stably gasified without plugging problems; a hydrogen yield of 32.26  mol/kg was obtained and the hydrogen fraction was 69.78%. The effects of operational parameters upon the gasification characteristics were investigated. The recycle of the liquid residual from the gasification system was also studied.     

Hydrogen production by biomass gasification in supercritical water: A parametric study

Hydrogen production by biomass gasification in supercritical water is a promising technology for utilizing high moisture content biomass, but reactor plugging is a critical problem when feedstocks with high biomass content are gasified. The objective of this paper is to prevent the plugging problem by studying the effects of the various parameters on biomass gasification in supercritical water. These parameters include pressure, temperature, residence time, reactor geometrical configuration, reactor types, heating rate, reactor wall properties, biomass types, biomass particle size, catalysts and solution concentration. Biomass model compounds (glucose, cellulose) and real biomass are used in this work. All the biomasses have been successfully gasified and the product gas is composed of hydrogen, carbon dioxide, methane, carbon monoxide and a small amount of ethane and ethylene. The results show that the gas yield of biomass gasification in supercritical water is sensitive to some of the parameters and the ways of reducing reactor plugging are obtained.     

Catalytic supercritical water gasification mechanism of coal

Catalytic supercritical water gasification (SCWG) for H₂ production is a hopeful way of coal conversion to replace the traditional coal utilization mode. At present, the detailed catalytic mechanism in the process remains unknown. Herein, a comprehensive catalytic SCWG mechanism of coal is proposed by establishing a novel catalytic kinetic model. It shows that catalysts (K₂CO₃) break up the coal matrix by a cyclic redox reaction to produce plenty of mesopores, accelerating steam reforming of fixed carbon and coal pyrolysis. Water-gas shift reaction is facilitated by K₂CO₃ via formation of formate, which then promotes steam reforming of CH₄ at high temperature (≥700 °C) due to the decreasing CO. The proposed mechanism provides important insights in catalytic SCWG process of coal.     

Molecular dynamic investigation on sulfur migration during hydrogen production by benzothiophene gasification in supercritical water

Benzothiophene (BT) is a key sulfur-containing intermediate product in the thermal conversion process of coal and heavy oil. The migration process of the sulfur element may affect the thermal utilization design of BT. In this paper, BT was used as a model compound to simulate the supercritical water gasification (SCWG) process by molecular dynamics with a reactive force field (ReaxFF) method, and the laws of hydrogen production and sulfur migration mechanisms were obtained. Increasing the molecule number of supercritical water (SCW) and increasing the reaction temperature can enhance the generation of hydrogen and promote the conversion of organic sulfur to inorganic sulfur. Water was the main source of H₂, and H₂S was the main gaseous sulfur-containing product. SCW had a certain degree of oxidation due to a large number of hydroxyl radicals, which could increase the valence of sulfur. The conversion process of BT in SCW was mainly divided into four stages, including thiophene ring-opening; sulfur separation or carbon chain broke with sulfur retention; carbon chain cleaved, and gas generation. The lumped kinetic parameters of the conversion of sulfur in BT to inorganic sulfur were calculated, and the activation energy was 369.98 kJ/mol, which was much lower than those under pyrolysis conditions. This article aims to clarify the synergistic characteristics of hydrogen production and sulfur migration in the SCWG process of BT from the molecular perspective, which is expected to provide a theoretical basis for pollutant directional removal during hydrogen production by sulfur-containing organic matters in SCW.     

Investigation of the conversion mechanism for hydrogen production by coal gasification in supercritical water

The technology of supercritical water gasification (SCWG) of coal has a great prospect because it converts coal into hydrogen-rich gas products efficiently and cleanly. However, there are bottlenecks affecting the complete gasification of coal in supercritical water (SCW) without catalyst under moderate conditions. This work is to explore the restricted factor for complete gasification of coal in SCW by investigating the conversion mechanism. The conversion mechanism of SCWG of coal with and without K₂CO₃ is proposed. Polycyclic aromatic hydrocarbons (PAHs) with graphite phase structures are formed by the condensation of aromatic structures at 550–750 °C. It is the restricted factor due to its characteristic of difficulty to be gasified. There is no condensation of aromatic structures in the process of SCWG of coal with K₂CO₃, which effectively inhibited the formation of PAHs with graphite phase structures. K₂CO₃ dramatically promoted the SCWG of coal, leading to carbon gasification efficiency (CE) reaching 98.43%.     

Hydrogen production by catalytic supercritical water gasification of nitriles

Supercritical water gasification (SCWG) of nitriles was studied in a tubular flow reactor at different temperatures. This article focuses on the product distributions and corresponding reaction pathways influenced by addition of Na₂CO₃ catalyst. Results showed that gas yield for both acetonitrile and acrylonitrile can be greatly enhanced by adding Na₂CO₃ catalyst. Especially, H₂ gasification efficiency can reach 55.4% and 123.3% at 550 °C, respectively. But the catalytic effect on the gas yield of benzonitrile was relatively insignificant. Na₂CO₃ can also accelerate the hydrolysis of cyanogen and amido as a base catalyst. Benzene and acetic acid were the primary intermediate products during the SCWG of benzonitrile and acetonitrile, respectively. The conversion of acrylonitrile was more complicated because of the activity of double bond. It is possible that 3,3′ iminodipropionitrile was formed by Na₂CO₃ catalyzed in the range of 490–520 °C, which dominated two thirds of pathways for the subsequent formation of acetic acid. Ammonia-nitrogen content in the liquid effluent was limited by the hydrolysis degree of cyano-group and the possible polymerization reaction of intermediate products. There was no obvious trend to reveal that NH₃ was converted into nitrogen under our experimental conditions.     

Hydrogen production by catalytic gasification of coal in supercritical water with alkaline catalysts: Explore the way to complete gasification of coal

Supercritical water gasification (SCWG) of coal is a promising technology for clean coal utilization. In this paper, hydrogen production by catalytic gasification of coal in supercritical water (SCW) was carried out in a micro batch reactor with various alkaline catalysts: Na₂CO₃, K₂CO₃, Ca(OH)₂, NaOH and KOH. H₂ yield in relation to the alkaline catalyst was in the following order: K₂CO₃ ≈ KOH ≈ NaOH > Na₂CO₃ > Ca(OH)₂. Then, hydrogen production by catalytic gasification of coal with K₂CO₃ was systematically investigated in supercritical water. The influences of the main operating parameters including feed concentration, catalyst loading and reaction temperature on the gasification characteristics of coal were investigated. The experimental results showed that carbon gasification efficiency (CE, mass of carbon in gaseous product/mass of carbon in coal × 100%) and H₂ yield increased with increasing catalyst loading, increasing temperature, and decreasing coal concentration. In particular, coal was completely gasified at 700 °C when the weight ratio of K₂CO₃ to coal was 1, and it was encouraging that raw coal was converted into white residual. At last, a reaction mechanism based on oxygen transfer and intermediate hybrid mechanism was proposed to understand coal gasification in supercritical water.     

Hydrogen production from coal gasification in supercritical water with a continuous flowing system

The technology of supercritical water gasification can convert coal to hydrogen-rich gaseous product efficiently and cleanly. A novel continuous-flow system for coal gasification in supercritical water was developed successfully in State Key Laboratory of Multiphase Flow in Power Engineering (SKLMF). The experimental device was designed for the temperature up to 800 °C and the pressure up to 30 MPa. The gasification characteristics of coal were investigated within the experimental condition range of temperature at 650–800 °C, pressure at 23–27 MPa and flow rate from 3 kg h⁻¹ to 7 kg h⁻¹. K₂CO₃ and Raney-Ni were used as catalyst and H₂O₂ as oxidant. The effects of main operation parameters (temperature, pressure, flow rate, catalyst, oxidant, concentration of coal slurry) upon gasification were carried out. The slurry of 16 wt% coal + 1.5 wt% CMC was successfully transported into the reactor and continuously gasified in supercritical water in the system. The hydrogen fraction reached up to 72.85%. The experimental results demonstrate the bright future of efficient and clean conversion of coal.     

Hydrogen production from dairy wastewater using catalytic supercritical water gasification: Mechanism and reaction pathway

The supercritical water gasification (SCWG) of real dairy wastewater (cheese-based or whey) was performed in a batch reactor in presence of two catalysts (MnO₂, MgO) and one additive (formic acid). The operational conditions of this work were at a temperature range of 350–400 C and the residence time of 30–60 min. The catalysts and formic acid were applied in 1 wt%, 3 wt%, and 5 wt% to determine their effect on hydrogen production. The concentrations of catalysts and formic acid were calculated based on the weight of feedstock without ash. The results showed that increased temperature and prolonged residence time contributed to the hydrogen production (HP) and gasification efficiency (GE). The gas yield of hydrogen in the optimum condition (400 C and 60 min) was achieved as 1.36 mmol/gr DAF (dry ash free). Formic acid addition was favored towards enhancing hydrogen content while the addition of metal oxides (MnO₂ and MgO) had an apex in their hydrogen production and they reached the highest hydrogen in 1 wt% concentration then ebbed. Moreover, GE was increased by the addition of the catalysts and formic acid concentrations. The highest hydrogen content (35.4%) was obtained in 1 wt% MnO₂ and the highest GE (32.22%) was attained in the 5 wt% formic acid concentration. A reaction pathway was proposed based on the GC-MS data of feedstock and produced liquid phase at different condition as well as similar studies.     

Hydrogen production through biomass gasification in supercritical water: A review from exergy aspect

Hydrogen production through supercritical water gasification (SWG) of biomass has been widely studied. This study reviews the main factors from exergy aspect, and these include feedstock characteristics, biomass concentration, gasification temperature, residence time, reaction catalyst, and reactor pressure. The results show that the exergy efficiencies of hydrogen production are mainly in the range of 0.04–42.05%. Biomass feedstock may affect hydrogen production by changing the H₂ yield and the heating value of biomass. Increases in biomass concentrations decrease the exergy efficiencies, increases in gasification temperatures generally increase the exergy efficiencies, and increases in residence times may initially increase and finally decrease the exergy efficiencies. Reaction catalysts also have positive effects on the exergy efficiencies, and the reviewed results show that the effects are followed KOH > K₂CO₃ > NaOH > Na₂CO₃. Reactor pressure may have positive, negative or negligible effects on the exergy efficiencies.     

Hydrogen production by non-catalytic partial oxidation of coal in supercritical water: Explore the way to complete gasification of lignite and bituminous coal

Supercritical water gasification (SCWG) of coal is a promising technology for clean coal utilization. In this paper, hydrogen production by non-catalytic partial oxidation of coal was systematically investigated in supercritical water (SCW) with quartz batch reactors for the first time. The influences of the main operating parameters including residence time, temperature, oxidant equivalent ratio (ER) and feed concentration on the gasification characteristics of coal were investigated. The experimental results showed that H₂ yield and carbon gasification efficiency (CE) increased with increasing temperature and decreasing feed concentration. CE increased with increasing ER, and H₂ yield peaked when ER equaled 0.1. CE increased quickly within 1 min and then tended to be stable between 2 and 3 min. In particular, complete gasification of lignite was obtained at 950 °C when ER equaled 0.1, as for bituminous coal, at a higher temperature of 980 °C when ER equaled 0.2.     

Hydrogen production by non-catalytic partial oxidation of coal in supercritical water: The study on reaction kinetics

Supercritical water gasification (SCWG) has attracted great attention for efficient and clean coal conversion recently. A novel kinetic model of non-catalytic partial oxidation of coal in supercritical water (SCW) that describes formation and consumption of gas products (H₂, CO, CH₄ and CO₂) is reported in this paper. The model comprises 7 reactions, and the reaction rate constants are obtained by fitting the experimental data. Activation energy analysis indicates that steam reforming of fixed carbon (FC) is the rate-determining step for the complete gasification of coal. Once CH₄ is produced by pyrolysis of coal, steam reforming of CH₄ will be the rate-determining step for directional hydrogen production.     

Supercritical water gasification of oil-containing wastewater with a homogeneous catalyst: Detailed reaction kinetic study

Supercritical water gasification (SCWG) is a promising technology for oil-containing wastewater treatment. This paper aims to establish a reaction kinetic model to provide better guidance for optimal industrial reactor design. The model is developed based on the experimental results obtained from K₂CO₃-catalyzed SCWG of diesel (the model compound of oil containment in wastewater) at various conditions of 500–650 °C and 15.23–64.45 s. Then the model validation by using the experimental data from other conditions. The validation results showed that the kinetic model can predict the gas concentration with an acceptable deviation. Afterward, the indicators of carbon gasification efficiency and gas yield versus residence time are predicted. The results show that the required residence time for the complete gasification is varied from 214.2 to 2150.8 s when the temperature changes from 500 to 650 °C. Moreover, the reaction rate analysis result indicates that the two reactions contributed most to the hydrogen production are the forward water-gas shift and the reverse CO methanation reaction. Additionally, the sensitivity analysis result reveals that the hydrolysis reaction of diesel has a significant influence at the initial stage, while the CO and CO₂ methane reactions play a vital role at the late stage for gas production.     

Hydrogen production from glycerol by supercritical water gasification in a continuous flow tubular reactor

In this work, glycerol was used for hydrogen production by supercritical water gasification. Experiments were conducted in a continuous flow tubular reactor at 445∼600 °C, 25 MPa, with a short residence time of 3.9∼9.0 s. The effects of reaction temperature, residence time, glycerol concentration and alkali catalysts on gasification were systematically studied. The results showed that the gasification efficiency increased sharply with increasing temperature above 487 °C. A short residence time of 7.0 s was enough for 10 wt% glycerol gasification at 567 °C. With the increase of glycerol concentration from 10 to 50 wt%, the gasification efficiency decreased from 88% to 71% at 567 °C. The alkali catalysts greatly enhanced water-gas shift reaction and the hydrogen yield in relation to catalysts was in the following order: NaOH > Na₂CO₃>KOH > K₂CO₃. The hydrogen yield of 4.93 mol/mol was achieved at 526 °C with 0.1 wt% NaOH. No char or tar was observed in all experiments. The apparent activation energy and apparent pre-exponential factor for glycerol carbon gasification were obtained by assuming pseudo first-order kinetics.     

Hydrogen production from catalytic gasification of switchgrass biocrude in supercritical water

Biomass can be liquefied to produce biocrude for ease of transportation and processing. Biocrude contains oxygenated hydrocarbons of varying molecular structure and molecular weights, including lignin derived products, sugars and their decomposition products. In this work several catalysts were screened for hydrogen production by gasification of switchgrass biocrude in supercritical water at 600 °C and 250 bar. Nickel, cobalt, and ruthenium catalysts were prepared and tested on titania, zirconia, and magnesium aluminum spinel supports. Magnesium aluminum spinel was seen to be an inappropriate support as reactors quickly plugged. Ni/ZrO₂ gave 0.98 mol H₂/mol C, the highest hydrogen yield of all tested catalysts; however, over time, increase in pressure drop lead to reactor plugging with all zirconia supported catalysts. Titania supported catalysts gave lower conversions, however they did not plug during the course of the study. Charring of all catalysts was seen to occur at the entrance of the reactor as the biocrude was heated. All support materials suffered significant surface area loss due to sintering.     

Hydrogen production from supercritical water gasification of alkaline wheat straw pulping black liquor in continuous flow system

Supercritical water gasification of alkaline black liquor was investigated in a continuous flow system. The experiments were carried out at 400–600 °C, 25 MPa, with residence times ranging from 4.94 to 13.71 s. The results showed that the increase of temperature and residence time and the decrease of feeding concentration enhanced the gasification. The gaseous product contained high level of hydrogen (40.26–61.02%). Maximum COD removal efficiency (88.69%) was obtained at 600 °C. The alkalis in black liquor were found to be precipitated in the reactor during the gasification, which decreased the pH of the effluent to the neutral region (6.4–8.0). The precipitated alkalis were dissolved in the water when the fluid temperature in the reactor was cooled to about 360 °C which increased the pH of the effluent to 11.0. A simplified kinetic study for COD removal efficiency was done by the pseudo-first order reaction assumption. The apparent activated energy was 74.38 kJ/mol and the apparent pre-exponential factor was 10^4.05 s⁻¹.     

Hydrogen production by biomass gasification in supercritical water using concentrated solar energy: System development and proof of concept

A novel system of hydrogen production by biomass gasification in supercritical water using concentrated solar energy has been constructed, installed and tested at the State Key Laboratory of Multiphase Flow in Power Engineering (SKLMF). The “proof of concept” tests for solar-thermal gasification of biomass in supercritical water (SCW) were successfully carried out. Biomass model compounds (glucose) and real biomass (corn meal, wheat stalk) were gasified continuously with the novel system to produce hydrogen-rich gas. The effect of direct normal solar irradiation (DNI) and catalyst on gasification of biomass was also investigated. The results showed that the maximal gasification efficiency (the mass of product gas/the mass of feedstock) in excess of 110% were reached, hydrogen fraction in the gas product also approached to 50%. The experimental results confirmed the feasibility of the system and the advantage of the process, which supports future work to address the technical issues and develop the technology of solar-thermal hydrogen production by gasification of biomass in supercritical water.     

Hydrogen production by supercritical water gasification of biomass: Explore the way to maximum hydrogen yield and high carbon gasification efficiency

Supercritical water gasification (SCWG) is a promising technology for wet biomass utilization. In this paper, orthogonal experimental design method, which can minimize the number of experiments compared with the full factorial experiments, was used to optimize the operation parameters of SCWG with a tubular reactor system. Using this method, the influences of the main parameters including pressure, temperature, residence time and solution concentration on biomass gasification were also investigated. Simultaneously, in order to further improve the gasification efficiency of biomass, acid hydrolysis pretreatment of feedstock, oxidizers addition and increasing reaction temperature were employed. Results from the experiments show that in the range of experimental parameters, the order of the effects of the factors on H₂ yield of corn cob gasification in SCW is temperature > pressure > feedstock concentration > residence time. Temperature and pressure have a significant and complicated effect on biomass gasification. Hydrogen yield increases by the acid hydrolysis pretreatment of feedstock, and oxidizer addition reduces the hydrogen yield but it promotes the increase in carbon gasification efficiency. Biomass feedstock with high concentration was gasified successfully at high reaction temperature.     

Regulation mechanism of coal gasification in supercritical water for hydrogen production: A ReaxFF-MD simulation

The regulation study on coal gasification process in supercritical water (SCW) can promote the hydrogen production and upgrading of coal utilization. ReaxFF molecular dynamics simulation integration with representative coal model was first introduced to investigate the regulation mechanism of liquid organics on coal gasification in SCW. Hongliulin coal model was constructed and verified its rationality and accuracy. Among the liquid organics, phenols exhibit a positive effect with the H₂ number increasing above 34%. The regulation mechanism is dug deeper into from the perspective of the intermolecular interaction and reactive sites. E_vdWaals is the main driving force and a maximum of reaction capability of coal molecules reaches 11.01 kJ/mol. The key reaction process in which the hydrogen is greatly improved is the degradation of heavy components under the regulatory effect of phenol. Moreover, the reactive sites of aromatic structure also change from the side chain to conjugated rings. Degradation mechanism of heavy components in the SCWG of coal is summarized. The experimental results verify that H₂ yield is increased by 59% and the solid mass is reduced to 0.72 mg with phenol. This conclusion demonstrated the feasibility of the ReaxFF MD simulation method to guide the clean utilization and industrial application of coal gasification in SCW.