Comparative study on corrosion characteristics of Al2O3/316L and TiO2/316L stainless steel in supercritical water

Al₂O₃ and TiO₂ coatings were fabricated on 316L stainless steel by atmospheric plasma spraying to improve the corrosion resistance of 316L stainless steel in supercritical water. The corrosion characteristics of the samples were evaluated in a batch reactor at 500 °C and 25 MPa with an oxygen concentration of 1000 mg/L for 80 h. The adhesive strengths of the coated samples were tested, and the weight changes, morphologies and elements distributions of the fresh and corroded samples were analyzed. Results showed that the bond strength of TiO₂/316L was 1.5 times than that of Al₂O₃/316L (26.639 N/mm²). The surface morphology of Al₂O₃/316L showed gully erosion with much pores and cracks after exposed in SCW, which provided channels for oxygen and SCW to get into the substrate and also the elements in substrate to diffuse to the surface of the coating. The corroded Al₂O₃/316L suffered significant weight loss, and most of the coatings were peeled off. However, the surface morphology of TiO₂/316L was relatively dense and the thickness of the coating was not found to decrease obviously.     

Influences of oxygen on corrosion characteristics of TiO2/316L stainless steel in supercritical water

Supercritical water gasification (SCWG) is a promising technology for converting organic wastes to hydrogen. Less amount of oxygen is beneficial for increasing hydrogen generation rate. However, the corrosion rate of reactor material would be accelerated. TiO₂ coating with a thickness of 0.1 mm was prepared on the surface of 316L stainless steel (SS316L) to improve its corrosion resistance in supercritical water (SCW). The corrosion performances of TiO₂/SS316L were tested in a bath SCW reactor at 400 °C, 25 MPa. The influences of oxygen concentration (0–1000 mg/L) on surface morphologies and corrosion depths were studied thoroughly. Results indicated that the surface of TiO₂/SS316L exhibited cracks and pores after exposed in SCW. And the average corrosion rates accelerated at higher oxygen concentrations. The interface between the coating and medium was relatively smooth and there was no obvious change in the thickness of the coating with oxygen concentration of 0 and 500 mg/L. While for that with 1000 mg/L oxygen, the surface of TiO₂/SS316L exhibited reticulate crack. The cross section showed a serrate structure, and only 0.08 mm thick of the coating was remained. In addition, the corrosion mechanism of coating was discussed.     

Effect of sulfide on corrosion behavior of stainless steel 316SS and Hastelloy C276 in sub/supercritical water

Stainless steel 316SS and Hastelloy C276, as the representatives of iron-based and nickel-based alloy, respectively, were employed to explore the corrosion properties under reducing subcritical and supercritical water containing sulfide. Experiments were executed at a pressure of 25 MPa, temperatures of 350 °C–520 °C, and sulfur concentrations of 1000 and 5000 ppm for 80 h. An isothermal equilibrium phase diagram involving the oxidation/sulfidation products of Fe, Cr, and Ni, was established by theoretical calculation in supercritical water system at 520 °C, in order to predict the corresponding products under various conditions and assist the discussion on corrosion mechanism. The results show that whether in subcritical water or in supercritical water, 316SS always exhibited better corrosion resistance relative to C276. In subcritical water at 350 °C, a portion of corrosion film peeled off from 316SS specimen, while numerous pores or cracks appeared on the surface of scale for C276. Under supercritical water at 520 °C, a compact scale grown on 316SS sample surface was composed of Fe₃O₄, FeCr₂O₄, and FeS. For C276, a duplex-layer scale formed on alloy surface. However, due to the higher content of Ni in C276, Ni-sulfide channels through the inner layer were developed, accelerating the sulfidation corrosion of alloys. Overall, the high-temperature alloys with high Cr content and low Ni/Cr ratio can be considered as the candidate material of equipment in supercritical water gasification of sulfur-containing coal.     

Supercritical water synthesized Ni/ZrO2 catalyst for hydrogen production from supercritical water gasification of glycerol

Catalysts are crucial to promote the technical feasibility of supercritical water gasification (SCWG) for H₂ production from wet biomass, yet catalysts prepared by conventional methods normally encounter sintering problems in supercritical water. Herein, a series of ZrO₂-supported Ni catalysts were tried to be prepared by supercritical water synthesis (SCWS) and evaluated for SCWG in terms of activity and property stability. The SCWS was conducted at 500 °C and 23 MPa using metal nitrates as starting materials. Effect of precursor concentration on property and catalytic performance of the SCWS-prepared catalysts for SCWG of 20 wt% glycerol were systematically studied. XRD, SEM-EDS, TEM and TGA were applied for catalyst characterization. Results verified the successful obtaining of Ni/ZrO₂ nanocatalysts with Ni crystals of 30–70 nm and ZrO₂ crystals of ~11 nm by the SCWS process, which were found to be active on the WGSR for SCWG to increase the H₂ yield as high as 155%. Importantly, the SCWS-prepared Ni/ZrO₂ catalysts exhibited excellent property stability and anti-coking ability for SCWG of glycerol.     

Co-gasification of catechol and starch in supercritical water for hydrogen production

Hydrogen production from waste feedstocks using supercritical water gasification (SCWG) is a promising approach towards cleaner fuel production and a solution for hard to treat wastes. In this study, the catalytic co-gasification of starch and catechol as models of carbohydrates and phenol compounds was investigated in a batch reactor at 28 MPa, 400–500 °C, from 10 to 30 min. The effects of reaction conditions, and the addition of calcium oxide (CaO) as a carbon dioxide (CO₂) sorbent and TiO₂ as catalyst on the gas yields and product distribution were investigated. Employing TiO₂ as a catalyst alone had no significant effect on the H₂ yield but when combined with CaO increased the hydrogen yield by 35% and promoted higher total organic carbon (TOC) reduction efficiencies. The process liquid effluent was characterized using GC–MS, with the results showing that the major non-polar components were phenol, substituted phenols, and cresols. An overall reaction scheme is provided.     

Solar receiver/reactor for hydrogen production with biomass gasification in supercritical water

A novel receiver/reactor driven by concentrating solar energy for hydrogen production by supercritical water gasification (SCWG) of biomass was designed, constructed and tested. Model compound (glucose) and real biomass (corncob) were successfully gasified under SCW conditions to generate hydrogen-rich fuel gas in the apparatus. It is found that the receiver/reactor temperature increased with the increment of the direct normal solar irradiation (DNI). Effects of the DNI, the flow rates and concentration of the feedstocks as well as alkali catalysts addition were investigated. The results showed that DNI and flow rates of reactants have prominent effects on the temperature of reactor wall and gasification results. Higher DNI and lower feed concentrations favor the biomass gasification for hydrogen production. The encouraging results indicate a promising approach for hydrogen production with biomass gasification in supercritical water using concentrated solar energy.     

Evaluation of modified Ni/ZrO2 catalysts for hydrogen production by supercritical water gasification of oil-containing wastewater

Supercritical water gasification (SCWG) technology is a clean and cost-effective conversion technology due to its unique chemical and physical properties. However, the unique properties also lead to instability and inactivity for the pure Ni/ZrO₂ catalyst in SCWG process. In this work, we investigated the effect of second metal addition on the catalytic performance by modifying Ni/ZrO₂ catalysts with different promoters (Co, Ce, La, Y, Mg), which prepared by a single-step sol-gel method. The analysis results of catalysts by XRD, SEM and automatic micropore & chemisorption analyzer showed that Ce, Y, La may be helpful promoters to stabilize the structure of ZrO₂. Compared to the non-catalytic experiment, all the catalysts showed significantly higher activities in the SCWG reaction. Among all catalysts, Ni-Co/ZrO₂ exhibited excellent activity, which achieved the highest carbon gasification efficiency (CE) and highest hydrogen yield. Additionally, two key factors, concentration and temperature, were also investigated for the optimum conditions, and the maximum carbon gasification efficiency (CE) of 98.8% was achieved at 600 °C with the Ni-Co/ZrO₂ catalyst.     

Assessment of sugarcane bagasse gasification in supercritical water for hydrogen production

Sugarcane bagasse is one of the major resources of agricultural biomass waste in the world. In this work, supercritical water gasification characteristics of sugarcane bagasse were investigated. The effect of temperature (600–750 °C), concentration (3–12 wt%), residence time (5–20 min) and catalysts (Raney-Ni, K₂CO₃ and Na₂CO₃) on bagasse gasification were studied. A kinetic study on the non-catalytic and Na₂CO₃ catalytic bagasse gasification was conducted to describe the kinetic information of the bagasse gasification reaction. The results showed that a higher reaction temperature, a lower bagasse concentration and a longer residence time could favor the gasification of bagasse, leading to a higher hydrogen yield. Bagasse was nearly completely gasified at 750 °C without using any catalyst and the carbon gasification efficiency could reach up to 96.28%. The addition of employed catalysts remarkably promoted the bagasse gasification reactivity. The maximum hydrogen yield (35.3 mol/kg) was achieved at 650 °C with the Na₂CO₃ loading of 20 wt%. The experimental data fitted well with a homogeneous model based on a Pseudo-first-order reaction hypothesis. The kinetic study showed that Na₂CO₃ catalyst could lower the activation energy E_a of bagasse gasification from 117.88 kJ/mol to 78.25 kJ/mol.     

Review of catalytic supercritical water gasification for hydrogen production from biomass

Hydrogen is defined as an attractive energy carrier due to its potentially higher energy efficiency and low generation of pollutants, which can replace conventional fossil fuels in the future. The governments have invested huge funds and made great efforts on the research of hydrogen production. Among the various options, supercritical water gasification (SCWG) is a most promising method of hydrogen production from biomass. Supercritical water (SCW) has received a great deal of attention as a most suitable reaction medium for biomass gasification because it is safe, non-toxic, readily available, inexpensive and environmentally benign. However, high temperature and pressure are required to meet the minimum reaction condition. Therefore, the high operating cost has become the biggest obstacle to the development of this technology. To overcome this bottleneck, many researchers have carried out intensive research work on the catalytic supercritical water gasification (CSCWG). Based on the previous studies stated in the literature, the authors try to give an overview (but not an exhaustive review) on the recent investigations of CSCWG. Besides, the physicochemical properties of SCW and its contributions in subcritical and supercritical water reaction are also summarized.     

Comparative study between supported and doped MgO catalysts in supercritical water gasification for hydrogen production

Different catalyst structures may influence the catalytic performance of catalysts in supercritical water gasification (SCWG). This study reports the catalytic activity of supported (SP) and doped (DP) MgO catalysts in catalyzing the gasification of oil palm frond (OPF) biomass in supercritical water to produce hydrogen. Two types of supported catalysts, labelled as Ni-SP (nickel supported MgO) and Zn-SP (zinc supported MgO), were synthesized via impregnation method. Another two types of doped catalysts, labelled as Ni-DP (nickel doped MgO) and Zn-DP (zinc doped MgO), were synthesized by using the self-propagating combustion method. All the synthesized catalysts were found to be pure with the doped catalysts exhibited small crystallites, in comparison to that produced by the supported catalysts. The specific surface area increased in the order of Ni-DP (67.9 m² g⁻¹) > Zn-DP (36.3 m² g⁻¹) > Ni-SP (30.1 m² g⁻¹) > Zn-SP (13.1 m² g⁻¹). Regardless of supported or doped, the Ni-based catalysts always had larger specific surface area than that in the Zn-based catalysts. Unexpectedly, the Zn-based catalysts with smaller surface area for SCWG produced higher hydrogen (H₂) yield from the OPF biomass. When compared to the non-catalytic reaction, the H₂ yield increased by 187.2% for Ni-SP, 269.0% for Zn-SP, 361.7% for Ni-DP, and 438.1% for Zn-DP. Among the studied catalysts, the Zn-DP displayed the highest H₂ yield because it had the highest number of basic sites; approximately twenty-fold higher than that of the Zn-SP catalyst. The Zn-DP also proved to be the most stable catalyst, as verified from the X-Ray photoelectron spectroscopy (XPS) results. As such, this study concludes that the catalytic performances of the synthesized catalysts do not only depend on the specific surface area, but they are also influenced by the number of basic sites and the catalyst stability. It is trustworthy to note that this is the initial study that associated SCWG with doped catalysts. The doped catalysts, hence, may serve as a new catalyst system to generate SCWG reactions.     

High-yield hydrogen production from glucose by supercritical water gasification without added catalyst

Continuous supercritical water gasification of glucose is investigated with a recently developed updraft gasification apparatus under various conditions: temperatures of 600–767 °C, residence times of 15–60 s, glucose concentrations of 1.8–15 wt% and without added a catalyst. The experimental gas yields are compared with predicted values at equilibrium that are estimated via Gibbs free energy minimization. Total gas yields and hydrogen gas yield increase with temperature. At 740 °C and 1.8 wt%, hydrogen gas yields become very high (10.5–11.2 mol/mol glucose). The hydrogen gas yields do not vary significantly with different residence times. The hydrogen gas yield decreases to 5.7 mol/mol glucose at 15 wt%, a value very close to the predicted value (6.3 mol/mol glucose). Only acetic acid is detected in the liquid effluents at temperatures above 740 °C, while 42 products are detected at 600 °C. The highest hydrogen gas yield obtained in this study is 11.5 mol/mol glucose at 25 MPa, 767 °C, and 1.8 wt%, for 60 s; this value is very close to the theoretical equilibrium hydrogen yield of 11.9 mol/mol glucose. Under these conditions, the carbon efficiency is very high (91%) and total organic carbon (TOC) in the liquid product is very low (23 ppm), indicating that glucose is almost completely converted to gaseous products. Comparison with other work under similar operating conditions shows that the current reactor is capable of attaining higher hydrogen gas yields at temperatures above 650 °C. Possible explanations for the higher hydrogen gas yields are presented.     

Partial oxidative gasification of phenol for hydrogen in supercritical water

The paper reports partial oxidative gasification of phenol for hydrogen in supercritical water (SCW) at lower temperature (<753 K), at which cleavages of aromatic ring occur difficultly and tend to undesirable polymerization. The results showed that O₂ is effective to gasification of phenol in SCW. ∼76% of phenol was gasified and 2.7 mol/mol of hydrogen was produced within 180 s with Na₂CO₃ as catalyst at the selected process conditions, a molar ratio of oxygen-to-phenol, 7.5–1, 723 K, and 24 MPa. It was found that unstable opening-rings products oxalic and maleic acid and stable dimmerization compounds in liquid water were formed during partial oxidation process. The process also indicated phenol was rapidly converted, and some opening-rings products were slowly gasified, which also confirmed oxygen served as effective reactant for ring-opening. Based on the given reaction conditions, a treatment process using a real wastewater from coking industry was performed. The data showed that the present technology provides an effective way to gasification of phenol wastewater for high-value energy utilization.     

Thermodynamic study on the integrated supercritical water gasification with reforming process for hydrogen production: Effects of operating parameters

In this paper, a conceptual process design of the integrated supercritical water gasification (SCWG) and reforming process for enhancing H₂ production has been developed. The influence of several operating parameters including SCWG temperature, SCWG pressure, reforming temperature, reforming pressure and feed concentration on the syngas composition and process efficiency was investigated. In addition, the thermodynamic equilibrium calculations have been carried out based on Gibbs free energy minimization by using Aspen Plus. The results showed that the higher H₂ production could be obtained at higher SCWG temperature, the H₂ concentration increased from 5.40% at 400 °C to 38.95% at 600 °C. The lower feed concentration was found to be favorable for achieving hydrogen-rich gas. However, pressure of SCWG had insignificant effect on the syngas composition. The addition of reformer to the SCWG system enhanced H₂ yield by converting high methane content in the syngas into H₂. The modified SCWG enhanced the productivity of syngas to 151.12 kg/100kg_feed compared to 120.61 kg/100kg_feed of the conventional SCWG system. Furthermore, H₂ yield and system efficiency increased significantly from 1.81 kg/100kg_feed and 9.18% to 8.91 kg/100kg_feed, and 45.09%, respectively, after the modification.     

Coupling of hydrothermal pretreatment and supercritical water gasification of sewage sludge for hydrogen production

In this study, hydrothermal pretreatment and supercritical water gasification were coupled to form a combined process for the treatment of dewatered sludge for hydrogen production. First, the effects of varying hydrothermal pretreatment conditions on the transformation of organic matter in sludge were studied. Results showed that about 31% of the carbon in sludge was transferred into liquid products at 250 °C for 60 min, which were considered to be the optimal pretreatment conditions considering both the hydrothermal pretreatment effects and the energy consumption requirements. The organic matter components were determined, showing that 87% of the carbohydrate components in sludge were transformed during the process of hydrothermal pretreatment, with 49% of crude proteins and 62% of humus remaining in the solid phase products. During the subsequent process of supercritical water gasification, AlCl₃, KOH, K₂CO₃ and CaO were selected as catalysts. Compared with directly catalyzed supercritical water gasification of sludge, the integrated process was found to improve H₂ selectivity, H₂ yield and energy recovery. Moreover, the use of AlCl₃ as a catalyst showed the highest H₂ yield and energy recovery. The H₂ yield and the energy recovery increased by 45.1% and 13.2%, respectively.     

CFD modelling of supercritical water reforming of glycerol for hydrogen production

Glycerol, as a main by-product of biodiesel synthesis, can be used in a large variety of applications including food, personal care, pharmaceutical and chemical industries However, due to the large production of biodiesel, the glycerol market was depressed. The conversion of glycerol into an energy carrier (syngas or hydrogen) could be a very interesting route to providing value as a renewable energy source. The reforming of glycerol leads to an almost complete conversion and very high carbon-to-gas efficiency with short residence time.In this work, the performances of packed bed reactor for hydrogen production from glycerol in supercritical conditions, by using a Ni-based catalyst supported on Al₂O₃ and SiO₂, through CFD modelling in three-dimensions were studied. The parameters of kinetic model were determined by using an optimization method to fit the experimental data. The developed model was been validated based on experimental results published in literature for three different feed concentration of glycerol of 5, 10 and 20 wt% (R² = 0.969).Varying the reaction temperature, between 500 and 800 °C, and residence time, between 1.5 and 10 s, the concentration of hydrogen increased with increasing the temperature and decreasing the residence time. At high temperature, the hydrogen can achieve a concentration of 65% and the present of methane is less than 5% and carbon monoxide maintain lower concentration. The simulation results show that high hydrogen yield can be obtained in short residence time with conversion of glycerol almost completed.     

Optimization of hydrogen production from three reforming approaches of glycerol via using supercritical water with in situ CO2 separation

A pathway for hydrogen production from supercritical water reforming of glycerol integrated with in situ CO₂ removal was proposed and analyzed. The thermodynamic analysis carried out by the minimizing Gibbs free energy method of three glycerol reforming processes for hydrogen production was investigated in terms of equilibrium compositions and energy consumption using AspenPlus™ simulator. The effect of operating condition, i.e., temperature, pressure, steam to glycerol (S/G) ratio, calcium oxide to glycerol (CaO/G) ratio, air to glycerol (A/G) ratio, and nickel oxide to glycerol (NiO/G) ratio on the hydrogen production was investigated. The optimum operating conditions under maximum H₂ production were predicted at 450 °C (only steam reforming), 400 °C (for autothermal reforming and chemical looping reforming), 240 atm, S/G ratio of 40, CaO/G ratio of 2.5, A/G ratio of 1 (for autothermal reforming), and NiO/G ratio of 1 (for chemical looping reforming). Compared to three reforming processes, the steam reforming obtained the highest hydrogen purity and yield. Moreover, it was found that only autothermal reforming and chemical looping reforming were possible to operate under the thermal self-sufficient condition, which the hydrogen purity of chemical looping reforming (92.14%) was higher than that of autothermal reforming (52.98%). Under both the maximum H₂ production and thermal self-sufficient conditions, the amount of CO was found below 50 ppm for all reforming processes.     

Experimental basic factors in the production of H2 via supercritical water gasification

This study aims to discuss some of the factors that influence the production of hydrogen via the gasification of organic matter in supercritical water. These factors have been investigated based on the reactions of organic matter with relatively simple chemical structures, such as ethanol, glycerol, and glucose. Investigations of these relatively simple organic materials demonstrate the characteristics and trends in the gasification in supercritical water. The results reported in the literature for these organic compounds can also be extrapolated to the reactions of biomass containing ethanol, glucose, (sugar cane industry) and glycerol (biodiesel industry) in supercritical water. Many organic compounds with different levels of molecular complexity can be used to produce hydrogen, which represents an interesting form of energy storage. Supercritical water (T_c ≥ 374 °C, P_c ≥ 22.1 MPa) has unique physical and chemical properties that minimize mass transport limitations, making it an excellent medium for the decomposition of organic compounds. Thus, understanding the key factors that influence organic compound gasification in supercritical water is extremely important. In this study, we summarize some of the key factors involved in these reactions. The main experimental factors were confirmed to be the temperature, concentration of organic matter in the feed, space time/feed rate, catalysts, oxidants, material and design of the reactor, and pressure. In addition, operational challenges, namely, catalyst deactivation and corrosion are mentioned in the text. Furthermore, the operational challenges were discussed, and the state of the art regarding the gasification of ethanol-, glycerol-, and glucose-containing biomass is also presented.     

Catalytic mechanism study on the gasification of depolymerizing slag in supercritical water for hydrogen production

Supercritical water gasification technology can realize efficient conversion of biomass, coal and other organics into hydrogen rich gas. But the efficiency of non-catalytic gasification at relative low temperature is not high. Besides, as for catalytic gasification, catalysis mechanism is complex. Thus how to improve efficiency and master the catalysis mechanism is a challenging issue. In this thesis, supercritical water gasification of depolymerizing slag experiments with the catalysis of different kinds of catalysts are conducted and the catalysis mechanism is analyzed. The results indicate that catalyst mechanism of K₂CO₃ is that it can promote the swelling and hydrolysis of lignocellulose and increase the amounts of phenolic intermediates. Ru/Al₂O₃ presents some different catalytic properties. It facilitates hydrogenation reaction of hydrolysis products, ring-opening reaction and the cleavage of carbon-carbon bonds then enhances gasification degree and increases gasification efficiency. Moreover, the binary catalyst displays a good synergic effect and the catalytic activity is higher than that of any single catalyst since these two catalysts promote various gasification stages. The gasification efficiency and hydrogen yield increase 13.22 mmol g^?1 and 66.46% respectively with the synergic catalyst of K₂CO₃ and Ru/Al₂O₃.     

Corrosion characteristics of 316L as transpiring wall material in supercritical water oxidation of sewage sludge

Systematical corrosion tests of austenitic stainless steel 316L exposed to sewage sludge SCWO (supercritical water oxidation) were conducted in a batch stirred reactor with hydrogen peroxide as oxidant. Experiment conditions such as temperature, oxidation coefficient, pH value, corrosion medium, were chosen mainly keeping in mind the place and environment of reactions (i.e. surrounding transpiring wall). The exposed samples were ultimately analyzed by weight measurement, scanning electron microscopy in conjunction with energy dispersive spectroscopy, and X-ray diffraction analysis. The results show that severe pitting corrosion occurred as the sample was exposed to complicated environments, and different oxides including Fe₃O₄, FeCr₂O₄ and MoO₃ were found on the sample surface. The corrosion rate at all test conditions (360–450 °C pH = 5.2–10.05, oxidation coefficient of 0–2.0, sewage sludge or its SCWO reactor effluent) was in the range of 0.12–0.66 mm/y, and it increased as temperature and OC increased at supercritical conditions. Moreover, potential corrosion mechanism of 316L in sewage sludge SCWO is proposed, and influences of operating parameters on 316L corrosion properties are summarized. 316L and reactor effluent could be considered as transpiring wall material and transpiring water in sewage sludge SCWO with transpiring wall reactor, respectively.     

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.