Experimental study on the energy conversion of food waste via supercritical water gasification: Improvement of hydrogen production

In this study, the model food waste was gasified to hydrogen-rich syngas in a batch reactor under supercritical water condition. The model food consisted of rice, chicken, cabbage, and cooking oil. The effects of the main operating parameters including temperature (420–500 °C), residence time (20–60 min) and feedstock concentration (2–10 wt%) were investigated. Under the optimal condition at 500 °C, 2 wt% feedstock and 60 min residence time, the highest H₂ yield of 13.34 mol/kg and total gas yield of 28.27 mol/kg were obtained from non-catalytic experiments. In addition, four commercial catalysts namely FeCl₃, K₂CO₃, activated carbon, and KOH were employed to investigate the catalytic effect of additives at the optimal condition. The results showed that the highest hydrogen yield of 20.37 mol/kg with H₂ selectivity of 113.19%, and the total gas yield of 38.36 mol/kg were achieved with 5 wt% KOH addition Moreover, the low heating value of gas products from catalytic experiments with KOH increased by 32.21% compared to the non-catalytic experiment. The catalytic performance of the catalysts can be ranked in descending order as KOH > activated carbon > FeCl₃ > K₂CO₃. The supercritical water gasification (SCWG) with KOH addition can be a potential applied technology for food waste treatment with production of hydrogen-rich gases.     

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.     

Assessment of supercritical water gasification of food waste under the background of waste sorting: Influences of plastic waste contents

Waste sorting is being gradually implemented as a key measure for circular and sustainable development in China, food waste will be separately collected and separated from municipal solid waste (MSW), thus the plastic content in food waste also will be reduced. In this study, supercritical water gasification (SCWG) of food waste with different contents of plastic (0–3.5 wt%) was experimentally investigated to simulate the influence of waste sorting on the food waste treatment. The results showed that lower plastic content in food waste favored higher gas yield and gasification efficiencies. The highest H₂ yield and total gas yield were 3.11 mol/kg and 8.41 mol/kg in the plastic-free case, respectively. When the plastic content decreased from 3.5 wt% to 0 wt%, the cold gas efficiency (CGE), carbon conversion efficiency (CE) and hydrogen gasification efficiency (HE) increased by 125.97%, 173.48% and 94.09%, respectively. However, lower plastic content negatively affected the quality of produced syngas through decreasing H₂ mole fraction and LHV. The solid residues from SCWG of food waste with lower plastic content had higher ratio of fixed carbon to volatile matter (FC/VM). Based on the analysis of pyrolysis properties and combustion behavior, decreasing the plastic content in food waste helped to improve the thermal stability of solid residues. Moreover, lower plastic content resulted in a decrease of total organic carbon (TOC) concentration in liquid effluent, which is favorable for further treatment of liquid effluent.     

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.     

Activity of Ni/CeO2 catalyst for gasification of phenol in supercritical water

An effective Ni/CeO₂ catalyst prepared by the polyol reduction method for degrading phenol into CH₄, H₂ and CO₂ in supercritical water (SCW) was developed. About 80% carbon gasification efficiency can be achieved at 525 °C and 60 min with 5 wt% phenol, 0.098 kg/m³ water density and 0.5 g Ni/CeO₂/g phenol catalyst, forming CH₄ and H₂ as the main gaseous products. Comparison study indicated that the efficiency of present Ni/CeO₂ catalyst was about 20% higher than that of a commercial catalyst, i.e., Ni/SiO₂Al₂O₃ from Sigma-Aldrich with 65 wt%Ni, at a reaction conditions of 500 °C and 30 min. The characterization analyses of BET, TPR, XRD, XPS and TEM indicated that there was a NiCe alloy formed in Ni/CeO₂, which could be important to enhance the activities of the carbon gasification efficiencies and gas yields. A kinetic modelings were conducted and the results showed that the lnA and the activation energy (Ea) of gasification were 7.1 ± 0.5 and 58.1 ± 3.2 kJ/mol for the gaseous product, and were 2.6 ± 0.9 and Ea is 36.6 ± 5.6 kJ/mol for the char formation, respectively. The present Ni-based-metal Ni/CeO₂ catalyst is cheaper and has a potential application for the gasification to convert phenol into gases fuels in SCW process.     

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.     

Supercritical water gasification of food waste: Effect of parameters on hydrogen production

Food waste is a type of municipal solid waste with abundant organic matter. Hydrogen contains high energy and can be produced by supercritical water gasification (SCWG) of organic waste. In this study, food waste was gasified at various reaction times (20–60 min) and temperatures (400 °C-450 °C) and with different food additives (NaOH, NaHCO₃, and NaCl) to investigate the effects of these factors on syngas yield and composition. The results showed that the increase in gasification temperature and time improved gasification efficiency. Also, the addition of food additives with Na⁺ promoted the SCWG of food waste. The highest H₂ yield obtained through non-catalytic experiments was 2.0 mol/kg, and the total gas yield was 7.89 mol/kg. NaOH demonstrated the best catalytic performance in SCWG of food waste, and the highest hydrogen production was 12.73 mol/kg. The results propose that supercritical water gasification could be a proficient technology for food waste to generate hydrogen-rich gas products.     

Review of heterogeneous catalysts for sub- and supercritical water gasification of biomass and wastes

Nowadays, substantial efforts are devoted to decrease our dependence on fossil fuels. This change will heavily rely on development of new and improved catalytic processes. Over the past two decades, catalytic hydrogen production from wet biomass and organic compounds in sub- and supercritical water (SCW) has gained significant attention. In this process, catalysts are employed to enhance the gas formation rate at moderate temperatures. Catalysts can be also utilized to shift the product distribution toward a more desirable compound (e.g. hydrogen). The effectiveness of various types of heterogeneous catalysts, mainly containing nickel and ruthenium, have been demonstrated for hydrothermal gasification of organic compounds. Catalyst formulation along with operating conditions such as temperature and feed concentration can significantly affect the conversion and selectivity of the process. This paper reviews the major findings of hydrothermal gasification over the past two decades with the aid of heterogeneous catalysts in terms of activity, hydrogen selectivity and stability. Commercially available and laboratory-prepared catalysts including supported and skeletal metal catalysts, activated carbon, oxides, metal wires and other innovative catalysts are considered. Results of supercritical water gasification (SCWG) of various feedstocks reported in the literature are compared and possible mechanisms and rates of deactivation of heterogeneous catalysts are discussed.     

Hydrogen production via supercritical water gasification of almond shell over algal and agricultural hydrochars as catalysts

Almond shell is one of the most abundant agricultural wastes in Kurdistan province of Iran. Conversion of almond shell into hydrogen-rich gas via supercritical water gasification (SCWG) was investigated in this study using a tubular batch micro-reactor system. Non-catalytic tests were carried out in different conditions to determine the optimum condition for H₂ production. Maximum hydrogen yield of 7.85 mmol/g, was observed in the temperature of 460 °C, residence time (RT) of 10 min and feed/water ratio (F/W) of 0.01. Catalytic experiments were performed using hydrochars as solid residues remained after SCWG of Cladophora glomerata (C. glomerata) macroalgae and wheat straw. Hydrochars were characterized by ICP-OES, FESEM and BET methods. For catalytic experiments, hydrochars were added to the almond shell by the weight ratio of 0.4. Conversion of almond shell and hydrogen production, were more influenced by the presence of inorganic compounds in the hydrochars rather than the surface area and pore volume. The maximum hydrogen yields of 10.77 and 11.63 mmol/g, were observed for catalytic experiments in the presence of wheat straw and C. glomerata hydrochars, respectively.     

Catalytic gasification of light and heavy gas oils in supercritical water

Canada has the third-largest oil sand reserves in the world as a result of which, it generates considerable amounts of light gas oil and heavy gas oil through petroleum distillation. With the escalating energy demands, it has become essential to explore alternative fuel resources from biomass and petrochemical residues. This study explores the potential of supercritical water gasification to transform light and heavy gas oils to hydrogen-rich syngas through the optimization of process conditions such as temperature (375–675 °C), feed concentration (20–35 wt%) and reaction time (30–75 min). Nickel-supported functionalized carbon nanotubes (10%Ni/FCNT) were synthesized for application in catalytic supercritical water gasification. The functionalization of carbon nanotubes resulted in an increase in their surface area from 108 m²/g (in pristine CNT) to 127 m²/g (in FCNT) and 122 m²/g (in 10%Ni/FCNT). The impregnation of catalytic nickel particles onto carbon nanotubes was confirmed through X-ray diffraction (XDR) and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). Fourier-transform infrared (FTIR) spectroscopy of both gas oils revealed the presence of aliphatics, alkyl-aryl ethers and sulfur-containing compounds among several other aromatics. Light gas oil revealed higher hydrogen yields of 3.32 mol/kg compared to that of heavy gas oil (2.79 mol/kg) at optimal process conditions, i.e. 675 °C and 75 min, 20 wt% feed concentration. However, 10%Ni/FCNT enhanced hydrogen yields (4.46 mol/kg), total gas yield (9.22 mol/kg), hydrogen selectivity (94%) and lower heating value (1685 MJ/kg) of product gases obtained from light gas oil in contrast to heavy gas oil. This study indicates a tremendous potential of gas oils for hydrogen generation via hydrothermal gasification.     

Pellet size dependent steam reforming of polyethylene terephthalate waste for hydrogen production over Ni/La promoted Al2O3 catalyst

The effect of different pellet sizes of nickel (Ni) and lanthanum (La) promoted Al₂O₃ support on the catalytic performance for selective hydrogen production from polyethylene terephthalate (PET) plastic waste via steam reforming process has been investigated. The catalysts were prepared by impregnation method and were characterized using XRD, BET, TPD-CO₂, TPR, SEM, EDX, TEM and TGA. The results showed that NiLa-co-impregnated Al₂O₃ catalyst has excellent activity for the production of hydrogen. Feed conversion of 88.53% was achieved over 10% Ni/Al₂O₃ catalyst which increased to 95.83% in the case of 10% Ni-5% La/Al₂O₃ catalysts with a H₂ selectivity of 70.44%. The catalyst performance in term of gas production and feed conversion was further investigated under various operating parameters, e.g., feed flow-rate, and catalyst pellet size. It was found that at 0.4 ml/min feed flow rate, highest feed conversion and H₂ selectivity were achieved. The Ni particles, which are the noble-based active species are highly effective, thus offered good hydrogen production in the phenol-PET steam reforming process. Incorporation of La as a promoter in Ni/Al₂O₃ catalyst has significantly increased the catalyst reusability with prolonged stability. The NiLa/Al₂O₃ catalyst with larger size showed remarkable activity due to the presence of significant temperature gradients inside the pellet compared to smaller size. Additionally, the catalyst showed only slight decrease in H₂ selectivity and feed conversion even after 24 h, although production of carbon nanotubes was evidenced on its surface.     

Oleic acid gasification over supported metal catalysts in supercritical water: Hydrogen production and product distribution

Oleic acid was examined as a model compound for lipids, which was gasified in supercritical water (SCW) using a batch reactor from 400 to 500 °C at 28 MPa. The influence of operating temperature and several commercial catalysts on the gasification efficiency, hydrogen gas yield, and residual liquid product quality was examined and discussed. The main gaseous components measured were carbon dioxide (CO₂), hydrogen (H₂), methane (CH₄), and traces of carbon monoxide (CO). The residual liquid after reaction was characterized by analyzing the chemical oxygen demand (COD), total organic carbon (TOC), volatile fatty acids (VFAs), and the long chain fatty acids (LCFAs), namely, palmitic, myristic, stearic, linoleic, and oleic acids. The results showed that an increase of temperature coupled with the use of catalyst enhanced the gas yield dramatically. The H₂ yield was 15 mol/mol oleic acid converted using both the pelletized Ru/Al₂O₃ and powder Ni/Silica-alumina catalysts which gave 4 times higher than the equilibrium yield. The COD reduction efficiency ranged from 31% at 400 °C without catalyst to 96 % at 500 °C in the presence of Ni/Silica-alumina catalyst. The composition of residual liquid products was studied using gas chromatography/mass spectrometry (GC-MS), with a generalized reaction pathway for oleic acid decomposition in SCW reported.     

Comprehensive experimental study on supercritical water gasification of oilfield sludge: Effect of operation parameters,and catalysts on the products

Supercritical water gasification (SCWG) was adopted to treat oilfield sludge and produce syngas. The effect of temperature (400–450 °C), reaction time (30–90 min) and catalyst addition on syngas production and residual products during SCWG of oilfield sludge was studied. When increasing SCWG temperature from 400 to 450 °C with reaction time of 60 min, the H₂ yield and the selectivity of H₂ increased significantly from 0.53 mol/kg and 75.53% to 0.98 mol/kg and 78.09%, respectively. It is noteworthy that when the reaction time was too long, CO₂ and CO were converted to CH₄ with the consumption of H₂ via methanation reaction. The addition of Ni/Al₂O₃ catalyst can substantially promote the production of high-quality syngas from SCWG of oilfield sludge. The H₂ yield and its selectivity at 450 °C and 60 min were as high as 1.37 mol/kg and 84.05% with 10Ni/Al catalyst. Moreover, the catalysts with bimetal loading (Fe–Ni, Rb–Ni or Ce–Ni) were found to be beneficial for improving gasification efficiency, H₂ yield, and the degradation of organic compounds. Among them, 5 wt% Rb on 10Ni/Al catalyst performed the best catalytic activity for SCWG at 450 °C and 60 min, which had the highest H₂ yield of 1.67 mol/kg and selectivity of 86.09%. More than 90% of total organic carbon in sludge was decomposed after the SCWG with all the catalysts. These findings indicated that catalytic SCWG is a promising alternative for efficiently dealing with oilfield sludge.     

Effect of nickel loading on hydrogen production and chemical oxygen demand (COD) destruction from glucose oxidation and gasification in supercritical water

Gasification and partial oxidation of 0.25 molar glucose solution was conducted over different metallic nickel (Ni) loadings (7.5, 11, and 18 wt%) on different catalyst supports (θ-Al₂O₃ and γ-Al₂O₃) in supercritical water. Experiments were carried out at three different temperatures (T) of 400, 450, and 500 °C at constant pressure of 28 MPa and a 30 min reaction time (t). For comparison, some experiments were conducted using high loading commercial catalyst (65 wt% Ni on Silica–alumina). Hydrogen peroxide (H₂O₂) was used as a source of oxygen in the partial oxidation experiments. Oxygen to carbon molar ratios (MR) of 0.5–0.9 were examined to increase the hydrogen production via carbon monoxide (CO) production. Results showed that in the absence of the catalyst, the optimum molar ratio was 0.8 i.e. 80% of the amount of oxygen required for complete oxidation of glucose. At a molar ratio of 0.8, the hydrogen yield was 0.3 mol/mol, as compared to 0.2 mol/mol glucose at molar ratio of 0.5 and 0.9. This optimized oxygen dose was adopted as a base line for catalysts evaluation. The main gaseous products were carbon dioxide (CO₂), carbon monoxide (CO), hydrogen (H₂), and methane (CH₄). Results also showed that the presence of Ni increased the total gas yield increased in the 7.5–18 wt Ni/Al₂O₃ catalyst. An increase in MR from 0.55 to 0.8 increased the of carbon dioxide and hydrogen yields from 1.8 to 3.8 mol/mol glucose and from 0.9 to 1.1 mol/mol. The carbon monoxide and methane yields remain constant at 2 and 0.5 mol/mol glucose, respectively. The introduction of hydrogen peroxide (H₂O₂) prior to the feed injection inhibited the catalyst activity and did not increase the hydrogen yield whereas the introduction of H₂O₂ after 15 min of reaction time increased the hydrogen yield from 0.62 mol/mol to 1.5 mol/mol. This study showed that approximately the same hydrogen yield can be obtained from the synthesized low nickel alumina loading (18 wt%) catalyst as with the 65 wt% nickel on silica–alumina loading commercial catalyst. The highest H₂ yield of 1.5 mol/mol glucose was obtained with commercial Ni/silica–alumina with a BET surface area of 190 m²/g compared to 1.2 mol/mol with the synthesized Ni/θ alumina with a BET surface area of 46 m²/g.     

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.     

Stability and activity of a co-precipitated Mg promoted Ni/Al2O3 catalyst for supercritical water gasification of biomass

We have investigated the stability and activity of a co-precipitated Mg promoted Ni/Al₂O₃ catalyst (Ni-Mg-Al) for supercritical water gasification (SCWG) of various biomass model compounds and real biomass. Phase stability and activity recovery of the Ni-Mg-Al catalyst were first compared with a catalyst prepared by impregnation method. It was found that the co-participated catalyst showed higher activity recoveries than the impregnated catalyst due to the stable Ni crystal size. Then, effects of SCWG variables including heating up rate, gasification temperature, catalyst loading amount and feedstock concentration, on the non-catalytic and catalytic gas yields and gasification efficiencies of glucose and phenol were evaluated. Results demonstrated that the presence of sufficient amount of Ni catalyst could realize complete carbon gasification of different organics, including phenol and real biomass. Catalyzed by Ni, CH₄ was the more favored produced gas at 400–500 °C while H₂ yields were more abundant at 500–600 °C. Without catalyst, carbon gasification efficiencies of SCWG of different feedstock were in the order: glycerol > glucose > cellulose ≈ corncob ≈ poplar leaf ≈ sawdust > phenol, while those catalyzed by Ni were in the order: glycerol ≈ glucose ≈ cellulose ≈ phenol > corncob ≈ poplar leaf ≈ sawdust, illustrating that the co-precipitated NiMgAl catalyst is more active on catalyzing the gasification of water-soluble organics than real biomass.     

Catalytic performances of Ni-based catalysts on supercritical water gasification of phenol solution and coal-gasification wastewater

Activity and stability of the supported Ni-based catalysts for the gasification performances of phenol solution and coal-gasification wastewater in supercritical water were studied in a continuous reactor at 480 °C, 25 MPa and oxygen ratio of 0.2 for 50 h operation. The influences of the supports (γ-Al₂O₃, active carbon (AC) and carbon nanotube (CNT)) on gas yields, gasification efficiencies for phenol solution were investigated, and the loading amount of Ni were optimized. Results showed that the catalytic activity and the stability of the catalysts followed the order of Ni/CNT > Ni/AC > Ni/γ-Al₂O₃. The activity of Ni/AC and Ni/γ-Al₂O₃ decreased after 30 h continuous operation, and there occurred significant leaching of Ni²⁺. For Ni/CNT catalyst, H₂ yield increased obviously when the loading amount of Ni lower than 15 wt%, while increased little at higher loading amount. Then, 15 wt% Ni/CNT with a thickness of 1.5 mm was coated on 316 L stainless steel (SS316L, an economic material usually used as the reactor material), which can act as a "catalytic tube wall" in reactor. The catalytic activity and corrosion resistance of Ni/CNT/SS316L for the gasification of real coal-gasification wastewater were studied. Results showed that Ni/CNT/SS316L gave a great positive effect on H₂ production. H₂ yield increased from 25.36 mmol/g (total organic carbon) without catalyst to 75.12 mmol/g (total organic carbon) with Ni/CNT/SS316L after operated for 20 h, respectively. However, obvious pealing of the coating was found after 50 h operation. Further study is necessary for the improvement of the coating preparation method.     

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.     

Evaluation of catalytic subcritical water gasification of food waste for hydrogen production: Effect of process conditions and different types of catalyst loading

Food waste is a kind of wet bio-waste which has been a challenge for the ecological environment and disposal. In this paper, hydrogen production from subcritical water gasification (SbWG) of food waste with and without catalyst loading was systematically investigated. The effects of reaction temperature (300–360 °C), residence time (30–90 min), food waste concentration (10–30 wt%) and catalysts (Ni/γ-Al₂O₃, Ni/ZrO₂, NaOH, KOH, and FeCl₃) were studied within a pressure range of 10.5–20 MPa. The optimal process condition for SbWG of food waste without catalysts loading was determined to be 360 °C and 90 min with 10 wt% food waste. The liquid products and hydrochar were characterized by TOC, TGA/DTG, and SEM. The TOC concentration of liquid products decreased vastly with increasing reaction temperature. The highest H₂ yield (1.88 mol/kg), H₂ mole fraction (35.01%), and H₂ selectivity (53.86%) were achieved at 360 °C for 90 min with 5 wt% loading of KOH. It can be concluded that the performance of the catalysts for improving hydrogen production in SbWG of food waste was in the following order: KOH > NaOH > Ni/γ-Al₂O₃ > Ni/ZrO₂ > FeCl₃. The catalytic SbWG can be a potential alternative for energy conversion of food waste and hydrogen production.     

Catalytic supercritical water gasification of black liquor along with lignocellulosic biomass

Supercritical water gasification (SCWG) is a novel technology for environmental pollution management and hydrogen production from biomass and wastes. In this study, the SCWG of black liquor (BL) which is high-potential biomass and rich in alkalis was investigated. The experiments were conducted in a batch reactor at 350–400 °C, reaction time of 1–60 min, and constant concentration of 9 wt% of BL in the absence and presence of heterogeneous catalysts (3–5 wt%), lignocellulosic biomass, and formic acid (5 and 7 wt %) in three parts. First, the SCWG of BL was performed without any additive. The experimental results showed that the maximum production of H₂, CO₂, and CH₄ was obtained at the highest temperature and reaction time; 400 °C and 60 min. The hydrogen yield was also enhanced by increasing the temperature, and reached 3.51 mol H₂/kg dry ash free-black liquor (DAF-BL) at 400 °C. Reaction time increment improved the gas product and gasification efficiency up to 28.03 mmol and 21.73%, respectively. Subsequently, three heterogeneous catalysts (MnO₂, CuO, and TiO₂) were used, however 5 wt% of MnO₂ was the best catalyst, significantly improving the hydrogen yield compared to the same condition of BL gasification without a catalyst. Hydrogen yield reached 5.09 mol H₂/kg (DAF-BL) at 400 °C and the reaction time of 10 min. Finally, BL with poplar wood residue as a lignocellulosic biomass and formic acid was gasified separately and the highest hydrogen yield was obtained in the case of 5 wt% of formic acid (10.79 mol H₂/kg (DAF-BL)). Overally, SCWG dramatically reduced the chemical oxygen demand of BL to 76% using 5 wt% of formic acid.