Hydrogen production by biomass gasification in supercritical water with bimetallic Ni-M/γAl2O3 catalysts (M = Cu, Co and Sn)

Supercritical water gasification (SCWG) of wet biomass is a very promising technology for hydrogen energy and the utilization of biomass resources. Ni-based catalysts are effective in catalyzing SCWG of original biomass and organic compounds for hydrogen production. In this paper, hydrogen production by SCWG of glucose over alumina-supported nickel catalysts modified with Cu, Co and Sn was studied. The bimetallic Ni-M (M = Cu, Co and Sn) catalysts were prepared by a co-impregnation method and tested in an autoclave reactor at 673 K with a feedstock concentration of 9.09 wt.%. XRD, XRF, N₂ adsorption/desorption, SEM and TGA were adopted to investigate the changes of chemical properties between Ni and Ni-M catalysts and the deactivation mechanism of catalysts. According to the experimental results, the hydrogen yield followed this order: Ni-Cu/γAl₂O₃ > Ni/γAl₂O₃ > Ni-Co/γAl₂O₃ > Ni-Sn/γAl₂O₃. The results show that Cu could improve the catalytic activity of Ni catalyst in reforming reaction of methane to produce hydrogen in SCWG. In addition, Cu can mitigate the sintering of alumina detected by SEM. Co was found to be an excellent promoter of Ni-based catalyst in relation to hydrogen selectivity.     

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 gasification of food waste in supercritical water over La promoted Ni/Al2O3 catalysts for enhancing H2 production

Ni/Al₂O₃ catalyst is the one of promising catalysts for enhancing H₂ production from supercritical water gasification (SCWG) of biomass. However, due to carbon deposition, the deactivation of Ni/Al₂O₃ catalyst is still a serious issue. In this work, the effects of lanthanum (La) as promoter on the properties and catalytic performance of Ni/Al₂O₃ in SCWG of food waste were investigated. La promoted Ni/Al₂O₃ catalysts with different La loading content (3–15 wt%) were prepared via impregnation method. The catalysts were characterized using XRD, SEM, BET techniques. The SCWG experiments were carried out in a Hastelloy batch reactor in the operating temperature range of 420–480 °C, and evaluated based on H₂ production. The stability of the catalysts was assessed by the amount of carbon deposition on catalyst surface and their catalytic activity after reuse cycles. The results showed that 9 wt% La promoter is the optimal loading as Ni/9La–Al₂O₃ catalyst performed best performance with the highest H₂ yield of 8.03 mol/kg, and H₂ mole fraction of 42.46% at 480 °C. La promoted Ni/Al₂O₃ catalysts have better anti-carbon deposition properties than bare Ni/Al₂O₃ catalyst, resulting in better gasification efficiency after reuse cycles. Ni/9La–Al₂O₃ catalyst showed high catalytic activity in SCWG of food waste and had good stability as it was still active for enhancing H₂ production when used in SCWG for the third time, which indicated that La promoted Ni/Al₂O₃ catalysts are potential additive to improve the SCWG of food waste.     

Glucose gasification in super-critical water conditions for both syngas production and green chemicals with a continuous process

The paper reports on experiments of glucose gasification with water in supercritical conditions (SCW). The adoption of these process conditions revealed advantages in terms of biomass conversion efficiency as the resulting liquid phase includes some important compounds (Acetic Acid, 5-HFM, furfurals). In addition the high operative pressures allow either to consider the possibility to use this technology inside the steam cycle in order to produce power and liquid/gaseous biofuels such as synthetic natural gas and/or methanol/DME(di methyl ether). In fact, from the experimental tests, it was possible to evaluate that using glucose, that is the main intermedia of SCW gasification from wet biomass, is possible to estimate a syngas production of about 100 lt – 200 lt for each kg of glucose fed, while the global gasification efficiency was of about 10–18%. Syngas product to SCWG has been analysed and the main results shows that, in the range investigated, CO content was 40–50%vol., H₂ 10–15%, CH₄ 10–20%, C₂+2–8% and at the end CO₂ with a volume content of about 20–30% and then with lower calorific value of about 20 MJ/Nm³. Analysis on the liquid phase was carried out and the main results has been an high production of both 5-hydromethil furfural and 2-Furaldehyde that have a great potential as “carbon-neutral” feedstock for fuels and green chemicals.     

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.     

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.     

Co-precipitated Ni–Mg–Al catalysts for hydrogen production by supercritical water gasification of glucose

Supercritical water gasification (SCWG) is a promising process for hydrogen production from biomass. In this study, a series of Ni–Mg–Al catalysts with different Mg/Al molar ratios has been synthesized by a co-precipitation method for hydrogen production by SCWG of glucose. Effects of Mg addition on the catalytic activity, hydrothermal stability and anti-carbon performance of alumina supported nickel catalyst were investigated. The highly dispersed nickel catalysts prepared by co-precipitation could greatly enhance the gasification efficiency of glucose in supercritical water. Among the tested Ni–Mg–Al catalysts, NiMg_0.6Al_1.9 showed the highest catalytic activity with the hydrogen yield of 11.77 mmol/g (912% as that of non-catalytic test). NiMg_0.6Al_1.9 also showed the best hydrothermal stability probably due to the formation of MgAl₂O₄. Mg could efficiently improve the anti-carbon ability of Ni–Al catalyst by inhibiting the formation of graphite carbon. It is also confirmed that MgO supported nickel catalyst is not suitable for SCWG process owing to the difficulty on nickel oxides reduction in the precursors and the phase change of MgO to Mg(OH)₂ under the hydrothermal condition.     

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.     

New sustainable bioconversion concept of date by-products (Phoenix dactylifera L.) to biohydrogen,biogas and date-syrup

The dates production is usually accompanied by considerable loss of fruit byproducts. The chemical analysis showed that ‘Deglet Nour’ discarded flesh is rich in soluble sugars (79.8% ± 0.8%) and fibers (12.3% ± 0.4%). A processing approach was implemented to permit the production of biohydrogen from the flesh and biogas from the crude fiber fraction after soluble sugars extraction. This approach showed interesting results since the obtained biochemical hydrogen potential and the maximum methane yield were 292 mL H₂/gVS _initial and 235 mL CH₄/gVS _fibers respectively. Parallelly, the “hot water” soluble sugar fraction (date syrup) was of interest for agro-alimentary applications and showed a high sucrose, glucose and fructose content of 33.5%, 11.8% and 13.17% respectively. This study presents a proof of concept allowing an efficient sustainable energetic conversion of the date by-products biomass to biohydrogen via dark fermentation or to soluble sugars fraction and biogas via a biorefinery approach.     

Influence of AlCl3 and oxidant catalysts on hydrogen production from the supercritical water gasification of dewatered sewage sludge and model compounds

Hydrogen has attracted significant attention as a clean energy source. Supercritical water gasification (SCWG) technology can produce hydrogen-rich gas while also disposing of sludge. The hydrogen yield from the SCWG of sludge is greatly increased when catalyzed by AlCl₃. In this paper, a combined catalyst based on AlCl₃ was proposed to further increase the hydrogen yield of SCWG of dewatered sewage sludge (DSS). Analysis of the products from catalytic gasified of DSS and its model compounds were used to propose a catalytic mechanism and reaction pathway of the catalytic SCWG of DSS. Among the combined catalysts used for the SCWG of DSS, 10 wt% AlCl₃–H₂O₂ (mass ratio 8:2) had the best hydrogen production effect, and the hydrogen yield reached 8.88 mol/kg organic matter. This was 14% higher than when catalyzed by 10 wt% AlCl₃. During catalysis with AlCl₃, Al³⁺ reacted with OH⁻ in water and precipitated as Al(OH)₃, which produced an acidic environment in the liquid product. Al(OH)₃ dehydrated to form an AlO(OH) and deposited in the solid product. A small amount of H₂O₂ promoted the steam reforming reaction of organic matter in DSS, which increased the hydrogen yield. H₂O₂ further promoted the hydrogen yield in an acidic environment. The catalytic effect of AlCl₃ was unaffected by H₂O₂. The H⁺ generated by AlCl₃ during catalysis promoted H₂O₂ to further depolymerized organic matter (such as humic substances) in DSS, so that AlCl₃–H₂O₂ catalyzed the SCWG of DSS to further increase the hydrogen yield. The order of hydrogen yield catalyzed by AlCl₃–H₂O₂ was guaiacol > humic acid > glycerol > alanine > glucose. Compared with AlCl₃, AlCl₃–H₂O₂ reduced the hydrogen yield of glucose by nearly 20% and increased the hydrogen yield of humic acid by about 17% (25.81 mol/kg feed).     

Investigation of the interaction between intermediates from gasification of biomass in supercritical water: Formaldehyde/formic acid mixtures

Supercritical water gasification (SCWG) is a promising technology for converting wet biomass and waste into renewable energy. While the fundamental mechanism involved in SCWG of biomass is not completely understood, especially hydrogen (H₂) production produced from the interaction among key intermediates. In the present study, formaldehyde mixed with formic acid as model intermediates were tested in a batch reactor at 400 °C and 25 MPa for 30 min. The gas and liquid phases were collected and analyzed to determine a possible mechanism for H₂ production. Results clearly showed that both gasification efficiency (GE) and hydrogen efficiency (HE) increased with addition of formic acid, and the maximum H₂ yield reached 17.92 mol/kg with a relative formic acid content of 66.67% in the mixtures. The total organic carbon removal rate and formaldehyde conversion rate also increased to 67.33% and 89.81% respectively. The reaction pathways for H₂ formation form mixtures was proposed and evaluated, formic acid promoted self-decomposition of formaldehyde to generate H₂, and induced a radical reaction of generated methanol to produce more H₂.     

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.     

Structural effect of ZrO2 on supported Ni-based catalysts for supercritical water gasification of oil-containing wastewater

Supercritical water gasification (SCWG) is a promising technology to treat oil-containing wastewater. This study reports a Ni/ZrO₂ catalyst with mixed phase of tetragonal ZrO₂ and monoclinic ZrO₂ synthesized by a one-step sol-gel method, which shows good catalytic activity and stability in SCWG of oil mixture. The evolution of particle size, crystal structure, and pore size caused by increasing calcination temperature is demonstrated by X-ray diffraction and transmission electron microscopy. When calcined at 700 °C, Ni/ZrO₂ shows superior catalytic activity and stability in SCWG reaction, with a high carbon gasification efficiency of 91.3% at 500 °C. The characterizations of fresh and spent catalysts suggest that Ni/ZrO₂ catalyst with the fraction of monoclinic ZrO₂ around 75% would be highly active and stable in SCWG reaction. In addition, two sets of optimal gasification conditions of SCWG of oil are obtained by varying operating parameters, which provides guidance for different concentrations of oil-containing wastewater treatment.     

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.     

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.     

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.     

Screening of supported transition metal catalysts for hydrogen production from glucose via catalytic supercritical water gasification

In total 17 heterogeneous catalysts, with combinations of 4 transition metals (Ni, Ru, Cu and Co) and various promoters (e.g., Na, K, Mg, or Ru) supported on different materials (γ-Al₂O₃, ZrO₂, and activated carbon (AC)), were investigated with respect to their catalytic activity and stability for H₂ production from glucose via supercritical water gasification (SCWG). The experiments were carried out at 600 °C and 24 MPa in a bench-scale continuous-flow tubular reactor. Ni (in metallic form) and Ru (in both metallic and oxidized forms) supported on γ-Al₂O₃ exhibited very high activity and H₂ selectivity among all of the catalysts investigated for a time-on-stream of 5-10 h. With Ni20/γ-Al₂O₃ (i.e., γ-Al₂O₃ with 20 wt% Ni), a H₂ yield of 38.4 mol/kg glucose was achieved, approximately 20 times higher than that obtained during the blank test without catalyst (1.8 mol/kg glucose). In contrast, Cu and Co catalysts were much less effective for glucose SCWG reactions. As for the effects of catalyst support materials on activity, the following order of sequence was observed: γ-Al₂O₃ > ZrO₂ > AC. In addition, Mg and Ru were found to be effective promoters for the Ni/γ-Al₂O₃ catalyst, suppressing coke and tar formation.     

Waste to energy by industrially integrated supercritical water gasification - Effects of alkali salts in residual by-products from the pulp and paper industry

Supercritical water gasification (SCWG) is a method by which biomass can be converted into a hydrogen-rich gas product. Wet industrial waste streams, which contain both organic and inorganic material, are well suited for treatment by SCWG. In this study, the gasification of two streams of biomass resulting from the pulp and paper industry, black liquor and paper sludge, has been investigated. The purpose is to convert these to useful products, both gaseous and solids, which can be used either in the papermaking process or in external applications. Simple compounds, such as glucose, have been fully gasified in SCWG, but gasification of more complex compounds, such as biomass and waste, have not reached as high conversions. The investigated paper sludge was not easily gasified. Improving gasification results with catalysts is an option and the use of alkali salts for this purpose was studied. The relationship between alkali concentration, temperature, and gasification yields was studied with the addition of KOH, K₂CO₃, NaOH and black liquor to the paper sludge. Addition of black liquor to the paper sludge resulted in similarly enhancing effects as when the alkali salts were added, which made it possible to raise the dry matter content and gasification yield without expensive additives.     

Supercritical water gasification of black liquor with wheat straw as the supplementary energy resource

Supercritical water gasification (SCWG) is a new treatment of black liquor (BL) for both energy recovery and pollution management. To provide more energy for the pulp mill, it is proposed to use the pulping raw material as supplementary energy source because it is readily available, inexpensive and renewable. In this study, co-gasification of BL and wheat straw (WS) in supercritical water was investigated. The synergistic effect was observed in the co-gasification because the addition of wheat straw can make better use of the alkali in BL. The maximum improvement of the gasification by the synergistic effect was obtained with the mixing ratio of 1:1. The influences of the temperature (500–750 °C), reaction time (5–40 min), mixture concentration (5.0–19.1 wt%), mixing ratio (0–100%) and the wheat straw particle diameter (74–150 μm) were studied. It was found that the increase of temperature and reaction time, and the decrease of concentration and wheat straw particle size favored the gasification by improving the hydrogen production and gasification efficiency. The highest carbon gasification efficiency of 97.87% was obtained at 750 °C. Meanwhile, the H₂ yield increased from 12.29  mol/kg at 500 °C to 46.02  mol/kg. This study can help to develop a distributed energy system based on SCWG of BL and raw biomass to supply energy for the pulp mill and surrounding communities.     

Supercritical water gasification and partial oxidation of municipal sewage sludge: An experimental and thermodynamic study

Supercritical gasification (SCWG) and supercritical partial oxidation (SCWPO) technologies have emerged as preferred means of converting wet biomass to hydrogen-rich gases. We experimentally investigated the effects of moisture content, pressure and oxidation coefficient (n) on mole fraction, yield, gasification efficiency and energy recovery of gaseous products from SCWG or SCWPO of municipal sewage sludge, as well as on the carbon and nitrogen contents in liquid products. Potential of sludge for producing gaseous products was thermodynamically analyzed by an Aspen Plus model. The results show that 87 wt%, 25 MPa and n = 0 were optimum conditions for sludge gasification. Sludge with 87 wt% moisture content was pumpable at 75 °C, and further increasing the moisture content decreased the heating value and energy recovery of gaseous products. Pressure played little role in both the experimental and equilibrium gas yields. Highest mole fractions and yields of H₂ and CH₄ were achieved at n = 0.