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 by sewage sludge gasification in supercritical water with a fluidized bed reactor

In this work, gasification of sewage sludge in supercritical water was investigated in a fluidized bed reactor. Effect of operating parameters such as temperature, concentration of the feedstock, alkali catalysts and catalyst loading on gaseous products and carbon distribution were systematically studied. The results showed that the increase of temperature and the decrease of feedstock concentration were both favorable for gasification, and the addition of catalyst enhanced the formation of hydrogen better. The K₂CO₃ catalyst could better enhance gasification efficiency and the catalytic activity of different catalysts for hydrogen production was in the following order: KOH > K₂CO₃ > NaOH > Na₂CO_3. The maximum molar fraction and yield of hydrogen reached to 55.96% and 15.49 mol/kg respectively with KOH at 540 °C. Most carbon in feedstock existed in gaseous and liquid products, and alkali catalysts mainly promoted the water-gas shift reaction rather than steam reforming.     

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.     

Valorization of sewage sludge through catalytic sub- and supercritical water gasification

Sub- and supercritical water gasification is applied to recover energy from sewage sludge in a batch reactor. The effects of reaction temperature and water-soluble additives as catalysts on gasification were examined. The resultant products, including syngas, hydrochar and liquid residues were characterized. The rise of temperature without the presence of catalysts increased the yield of H₂ (0.06 (350 °C) to 1.91 mol/kg (450 °C) and enhanced the gasification efficiency (1.29–19.61%), and decreased total organic carbon (TOC) by 68.50% in liquid residue. The changes in product distribution and characteristics of hydrochar and liquid residue implied that the organic matters in sewage sludge were dissolved and hydrolyzed in sub- and supercritical water, resulting in the production of syngas. The catalytic effect of different catalysts in relation to the H₂ gas yield was in the following order: KOH > NaOH > Na₂CO₃ ≈ K₂CO₃. In the case of catalytic supercritical water gasification at 400 °C, the highest molar fraction (37.28%) and yield of H₂ (1.60 mol/kg) were obtained in the presence of KOH. Furthermore, the scanning electron microscopy (SEM) analysis indicated that a conversion and dissolution of the organic matters in sewage sludge to liquid and gas, produced a porous, fragmented structure and disintegrated surface of hydrochar.     

Influence of NaOH and Ni catalysts on hydrogen production from the supercritical water gasification of dewatered sewage sludge

Dewatered sewage sludge was treated with NaOH additive and Ni catalyst in supercritical water in a high-pressure autoclave to examine the effects of separate and combined NaOH additive and Ni catalyst on hydrogen generation. The effects of Ni/NaOH ratio on hydrogen production were also investigated to identify possible catalytic mechanism and interactions. NaOH and Ni, separately or in combination, improved the hydrogen production and hydrogen gasification efficiency. The addition of NaOH additive not only promoted the water–gas shift reaction, but also favored H₂ generation of Ni catalyst by capturing CO₂. The hydrogen yield of combined catalysts with different Ni/NaOH ratios was higher than the theoretical sum of hydrogen yield from the mixture by 10–33%. The largest hydrogen yield, of 4.8 mol per kilogram of organic matter, which was almost five times as much as without catalyst, was achieved with the addition of 3.33 wt% Ni and 1.67 wt% NaOH. The combined NaOH additive and Ni catalyst also improved the gasification of several other dewatered sewage sludges, increasing the hydrogen yield by four to twelve times that seen without catalyst. Combined NaOH additive and Ni catalyst are effective in dewatered sewage sludge gasification at low temperature.     

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.     

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.     

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.     

Hydrogen production from 2-propanol over Pt/Al2O3 and Ru/Al2O3 catalysts in supercritical water

One of the alternative energy sources to fossil fuels is the use of hydrogen as an energy carrier, which provides zero emission of pollutants and high-energy efficiency when used in fuel cells, hydrogen internal combustion engines (HICE) or hydrogen-blend gaseous fueled internal combustion engines (HBICE). The gasification of organics in supercritical water is a promising method for the direct production of hydrogen at high pressures, with very short reaction times. In this study, hydrogen production from 2-propanol over Pt/Al₂O₃ and Ru/Al₂O₃ catalysts was investigated in supercritical water. To investigate the influences on hydrogen production, the experiments were carried out in the temperature range of 400–550 °C and in the reaction time range of 10–30 s, under a pressure of 25 MPa. In addition, different 2-propanol concentrations and reaction pressures were tested in order to comprehend the effects on the gasification yield and hydrogen production. It was found that Pt/Al₂O₃ catalyst was much more selective and effective for hydrogen production when compared to Ru/Al₂O₃. During the catalytic gasification of a 0.5 M solution of 2-propanol, a hydrogen content up to 96 mol% for a gasification yield of 5 L/L feed was obtained.     

Gasification of diosgenin solid waste for hydrogen production in supercritical water

The potential of diosgenin solid waste (DSW) to be a proper feedstock for hydrogen production from supercritical water gasification was assessed through thermodynamic analysis and experimental study. The thermodynamic analysis of DSW gasification in SCW was performed by Aspen Plus software based on the principle of minimum Gibbs free energy. The effects of temperature (500–650 °C), flow ratio of feedstock slurry to preheated water on the gasification were studied. K₂CO₃ and black liquor were used to catalyze the gasification of DSW. The morphological structures of DSW and residue char were characterized by SEM. The results showed that DSW was almost completely gasified at 650 °C without catalyst and the carbon gasification efficiency reached up to 98.55%. K₂CO₃ could significantly promote the gasification reactivity of DSW at a lower temperature. H₂ yield was remarkably improved by adding black liquor. The SEM analysis indicated that parts of the organic matters reacted to form gases and liquid products, and K₂CO₃ was found to migrate into the residue char during the reactions.     

Characteristics and prediction model of hydrogen production of oily sludge by supercritical water gasification

Harmless treatment and resource utilization of oily sludge are urgent and related to the sustainable green, and low-carbon development of the petroleum industry. Aiming to the supercritical water gasification (SCWG) of oily sludge for hydrogen production, this paper investigated the effects of critical factors, including reaction temperature, initial pressure, retention time, and feed concentration, on the mole fraction, the gas yield, the gasification efficiency, and the hydrogen yield potential. The interaction mechanisms among these four factors were discussed and revealed with a reasonable prediction model of hydrogen production. Results showed that the longer retention time, higher temperature, and lower feed concentration could accelerate hydrogen production from oily sludge by SCWG. The synthetic promotion of the hydrogen yield exists between the temperature and the retention time, while the temperature predominates. A 2.63-fold increase in the H₂ yield was obtained when the condition changed from 135 min to 380 °C to 10 min and 555 °C. The hydrogen production of oily sludge by SCWG, at lower temperature and higher pressure was worse than that at higher temperature and lower pressure.     

Influence of moisture content on the direct gasification of dewatered sludge via supercritical water

In the present study, the feasibility of the direct gasification of dewatered sludge in supercritical water and the effect of water content on supercritical water gasification of the dewatered sludge were investigated using a high-pressure autoclave at a constant temperature of 400 °C with residence time of 60 min and by adjusting water content by adding distilled water or using air-dried dewatered sludge. The results showed that dewatered sludge can be directly gasified in supercritical water, with water content ranging from 75 to 95 wt%. The total gas production was increased by decreasing the water content, and the gas yield was decreased. The CO₂ yield was significantly affected by water content, whereas H₂, CH₄, and CO yields were slightly reduced. The liquid residue contained large amounts of organic matter (OM) and total phenols, thereby requiring further treatment before being discharged. The concentrations of OM and total phenols increased with a decrease in water content. Moreover, a serious carbonization reaction happened while carbon particles higher than 10 wt% (char/coke) were being formed in the solid residue.     

Catalytic gasification of pine-sawdust: Effect of primary and secondary catalysts

Pine sawdust steam gasification in a fixed double bed reactor and continuous flow was investigated. K₂CO₃ as primary catalyst and cobalt supported on γ-Al₂O₃ and SiO₂-Al₂O₃ as secondary catalyst was investigated. Thermal and catalytic steam gasification was compared. The effect of the support in tar yield and the H₂/CO ratio was pursued. It is noteworthy to observe that the primary catalyst increases the biomass gasification. It is also marked the total consumption of CH₄ species by the primary catalyst. The catalysts (K₂CO₃ and K₂CO₃-Co/γ-Al₂O₃) reduced tar formation from 11% in the thermal gasification to a value of 2.0% and 0.5% respectively. This tar yield reduction could be explained due to the action of potassium actives species of the primary catalyst combined with the lower acid strength of the support; high metal dispersion of cobalt species and the higher fraction of metallic cobalt species in Co/γ-Al₂O₃ catalyst. The catalysts decrease the formation of CO₂ from 21% in the thermal gasification to values on the order of 3%. The highest H₂/CO ratio with a value of 1.6 was obtained by K₂CO₃-γ-Al₂O₃ catalytic system. The presence of cobalt supported catalysts favored hydrogen consumption reactions such as reverse water gas shift reaction.     

Sustainable hydrogen production options from food wastes

In this study, two thermochemical processes, namely steam gasification and supercritical water gasification (SCWG), were comparatively studied to produce hydrogen from food wastes containing about 90% water. The SCWG experiments were performed at 400 and 450 °C in presence of catalyst (Trona, K₂CO₃ and seaweed ash). The maximum hydrogen yield was obtained at 450 °C in presence of K₂CO₃ catalyst. In second process, hydrothermal carbonization was used to convert food wastes into a high-quality solid fuel (hydrochar) that was further gasified in a dual-bed reactor in presence of steam. The steam gasification of hydrochar was carried out with and without catalysts (iron?ceria catalyst and dolomite). The maximum hydrogen yield obtained from steam gasification process was 28.08 mmol/g dry waste, about 7.7 times of that from SCWG. This study proposed a new concept for hydrogen production from wet biomass, combination of hydrothermal carbonization following steam gasification.     

Direct gasification of dewatered sewage sludge in supercritical water. Part 1: Effects of alkali salts

In the present study, the catalytic effects of alkali salts [NaOH, KOH, K₂CO₃, Na₂CO₃ and Ca(OH)₂] on the direct gasification of dewatered sludge in supercritical water were investigated by using a high-pressure autoclave at a constant temperature of 450 °C and a residence time of 30 min. The hydrogen yield increased in the presence of the alkali salts, except for Ca(OH)₂. Specifically, the hydrogen yield increased from 0.68 to 3.45 mol/(kg OM) as the K₂CO₃ concentration increased from 0 to 8 wt%. Although Ca(OH)₂ did not significantly impact the catalytic effect on the hydrogen yield, it did impact the CO₂ yield. Generally, the addition of alkali salts did not affect the organic matter or total phenol concentrations in the liquid residue. Moreover, char formation was considerably suppressed by the alkaline catalyzed hydrolysis of the dewatered sludge [except in the case of Ca(OH)₂].     

Hydrogen production from wood gasification promoted by waste eggshell catalyst

Bio‐hydrogen renowned as a future potential hydrogen source and studies were devoted in developing the efficient way to obtain the hydrogen. Biomass gasification of Azadirachta excelsa wood was carried out with addition of naturally derived CaO catalyst using temperature‐programmed gasification (TPG) technique. The reaction (TPG) was performed at 50–1000°C in 5% O₂/He with flow rate 10 ml/min, and the product gas evolution (H₂, CH₄, CO and CO₂) was detected by online mass spectrometer. The waste eggshell was chosen as a natural source of CaO, and the effect of catalyst loading was investigated in this study. All the fresh and used catalysts were characterized, and the physicochemical changes of the eggshell were observed through scanning electron microscopy, X‐ray fluorescence and X‐ray diffraction techniques. Hydrogen yield were increased along with the catalyst loading (20%, 40% and 60%) from 57 to 73%, respectively, compared to the reaction without catalyst. The additions of waste eggshell enhanced the catalytic activity and suppressed CO₂ production through CaO absorption property which induced the water gas shift reaction that promotes H₂ production at lower temperature. Copyright © 2013 John Wiley & Sons, Ltd.     

Potassium catalytic hydrogen production in sorption enhanced gasification of biomass with steam

Sorption enhanced gasification (SEG) of biomass with steam was investigated in a fixed-bed reactor to elucidate the effects of temperature, catalyst type and loading on hydrogen production. K₂CO₃, CH₃COOK and KCl were chosen as potassium catalyst precursors to improve carbon conversion efficiency in gasification process. It was indicated that from 600 °C to 700 °C, the addition of K₂CO₃ or CH₃COOK catalyzed the gasification for hydrogen production, and hydrogen yield and carbon conversion increased with increasing catalyst loadings of K₂CO₃ or CH₃COOK. However, the hydrogen yield and carbon conversion decreased as the amount of KCl was increased due to inhibition of KCl on gasification. The maximum carbon conversion efficiency (88.0%) was obtained at 700 °C corresponding to hydrogen yield of 73.0 vol.% when K₂CO₃ of 20 wt.% K loading was used. In particular, discrepant catalytic performance was observed between K₂CO₃ and CH₃COOK at different temperatures and the corresponding mechanism was also discussed.     

Biomass gasification in supercritical water: II. Effect of catalyst

In this study, the effect of the type of catalyst on hydrothermal gasification of three specifically chosen samples of natural biomass was investigated. Biomass feedstocks, including lignocellulosic materials (cotton stalk and corncob) and the tannery waste, were gasified in supercritical water by the addition of catalyst. The catalysts used were K₂CO₃, Trona (NaHCO₃·Na₂CO₃·2H₂O), red mud (Fe-oxide containing residue from Al-production) and Raney-Ni. The gasification experiments were performed in a batch autoclave at 500 °C. The amounts and compositions of the gases and the amounts of water soluble compounds from gasification were determined. The effect of catalysts on gasification varied with the type of biomass. The catalysts significantly increased the hydrogen yield by supporting the water–gas shift reaction and the methane reformation.     

Catalytic supercritical water gasification of glucose with in-situ generated nickel nanoparticles for hydrogen production

Hydrogen production from catalytic supercritical water gasification of glucose with in-situ generated nickel nanoparticles in a quartz tube reactor is demonstrated. The effects of various operating parameters such as the presence of catalyst, resident time, reaction temperature and feed concentration on the gasification performances are studied. The results show that both the carbon gasification efficiency and the hydrogen gasification efficiency of glucose in supercritical water were improved with in-situ generated nickel nanoparticles as catalyst compared to those without catalyst. The catalyst promotes the water-gas shift reaction and CO methanation reaction, resulting in increased yields of H₂, CH₄ and CO₂ and decreased yield of CO. At the presence of catalyst, 10 wt% glucose solution exhibits the best gasification performances at 500 °C. Highly dispersed nickel nanoparticles identified by high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) are assumed to be generated via supercritical hydrothermal synthesis through hydrolysis, dehydration and in-situ reduction. However, the in-situ generated nano-nickel catalyst underwent an activation to deactivation transition due to carbon deposition on the surface of nickel nanoparticles. Regeneration strategies of the deactivated catalysts need further study for practical application.     

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.