Hydrogen promotion by Co/SiO2@HZSM-5 core-shell catalyst for syngas from plastic waste gasification: The combination of functional materials

In the present work, a core-shell structured Co/SiO₂@HZSM-5 catalyst was prepared for hydrogen production from syngas of plastic waste gasification. The cobalt catalyst was coated with HZSM-5 shell through a hydrothermal process, and the Co/SiO₂@HZSM-5, with different loadings of HZSM-5 (e.g., 10–30 wt %) exhibited excellent activity and durability for dehydrogenation reactions. The amount of HZSM-5 was found to be an important factor for hydrogen production. Temperature-programmed reduction with H₂ and temperature-programmed desorption of ammonia was applied to determine the active site and the acidity of prepared catalyst, respectively. The prepared Co/SiO₂@HZSM-5 was tested through reforming of plastic gasification syngas and shown superior hydrogen production ability (∼90%) and stability (over 15 h). The effects of reduction-oxidation behavior on the catalytic performance were also discussed.     

Hydrogen and syngas production from biomass gasification for fuel cell application

Gasification process is being developed to produce a clean and efficient gas flue from fuels such as coal, biomass, and solid/liquid wastes for power generation. In this work, a biomass gasification kinetic model that can predict reaction temperature, gasification performance, and gas composition has been developed for a circulating fluidized bed (CFB). Experimental data from a CFB power plant have been used to validate the model. It is confirmed that the addition of steam is important for increasing the hydrogen concentration and syngas caloric value. Based on the predicted results, an optimal condition is suggested for air and steam gasification in the CFB gasifier.     

Hydrogen production from autothermal CO2 gasification of cellulose in a fixed-bed reactor: Influence of thermal compensation from CaO carbonation

Biomass gasification is a promising technology to produce renewable syngas used for energy and chemical applications. However, biomass gasification has challenges of low process energy efficiency, low syngas production with low H₂/CO ratio and the sintering of biomass ash which limit the deployment of the technology. This work investigated the influence of in-situ generated heat from CaO–CO₂ on cellulose CO₂ gasification using a fixed bed reactor, thermogravimetric analysis-Fourier transform infrared spectroscopy (TGA-FTIR) and differential scanning calorimetry (DSC). Experimental results indicate an approximate 20 °C temperature difference in the fix-bed reactor between cellulose CO₂ gasification with the energy compensation of CaO carbonation (denoted auto-thermal biomass gasification) and conventional CO₂ gasification of cellulose after the power of external furnaces were turned off. Around 5 times H₂/CO molar ratio is obtained after switching off the power in the auto-thermal biomass gasification compared with conventional gasification. The gas yield enhances significantly from 0.29 g g^?1 cellulose to 0.56 g g^?1 cellulose when CaO/cellulose mass ratio increases from 0 to 5. Furthermore, the TGA-FTIR results demonstrate the feasibility of adopting energy compensation of CaO carbonation to reduce the gasification temperature. DSC analysis also proves that the released heat from the CaO–CO₂ reaction reduces the required energy for cellulose degradation.     

A bone-based catalyst for biodiesel production from waste cooking oil

Biodiesel production via transesterification of waste cooking oil (WCO) with methanol using waste chicken bone-derived catalyst was investigated. The calcium carbonate content in the waste chicken bone was converted to calcium oxide (CaO) at a calcinations temperature of 800°C. The catalysts were prepared by calcination at 300–800°C for 5 h and catalyst characterization was carried out by X-ray diffraction (XRD) and Brunauer–Emmett–Teller (BET) surface area measurement. CaO was used as catalyst for biodiesel production. The results of the optimization imply that the catalyst concentration of 3.0 wt%, methanol to oil ratio of 3:1, and reaction temperature of 80°C for 3 h provide the maximum values of yield in methyl ester production. Reusability of the catalyst from calcined waste chicken bone was studied for four times, with a good yield.     

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.     

Optimization of biodiesel production from waste cooking oil using waste bone as a catalyst

This work determined the association between several parameters of biodiesel production from waste cooking oil (WCO) using waste bovine bone (WBB) as catalyst to achieve a high conversion to fatty acid methyl ester (%FAME). The effect of three independent variables was used as the optimum condition using response surface methodology (RSM) for maximizing the %FAME. The RSM analysis showed that the ratio of MeOH to oil (mol/mol), catalyst amount (%wt), and time of reaction have the maximum effects on the transform to FAME. Moreover, the coefficient of determination (R²) for regression equations was 99.19%. Probability value (P < 0.05) demonstrated a very good significance for the regression model. The optimal values of variables were MeOH/WCO ratio of 15.49:1 mol/mol, weight of catalyst as 6.42 wt%, and reaction time of 128.67 min. Under the optimum conditions, %FAME reached 97.59%. RSM was confirmed to sufficiently describe the range of the transesterification parameters studied and provide a statistically accurate estimate of the best transform to FAME using WBB as the catalyst.     

Catalytic steam reforming of tar for enhancing hydrogen production from biomass gasification: a review

Presently, the global search for alternative renewable energy sources is rising due to the depletion of fossil fuel and rising greenhouse gas (GHG) emissions. Among alternatives, hydrogen (H₂) produced from biomass gasification is considered a green energy sector, due to its environmentally friendly, sustainable, and renewable characteristics. However, tar formation along with syngas is a severe impediment to biomass conversion efficiency, which results in process-related problems. Typically, tar consists of various hydrocarbons (HCs), which are also sources for syngas. Hence, catalytic steam reforming is an effective technique to address tar formation and improve H₂ production from biomass gasification. Of the various classes in existence, supported metal catalysts are considered the most promising. This paper focuses on the current researching status, prospects, and challenges of steam reforming of gasified biomass tar. Besides, it includes recent developments in tar compositional analysis, supported metal catalysts, along with the reactions and process conditions for catalytic steam reforming. Moreover, it discusses alternatives such as dry and autothermal reforming of tar.     

Hydrogen production by biomass gasification in a fluidized-bed reactor promoted by an Fe/CaO catalyst

Biomass gasification for hydrogen production was performed in a continuous-feeding fluidized-bed with the use of Fe/CaO catalysts. The relationship between catalyst properties and biomass gasification efficiencies was studied. The findings indicated that only CaO was involved in the enhancement of char gasification, resulting in an increased hydrogen production. However, CaO was also easily deactivated by biomass tar. The characterization results indicated that when CaO was impregnated with Fe, Ca₂Fe₂O₅ formed on the surface of the support. Ca₂Fe₂O₅ decomposed polyaromatic tar but was not effective in char gasification. The synergistic effects between Fe and CaO that effectively enhanced biomass gasification mainly involved combustion and pyrolysis, and the biomass gasification products, i.e., char and tar, were further gasified, indicating that tailor-made Fe/CaO catalysts prevented CaO deactivation by tar, thus promoting biomass gasification and hydrogen production.     

Biodiesel production from waste sunflower oil by using Amberlyst 46 as a catalyst

In this study, simultaneous transesterification and esterification of high acid value sunflower oil to fatty acid methyl esters was studied using Amberlyst 46 as a heterogeneous catalyst. The influence of reaction conditions such as molar ratio of methanol/oil, reaction time, and reaction temperature was investigated. The highest fatty acids methyl esters yield of 75.8% was obtained in presence of 6 wt% oleic acid content under reaction conditions of 20 wt% Amberlyst 46 catalyst amount, 6/1 methanol/oil molar ratio, reaction temperature of 130°C, and reaction time of 10 h.     

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.     

Production of useful energy from solid waste materials by steam gasification

A steam gasification processes is an energy conversion pathway through which organic materials are converted to useful energy. In spite of the high energy content in organic waste materials, they have been mostly disposed of in landfills, which causes harmful environmental issues such as methane emissions and ground water pollution and contaminations. In this sense, organic solid waste materials are regarded as alternative resources for conversion to useful energy in the steam gasification process. In this study, three types of waste materials – municipal solid waste (MSW), used tires and sewage sludge – were used to generate syngas through the gasification process in a 1000 °C steam atmosphere. The syngas generation rates and its chemical compositions were measured and evaluated over time to determine the characteristics and dynamics of the gasification process. Also, carbon conversion, and mass and energy balances are presented which demonstrates the feasibility of steam gasification as a waste conversion pathway. The results show that the syngas contains high concentrations of H₂, around 41–55% by volume. The syngas generation rate was found to depend on the carbon content in the feedstock regardless of the types of input materials. Comparing to the hydrogen production from water splitting that requires extremely high temperatures at around 1500 °C, hydrogen production by steam gasification of organic materials can be regarded as equally effective but requires lower system temperatures. Copyright © 2016 John Wiley & Sons, Ltd.     

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

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

Pyrolysis and gasification of food waste: Syngas characteristics and char gasification kinetics

Characteristics of syngas from the pyrolysis and gasification of food waste has been investigated. Characteristic differences in syngas properties and overall yields from pyrolysis and gasification were determined at two distinct high temperatures of 800 and 900 °C. Pyrolysis and gasification behavior were evaluated in terms of syngas flow rate, hydrogen flow rate, output power, total syngas yield, total hydrogen yield, total energy yield, and apparent thermal efficiency. Gasification was more beneficial than pyrolysis based on investigated criteria, but longer time was needed to finish the gasification process. Longer time of gasification is attributed to slow reactions between the residual char and gasifying agent. Consequently, the char gasification kinetics was investigated. Inorganic constituents of food char were found to have a catalytic effect. Char reactivity increased with increased degree of conversion. In the conversion range from 0.1 to 0.9 the increase in reactivity was accompanied by an increase in pre-exponential factor, which suggested an increase in gasifying agent adsorption rate to char surface. However, in the conversion range from 0.93 to 0.98 the increase in reactivity was accompanied by a decrease in activation energy. A compensation effect was observed in this range of conversion of 0.93–0.98.     

Hydrogen production by catalytic supercritical water gasification of nitriles

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

Absorption-enhanced steam gasification of biomass for hydrogen production: Effect of calcium oxide addition on steam gasification of pyrolytic volatiles

The effect mechanism of calcium oxide (CaO) addition on gasification of pyrolytic volatiles as a key sub-process in the absorption-enhanced steam gasification of biomass (AESGB) for H₂ production at different conditions was investigated using a two-stage fixed-bed pyrolysis–gasification system. The results indicate that CaO functions as a CO₂ absorbent and a catalyst in the volatiles gasification process. CaO triggers the chemical equilibrium shift to produce more H₂ and accelerates volatile cracking and gasification reactions to obtain high volatile conversion rates. Increasing the gasification temperature could improve the reaction rate of cracking and gasification of volatiles as well as the catalytic effect of CaO, which continuously increase H₂ yield. When the gasification temperature exceeds 700 °C, the sharp decrease in CO₂ absorption capability of CaO drastically increases the CO₂ concentration and yield, which significantly decrease H₂ concentration. The appropriate temperature for the absorption-enhanced gasification process should be selected between 600 °C and 700 °C in atmospheric pressure. Increasing the water injection rate (represented as the mass ratio of steam to biomass) could also improve H₂ yield. The type of biomasses is closely associated with H₂ yield, which is closely related to the volatile content of biomass materials.     

Hydrogen and syngas production from sewage sludge via steam gasification

High temperature steam gasification is an attractive alternative technology which can allow one to obtain high percentage of hydrogen in the syngas from low-grade fuels. Gasification is considered a clean technology for energy conversion without environmental impact using biomass and solid wastes as feedstock. Sewage sludge is considered a renewable fuel because it is sustainable and has good potential for energy recovery. In this investigation, sewage sludge samples were gasified at various temperatures to determine the evolutionary behavior of syngas characteristics and other properties of the syngas produced. The syngas characteristics were evaluated in terms of syngas yield, hydrogen production, syngas chemical analysis, and efficiency of energy conversion. In addition to gasification experiments, pyrolysis experiments were conducted for evaluating the performance of gasification over pyrolysis. The increase in reactor temperature resulted in increased generation of hydrogen. Hydrogen yield at 1000 °C was found to be 0.076 g_gas g_sample⁻¹. Steam as the gasifying agent increased the hydrogen yield three times as compared to air gasification. Sewage sludge gasification results were compared with other samples, such as, paper, food wastes and plastics. The time duration for sewage sludge gasification was longer as compared to other samples. On the other hand sewage sludge yielded more hydrogen than that from paper and food wastes.     

Hydrogen‐rich gas production from catalytic gasification of pine sawdust over Fe‐Ce/olivine catalyst

In order to improve hydrogen production and reduce tar generation during the biomass gasification, a catalyst loaded Fe‐Ce using calcined olivine as the support (Fe‐Ce/olivine catalysts) was prepared through deposition‐precipitation method. The characteristics of catalysts were determined by XRF, BET, XRD, and FTIR. Syngas yield, hydrogen yield, and tar yield were used to evaluate the catalyst activity. Meanwhile, the stability of catalysts was also studied. The results showed that the specific surface area and pore volume of olivine after calcined at high temperature were improved which was beneficial for the load of metals. α‐Fe₂O₃ and CeO₂ were the main active component of Fe‐Ce/olivine catalyst. The Fe‐Ce/olivine catalyst displayed a good performance on the catalytic gasification of pine sawdust with a syngas yield of 0.93 Nm³/kg, H₂ yield of 21.37 mol/kg, and carbon conversion rate of 55.14% at a catalytic temperature and gasification temperature of 800°C. Meanwhile, the Fe‐Ce/olivine catalyst could maintain a good stability after 150 minutes used.     

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

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

Hydrogen-rich gas production with CO2 capture from steam gasification of pine needle using calcium oxide: Experimental and modeling study

A research-scale bubbling fluidized bed reactor (BFBR) has been assembled and used to study the steam gasification of pine needles with calcium oxide (CaO) as sorbent and catalyst. The output parameters such as syngas composition, higher heating value, lower heating value, and cold gas efficiency, have been analyzed at the operating conditions of a temperature of 650°C to 850°C, steam/biomass (S/B) ratio of 0.4 to 1.6, and CaO/biomass ratio of 0.3 to 1.5. Furthermore, an ASPEN PLUS model of BFBR has been developed using Gibbs free energy minimization technique and model values have been compared with experimental values. From the experimental results, it is analyzed that the concentration of H₂ is increased from 37.02 vol% to 68.36 vol% with an increase in temperature from 650°C to 750°C at the S/B ratio of 1 and CaO/biomass ratio of 0.9 and after that, it decreased slightly. Furthermore, the concentration of CO₂ in syngas captured from 5.49 vol% to 0 vol%, when the CaO/biomass ratio is varied from 0.3 to 1.5. From the result analysis, it is concluded that higher temperature and higher CaO/biomass ratio has a significant impact on H₂ production while excess S/B ratio has a negative impact.     

Hydrogen production via steam gasification of ash free coals

The kinetics of the coal to hydrogen conversion can be significantly enhanced by introducing catalysts. The catalysts are, however, commonly deactivated by irreversible interaction with mineral matters in coal. This work addresses hydrogen production via steam gasification of ash free coals. Following the production of ash free coals (AFCs) derived from various raw coals (brown, bituminous, and coking coal), fixed-bed steam gasification of the AFCs was performed as a function of temperature and which was compared with one another and also with that of the matching raw coals. In the absence of a catalyst, AFCs produced from different parent coals exhibited similarly low gasification reactivity, comparable to a high rank coal (coking coal) at 700 °C. As expected, the reaction became faster with increasing temperature in the range, 700–900 °C. The steam gasification of AFCs was highly activated by K₂CO₃ above 700 °C. It was very likely that water–gas shift reaction associated with the gasification of AFCs was also catalyzed.