Syngas production from catalytic gasification of waste polyethylene: Influence of temperature on gas yield and composition

The catalytic steam gasification of waste polyethylene (PE) from municipal solid waste (MSW) to produce syngas (H₂ + CO) with NiO/γ-Al₂O₃ as catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the reactor temperature on the gas yield, gas composition, steam decomposition, low heating value (LHV), cold gas efficiency and carbon conversion efficiency was investigated at the temperature range of 700–900 °C, with a steam to waste polyethylene ratio of 1.33. Over the ranges of experimental conditions examined, NiO/γ-Al₂O₃ catalyst revealed better catalytic performance as a view of increasing product gas yield and of decreasing char and liquid yields in the presence of steam. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and product gas yield. The highest syngas (H₂ + CO) content of 64.35 mol%, the highest H₂ content of 36.98 mol%, and the highest CO content of 27.37 mol%, were achieved at the highest temperature level of 900 °C. Syngas produced with a H₂/CO molar ratio in the range of 0.83–1.35, was highly desirable as feedstock for Fischer–Tropsch synthesis for the production of transportation fuels.     

Valorizing petroleum coke into hydrogen-rich syngas through K-promoted catalytic steam gasification

Hydrogen-rich syngas was successfully produced from catalytic steam gasification of petroleum coke. This work studied the steam gasification of petroleum coke over KOH, K₂CO₃, KNO₃, CaO, Fe₂O₃, K₂CO₃–CaO and K₂CO₃–Fe₂O₃ in a pressurized fixed bed. KOH and K₂CO₃ demonstrated good catalytic activity compared with other catalysts. The carbon conversion efficiency (CCE) increased from 14.7 wt% to 61.4 wt% and 87.9 wt% after adding 10 wt% K₂CO₃ and 10 wt% KOH, respectively, and H₂ content increased from 60.9 vol% to 66.7 vol% and 64.2 vol%. The increase of gasification temperature and pressure resulted in the increase of CCE. However, raising temperature was beneficial to the increase of H₂ and CO contents, while the elevated pressure was in favor of the formation of CH₄. In addition, the K-catalytic steam gasification of petroleum coke accorded with the oxygen transfer and intermediate hybrid mechanism.     

Application of response surface methodology to assess the combined effect of operating variables on high-pressure coal gasification for H2-rich gas production

Coal gasification was performed by means of a high-pressure fixed bed gasifier fitted with a solids feeding system in continuous mode, using oxygen and steam as gasifying agents. The main aim of the paper was to assess the combined effects of the operating variables (temperature, oxygen and steam concentrations) on high-pressure coal gasification. To this end a face centered central composite design (FCCCD) based on response surface methodology (RSM) was used. The response variables studied were: H₂, CO and syngas production, H₂/CO ratio, cold gas efficiency (η), and carbon conversion (X). The study was carried out at temperatures of 900, 950 and 1000 °C, using oxygen concentrations of 5, 10 and 15 vol.%, and steam concentrations of 25, 40 and 55 vol.%. The gasification temperature was found to be the most influential variable, with high temperatures leading to an increase in all the response variables studied. An increase in the oxygen content of the gasifying agent led to a decrease in H₂ and CO production, and cold gas efficiency, whilst carbon conversion was favoured. An increase in steam concentration, on the other hand, favoured the production of H₂ and syngas production, whereas CO production underwent a reduction; cold gas efficiency and carbon conversion were observed to increase. Response surface methodology (RSM) revealed the effects of interaction between the operating variables, which would not have been identified by the traditional “one-factor-at-a-time” method. The models developed successfully fitted the experimental results for all the response variables studied.     

Char and char-supported nickel catalysts for secondary syngas cleanup and conditioning

Tars in biomass gasification systems need to be removed to avoid damaging and clogging downstream pipes or equipment. In this study, Ni-based catalysts were made by mechanically mixing NiO and char particles at various ratios. Catalytic performance of the Ni/char catalysts was studied and compared with performance of wood char and coal char without Ni for syngas cleanup in a laboratory-scale updraft biomass gasifier. Reforming parameters investigated were reaction temperature (650–850 °C), NiO loading (5–20% of the weight of char support), and gas residence time (0.1–1.2 s). The Ni/coalchar and Ni/woodchar catalysts removed more than 97% of tars in syngas at 800 °C reforming temperature, 15% NiO loading, and 0.3 s gas residence time. Analysis of syngas composition indicated that concentrations of H₂ and CO in syngas significantly. Furthermore, performance of the Ni/coalchar catalyst was continuously tested for 8 h. There was slight deactivation of the catalyst in the early stage of tar/syngas reforming; however, the catalyst was able to stabilize soon after. It was concluded that chars especially coal char can be an effective and inexpensive support of NiO for biomass gasification tar removal and syngas conditioning.     

Thermodynamic optimization of biomass gasification for decentralized power generation and Fischer–Tropsch synthesis

In recent years, biomass gasification has emerged as a viable option for decentralized power generation, especially in developing countries. Another potential use of producer gas from biomass gasification is in terms of feedstock for Fischer–Tropsch (FT) synthesis – a process for manufacture of synthetic gasoline and diesel. This paper reports optimization of biomass gasification process for these two applications. Using the non–stoichometric equilibrium model (SOLGASMIX), we have assessed the outcome of gasification process for different combinations of operating conditions. Four key parameters have been used for optimization, viz. biomass type (saw dust, rice husk, bamboo dust), air or equivalence ratio (AR = 0, 0.2, 0.4, 0.6, 0.8 and 1), temperature of gasification (T = 400, 500, 600, 700, 800, 900 and 1000 °C), and gasification medium (air, air–steam 10% mole/mole mixture, air–steam 30%mole/mole mixture). Performance of the gasification process has been assessed with four measures, viz. molar content of H₂ and CO in the producer gas, H₂/CO molar ratio, LHV of producer gas and overall efficiency of gasifier. The optimum sets of operating conditions for gasifier for FT synthesis are: AR = 0.2–0.4, Temp = 800–1000 °C, and gasification medium as air. The optimum sets of operating conditions for decentralized power generation are: AR = 0.3–0.4, Temp = 700–800 °C with gasification medium being air. The thermodynamic model and methodology presented in this work also presents a general framework, which could be extended for optimization of biomass gasification for any other application.     

Catalytic effect of black liquor on the gasification reactivity of petroleum coke

CO₂ gasification of petroleum coke using black liquor as a catalyst was performed in a thermogravimetric analyzer (TGA) under temperatures 1223–1673 K at ambient pressure to evaluate the effect of black liquor loading on petroleum coke gasification. It was found that the gasification reactivity of petroleum coke was improved greatly by black liquor. The gasification reactivity was affected by different loading methods in the order: wet grinding > dry grinding > physical impregnation > dry mix. The catalytic activity of black liquor was higher than that of pure alkali metal. The effect of temperature on the gasification reactivity of petroleum coke was changed by black liquor. The reactivity reaches its maximum at 1573 K. The reactivity of petroleum coke was found higher than that of Shenfu coal when black liquor loading is 5 wt.% (of petroleum coke), clearly demonstrating that black liquor could be an effective catalyst for petroleum coke gasification.     

Hydrogen-rich gas from catalytic steam gasification of municipal solid waste (MSW): Influence of catalyst and temperature on yield and product composition

In the present study the catalytic steam gasification of MSW to produce hydrogen-rich gas or syngas (H₂ + CO) with calcined dolomite as a catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 750–950 °C, with a steam to MSW ratio of 0.77, for weight hourly space velocity of 1.29 h⁻¹. Over the ranges of experimental conditions examined, calcined dolomite revealed better catalytic performance, at the presence of steam, tar was completely decomposed as temperature increases from 850 to 950 °C. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and dry gas yield. The highest H₂ content of 53.29 mol%, and the highest H₂ yield of 38.60 mol H₂/kg MSW were observed at the highest temperature level of 950 °C, while, the maximum H₂ yield potential reached 70.14 mol H₂/kg dry MSW at 900 °C. Syngas produced by catalytic steam gasification of MSW varied in the range of 36.35–70.21 mol%. The char had a highest ash content of 84.01% at 950 °C, and negligible hydrogen, nitrogen and sulphur contents.     

Hydrogen-rich syngas production through coal and charcoal gasification using microwave steam and air plasma torch

In the present study, microwave plasma gasification of two kinds of coal and one kind of charcoal was performed with various O₂/fuel ratios of 0–0.544. Plasma-forming gases used under 5 kW microwave plasma power were steam and air. The changes in the syngas composition and gasification efficiency in relation to the location of the coal supply to the reactor were also compared. As the O₂/fuel ratio was increased, the H₂ and CH₄ contents in the syngas decreased, and CO and CO₂ increased. When steam plasma was used to gasify the fuel with the O₂/fuel ratio being zero, it was possible to produce syngas with a high content of hydrogen in excess of 60% with an H₂/CO ratio greater than 3. Depending on the O₂/fuel ratio, the composition of the syngas varied widely, and the H₂/CO ratio necessary for using the syngas to produce synthetic fuel could be adjusted by changing the O₂/fuel ratio alone. Carbon conversion increased as the O₂/fuel ratio was increased, and cold gas efficiency was maximized when the O₂/fuel ratio was 0.272. Charcoal with high carbon and fixed carbon content had a lower carbon conversion and cold gas efficiency than the coals used in this study.     

Hydrogen and syngas production from glycerol through microwave plasma gasification

Glycerol which is a byproduct of biodiesel production is considered as a potential feedstock for syngas production with the increase of biodiesel demand. In this study, the characteristics of glycerol gasification under a microwave plasma torch with varying oxygen and steam supply conditions were investigated. The experimental results demonstrated that the gasification efficiency and syngas heating value increased with the supplied microwave power while the increase of oxygen and steam led to a lower gasification performance. In order to achieve high carbon conversion and cold gas efficiency in the microwave plasma gasification of glycerol, the O₂/fuel ratio should be maintained at 0–0.4. It was revealed that the fuel droplet size and the mixing effect and retention time inside the plasma flames are critical factors that influence the product gas yield and gasification efficiency. This study verified that syngas with a high content of H₂ and CO could be effectively produced from glycerol through microwave plasma gasification.     

Comparison between isothermal and microwave gasification of lignite char for high syngas production

Using the water of lignite as gasification agent, this paper mainly studies the influence of microwave and isothermal gasification on the syngas production and H₂/CO ratio to obtain the maximum possible amount of high-quality syngas. The results show that microwave heating produced syngas had an immensely superior performance over conventional heating. The total gas yields of 1,000 W microwave gasification is 1.75 times more than that of the 1,000°C isothermal gasification. Moreover, the values of H₂/CO ratio obtained from microwave gasification was higher than 1,000°C isothermal gasification.     

Characteristics of hydrogen-rich gas production of biomass gasification with porous ceramic reforming

In the present study, an updraft biomass gasifier combined with a porous ceramic reformer was used to carry out the gasification reforming experiments for hydrogen-rich gas production. The effects of reactor temperature, equivalence ratio (ER) and gasifying agents on the gas yields were investigated. The results indicated that the ratio of CO/CO₂ presented a clear increasing trend, and hydrogen yield increased from 33.17 to 44.26 g H₂/kg biomass with the reactor temperature increase, The H₂ concentration of production gas in oxygen gasification (oxygen as gasifying agent) was much higher than that in air gasification (air as gasifying agent). The ER values at maximum gas yield were found at ER = 0.22 in air gasification and at 0.05 in oxygen gasification, respectively. The hydrogen yields in air and oxygen gasification varied in the range of 25.05–29.58 and 25.68–51.29 g H₂/kg biomass, respectively. Isothermal standard reduced time plots (RTPs) were employed to determine the best-fit kinetic model of large weight biomass air gasification isothermal thermogravimetric, and the relevant kinetic parameters corresponding to the air gasification were evaluated by isothermal kinetic analysis.     

Hydrogen-rich gas from catalytic steam gasification of municipal solid waste (MSW): Influence of steam to MSW ratios and weight hourly space velocity on gas production and composition

The present work deals with a study coupling experiments and modeling of catalytic steam gasification of municipal solid waste (MSW) for producing hydrogen-rich gas or syngas (H₂ + CO) with calcined dolomite as a catalyst in a bench-scale downstream fixed bed reactor. The influence of steam to MSW ratios (S/M) on gas production and composition was studied at 900 °C over the S/M range of 0.39–1.04, for weight hourly space velocity (WHSV) in the range of 1.22–1.51 h⁻¹. Over the ranges of experimental conditions examined, calcined dolomite revealed better catalytic performance at the presence of steam. H₂ and CO₂ contents increased with S/M increasing, while CO and CH₄ contents decreased sharply, the contents of CH₄, C₂H₄ and C₂H₆ were relatively small, and the influence of S/M was insignificant. The highest H₂ content of 53.22 mol %, the highest H₂ yield of 42.98 mol H₂/kg MSW, and the highest H₂ potential yield of 59.83 mol H₂/kg MSW were achieved at the highest S/M level of 1.04. Furthermore, there was a good agreement between the experimental gas composition and that corresponding to thermodynamic equilibrium data calculated using GasEq model. Consequently, a kinetic model was proposed for describing the variation of H₂ yield and carbon conversion efficiency with S/M during the catalytic steam gasification of MSW. The kinetic model revealed a good performance between experimental results and the kinetic model.     

Evaluation of biomass gasification in a ternary diagram

The present paper addresses the development of an alternative approach to illustrate biomass gasification in a ternary diagram which is constructed using data from thermodynamic equilibrium modeling of air-blown atmospheric wood gasification. It allows the location of operation domains of slagging entrained-flow, fluidized-bed/dry-ash entrained-flow and fixed/moving-bed gasification systems depending on technical limitations mainly due to ash melting behavior. Performance parameters, e.g. cold gas efficiency or specific syngas production, and process parameters such as temperature and carbon conversion are displayed in the diagram depending on the three independent mass flows representing (1) the gasifying agent, (2) the dry biomass and (3) the moisture content of the biomass. The graphical approach indicates the existence of maxima for cold gas efficiency (84.9%), syngas yield (1.35 m³ (H₂ + CO STP)/kg (waf)) and conversion of carbon to CO (81.1%) under dry air-blown conditions. The fluidized-bed/dry-ash entrained-flow processes have the potential to reach these global maxima since they can operate in the identified temperature range from 700 to 950 °C. Although using air as a gasifying agent, the same temperature range posses a potential of H₂/CO ratios up to 2.0 at specific syngas productions of 1.15 m³ (H₂ + CO STP)/kg (waf). Fixed/moving-bed and fluidized-bed systems can approach a dry product gas LHV from 3.0 to 5.5 MJ/m³ (dry STP). The ternary diagram was also used to study the increase of gasifying agent oxygen fraction from 21 to 99 vol.%. While the dry gas LHV can be increased significantly, the maxima of cold gas efficiency (+6.5%) and syngas yield (+7.4%) are elevated only slightly.     

Hydrogen production by steam reforming of ethanol over an Ir/CeO2 catalyst: Reaction mechanism and stability of the catalyst

Steam reforming of ethanol over an Ir/CeO₂ catalyst has been studied with regard to the reaction mechanism and the stability of the catalyst. It was found that ethanol dehydrogenation to acetaldehyde was the primary reaction, and acetaldehyde was then decomposed to methane and CO and/or converted to acetone at low temperatures. Methane was further reformed to H₂ and CO, and acetone was directly converted into H₂ and CO₂. Addition of CO, CO₂, and CH₄ to the water/ethanol mixture proved that steam reforming of methane and the water gas shift were the major reactions at high temperatures. The Ir/CeO₂ catalyst displayed rather stable performance in the steam reforming of ethanol at 650 °C even with a stoichiometric feed composition of water/ethanol, and the effluent gas composition remained constant for 300 h on-stream. The CeO₂ in the catalyst prevented the highly dispersed Ir particles from sintering and facilitated coke gasification through strong Ir–CeO₂ interaction.     

Air gasification of high-ash sewage sludge for hydrogen production: Experimental,sensitivity and predictive analysis

In this work, air gasification of sewage sludge was conducted in a lab-scale bubbling fluidized bed gasifier. Further, the gasification process was modeled using artificial neural networks for the product gas composition with varying temperatures and equivalence ratios. Neural network-based prediction will help to predict the hydrogen production from product gas composition at various temperatures and equivalence ratios. The gasification efficiency and lower heating values were also established as a function of temperatures and equivalence ratios. The maximum H₂ and CO was recorded as 16.26 vol% and 33.55 vol%. Intraileally at ER 0.2 gas composition H₂, CO, and CH₄ show high concentrations of 20.56 vol%, 45.91 vol%, and 13.32 vol%, respectively. At the same time, CO₂ was lower as 20.20 vol% at ER 0.2. Therefore, optimum values are suggested for maximum H₂ and CO yield and lower concentration of CO₂ at ER 0.25 and temperature of 850 °C. A predictive model based on an Artificial Neural network is also developed to predict the hydrogen production from product gas composition at various temperatures and equivalence ratios. The network has been trained with different topologies to find the optimal structure for temperature and equivalence ratio. The obtained results showed that the regression coefficients for training, validation, and testing are 0.99999, 0.99998, and 0.99992, respectively, which clearly identifies the training efficiency of the trained model.     

Characteristics of cardboard and paper gasification with CO2

Evolutionary behavior of syngas chemical composition and yield have been examined for paper and cardboard at three different temperatures of 800, 900 and 1000 °C using CO₂ as the gasifying agent at constant flow rate. Specifically the evolution of syngas chemical composition with time has been investigated. Pyrolysis of the sample was dominant at the beginning of the gasification process as observed from the high initial devolatilization of the sample followed by char gasification of material to form syngas for a long period of time. Results provided the role of gasification temperature on kinetics of the CO₂ gasification process. Increase in gasification temperature provided increased conversion of the sample material to syngas. Thus the sample conversion to syngas was low at the low temperature of 800 °C while at elevated temperatures of 900 and 1000 °C substantial enhancement of the kinetics process occurred. The evolution of extensive reaction rate of carbon-monoxide was calculated. Results show that increase in temperature increased the extensive reaction rate of carbon-monoxide. The global behavior of syngas chemical composition examined at three different temperatures revealed a peak in concentration of H₂ to exhibit after few minutes into the gasification that changed with gasification temperature. At 800 °C gasification temperature peak in H₂ was displayed at 3 min into gasification while it decreased to only 2 min, approximately, at gasification temperatures of 900 and 1000 °C. The effect of reactor temperature on CO mole fraction has also been examined. Increase in the gasification temperature enhances the mole fraction of CO yields. This is attributed to the increase in forward reaction rate of the Boudouard reaction (C+CO₂2CO). The results show important role of CO₂ gas for the gasification of wastes and low grade fuels to clean syngas.     

High temperature steam-only gasification of woody biomass

We have studied a high temperature steam gasification process to generate hydrogen-rich fuel gas from woody biomass. In this study, the performance of the gasification system which employs only high temperature steam exceeding 1200 K as the gasifying agent was evaluated in a 1.2 ton/day-scale demonstration plant. A numerical analysis was also carried out to analyze the experimental results. Both the steam temperature and the molar ratio of steam to carbon (S/C ratio) affected the reaction temperature which strongly affects the gasified gas composition. The H₂ fraction in the produced gas was 35–55 vol.% at the outlet of the gasifier. Under the experimental conditions, S/C ratio had a significant effect on the gas composition through the dominant reaction, water–gas shift reaction. The tar concentration in the produced gas from the high temperature steam gasification process was higher than that from the oxygen-blown gasification processes. The highest cold gas efficiency was 60.4%. However, the gross cold gas efficiency was 35%, which considers the heat supplied by high temperature steam. The ideal cold gas efficiency of the whole system with heat recovery processes was 71%.     

The synergistic effect of Ca(OH)2 on the process of lignite steam gasification to produce hydrogen-rich gas

The synergistic effect of Ca(OH)₂ prepared by the wet-mixing method on lignite steam gasification process at different temperatures (700–900 °C) was analyzed in a spout-fluid bed reactor. Firstly, to avoid disturbance of volatile and tar, active carbon was used as a model compound. On the one hand, Ca(OH)₂ effectively catalyzed the water-gas shift (WGS) reaction to improve H₂ concentration, but the performance was weaker at higher temperature due to the enhancement of boudouard reaction and the weakening of WGS reaction. On the other hand, it was found that the (CO+2CO₂)/H₂ ratio of syngas produced at 700 °C in the presence of Ca(OH)₂ was 0.82, which was much lower than that of the other cases, owning to the absorption of CO₂. The synergistic effect was observed at this temperature, for the adsorption of CO₂ altered equilibrium of the WGS reaction and further improved H₂ concentration. Then two kinds of Chinese lignite (HLH and XM) were selected to further study the performance of Ca(OH)₂ on optimizing the lignite steam gasification process. In the presence of Ca(OH)₂, tar and char yields greatly reduced at the same reaction temperature, whereas the gas yields significantly increased. As a catalyst, Ca(OH)₂ can not only promote solid–gas reaction to decrease char yield, but also accelerate tar decomposition to reduce its yield in syngas. Based on GC–MS data, it can be deduced that Ca(OH)₂ has different catalytic activity on the steam reforming of tar with different molecular structures. Contrast to Class 4, tars of aliphatic hydrocarbons, Class 2 and Class 5 were clearly catalytic reformed. Hydrogen-rich gas can be produced at 800 °C and 900 °C owning to the catalytic effect of Ca(OH)₂, but the highest H₂ concentration was found at 700 °C due to the additional effect of CO₂ absorption, which was supported by the results of thermogravity experiments.     

GC-MS determination of low hydrocarbon species (C1–C6) from a diesel partial oxidation reformer

The partial oxidation (POx) reforming of Ultra Low Sulphur-Diesel (ULSD), rapeseed methyl ester (RME) - biodiesel and Fischer–Tropsch synthetic diesel fuels (SD) were studied by using a fixed-bed reactor. The ease of reforming the three fuels was first examined at different O/C feed ratios at constant gas hourly space velocity (GHSV) of 35 k h⁻¹ over a prototype monolith catalyst (1%Rh/CeO₂–ZrO₂). The hydrocarbon species (C₁–C₆) produced in the reformer were analyzed using direct gas injection gas chromatography mass spectrometry (GC-MS). Under the same O/C ratios for 35 k h⁻¹ the fuels conversion and process efficiency was dependent on the fuel type, and followed the general trend: SD > biodiesel > ULSD. The GC-MS analysis shows that both, biodiesel and ULSD diesel produced significantly higher amounts of alkenes compared to SD fuel. Fuel with relatively high aromatics content such diesel can be efficiently reformed to syngas over the catalyst used in this study but the reformer operating range (e.g. O/C ratio and space velocity) is limited compared to paraffinic fuels such as FT-SD. At increased GHSV of 45 k h⁻¹ and O/C = 1.75, the diesel fuel conversion efficiency to syngas (H₂ and CO) was improved significantly and the formation of intermediate species such as methane, ethylene, and propylene was reduced considerably as a result of the increased peak reaction temperatures. The reduced HC species and increased H₂ concentration in the reactor product gas from the reforming of FT-SD fuel can provide significant advantages to the IC engine applications.     

Steam gasification of Greek lignite and its chars by co-feeding CO2 toward syngas production with an adjustable H2/CO ratio

Low-rank lignite is among the most abundant and cheap fossil fuels, linked, however, to serious environmental implications when employed as feedstock in conventional thermoelectric power plants. Hence, toward a low-carbon energy transition, the role of coal in world's energy mix should be reconsidered. In this regard, coal gasification for synthesis gas generation and consequently through its upgrade to a variety of value-added chemicals and fuels constitutes a promising alternative. Herein, we thoroughly explored for a first time the steam gasification reactivity of Greek Lignite (LG) and its derived chars obtained by raw LG thermal treatment at 300, 500 and 800 °C. Moreover, the impact of CO₂ addition on H₂O gasifying agent mixtures was also investigated. Both the pristine and char samples were fully characterized by various physicochemical techniques to gain insight into possible structure-gasification relationships. The highest syngas yield was obtained for chars derived after LG thermal treatment at 800 °C, due mainly to their high content in fixed carbon, improved textural properties and high alkali index. Steam gasification of lignite and char samples led to H₂-rich syngas mixtures with a H₂/CO ratio of approximately 3.8. However, upon co-feeding CO₂ and H₂O, the H₂/CO ratio can be suitably adjusted for several potential downstream processes.