Investigation of Indonesian low rank coals gasification in a fixed bed reactor with K2CO3 catalyst loading

Catalytic steam gasification is considered one of promising technologies for converting solid carbonaceous feedstocks into hydrogen-rich syngas, which is an important source of hydrogen for various industrial sectors. The K₂CO₃-catalyzed steam gasification of low rank coals (LRCs) was conducted in a fixed bed reactor for elucidating the effects of gasifying temperature and catalyst loading amount on hydrogen yield. Hydrogen-rich syngas can be obtained at gasifying temperature of 800 °C and loading amount of 10 wt% K₂CO₃. The loading amount of 10 wt% K₂CO₃ was the saturation point and provided a good gasification reactivity in catalytic steam gasification of three LRCs. The experimental data of these three LRCs were well described by the random pore model (RPM). The RPM fitted the experimental data at 800 °C better than the experimental data obtained at 700 °C and 600 °C. Reactivity index (R_0.5), activation energy (Ea) and reaction rate constant (k) were also used to predict the characteristics of the K₂CO₃-catalyzed steam gasification process. Catalytic steam gasification utilizing the mixture of three LRCs as a feedstock was also investigated and displayed X_C of 86.22% and 0.95 mol mol^?1-C, indicating a good feasibility and potential industrial applications.     

Influence of pyrolysis conditions on nitrogen speciation in a biochar ‘preparation-application’ process

To investigate biochar nitrogen conversion in a ‘preparation-application’ system and the response of its transportation in plants, biochar samples were produced from rice straw at different pyrolysis temperatures (400 °C and 800 °C) and atmospheres (N₂ and CO₂). Subsequently, biochar was synthesized under CO₂ atmosphere to explore its nitrogen nutrient characteristics and further improve the chemical and physical properties of soil. Nitrogen speciation of the biochar and plant root samples were evaluated by X-ray photoelectron spectroscopy. Research has shown that organic nitrogen such as protein-N, free amino acid-N, and alkaloid-N in rice straw is converted into organic (nitrile-N, pyridine-N, amino-N, and pyrrole-N) and inorganic (NH₄⁺-N, NO₂^?-N, and NO₃^?-N) species in biochar during the biomass pyrolysis process. In turn, biochar nitrogen is transported to plants as protein-N, free amino acid-N, alkaloid-N, NH₄⁺-N, NO₂^?-N, and NO₃^?-N. Comprehensive consideration of the biochar quality and preparation cost indicated the lower pyrolysis temperature (400 °C) under CO₂ atmosphere as the best conditions for biochar preparation.     

Entrained flow gasification of straw- and wood-derived pyrolysis oil in a pressurized oxygen blown gasifier

Fast pyrolysis oil can be used as a feedstock for syngas production. This approach can have certain advantages over direct biomass gasification. Pilot scale tests were performed to investigate the route from biomass via fast pyrolysis and entrained flow gasification to syngas. Wheat straw and clean pine wood were used as feedstocks; both were converted into homogeneous pyrolysis oils with very similar properties using in-situ water removal. These pyrolysis oils were subsequently gasified in a pressurized, oxygen blown entrained flow gasifier using a thermal load of 0.4 MW. At a pressure of 0.4 MPa and a lambda value of 0.4, temperatures around 1250 °C were obtained. Syngas volume fractions of 46% CO, 30% H₂ and 23% CO₂ were obtained for both pyrolysis oils. 2% of CH₄ remained in the product gas, along with 0.1% of both C₂H₂ and C₂H₄. Minor quantities of H₂S (3 vs. 23) cm³ m⁻³, COS (22 vs. 94) cm³ m⁻³ and benzene (310 vs. 532) cm³ m⁻³ were measured for wood- and straw derived pyrolysis oils respectively. A continuous 2-day gasification run with wood derived pyrolysis oil demonstrated full steady state operation. The experimental results show that pyrolysis oils from different biomass feedstocks can be processed in the same gasifier, and issues with ash composition and melting behaviour of the feedstocks are avoided by applying fast pyrolysis pre-treatment.     

Distribution of Nitrogen Species During Vitrinite Pyrolysis and Gasification

The formation of HCN and NH₃ during pyrolysis in Ar and gasification in CO₂ and steam/Ar was investigated. Vitrinites were separated and purified from different rank coal from lignite to anthracite. Pyrolysis and gasification were carried out in the drop-tube/fixed-bed reactor at temperatures of 600–900°C. Results showed that with increase of reaction temperature the yield of HCN increased significantly during pyrolysis and gasification. Decrease of coal rank also increased the yield of HCN. Vitrinite from lower rank of coal with high volatile content released more HCN. The yield of NH₃ was the highest at 800°C during pyrolysis and gasification. And the yield of NH₃ from gasification in steam/Ar was far higher than that from gasification in CO₂, where the hydrogen radicals play a key role. Nitrogen retained in char was also investigated. The yield of char-N decreased with an increase of pyrolysis temperature. Vitrinite from lower rank coal had lower yield of char-N than that from the high rank coal.     

Kinetic characteristics of in-situ char-steam gasification following pyrolysis of a demineralized coal

This study aims to examine the char-steam reactions in-situ, following the pyrolysis process of a demineralized coal in a micro fluidized bed reactor, with particular focuses on gas release and its kinetics characteristics. The main experimental variables were temperatures (925 °C?1075 °C) and steam concentrations (15%–35% H₂O), and the combination of pyrolysis and subsequent gasification in one experiment was achieved switching the atmosphere from pure argon to steam and argon mixture. The results indicate that when temperature was higher than 975 °C, the absolute carbon conversion rate during the char gasification could easily reach 100%. When temperature was 1025 °C and 1075 °C, the carbon conversion rate changed little with steam concentration increasing from 25% to 35%. The activation energy calculated from shrinking core model and random pore model was all between 186 and 194 kJ/mol, and the fitting accuracy of shrinking core model was higher than that of the random pore model in this study. The char reactivity from demineralized coal pyrolysis gradually worsened with decreasing temperature and steam partial pressure. The range of reaction order of steam gasification was 0.49–0.61. Compared to raw coal, the progress of water gas shift reaction (CO + H₂O ? CO₂ + H₂) was hindered during the steam gasification of char obtained from the demineralized coal pyrolysis. Meanwhile, the gas content from the char gasification after the demineralized coal pyrolysis showed a low sensitivity to the change in temperature.     

Syngas production by chemical looping gasification of rice husk using Fe-based oxygen carrier

The chemical looping gasification (CLG) of rice husk was conducted in a fixed bed reactor to analyze the effects of the ratio of oxygen carrier to rice husk (O/C), temperature, residence time and preparation methods of Fe-based oxygen carriers. The yield of gas, H₂/CO, lower heating value of syngas (LHV), conversion efficiency and performance parameters were analyzed to obtain CLG reaction characterization and optimal reaction conditions. Results showed that when O/C increased from 0.5 to 3.0, the gas production, H₂/CO, CO₂ yield and carbon conversion efficiency gradually increased, while the yield of H₂, CO and CH₄ and LHV gradually decreased. At the same time, a highest gasification efficiency was obtained when O/C was 1.5. As increasing temperature, the gas production, CO yield, carbon conversion efficiency and gasification efficiency gradually increased, while the yield of H₂, CH₄ and CO₂, H₂/CO and LHV gradually decreased. Sintering and agglomeration was obvious when the temperature was higher than 850 °C. When the reaction time increased from 10 min to 60 min, the gas production, CO yield, carbon conversion efficiency and gasification efficiency gradually increased, but the yield of H₂, H₂/CO and LHV decreased, among which 30 min was the best reaction residence time. In addition, coprecipitation was the best preparation method among several preparation methods of oxygen carrier. Finally, O/C of 1.5, 800 °C, 30 min and coprecipitation preparation method of oxygen carrier were the optimal parameters to obtain a gasification efficiency of 26.88%, H₂ content of 35.64%, syngas content of 56.40%, H₂/CO ratio of 1.72 and LHV of 12.25 MJ/Nm³.     

Simulation and economic evaluation of biomass gasification with sets for heating,cooling and power production

In this work, syngas was used directly as fuel source for the renewable CCHP system, which can be producted through biomass gasification process. The advantages and limitation of entrained flow gasifier are compared, followed by discussion on the key parameters that are critical for the optimum production of syngas. Gasification agent of 450 °C temperature and 30 atm pressure has been proposed as a optical solution to a entrained flow gasifier using air as gasification agent at 0.27 ER (oxygen equivalence ratio), in that it provides a syngas of 5.665 MJ/m³ LHV and up to 77% gasification efficiency. Depending on the key parameters of gasification process, the properties of syngas produced can be varied. It is thus essential to thoroughly understand the cogeneration system to identify the suitable methods for a renewable CCHP system. These process was simulated using Aspen Plus to perform the rigorous material and energy balances. The results obtained from simulation and experiment agreed well. This paper later focused on economic evaluation of the entire process, as well as the environmental benefits. The renewable CCHP system could able to attain lower CO₂ and SO₂ emission with total energy efficiency and gas yield of 75.43% and 2.476 m³/kg respectively.     

Experimental study of dual fixed bed biochar-catalytic gasification with simultaneous feed of O2-steam-CO2 for synthesis gas or hydrogen production

The catalytic gasification of biochar was investigated in the presence of a Ni/SiO₂ catalyst in a fixed bed reactor with an O₂-steam-CO₂ gas feed. The effects of operating temperature, catalyst nickel loading and composition of O₂-steam-CO₂ feed gas on biochar carbon conversion and gas products were investigated. The results indicate that the highest biochar carbon conversion could be obtained at approximately 800 °C, whilst the 10% Ni/SiO₂ catalyst was shown to produce the greatest syngas yields. The presence of O₂ in the feed gas can result in slightly more CO in the gas product, whilst a higher steam content leads to more H₂ in the gas product. The CO₂ offered a benefit as an adjusting agent for achieving a desired H₂/CO ratio. No evidence of coke deposition on the catalyst was found under any of the tested conditions.     

Downdraft gasifier structure and process improvement for high quality and quantity producer gas production

The current study reveals several efficient amenities that can affect the gasification process to improve syngas quality and yield. A comprehensive study was carried out using a 24 kW downdraft gasifier to evaluate the effect of uniform air distribution in the oxidation zone, additional throat on the reactor temperature distribution and the overall gasification process. The effect of fuel moisture, equivalence ratio, gasifying agent type and pre-treatment of the gasifying agent on producer gas yield and composition were also evaluated. The biomass feeding rate was 30–40 kg/h, and the maximum gas flow rate was 90 m³/h. When corn cobs and waste wood (carpenter waste) with moisture content from 5 to 30% were used as feed stock, with 70 °C air as the gasifying/oxidizing agent, the energy value of the producer/syngas obtained was 6.31 and 6.66 MJ/m³, respectively. The heating value was improved to 6.72 and 8.43 MJ/m³ when using 150 °C air-steam mixture as the gasifying agent, with the optimum equivalence ratio of 0.30. The methane, hydrogen and carbon monoxide concentration (on volume basis) were 6.20, 19.32 and 21.00. The average amount of syngas produced from 1 kg of corn cobs and waste wood were 2.94 and 2.62 m³, while the average amount of tar produced was 2.2 and 1.8 g/Nm³ respectively. The investigation revealed that uniform air distribution in the oxidation zone, fuel moisture content, gasifying agent type and the pre-treatment of gasifying agent played a significant role in enhancing the quantity and quality of the producer gas.     

Synthesis and evaluation of biochar-derived catalysts for removal of toluene (model tar) from biomass-generated producer gas

Challenges in removal of contaminants, especially tars, from biomass-generated producer gas continue to hinder commercialization efforts in biomass gasification. The objectives of this study were to synthesize catalysts made from biochar, a byproduct of biomass gasification and to evaluate their performance for tar removal. The three catalysts selected for this study were original biochar, activated carbon, and acidic surface activated carbon derived from biochar. Experiments were carried out in a fixed bed tubular catalytic reactor at temperatures of 700 and 800 °C using toluene as a model tar compound to measure effectiveness of the catalysts to remove tar. Steam was supplied to promote reforming reactions of tar. Results showed that all three catalysts were effective in toluene removal with removal efficiency of 69–92%. Activated carbon catalysts resulted in higher toluene removal because of their higher surface area (∼900 m²/g compared to less than 10 m²/g of biochar), larger pore diameter (19 A° compared to 15.5 A° of biochar) and larger pore volume (0.44 cc/g compared to 0.085 cc/g of biochar). An increase in reactor temperature from 700 to 800 °C resulted in 3–10% increase in toluene removal efficiency. Activated carbons had higher toluene removal efficiency compared to biochar catalysts.     

Syngas production by integrating CO2 partial gasification of pine sawdust and methane pyrolysis over the gasification residue

The aim of this work was to study syngas production by integrating CO₂ partial gasification (for CO production) of pine sawdust (PS) and methane pyrolysis (for H₂ production) over the gasification residue. Effect of the gasification conditions (including CO₂ flow rate, reaction temperature, mass ratio of PS:Ni and reaction time) was investigated on properties of the gasification residue. Besides CO-rich gas released from the gasification process with CO₂ conversion up to about 92%, the gasification residue could serve as robust catalyst for H₂ production by methane pyrolysis. Thanks to the nickel crystallites formed with high reduction degree and high dispersion on the surface after the gasification process, the gasification residue was competent for high and stable methane conversion (about 91%) at 850 °C. In addition to the flexible syngas output (in theory, with an arbitrary ratio of H₂/CO), valuable filamentous carbons can be achieved by regulating the process parameters.     

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.     

Characteristics of microalgae gasification through chemical looping in the presence of steam

As a novel gasification technology, chemical looping gasification (CLG) was considered as a promising technology in solid fuel gasification. In this work, CLG was applied into microalgae, and the characteristics of syngas production and oxygen carrier in the presence of steam were obtained through experiments in a fixed bed reactor. The results showed that the partial oxidation of oxygen carrier improved the gasification efficiency from 61.65% to 81.64%, with the combustible gas yield of 1.05 Nm³/kg, and this promotion effect mainly occurred at char gasification stage. Also, an optimal Fe₂O₃/C molar ratio of 0.25 was determined for the maximum gasification efficiency. 800 °C was needed for the gasification efficiency over 70%, but excess temperature caused the formation of dense layer on oxygen carrier particle surface. Steam as gasification agent promoted syngas production, but excess steam decreased the gasification efficiency. Steam also enhanced the hydrogen production by the conversion of Fe/FeO into Fe₃O₄, avoiding the intensive reduction of oxygen carrier. The Fe₂O₃ oxygen carrier maintained a good reactivity in 10th cycle while used for microalgae CLG. The results indicated that CLG provided a potential route for producing combustible gas from microalgae.     

Characteristic of hydrogen and syngas evolution from gasification and pyrolysis of rubber

The characteristics of syngas evolution during pyrolysis and gasification of waste rubber have been investigated. A semi-batch reactor was used for the thermal decomposition of the material under various conditions of pyrolysis and high temperature steam gasification. The results are reported at two different reactor temperatures of 800 and 900 °C and at constant steam gasifying agent flow rate of 7.0 g/min and a fixed sample mass. The characteristics of syngas were evaluated in terms of syngas flow rate, hydrogen flow rate, syngas yield, hydrogen yield and energy yield. Gasification resulted in 500% increase in hydrogen yield as compared to pyrolysis at 800 °C. However, at 900 °C the increase in hydrogen was more than 700% as compared to pyrolysis. For pyrolysis conditions, increase in reactor temperature from 800 to 900 °C resulted in 64% increase in hydrogen yield while for gasification conditions a 124% increase in hydrogen yield was obtained. Results of syngas yield, hydrogen yield and energy yield from the rubber sample are evaluated with that obtained from woody biomass samples, namely hard wood and wood chips. Rubber gasification yielded more energy at the 900 °C as compared to biomass feedstock samples. However, less syngas and less hydrogen were obtained from rubber than the biomass samples at both the temperatures reported here.     

Study on catalytic properties of potassium carbonate during the process of sawdust pyrolysis

In order to investigate the effect of potassium carbonate on biomass pyrolysis properties, sawdust was used as raw material and different amounts of K₂CO₃ were added by impregnation method to carry out thermogravimetric and pyrolysis experiments. The effects of pyrolysis temperature and the amount of K₂CO₃ addition on the pyrolysis of sawdust were studied using a self-made fixed-bed pyrolysis furnace. Calculation of pyrolysis kinetics shows that the existence of K₂CO₃ catalyst changes the pyrolysis path of sawdust, so that the activation energy of pyrolysis sawdust decreases at low temperature and increases at high temperature. The pyrolysis experiments shows that the addition of K₂CO₃ and the increase of pyrolysis temperature both reduce the yield of the pyrolysis oil of sawdust and increase the yield of the pyrolysis syngas. However, K₂CO₃ catalyst promotes the yield of char, the increase of pyrolysis temperature decreases the yield of char. Analysis of the pyrolysis products finds that the addition of K₂CO₃ and the increase of pyrolysis temperature both improve quality of the pyrolysis oil, form more microporous surface of char, and increase the hydrogen content in the pyrolysis syngas. It is considered that the optimal process for producing pyrolysis syngas is 900 °C of pyrolysis temperature and 10% of K₂CO₃ addition.     

Analysis of syngas production rate in empty fruit bunch steam gasification with varying control factors

Biomass gasification is a prevailing approach for mitigating irreversible fossil fuel depletion. In this study, palm empty fruit bunch (EFB) was steam-gasified in a fixed-bed, batch-fed gasifier, and the effect of four control factors—namely torrefaction temperature for EFB pretreatment, gasification temperature, carrier-gas flow rate, and steam flow rate—on syngas production were investigated. The results showed that steam flow rate is the least influential control factor, with no effect on syngas composition or yield. The gasification temperature of biomass significantly affects the composition of syngas generated during steam gasification, and the H₂/CO ratio increases by approximately 50% with an increase in temperature ranging from 680 °C to 780 °C. The higher H₂/CO ratio at a lower gasification temperature increased the energy density of the combustible constituents of the syngas by 3.43%.     

Influence of torrefaction on properties of activated carbon obtained from physical activation of pyrolysis char

In this paper, the method of ‘torrefaction–fast pyrolysis–physical activation’ was conducted to investigate the impact of torrefaction on the properties of activated carbon through CO₂ activation. It was found that torrefaction had a significantly positive influence on the quality of activated carbon and 280°C was the optimal torrefaction temperature. The activated carbon obtained under the recommended condition had a higher yield (13.0 ± 0.3% based on dried rice husk) and most developed pore structure (specific surface area of 1090.7 m²/g). The results may be helpful for the potential utilization of high ash content biomass like rice husk.     

Production of H2- and CO-rich syngas from the CO2 gasification of cow manure over (Sr/Mg)-promoted-Ni/Al2O3 catalysts

The valorization of cow manure (CM), as bio-waste, under a CO₂ atmosphere could be an attractive strategy for tackling the environmental problems related to waste management and CO₂ emission and producing valuable syngas. For this purpose, highly loaded Ni–Al₂O₃ catalysts with alkaline-earth metals (Mg and Sr) were synthesized and applied to the gasification of CM under CO₂. The lowest yields of bio-oil (16.98 wt %) and coke (0.34 wt %) and the highest yield of syngas (55.09 wt %) were obtained from the catalytic decomposition of hydrocarbons when Sr was incorporated into Ni/Al₂O₃ (SN-AO). The highest selectivity for H₂ (34.23 vol %) and CO (37.16 vol %) were obtained applying SN-AO followed by Mg-promoted Ni/Al₂O₃ (MN-AO) and Ni/Al₂O₃ (N-AO) catalysts. With increasing gasification temperature from 750 °C to 850 °C, the syngas yield (from 55.09 to 70.17 wt %) and H₂ concentration (from 34.23 to 38.03 vol %) increased considerably because of the endothermic gasification process. The yield and selectivity of syngas (H₂ and CO) increased under CO₂ compared to those obtained under N₂, indicating the high potential of CO₂ for the thermal decomposition and dehydrogenation of the volatile matter.     

Optimization of renewable hydrogen-rich syngas production from catalytic reforming of greenhouse gases (CH4 and CO2) over calcium iron oxide supported nickel catalyst

Multi-response optimization of hydrogen-rich syngas from catalytic reforming of greenhouses (methane and carbon dioxide over Calcium iron oxide supported Nickel (15 wt%Ni/CaFe₂O₄) catalyst was performed by varying reaction temperature (700–800 °C), feed ratio (0.4–1.0) and gas hourly space velocity (10,000–60,000 h^?1)) using response surface methodology. Four response surface methodology (RSM) models were obtained for the prediction of reactant conversion and the product yield. The analysis of variance (ANOVA) conducted on the model showed that the parameters have significant effect on the responses. Optimum conditions for the methane dry reforming over the 15 wt%Ni/CaFe₂O₄ catalyst were obtained at reaction temperature, feed ratio and gas hourly space velocity (GHSV) of 832.45 °C, 0.96 and 35,000 mL g^?1 h^?1 respectively with overall desirability value of 0.999 resulting in the highest methane (CH₄) and carbon dioxide (CO₂) conversions of 85.00%, 88.00% and hydrogen (H₂) and carbon monoxide (CO) yields of 77.82% and 75.76%, respectively.     

High quality syngas production from pressurized K2CO3 catalytic coal gasification with in-situ CO2 capture

The enhanced K-catalytic coal gasification by CO₂ sorption reaction (EKcSG) was proposed to produce syngas with high content of H₂ and CH₄ and perform in-situ CO₂ capture. CO₂ is reduced dramatically with the introduction of the CaO into the reactor under typical K-catalytic coal gasification condition (3.5 MPa, 700 °C). The carbonation reaction of CaO can promote the syngas production by improving the equilibrium of the water-gas shift reaction and supplying heat for coal gasification reaction. In the presence of the CaO sorbent (Ca/C = 0.5), the CO₂ concentration in the product gas decreased from 25.61% to 12.80% compared with that without CaO. Correspondingly, the total concentration of H₂ and CH₄ is improved from 65.61% to 82.99% and the carbon conversion reached above 95%. The effect of Ca/C ratio and reaction temperature was investigated during the EKcSG process. It is considered that Ca/C ratio of 0.5 is the best proportion in terms of carbon conversion and CO₂ absorption in our experimental conditions.