Kinetic characterizations of biomass char CO2-gasification reaction within granulated blast furnace slag

The reactions of biomass char CO₂-gasification within granulated blast furnace slag (BFS) were systematically conducted by the non-isothermal program using a thermogravimetric analyzer. At the same time during reaction proceeded, the conversion of biomass char CO₂-gasification reaction increased with the increasing heating rate. However, at the same temperature during reaction proceeded, the conversion of biomass char CO₂-gasification reaction decreased with the increasing heating rate. The granulated BFS could be used as a catalyst in the biomass char CO₂-gasification reaction and its catalytic effect became more obvious with the increasing content of BFS in the mixture. The A₄ model (nuclei production (m = 4) model) selected through the novel two-step method firstly proposed in the study was the best match with all the gasification reactions. The activation energy was from 52.75 kJ/mol to 64.42 kJ/mol and was lower with the increase of heating rate and the content of BFS in the mixture. The kinetic equations of biomass char CO₂-gasification reaction within granulated BFS were developed through the selected model and calculated kinetic parameters.     

Effect of pore structure on CO2 gasification reactivity of biomass chars under high-temperature pyrolysis

The CO₂ gasification reactivity of pine sawdust chars (PS char) obtained from the different high-temperature pyrolysis is studied based on non-isothermal thermogravimetric method. Results show that the order of gasification reactivity is PS char-1073 > PS char-1273 > PS char-1473. Under the effect of high-temperature pyrolysis, the surface structure of biomass char is gradually destroyed and the pore structure parameters of specific surface area, total pore volume and average pore diameter increase. By means of the N₂ adsorption-desorption isotherms, it is seen that biomass char has more micro- and mesoporous at higher pyrolysis temperature. Besides, the PS char-1073 mostly has rich closed cylinder pores and parallel plate pores, and the PS char-1273 and PS char-1473 have plentiful open cylinder pores and parallel plate pores. An increase of pyrolysis temperature contributes to the development of porosity and improves diffusion path, which promotes the gasification reactivity. But, its effect on the decline of active site hinders the gasification reactivity. What's more, the kinetic model of distributed activation energy model (DAEM) is applied to calculate activation energy and pre-exponential factor with the integral and differential methods. The calculation results of integral method is more accurate and precise because the differential method is more sensitive than integral method for experimental noise. There is a compensation effect in the CO₂ gasification process.     

The characteristics of syngas production from bio-oil dry reforming utilizing the waste heat of granulated blast furnace slag

A two-stage utilization of the waste heat of granulated blast furnace slag (BFS) was proposed, and the characteristics of bio-oil dry reforming under different conditions were investigated. For the bio-oil dry reforming utilizing granulated BFS as the heat carrier, when the temperature was higher than 800 °C, changes in the characteristics as bio-oil conversion and lower heating value (LHV) were not pronounced in response to the increasing temperature. The bio-oil conversion reached its maximum value with a CO₂/C (molar ratio of CO₂ to carbon in bio-oil) of 0.85. When the liquid hourly space velocity (LHSV) was higher than 0.45 h^?1, the bio-oil conversion and LHV dropped quickly as the LHSV increased. At the optimal condition with a temperature of 800 °C, a CO₂/C of 0.85 and an LHSV of 0.45 h^?1, the bio-oil conversion and LHV reached 90.15% and 511.02 kJ per mole of bio-oil, respectively. Granulated BFS could be beneficial for the bio-oil dry reforming process. Combining biomass pyrolysis and bio-oil dry reforming, a feasible industry application utilizing the waste heat of granulated BFS was presented systematically.     

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.     

Gasification reactivity and synergistic effect of conventional and microwave pyrolysis derived algae chars in CO2 atmosphere

This research focuses on the isothermal and non-isothermal CO₂ gasification of an algal (Chlorella) char prepared via two different thermal processing systems, i.e. conventional and microwave-assisted pyrolysis. It was found that chars prepared via microwave irradiation showed higher CO₂ gasification reactivity than that of chars prepared via the conventional method. Meanwhile, the activation energy of microwave char was found to be 127.89 kJ/mol, which was 46.3 kJ/mol lower than that of conventional char, indicating improved reactivity of microwave char. The systematic characterisation of both conventional and microwave chars shows that the higher reactivity of microwave char could be attributed to its large BET surface area, low crystalline index and high active sites. In addition, it was found that microwave heating contributed to high reactivity of chars through generating large amount of primary char, the formation of hot spot and high specific surface area and pore volume. Results of co-gasification under isothermal conditions revealed the existence of greater synergistic effects between coal char and microwave algae char than those of coal char and conventional algae char. Furthermore, based on the relative Rs (average gasification rate), a novel index proposed to quantify the interactions in co-gasification process, Australian coal char/microwave assisted char blend experienced 10% higher interactions compared to Australian coal char/conventional assisted char blend.     

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.     

Reactivity investigation on chemical looping gasification of biomass char using nickel ferrite oxygen carrier

Chemical looping gasification (CLG) involves the use of an oxygen carrier (OC) which transfers oxygen from air to solid fuel to convert the fuel into synthesis gas, and the traditional gasifying agents such as oxygen-enriched air or high temperature steam are avoided. In order to improve the reactivity of OC with biomass char, facilitating biomass high-efficiency conversion, a compound Fe/Ni bimetallic oxide (NiFe₂O₄) was used as an OC in the present work. Effect of OC content and oxygen sources on char gasification were firstly investigated through a TG reactor. When the OC content in mixture sample attains 65 wt.%, the sample shows the maximum weight loss rate at relatively low temperature, indicating that it is very favorable for the redox reactions between OC and biomass char. The NiFe₂O₄ OC exhibits a good performance for char gasification, which is obvious higher than that of individual Fe₂O₃ OC and mechanically mixed Fe₂O₃ + NiO OC due to the Fe/Ni synergistic effect in unique spinel structure. According to the TGA experimental results, effect of the steam content and cyclic numbers on char gasification were investigated in a fixed bed reactor. Either too low steam content or too high steam content doesn't facilitate the char gasification. And suitable steam content of 56.33% is determined with maximum carbon conversion of 88.12% and synthesis gas yield of 2.58 L/g char. The reactivity of NiFe₂O₄ OC particles shows a downtrend within 20 cycles (～64 h) due to the formation of Fe₂O₃ phase, which is derived from the iron element divorced from the Fe/Ni spinel structure. Secondly, the sintering of OC particles and ash deposit on the surface are also the reasons for the deactivation of NiFe₂O₄ OC. However, the carbon conversion and synthesis gas yield at the 20th cycle are still higher than those of the blank experiment. It indicates that the reactivity of NiFe₂O₄ OC can be maintained at a relatively long time and NiFe₂O₄ material can be used as a good OC candidate for char gasification in the long time running.     

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.     

Assessment of the catalytic effect of various biomass ashes on CO2 gasification of tire char

The aim of this study was to determine the effect of various biomass ashes, comprising catalytically active components, on tire char reactivity during the CO₂ gasification process. Ashes from the combustion of corn cobs, beet pulp, sunflower husks and beech chips were selected for the research. Moreover, industrial fly ash from a coal-fired power plant was used as a reference. The tire char-ash blends with different ash contents (0–15 wt%) were gasified in the CO₂ atmosphere under non-isothermal conditions using dynTHERM Rubotherm thermobalance. Based on the n-order Coats and Redfern method, gasification reactivity indicators and kinetics parameters were calculated. The results showed that the addition of biomass ashes enhanced reactivity of tire char, and the magnitude of these changes depended on both the quantity and type of the additive. With the increase in the amount of added biomass ashes, the catalytic effect increased, and their efficiency can be ranked as follows: sunflower husk ash > corn cobs ash ≅ beet pulp ash > beech chips ash. In turn, reference fly ash from a power plant slightly affected the CO₂ gasification of tire char, regardless of its amount. Moreover, a statistically significant correlation between the reactivity indicator and the amount of K₂O, MgO and P₂O₅ in ashes analysed has been proved (reactivity indicator improved with an increase in these components amount). The performed analysis provides valuable information regarding the composition of catalysts characterised by high catalytic activity in the tire char gasification process.     

Gasification of woody biomass under high heating rate conditions in pure CO2: Experiments and modelling

The present paper focuses on the gasification of thin wood particles in pure CO₂ at 850 °C under high heating rate conditions (similar to fluidized bed gasifiers). The aim is to assess the potential use of CO₂ as gasifying medium and to learn more about its effects on the pyrolysis as well as on the char gasification stages. Experimental and numerical modelling results provide answers on the unfolding of the whole CO₂ biomass pyro-gasification process. It was found that despite the CO₂ is present inside the particle during the pyrolysis stage, it has no noticeable impacts neither on the reaction rate nor on the char yield due to the relatively low temperature inside the particle. The CO₂ char gasification is the rate limiting step of the global pyro-gasification reaction as its duration is near to 95% of the entire biomass conversion time.     

Kinetics,thermodynamics and synergistic effects analyses of petroleum coke and biomass wastes during H2O co-gasification

In this study, the H₂O co-gasification of petroleum coke (PC) with low (sulfur and V₂O₅ contents) and different five kinds of biomass wastes were conducted using a thermogravimetric analyzer (TGA). The biomass used were the agricultural wastes (rice husk (RH), rice stalk (RS), and cotton straw (CS)) and by-product wastes (sawdust (SD) and sugar cane bagasse (SCB)). Their reactivities, kinetics and thermodynamics parameters were investigated and compared in detail as well as a synergistic effect during co-gasification of the blends. The kinetics and thermodynamics parameters were estimated by using the homogeneous model (HM) or the first-order chemical reaction (O1) and shrinking core models (SCM) or Phase boundary controlled reactions (R2 and R3). It was found that the biomass wastes was significantly improved the blends gasification reactivity. The obvious significant synergistic effect was observed in the char gasification stage of the blends compared with the pyrolysis stage. Compared to other models the phase boundary controlled reaction (R2) was found to be the best model to predict the experimental data of the co-gasification process. For both reaction stages of single fuels, SD showed the lowest values of activation energy and thermodynamics parameters. The blends of PC: SD and PC: CS provided the lowest activation energy and thermodynamics parameters for the pyrolysis stage and the char gasification stage, respectively. The co-gasification of PC and biomass wastes are a promising technique for the efficient utilization of PC and biomass wastes.     

Gasification reactivity of biomass chars with CO2

In this study, carbon conversion was calculated from the data obtained with a real-time gas analyzer. In a lab-scale furnace, each biomass sample was pyrolyzed in a nitrogen environment and became biomass char. For preparation of the char, the furnace was electrically heated over 40 min up to the wall temperature of 850 °C, and maintained at the same temperature over 17 min. The furnace was again heated over 3 min to a temperature higher than 850 °C and then CO₂ was injected. The biomass char was then gasified with CO₂ under isothermal conditions. The reactivity of biomass char was investigated at various temperatures and CO₂ concentrations. The VRM (volume reaction model), SCM (shrinking core model), and RPM (random pore model) were used to interpret the experimental data. For each model, the activation energy (E) and pre-exponential factor (A) of the biomass char-CO₂ reaction were determined from gas-analysis data by using the Arrhenius equation. For the RPM, the apparent reaction order was determined. According to this study, it was found that the experimental data agreed better with the RPM than with the other two models. Through BET analyses, it was found that the structural parameter (ψ) of the surface area for the RPM was obtained as 4.22.     

Gasification of landfill leachate in supercritical water: Effects on hydrogen yield and tar formation

Landfill leachate was gasified in supercritical water (SCW) in a batch reactor made of 316 SS. The effects of temperature, pressure, reaction time and oxidation coefficient (OC) on the pollutant removal efficiencies and gasification characteristics were investigated. To observe the formation of tar and char visually, a capillary quartz reactor was also used. Results indicated that CO₂, H₂ and CH₄ were the most abundant gaseous products. Temperature has an appreciable effect on the gasification process. Increasing temperature enhanced the H₂ yield (GY_H2) and TOC removal efficiency (TRE) significantly. Although the influence of reaction time on the fractions of gaseous products was negligible at time above 300 s, the yields of H₂, CH₄, and CO₂ increased with reaction time whereas the CO, C₂H₄ and C₂H₆ yields decreased. Tar and char formation was evident on the interior surface of capillary quartz reactor. Adding a little oxidant could increase H₂ and CH₄ yields and decrease tar and char formation. GY_H2 reached up to the maximum of 231.3 mmol L^?1 leachate at 500 °C, 25 MPa, 600 s and 0.2 OC, which was 2.4 times of that without oxidant.     

Effect of CO2 and steam gasification reactions on the oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, elevated levels of CO₂ and steam affect the heat capacity of the gas, radiant transport, and other gas transport properties. A topic of widespread speculation has concerned the effect of gasification reactions of coal char on the char burning rate. To asses the impact of these reactions on the oxy-fuel combustion of pulverized coal char, we computed the char consumption characteristics for a range of CO₂ and H₂O reaction rate coefficients for a 100 μm coal char particle reacting in environments of varying O₂, H₂O, and CO₂ concentrations using the kinetics code SKIPPY (Surface Kinetics in Porous Particles). Results indicate that gasification reactions reduce the char particle temperature significantly (because of the reaction endothermicity) and thereby reduce the rate of char oxidation and the radiant emission from burning char particles. However, the overall effect of the combined steam and CO₂ gasification reactions is to increase the carbon consumption rate by approximately 10% in typical oxy-fuel combustion environments. The gasification reactions have a greater influence on char combustion in oxygen-enriched environments, due to the higher char combustion temperature under these conditions. In addition, the gasification reactions have increasing influence as the gas temperature increases (for a given O₂ concentration) and as the particle size increases. Gasification reactions account for roughly 20% of the carbon consumption in low oxygen conditions, and for about 30% under oxygen-enriched conditions. An increase in the carbon consumption rate and a decrease in particle temperature are also evident under conventional air-blown combustion conditions when the gasification reactions are included in the model.     

Impacts of char structure evolution and inherent alkali and alkaline earth metallic species catalysis on reactivity during the coal char gasification with CO2/H2O

In this work, we studied the effects of char structural evolution and alkali and alkaline earth metallic species (AAEMs) catalysis on the reactivity during the char gasification with CO₂, H₂O, and their mixture. The gasified chars with different carbon conversion levels were prepared, and their physicochemical structures were characterized via nitrogen adsorption and FT‐Raman techniques. The concentrations of AAEMs in different modes were obtained by the sequential chemical extraction method. The reactivities of the raw and gasified chars were analyzed by the thermogravimetric analysis. The gasification atmospheres had varied effects on the physicochemical structure of coal char. The gasified char obtained in the CO₂ atmosphere had a lower aromatic condensation degree compared with that obtained in the H₂O atmosphere, irrespective of the temperature. The impact of the atmospheres on the specific surface area of the char varied with the temperature because H₂O and CO₂ have different routes of development of pore structure with coal char. A large specific surface area facilitates the exposure and dispersion of more AAEMs on the surface of the channel, which is conducive to their contact with the gasification agent to play the catalytic role. Thus, the reactivity of the gasified char is well correlated with its specific surface area at different gasification temperatures. In the absence of AAEMs, the chemical structure of coal char becomes the dominant factor affecting the reactivity.     

Integrated drying and gasification of wet microalgae biomass to produce H2 rich syngas – A thermodynamic approach by considering in-situ energy supply

A novel integrated drying and gasification of microalgae wet biomass process, involving a chemical-looping combustion (CLC) option to supply energy, is developed using Aspen Plus. The integrated gasification system consists of four primary units, including (i) a wet biomass drying unit, (ii) the gasification system, (iii) the CLC section, and (iv) the gas purification process. The model shows a good accuracy (relative error < 10%) in predicting the product compositions as compared to the experimental results under consistent operating conditions. The performance of the integrated gasification system is evaluated using Spirulina microalgae at various moisture contents (0–45 wt%). The effect of gasifying agents O₂/steam and the fraction of the produced char used in the CLC section on the gasification performance is also evaluated. The tar is successfully reformed into syngas in the pyrolysis stage by adjusting the O₂ flow rate. The C (char) to CLC provides to a positive effect on the syngas composition, particularly for gasification of wet biomass, but brings an adverse impact on the yield of the syngas product. The integration of the CLC process and CO₂ absorber in the gasification system provides high-quality syngas by removing CO₂. The separated pure CO₂ can be used as a feedstock for other chemical industries.     

Detailed kinetic analysis and modelling of the dry gasification reaction of olive kernel and lignite coal chars

The dry gasification process of solid fuels is a promising pathway to mitigate and utilize captured CO₂ emissions toward syngas generation with tailored composition for several downstream energy conversion and chemical production processes. In the present work, comprehensive kinetic analysis and reaction modelling studies were carried out for olive kernel and lignite coal chars gasification reaction using pure CO₂ as gasifying agent. Chars reactivity and kinetics of the gasification reactions were thoroughly examined by thermogravimetric analysis at three different heating rates and correlated with their physicochemical properties. The reactivity of olive kernel char, as determined by the mean gasification reactivity and the comprehensive gasification characteristic index, S, was almost three times higher compared to that of the lignite coal char. It was disclosed that the fixed carbon content and alkali index (AI) have a major impact on the reactivity of chars. The activation energy, E_a, estimated by three different model-free kinetic methods was ranged between 140 and 170 kJ/mol and 250–350 kJ/mol for the olive kernel and lignite coal chars, respectively. The activation energy values for the lignite coal char significantly varied with carbon conversion degree, whereas this was not the case for olive kernel char, where the activation energy remained essentially unmodified throughout the whole carbon conversion range. Finally, the combined Malek and Coats-Rendfrem method was applied to unravel the mechanism of chars-CO₂ gasification reaction. It was found that the olive kernel char-CO₂ gasification can be described with a 2D-diffusion mechanism function (D2) whereas the lignite coal char-CO₂ gasification follows a second order chemical reaction mechanism function (F2).     

Isothermal and non-isothermal kinetic study on CO2 gasification of torrefied forest residues

CO₂ gasification of torrefied forest residues (birch and spruce branches) was investigated by means of a thermogravimetric analyser operated non-isothermally (400–1273 K) and isothermally (1123 K) under the kinetic regime, followed by kinetic analyses assuming different models. For the non-isothermal gasification, the distributed activation energy model (DAEM) with four or five pseudo-components was assumed. It is found that the severity level of torrefaction had great influences on gasification behaviour as well as devolatilization step. The activation energy of non-isothermal gasification step of three samples varied in the range of 260–290 kJ/mol. The char reactivity decreased with increased torrefaction temperature. For the isothermal gasification, the random pore model (RPM), shrinking core model (SCM), and homogeneous model (HM) were tested. The result has confirmed the trend of decrease in char reactivity with increased torrefaction temperature observed from the non-isothermal gasification. However, different trends in char reactivity due to different wood types were observed by the two methods of gasification.     

Inhibition of steam gasification of biomass char by hydrogen and tar

The influence of hydrogen and tar on the reaction rate of woody biomass char in steam gasification was investigated by varying the concentrations in a rapid-heating thermobalance reactor. It was observed that the steam gasification of biomass char can be separated into two periods. Compared with the first period, in the second period (in which the relative mass of remaining char is smaller than 0.4) the gasification rate is increased. These effects are probably due to inherent potassium catalyst. Higher hydrogen partial pressure greatly inhibits the gasification of biomass char in the first and second periods. By calculating the first-order rate constants of char gasification in the first and second periods, we found that the hydrogen inhibition on biomass char gasification is caused by the reverse oxygen exchange reaction in the first period. In the second period, dissociative hydrogen adsorption on the char is the major inhibition reaction. The influence of levoglucosan, a major tar component derived from cellulose, was also examined. We found that not only hydrogen but also vapor-phase levoglucosan and its pyrolysates inhibited the steam gasification of woody biomass char. By mixing levoglucosan with woody biomass sample, the pyrolysis of char proceeds slightly more rapidly than with woody biomass alone, and gas evolution rates of H₂ and CO₂ are larger in steam gasification.     

Characterization of the physicochemical and structural evolution of biomass particles during combined pyrolysis and CO2 gasification

The combination of pyrolysis and CO₂ gasification was studied to synergistically improve the syngas yield and biochar quality. The subsequent 60-min CO₂ gasification at 800 °C after pyrolysis increased the syngas yield from 23.4% to 40.7% while decreasing the yields of biochar and bio-oil from 27.3% to 17.1% and from 49.3% to 42.2%, respectively. The BET area of the biochar obtained by the subsequent 60-min CO₂ gasification at 800 °C was 384.5 m²/g, compared to 6.8 m²/g for the biochar obtained by the 60-min pyrolysis at 800 °C, and 1.4 m²/g for the raw biomass. The biochar obtained above 500 °C was virtually amorphous.