Char Gasification Research Articles

Nitrogen migration and transformation in gasification chars prepared from torrefied fiberboard

Nitrogen migration and transformation in gasification chars prepared from torrefied fiberboard

Experimental and kinetic study of pressurized CO2 gasification of biomass chars

Pressurized CO2 gasification of biomass represents an effective approach for the utilization of biomass and the reduction of CO2 emissions. The impact of CO2 partial pressure on the gasification kinetics of biomass chars was examined on a pressurized thermogravimetric analyzer at temperatures between 750 and 950 °C and elevated pressures (up to 1MPa). The findings demonstrated that the gasification rates of corn stalk char (CSC), toonasinesis sawdust char (TSC), and rice husk char (RHC) exhibited an increase with rising CO2 partial pressure. The reaction order exhibited variability with respect to CO2 partial pressure, gasification temperature, and biomass type. The reaction order associated with biomass char exhibited a higher value at the elevated CO2 partial pressure range (0.25–1.0MPa) relative to the low CO2 partial pressure range (0.025–0.1MPa). The nth-order model was employed to elucidate the gasification behaviors of biomass chars. The results indicated that the modified random pore model was successfully applied to model the gasification of CSC and TSC. The grain model was effective in predicting the gasification behavior of RHC. The gasification rates of the three biomass chars were accurately predicted by the Langmuir-Hinshelwood model at both low and high CO2 partial pressures. This study presents information on the effect of CO2 partial pressure on biomass char gasification and methods for predicting biomass char gasification under pressurized conditions.

Study on the comprehensive influence of Si-Al-based additives on hydrogen production and K deposition during biomass gasification

Green hydrogen production through gasification is a prospective utilization of biomass. Operational issues (slagging, corrosion and catalyst poisoning) due to inherent alkali metal deposition are main factors affecting gasification. The adoption of Si-Al-based additives as alkali metal inhibitors is a promising approach. In this work, the influence of additive types and placement methods on K deposition and gasification characteristics were studied through a decoupled gasification with online analysis. As a result, separative placement (Sep) method could reduce K deposition without decreasing hydrogen yield compared to mechanical mixture (Mix) method. This advantage is particularly prominent in char gasification. SiO2 is recommended to be added by the Mix to react with alkali and alkaline earth metal species individually to inhibit K release. This match could reduce peak of K deposition content by 55.80 % with less impact on hydrogen yield. Meanwhile, Al2O3 is recommended to be added by the Sep due to its unique comprehensive performance, which could increase hydrogen yield by 4.34 % and reduce peak of K deposition content by 52.72 %. Two recommended addition strategies could be used in different scenarios. This study is expected to guide the design of corrosion-resistant reactors and multifunctional catalysts.

Investigation on steam co-gasification of torrefied biomass and coal: Thermal behavior, reactivity, product characteristic and synergy

The steam gasification of rice straw torrefied at 200–300 °C and its co-gasification with coal were examined in this study. The effect of torrefaction temperature on thermal behavior, reactivity, product characteristic, and synergy were investigated. The results showed that torrefaction temperature influenced the pyrolysis and char gasification stages by shifting them to higher temperature ranges. As torrefaction temperature increased, the H2 content increased while the CO and CH4 contents decreased, with H2/CO molar ratio increasing from 1.8 to 2.4. The total gas yield also increased from 0.95 to 1.30 Nm3/kg, especially with a large increase up to 27.4 %. As for the co-gasification, stages of biomass pyrolysis and coal pyrolysis overlapped at torrefaction temperature of 300 °C. The pyrolysis reactivity decreased while the char gasification reactivity increased with the torrefaction temperature increasing. The H2/CO molar ratio decreased slightly from 3.55 to 3.40, while the total gas yield increased from 1.87 to 1.96 Nm3/kg as well as the cold gas efficiency from 75 % to 77 %. The strongest synergistic effect on the reactivity occurred at torrefaction temperature of 250 °C. The increased torrefaction temperature enhanced the synergistic effect on the total gas yield but weakened it on the H2 yield.

Kinetic analysis and model evaluation for steam co-gasification of coal-biomass blended chars using macro-TGA

A macro-thermobalance (macro-TGA) was applied to investigate the steam co-gasification characteristics of the chars produced from Huainan coal (HN), two types of biomasses, sawdust (SD) and wheat straw (WS), and coal-biomass blends at 900–1200 °C under rapid heating conditions. The gasification reaction kinetics were determined by the homogeneous reaction model (VM), shrinking core model (SCM) and random pore model (RPM), and the optimal model was selected by deviation calculation. The results show that the char gasification reactivity increased with the increase of temperature. The promotion effect of biomass semi-coke on coal char mainly occurred in the stage when the carbon conversion rate was greater than 0.5, which is mainly attributed to the migration of active AAEMs to the surface of coal char to catalyze the gasification reaction in the later stage. However, with the increase in temperature, this promoting effect is weakened due to the increasing influence of mass transfer effects over chemical rate control, and increased volatilization of the inorganic species. The RPM model is suitable for describing the coal char gasification process, while the SCM was the model that best fitted the biomass semi-coke and coal/biomass blends, which elucidates the kinetic mechanisms governing the gasification process.

Exploring the mechanism of alkali metal K-catalyzed biomass char gasification using in-situ DRIFTS and molecular simulation

Although alkali metal potassium (K)-catalyzed char gasification has been widely studied, the detailed mechanism of this process is still not fully understood. To study this catalytic mechanism in more detail, high-temperature in-situ DRIFTS experiments were carried out for the gasification of cellulose char with K and cellulose char without K under H2O and O2 atmospheres, transient gasification experiment of char with K under H2O atmosphere, and char with K gasification under isotope water atmospheres. Peaks at 1945 cm−1 and 2020 cm−1 were observed. Combined with the theoretical spectra obtained by quantum chemical simulations and the prediction of catalytic gasification intermediates by molecular dynamics simulations, these two peaks were confirmed to represent char-polyynes species. Based on this result, a new mechanism is proposed: K interacts with carboxyl groups and aromatic ketones to promote desorption, thereby exposing active sites. Then, K reacts with the edge of the activated char to form numerous highly active char-polyynes species. The polyynes edge of this char-polyynes phase provides ideal adsorption–desorption sites, enabling further reaction with the gasifier. Thus, gas desorption is promoted. The adsorption and desorption peaks of catalytic gasification under the H2O atmosphere were located at 1400 cm−1 and 1300 cm−1, and these peaks represented stable adsorption states and unstable desorption precursors, respectively. Based on this, adsorption–desorption theory was analyzed more comprehensively, and the adsorption–desorption process was divided into three stages: initial adsorption, intermediate conversion, and desorption. The comprehensive new mechanism proposed in this paper provides a better understanding of the nature of char catalytic gasification at a deeper level.

Determination of the apparent activation energy surface from isothermal data of char combustion and gasification

In this paper, the apparent activation energy (AAE) surface was determined by using isothermal data of char combustion and gasification and the apparent Arrhenius equations where the activation parameters depended on temperature and conversion. The dependence of the logarithm of the reaction rate on temperature and conversion was described by the empirical polynomial to increase the accuracy of fitting and the AAE was calculated by the isoconversional method and the fitting of reaction rate and conversion. The AAE surfaces determined for the four examples of char combustion and gasification varied considerably and differently from each other with temperature and conversion. This provides new information for a better understanding of these processes and their kinetic models.

Numerical study of a chemical looping combustion system: Effects of fuel type and particle size distributions on the operating performance

Chemical looping combustion (CLC) using biomass offers a promising pathway for achieving negative carbon emissions. However, the different properties of coal and biomass affect reaction performance, which has not been fully explored in the CLC system. Additionally, the effects of particle size distributions (PSDs) of solid fuels and oxygen carriers (OCs) are inadequately addressed. In this study, a 3D reactive model using the computational particle fluid dynamics (CPFD) method is developed to investigate the effects of PSDs of both solid fuels and oxygen carriers on operating performance with coal and biomass as fuels. Results indicate that the average residence time in FR of coal and biomass particles is 0.86 s and 0.68 s, respectively, but biomass outperforms coal in reaction efficiency. For coal-fueled CLC, the average residence time is 0.46 s for coal particles with diameters of 100–200 μm, whereas it reaches 0.86 s for coal diameters of 300–700 μm. However, the reaction performance is better with smaller coal sizes due to char gasification being the rate-limiting step. In comparison, for biomass-fueled CLC, the reaction efficiency remains consistent across various particle sizes under the specified conditions due to the rapid release of volatile components and the low content of char. Additionally, it is found that the OC conversion ratio is mainly determined by their residence time in the zones with relatively higher concentrations of the combustible gas in FR. Employing OCs with overly wide PSDs such as 300–800 μm can compromise the material seal above the AR, increase the risk of gas leakage and decrease the separation efficiency of the inertial separator.

Decoupling study of municipal solid waste gasification: Effect of pelletization on pyrolysis and gasification of pyrolytic char

To explore the influence of pelletization on the thermal conversion of municipal solid waste (MSW), pyrolysis characteristics and gasification reactivity of MSW pellet and powder were investigated in this study. Besides, the physicochemical properties of internal char and external char within the char pellet were separately characterized. Moreover, the relationship between the physicochemical properties of char pellet and its gasification reactivity was clarified. Results showed that the pyrolytic gas yields of MSW pellets were increased by 15.47 % and 11.55 % at 700 °C and 800 °C, respectively, compared to powder MSW. It was mainly attributed that the conversion of monocyclic aromatic hydrocarbons to polycyclic aromatic hydrocarbons was promoted by the longer residence time within the pellets. Meanwhile, the physicochemical properties of pyrolytic char pellets exhibited a significant heterogeneity. Specifically, the number of ordered aromatic rings of char pellet was reduced, while the order degree of carbon structure was enhanced, particularly the internal char. However, the difference magnitude between internal and external char was diminished with temperature. This was due to the higher temperature resulting in a larger surface specific area and pore volume of the char pellet, especially the internal char, thereby enhancing the pyrolysis process. Furthermore, an increase in pore volume within the char pellet improved gasification reactivity when the conversion rate > 0.4. These findings provide a reference for the pyrolysis and gasification process of MSW pellets.

Catalytic effects of red mud on coal char gasification and the transformation of active lattice oxygen in iron oxides

Catalytic gasification can obviously accelerate gasification reaction rate. However, recovery of catalysts is currently the main challenge. In this work, a kind of industrial solid waste called red mud was tested as a disposable catalyst for coal gasification and its catalytic behaviors were preferentially investigated. The results show that red mud has well-developed pore structures. A variety of catalytic species were found in it and more active sites were formed, consequently resulting in outstanding catalytic ability. Gasification temperature, O/C ratio, and steam flow rate are suggested to be key points influencing the gasification process. Under the same conditions (950 °C, O/C ratio: 3, and steam flow: 0.05 mL/min), carbon conversion, syngas selectivity, and syngas yield of coal gasification catalyzed by red mud reached up to 83.7 %, 88.6 %, and 119.0 mol/g, respectively, which were enhanced by 21.0 %, 22.5 %, and 2.4 % compared with that using pure Fe2O3. XRD and XPS analyses proved that in the early reduction process, the lattice oxygen gradually dissociated from inside of Fe2O3 crystals and migrated to the outside surface to react with char and reducing gases, leading to the formation of Fe3O4 and Fe. Subsequently, with continuous addition of steam, Fe was oxidized to regenerate Fe3O4 and the oxidation–reduction performance of Fe was hence improved.

Usefulness of insights into the kinetic compensation effects in the kinetic analysis of the coal gasification process

AbstractIn this paper, an attempt has been made to understand the kinetic compensation effects and their usefulness in the kinetic analysis of a lab‐based gasification study. The gasification experiment was carried out in two different gasifying environments, that is, 0.4%O₂ + 8%H₂O‐Ar and 8%H₂O‐Ar, for two different particle sizes of Loy Yang brown coal. Analysis of kinetic values with the change in particle size and gasifying environment was investigated. This provides information on the path of product gas formation and how the overall controlling factor affects the path of char gasification, including the rate‐limiting step. Furthermore, the results indicate that having multiple sets of kinetic parameters caused by the inclusion of the change in char properties into kinetics during solid–gas heterogeneous reactions opens up the scope for wider applications in chemical reaction engineering. This includes the design of a reactor with a proper kinetic model, optimization of feedstock, and process parameters with the identification of pathways for product gas formation, which ultimately plays a key role in scaling up technology from bench‐scale to plant‐scale. In contrast, the study of kinetics with having a single set of kinetic data based on the initial change in char properties limits its applications.

Structure characteristics and gasification reactivity of co-pyrolysis char from lignocellulosic biomass and waste plastics: Effect of polyethylene

The rate limiting stage is char reactivity during gasification that can be influenced by its physicochemical structural characteristics. In this study, the effects of feedstock share, rice straw (RS) and polyethylene (PE), on the physicochemical properties and gasification reactivity of chars were investigated and their relationships were discussed. The char gasification reactivity was investigated via isothermal experiments using a thermal analyzer. The results indicated that the PE addition improved the specific surface area (SSA) and pore volume (Vp) of the char obtained from co-pyrolysis RS with PE. The SSA of the char increased by 1.31 times when the PE content was 60 wt%, compared with that of RS char. The order degree and gasification reactivity of the co-pyrolysis char samples increased with increasing PE content beyond 40 wt%. The char reactivity in the early stage of co-gasification was primarily determined by the order degree of carbonaceous and pore structure. The char reactivity in the later stage was influenced by these two factors and the silicon dioxide content could inhibit the char co-gasification reactivity.

Chemical looping gasification of biomass char in fluidized bed and CO2-enriched atmosphere

Chemical looping gasification of biomass char in fluidized bed and CO2-enriched atmosphere

Assessment of sewage sludge as a component for the tire char co-gasification process

The work aimed to assess various sewage sludge (from coking, refinery, and fat-processing plants) as components for tire char co-gasification. The sewage sludge were analysed (basic characteristics, thermal stability, ash characteristics). Then, CO2 gasification and co-gasification measurements of individual materials and their blends (ratio: 70:30, 40:60) were made using the TGA, based on which the process and synergy effect were assessed. Moreover, a detailed analysis of char gasification formed during the pyrolysis was performed (reactivity assessment, kinetic parameters determined using the n-order Coats and Redfern model, and correlation between the individual elements in materials and their reactivity). Co-gasification measurements proved that the addition and increasing sewage sludge share in blends enhanced the process (TG curves were shifted towards lower temperatures, reactivity indicators, and final conversion degrees were improved compared to tire char). The greatest impact on the pyrolysis stage had the sludge from the refinery, while on the gasification stage sewage sludge from coking and fat-processing plants (where the synergy was observed). Moreover, the addition of sewage sludge to tire char reduces the activation energy and, in most cases, the pre-exponential factor. Finally, the correlation between reactivity and the Na, Mg, and P amount in the samples has been proved.

Comparative experimental study of ash formation behaviors during the fixed-bed gasification of coal water slurry and dry pulverized coal prepared from Shenmu coal

The mechanism of ash formation during coal gasification is very important for the safety and stability of gasifier operation. This study comparatively investigated the ash formation behaviors during the gasification of coal water slurry and dry pulverized coal. Shenmu coal was gasified in a CO2 atmosphere at 900 °C using a fixed-bed reactor to prepare chars and ashes. Computer-controlled scanning electron microscopy was employed to characterize the compositions and particle sizes of minerals in the raw coal, coal water slurry gasification ash, and dry pulverized coal gasification ash. Morphological characteristics reveal that, during gasification, coal water slurry gasification char exhibits obvious agglomeration compared to the dry pulverized coal gasification char. The changes of mineral compositions indicate that, during both coal water slurry and dry pulverized coal gasification, minerals follow nearly identical transformation pathways, but the degrees of transformation are different. The influence of char agglomeration on heat transfer may be the reason for the less transformation of K Al-silicate and kaolinite during the coal water slurry gasification. Furthermore, in comparison to dry pulverized coal gasification, more Ca in calcite and S in pyrite transfer into gypsum during the coal water slurry gasification. The results from thermodynamic equilibrium calculations indirectly suggest that this may be attributed to the limited internal diffusion of CO2 within coal water slurry gasification char resulting from char agglomeration during gasification. Overall particle size distributions of minerals in raw coal, coal water slurry gasification ash, and dry pulverized coal gasification ash demonstrate that the degrees of mineral fragmentation are almost consistent during both coal water slurry and dry pulverized coal gasification. However, differences in the degrees of mineral transformation led to different particle size distributions of various minerals between coal water slurry gasification ash and dry pulverized coal gasification ash. This study mainly focuses on the influence of water in coal water slurry on ash formation, and it has not considered the influence of other factors, such as ash content, hydrophilicity, caking property, and gasification reactivity of coal, which need further research to explore.

Unravelling the kinetics and thermodynamics of CO2 gasification of lignin char: an isoconversional and multi-methodological analysis

Unravelling the kinetics and thermodynamics of CO2 gasification of lignin char: an isoconversional and multi-methodological analysis

Density functional theory and ReaxFF MD study on steam-induced nitrogen migration mechanism during char gasification

The formation of nitrogen-containing species during char gasification is crucial for emission of nitrogenous pollutants. In this work, the detailed nitrogen migration mechanism during char gasification is studied. Density functional theory (DFT) coupled with ReaxFF MD methods are used to conduct an in-depth analysis on the intrinsic reaction mechanism during Char(N) and steam interaction. DFT results show that orbital electrons of carbon atoms on char surface are driven towards nitrogen atoms by nitrogen functional groups. The electron density of adjacent carbon atoms is weakened, which has a positive charge. Orbital electron properties show that the band energy gaps of three Char(N) models are 3.063 eV, 1.092 eV and 3.328 eV, indicating the reactivity order for three Char(N) models is as follows: Char(N)-2＞Char(N)-1＞Char(N)-3. DFT calculation indicates that the interaction between Char(N) and steam reduces unsaturated carbon atoms and lower the char decomposition activity, which will inhibit the yield of HCN. In contrast, through hydrogen transfer reactions, nitrogen atoms are easily combined with hydrogen atoms, which is more conducive to the formation of ammonia. ReaxFF MD modeling proves that HCN is the main product for Char(N) decomposition under inert atmosphere. Under steam atmosphere, nitrogen atoms in char are more likely to be converted into amino products. The induction of steam provides a large number of active hydrogen radicals, which is able to attack the nitrogen atoms of char and form N–H bonds, thus promoting the formation of ammonia.

Advancing hydrogen generation: Kinetic insights and process refinement for sorption-enhanced steam gasification of biomass utilizing waste carbide slag

Sorption enhanced steam gasification of biomass (SESGB) presents a promising approach for producing high-purity H2 with potential for zero or negative carbon emissions. This study investigated the effects of gasification temperature, CaO to carbon in biomass molar ratio [CaO/C], and steam flow on the SESGB process, employing carbide slag (CS) and its modifications, CSSi2 (mass ratio of CS to SiO2 is 98:2) and CSCG5 (mass ratio of CS to coal gangue (CG) is 95:5), as CaO-based sorbents. The investigation included non-isothermal and isothermal gasification experiments and kinetic analyses using corn cob (CC) in a macro-weight thermogravimetric setup, alongside a fixed-bed pyrolysis-gasification system to assess operational parameter effects on gas product. The results suggested that CO2 capture by CaO reduced the mass loss during the main gasification as the [CaO/C] increased. The appropriate temperature for SESGB process should be selected between 550 and 700 °C at atmospheric pressure. The appropriate amount of sorbent or steam could facilitate the gasification reaction, but excessive addition led to adverse effects. Operational parameters influenced the apparent activation energy (Ea) by affecting various gasification reactions. For each test, Ea at the char gasification stage was significantly higher than that at the rapid pyrolysis stage. The addition of CS notably increased H2 concentration and yield, while sharply reducing CO2 levels. H2 concentration initially rose and then fell with greater steam flow, peaking at 76.11 vol% for a steam flow of 1.0 g/min. H2 yield peaked at 298 mL/g biomass with a steam flow of 1.5 g/min, a gasification temperature of 600 °C and a [CaO/C] of 1.0. Increasing gasification temperature remarkably boosted the H2 and CO2 yields. Optimal conditions for the SESGB using CS as a sorbent, determined via response surface methodology (RSM), include a gasification temperature of 666 °C, a [CaO/C] of 1.99, and a steam flow of 0.5 g/min, under which H2 and CO2 yields were 464 and 48 mL/g biomass, respectively. CSSi2 and CSCG5 demonstrated excellent cyclic H2 production stability, maintaining H2 yields around 440 mL/g biomass and low CO2 yields (∼60 mL/g biomass) across five cycles. The study results offer new insights for the high-value utilization of agroforestry biomass and the reduction and resource utilization of industrial waste.

Investigation on the steam gasification mechanism of different chars using isotopic tracing method

Gasification can provide syn-gas for consequent chemical production from carbon resources. The control of CO2 emission produced from gasification calls for the lower temperature and the more biomass char for the feed compared with traditional gasification, and the mechanism for steam gasification of different chars is more important. The gasification behaviors of four biomass chars and four coal chars are studied. The mechanism is probed using H216O/H218O period step tracing method coupled with various solid-state analyses on char structures. The increment of intermediates with increasing conversion demonstrate other slow step exists during gasification, and the solid state spectra of chars after and before gasification demonstrates that the condensation of poly-aromatic clusters in chars occurs accompanied with gasification. The addition reactions of radicals generated from gasifying agents and unsaturated carbon bonds C = C in chars is the slower step during gasification and enhancing the addition of radicals to unsaturated C = C bonds may be helpful for the higher gasification rate.

Leaching char with acidic aqueous phase from biomass pyrolysis: Valorization of the leachate via catalytic hydrothermal gasification

Aqueous phase of bio-oil (APB) is a general stream of waste produced from biomass pyrolysis and fractional condensation of pyrolytic volatiles and has very limited applications. We have demonstrated a sequence of leaching of alkali and alkaline earth metallic species (AAEMs) from char and catalytic hydrothermal gasification (CHTG) for valorizing char and APB, respectively. The majority of AAEMs can be removed from the char by leaching with APB and the removal rates were almost equivalent to those leached with HCl (1.0 M). CHTG of an aqueous solution of the spent APB with a total organic carbon of 14,450 ppm was performed in a continuous flow reactor, employing an activated carbon-supported Ru catalyst (Ru loading, 4.6 wt%). The catalyst exhibited a stable activity for carbon conversion of 98.8 % at 350 °C for at least 360 min while gaseous product consisting of H2, CH4, and CO2 was produced with a cold gas efficiency of 101–103 %, on a higher heating value basis. The cold gas efficiency exceeding 100 % is mainly because of the generation of H2 from water through water-gas shift reaction. The CHTG performance of APB was enhanced by char leaching through the uptake of coke-forming precursors of APB onto char and the enrichment of AAEMs in the spent APB. These AAEMs played roles in suppressing coke formation and deposition onto the catalyst and maintaining Ru particle size by providing a less acidic hydrothermal environment.