• Energy Research

Abstract This study aims to gain insight into the mechanism and kinetics during the gasification of biochar in steam, which was formed in situ in a fluidised-bed reactor using mallee wood in two particle size ranges of 0.80–1.0 mm and 2.0–3.3 mm. The overall biochar gasification rate and the formation rates of key product components were calculated by continuously monitoring the product gas stream with a quadrupole mass spectrometer. The kinetic compensation effects reveal that CO and CO2 are both formed from the heterogeneous reactions between the biochar surface and H2O. CO2 is formed either by the surface (biochar)-catalysed water-gas-shift reaction or directly from the carbon active sites involving the same intermediate for the formation of CO, as revealed by the apparent activation energies and apparent pre-exponential factors for CO and CO2 formation. The changes in the particle size of biomass substrate do not affect the extent of the kinetic compensation effects of biochar consumption and formation of CO, CO2 and H2 in the kinetics-controlled and mixed regimes. The similar extent of the kinetic compensation effects of H2 formation and biochar consumption for both particle sizes indicates that the formation of H2 also mainly involve the carbon active sites on the biochar surface instead of the gas-phase water-gas-shift reaction.

Abstract 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.

Abstract In the oxy-coal combustion steam system (OCCSS), the demineralized coal is consumed by reacting with O2 and steam. The stability and efficiency of demineralized coal combustion at high steam concentrations could be a critical issue to the development of mature OCCSS technology. In this study, Zhundong coal and its acid-washed sample were used for conducting experiments. Pyrolysis chars were firstly prepared from the raw coal and the demineralized coal in a high-temperature drop tube furnace at 1200 °C. The effects of the reaction atmosphere (O2/steam and O2/N2) and temperature (1100–1400 °C) on the combustion characteristics of the two char samples were then investigated. The results show that compared to the char from pyrolysis of raw coal, the char from demineralized coal contained abundant macropores with low specific surface area. For the pyrolysis char from demineralized coal at 1200 °C, the steam-char gasification reaction rate was significantly lower than that of O2-char reaction. The presence of high concentration of steam could alter the heat/mass transfer on the char surface, thus indirectly reducing the rate of O2-char reactions. The combustion of char without minerals in an O2/steam atmosphere accelerated significantly with increasing temperature, while the increase in combustion rate with increasing reaction temperature for char containing minerals was very limited. The steam-char gasification reaction of demineralized char at 1300 °C has promoted the carbon conversion of char. The demineralized char combustion reaction required a relatively high oxygen concentration (i.e. above 40%) to show high burning rate.

It remains challenging to develop a techno-economically feasible method to remove alkali and alkaline earth metal species (AAEMs) from rice husk (RH), which is a widely available bioresource across the world. In this study, the AAEMs leaching effect of aqueous phases of both bio-crude prepared by hydrothermal liquefaction (AP-HT) and bio-oil prepared by pyrolysis (AP-Pyro) of RH were systematically investigated. The results indicated that although the acidity of AP-HT and AP-Pyro are much lower than that of HCl, they performed a comparable removal efficiency on AAEMs (Na: 56.2%, K: 96.7%, Mg: 91.0%, Ca: 46.1% for AP-HT, while Na: 58.9%, K: 96.9%, Mg: 94.0%, Ca: 86.3% for AP-Pyro) with HCl. The presence of phenolics in bio-oil could facilitate the penetration of water and organic acids into the inner area of RH cells, thus enhancing the AAEMs removal via chelate reactions. The thermal stability of leached RH during thermochemical conversions was studied via TG and Py-GC-MS. The results showed that the heat conduction efficiency in leached RH was enhanced with a high pyrolysis rate, resulting in a narrow carbon chain distribution (C5–C10) of derived chemical compounds.

Co-hydrothermal carbonization (HTC) of livestock manure and biomass might improve the fuel properties of the hydrochar due to the high reactivity of the biomass-derived intermediates with the abundant oxygen-containing functionalities. However, the complicated compositions make it difficult to explicit the specific roles of the individual components of biomass played in the co-HTC process. In this study, cellulose was used for co-HTC with swine manure to investigate the influence on the properties of the hydrochar. The yield of hydrochar obtained from co-HTC reduced gradually with the cellulose proportion increased, and the solid yield was lower than the theoretical value. This was because the cellulose-derived intermediates favored the stability of the fragments from hydrolysis of swine manure. The increased temperature resulted in the reduction of the hydrochar yield whereas the prolonged time enhanced the formation of solid product. The interaction of the co-HTC intermediates facilitated the formation of O-containing species, thus making the solid more oxygen- and hydrogen-rich with a higher volatility. In addition, the co-HTC affected the evolution of functionalities like -OH and CO during the thermal treatment of the hydrochar and altered its morphology by stuffing the pores from swine manure-derived solid with the microspheres from HTC of cellulose. The interaction of the varied intermediates also impacted the formation of amines, ketones, carboxylic acids, esters, aromatics and the polymeric products in distinct ways.

The high content of nitrogen in hydrochar produced from hydrothermal carbonization (HTC) of sewage sludge (SS) leads to serious NOx pollution when the hydrochar is used as a solid fuel. Mg-Ga layered double hydroxides (LDHs), Mg-Al LDHs and their calcined samples (layered double oxides, LDO) were prepared. The LDHs and LDO all can notably promote the removal of nitrogen element, in which organic-N was transferred to NH4+-N to cause increasing pH value. Mg-Al LDO showed the highest efficiency for the removal of nitrogen among the catalysts. The thermal decomposition of the N-organic matter with acidic sites in catalyst was the key step to release NH3. The key role of basic sites in Mg-Al LDO was that it can effectively destroy the cell wall and extracellular polymeric substances structure. The lipid-like substance did not participate in the carbonization reaction, but they can be absorbed by the hydrochar. Partial SS floc directly transformed to hydrochar according to "solid-solid" reaction. The reaction pathways of remove nitrogen were proposed.

Abstract The pyrolysis of cellulose at 200–800 °C with an increment of 50 °C was conducted in this study, aiming to understand impacts of temperature on evolution of the of organics and the structures of bio-char. Extensively pyrolysis of cellulose to bio-oil initiated at 300 °C, reached maximum at 450 °C, and shifted to gasification to produce gases as the main products above 650 °C. Dehydrate sugars were the initial products formed below 350 °C, which soon dehydrated to form furans at ca. 400 °C and then generate aliphatic aldehydes, ketones and carboxylic acids at ca. 650 °C via the session of the C–C bonds. Aromatization of the volatiles initiated at 350 °C, producing phenolics and then further to aromatic hydrocarbons. The medium pyrolysis temperature (i.e. 450 °C) tended to produce the heavier bio-oil. The in situ DRIFTS characterization of cellulose pyrolysis showed that the structural reconstruction of the feedstock occurred at ca. 430–440 °C, forming abundant C O functionalities in bio-char. The increasing pyrolysis temperature led to staged change of carbon, hydrogen and oxygen contents in bio-char. The bio-char produced at the low temperature was quite aliphatic, and increasing pyrolysis temperature enhanced the formation of graphite structure, thermal stability and the porosity of bio-char. The bio-char from cellulose had a compact structure with small surface area and very limited mesopores. The results of kinetic analysis showed that the pyrolysis of cellulose was a complex multi-step reaction process.

The development of reactors with varied configurations for the pyrolysis of municipal waste is discussed in this review.