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1. Comparing Physicochemical Properties and Sorption Behaviors of Pyrolysis-Derived and Microwave-Mediated Biochar

   https://doi.org/10.3390/su13042359  

   Brickler, Colten A.; Wu, Yudi; Li, Simeng; Anandhi, Aavudai; Chen, Gang (February 2021, Sustainability)

   null (Ed.)

   Biochar’s ability to amend and remediate agricultural soil has been a growing interest, though the energy expenses from high-temperature pyrolysis deter the product’s use. Therefore, it is urgent to improve the pyrolysis efficiency while ensuring the quality of produced biochar. The present study utilized three types of feedstock (i.e., switchgrass, biosolid, and water oak leaves) to produce biochar via conventional slow pyrolysis and microwave pyrolysis at different temperature/energy input. The produced biochar was characterized and comprehensively compared in terms of their physiochemical properties (e.g., surface functionality, elemental composition, and thermal stability). It was discovered that microwave-mediated biochar was more resistant to thermal decomposition, indicated by a higher production yield, yet more diverse surface functional groups were preserved than slow pyrolysis-derived biochar. A nutrient (NO3-N) adsorption isotherm study displayed that microwave-mediated biochar exhibited greater adsorption (13.3 mg g−1) than that of slow pyrolysis-derived biochar (3.1 mg g−1), proving its potential for future applications. Results suggested that microwaves pyrolysis is a promising method for biochar production. 

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2. Nanostructured molybdenum carbide on biochar for CO2 reforming of CH4

   Li, Rui (January 2018, Fuel)

   A simple procedure was developed to synthesize molybdenum carbide nanoparticles (Mo2C/BC) by carburization of molybdate salts supported on the biochar from pyrolysis of biomass without using extra carbon source or reducing gas. The molybdenum carbide formation procedure investigated by in-situ XRD and TGA-MS indicated that the phase transitions followed the path of (NH4)6Mo7O24·4H2O → (NH4)2Mo3O10 → (NH4)2Mo14O42 → Mo8O23 → Mo4O11 → MoO2 → Mo2C. The volatile gases CO, H2, and CH4 evolved from biochar and the biochar solid carbon participated in the reduction of molybdenum species, while the biochar and CH4 served as carbon sources for the carburization. Temperature programmed surface reactions of Mo2C/BC indicated that CH4 dissociated as CH4 ⇋ C∗ + 2H2 on the catalyst surface, and CO2 reacted as CO2 + C∗ ⇋ 2CO+ ∗ due to oxidation of Mo2C. Both experiment data and thermodynamic analysis for the study of operation conditions of CO2 reforming of CH4 clearly demonstrated that the yields of H2 and CO increased with the increased temperature and the reasonable conversions should be performed at 850 °C, at which both CH4 and CO2 conversions were higher than 80%. 

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3. Thermal air oxidation changes surface and adsorptive properties of black carbon (char/biochar)

   Feng Xiao, Alemayehu H. (January 2018, Science of the total environment)

   In this study, we systematically investigated the effects of thermal air oxidation on the properties of biomass-derived BC made at carbonization temperatures (HTTs) of 300–700 ˚C. BC produced by including air in the carbonization step was found to have a low surface area and underdeveloped pore structure. Substantial changes of BC were observed after post-pyrolysis thermal air oxidation (PPAO). Well-carbonized BC samples made anoxically at relatively high HTTs (600 and 700 ˚C) showed, after PPAO, significant increases in N2 BET surface area (SA) (up to 700 times), porosity (< 60 Å) (up to 95 times), and adsorptivity (up to 120 times) of neutral organic species including two triazine herbicides and one natural estrogen. Partially carbonized BC made at a lower HTT (300 or 400 ˚C) showed moderate increases in these properties after PPAO, but a large increase in the intensity of Fourier transform infrared spectroscopy bands corresponding to various oxygen-containing functional groups. Well-carbonized BC samples, on the other hand, were deficient in surface oxygen functionality even after the PPAO treatment. Adsorption of the test organic compounds on BC generally trended with BET SA when it was less than 300 m2/g, but BET SA was poorly predictive of adsorption when it was greater than 300 m2/g. Overall, our results suggest that thermal reactions between molecular oxygen and BC 1) increase surface oxygen functionality more effectively for low-HTT than for high-HTT BC samples; 2) increase SA and porosity (< 60 Å) especially for high-HTT BC samples; and 3) create new adsorption sites and/or relieve steric restriction of organic molecules to micropores, thereby enhancing the adsorptivity of BC. These results will prove useful not only for understanding the fate of environmental BC but also in devising strategies for improving the practical performance of the engineered form of BC (i.e., biochar). 

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4. Catalytic pyrolysis of raw and hydrothermally carbonized Chlamydomonas debaryana microalgae for denitrogenation and production of aromatic hydrocarbons

   Ansah, Emmauel (January 2018, Fuel)

   Pyrolysis of raw and hydrothermally carbonized (HTC) Chlamydomonas debaryana with and without activated carbon (AC) or β-zeolite as the catalyst were studied. Monoaromatic hydrocarbon yields from the pyrolysis of raw and HTC treated algae without a catalyst were relatively low at optimum yields of 11.2% and 12.0% obtained at 600 °C, respectively. The maximum yields of monoaromatic hydrocarbons from the AC catalyzed pyrolysis of raw and HTC treated algae were 43.8% obtained at 600 °C and 43.5% obtained at 800 °C, respectively, compared to 32.3% and 32.7% for the maximum yields from the β-zeolite catalyzed pyrolysis at 500 °C and 600 °C, respectively. However, β-zeolite catalyzed pyrolysis produced higher yields of total hydrocarbons (aromatic + aliphatic) for raw and HTC algae compared to AC catalyzed pyrolysis. This means while β-zeolite was more effective in producing total hydrocarbon content, AC was more effective in aromatization of oxygenates. The combination of HTC pretreatment and catalytic pyrolysis were effective in reducing nitrogen content in bio-oil. The yields of nitriles and nitrogenous compounds were negligible for the AC catalyzed pyrolysis of HTC treated algae at 600 °C, compared to 8.3% using the β-zeolite at the same temperature. The AC catalyst had a lower tendency towards coking 

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5. CO2 Sequestration using BOF slag: Application in landfill cover

   Reddy, K.R.; Kumar, G.; Gopakumar, A.; Rai, R.K.; Grubb, D.G. (July 2018, International Conference on Protection and Restoration of the Environment XIV)

   Fugitive methane (CH4) and carbon dioxide (CO2) emissions at municipal solid waste (MSW) landfills constitute one of the major anthropogenic sources of greenhouse gas (GHG) emissions to the atmosphere. In recent years, biocovers involving the addition of organic-rich amendments to landfill cover soils is proposed to promote microbial oxidation of CH4 to CO2. However, most of the organic amendments used have limitations. Biochar, a solid byproduct obtained from gasification of biomass under anoxic or low oxygen conditions, has characteristics that are favorable for enhanced microbial oxidation in landfill covers. Recent investigations have shown the significant potential of biochar-amended cover soils in mitigating the CH4 emissions from MSW landfills. Although the CH4 emissions are mitigated, there is still considerable amount of CO2 that is emitted to the atmosphere as a result of microbial oxidation of CH4 in landfill covers as well as the CO2 derived from MSW decomposition. Basic oxygen furnace (BOF) slag is a product of steel making has great potential for CO2 sequestration due to its strong alkaline buffering and high carbonation capacity. In an ongoing project, funded by the U.S. National Science Foundation, the potential use of BOF slag in landfill covers along with biochar-amended soils to mitigate both CH4 and CO2 emissions is being investigated. This paper presents the initial results from this study and it includes detailed physical and chemical and leachability characteristics of BOF slag, and a series of batch tests conducted on BOF slag to determine its CH4 and CO2 uptake capacity. The effect of moisture content on the carbonation capacity of BOF slag was also evaluated by conducting batch tests at different moisture contents. In addition, small column experiments were conducted to evaluate the gas migration, transport parameters and the CO2 sequestration potential of BOF slag under simulated landfill gas conditions. The result from the batch and column tests show a significant uptake of CO2 by BOF slag for the tested conditions and demonstrates excellent potential for its use in a landfill cover system. 

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