Thermogravimetric and kinetic analysis to discern synergy during the co-pyrolysis of microalgae and swine manure digestate.

BACKGROUND: Co-pyrolysis of wastes with other feedstock can synergistically improve the rate of biomass decomposition and also help to resolve the issues related to limited availability feedstock. In this regards, synergistic interaction between feedstock during co-pyrolysis is an important aspect of research. As the constituents of aquatic and lignocellulosic biomass are different, and the decomposition pattern of aquatic biomass is dissimilar when compared to lignocellulosic biomass, it is important to understand whether these two biomasses interact during co-pyrolysis. RESULTS: Synergism in the co-pyrolysis of microalgae (MA), swine manure digestate (SWD), and their blends (MA/SWD) (w/w %), 2.5/7.5 (MD-1), 5/5 (MD-2), and 7.5/2.5 (MD-3), was evaluated based on decomposition behavior, gas yields, extent of thermal degradation, and kinetics. Extractives and volatiles in biomass enhanced the reaction kinetics and products yields, as indicated by the reduction in apparent activation energy of the blends, accompanied by an increase in H2, total gas yield, and extent in degradation. Thermogravimetric data, via isoconversional methods, were interpreted to achieve the apparent activation energies for the thermal degradation of the MA, SWD, and their blends. The best fit reaction models were identified using compensation effect and generalized master plots methods. Semi-quantitative method was used to quantify the evolved gas species. H2, CO, and CO2 were noted to be the dominant gases, implying that tar cracking and reforming reactions were predominant. CONCLUSIONS: Overall, synergy was noticed with respect to the pyrolysis of SWD biomass to gas products in the presence of MA biomass, whereas synergy was witnessed up to 50 w/w % MA in view of kinetic parameters as evaluation criteria.

Kinetic analysis for cyclic CO2 capture using lithium orthosilicate sorbents derived from different silicon precursors.

A series of Li4SiO4 was synthesized using LiNO3 and six different silicon precursors. The precipitated-silica-derived Li4SiO4 presented the highest CO2 capacity in a 10 h sorption test, and ZSM-5-derived Li4SiO4 demonstrated the most rapid CO2 sorption. The CO2 sorption kinetics predominantly followed the nucleation mode and could be accurately described by the Avrami-Erofeev model. The Avrami-Erofeev model provided an in-depth analysis of correlation between sorption performance and material properties. Both the nucleation speed and nucleation dimensionality affected the overall sorption kinetics. The kinetics and pore-size distribution suggest that the sorption kinetics was dependent on the quantity of ∼4 nm-pores which favors nucleation dimensionality. For the cyclic tests, the precipitated-silica-derived sample presented the poorest performance with the capacity decreasing from 31.33 wt% at the 1st cycle to only 11.52 wt% at the 30th cycle. However, the sample made from fumed silica displayed an opposite trend with the capacity increasing from 19.90 wt% at the 1st cycle to 34.23 wt% at the 30th cycle. The radically distinct behaviour of samples during cycles was on account of the alternation of sorption kinetics. The decrease in ∼4 nm-pores after cycles was responsible for the decrease of nucleation dimensionality for the precipitated-silica-derived sample. The rearrangement during cycles could enrich the pores of ∼4 nm for the fumed silica-derived sample, which improved the nucleation growth, thus enhancing the kinetics with cycles.

Alkali Metal CO2 Sorbents and the Resulting Metal Carbonates: Potential for Process Intensification of Sorption-Enhanced Steam Reforming.

Sorption-enhanced steam reforming (SESR) is an energy and cost efficient approach to produce hydrogen with high purity. SESR makes it economically feasible to use a wide range of feedstocks for hydrogen production such as methane, ethanol, and biomass. Selection of catalysts and sorbents plays a vital role in SESR. This article reviews the recent research aimed at process intensification by the integration of catalysis and chemisorption functions into a single material. Alkali metal ceramic powders, including Li2ZrO3, Li4SiO4 and Na2ZrO3 display characteristics suitable for capturing CO2 at low concentrations (<15% CO2) and high temperatures (>500 °C), and thus are applicable to precombustion technologies such as SESR, as well as postcombustion capture of CO2 from flue gases. This paper reviews the progress made in improving the operational performance of alkali metal ceramics under conditions that simulate power plant and SESR operation, by adopting new methods of sorbent synthesis and doping with additional elements. The paper also discusses the role of carbonates formed after in situ CO2 chemisorption during a steam reforming process in respect of catalysts for tar cracking.