Unlocking high-performance HCl adsorption at elevated temperatures: the synthesis and characterization of robust Ca-Mg-Al mixed oxides.

The presence of HCl and SO2 gas imposes limitations on syngas utilization obtained from household waste in a wide range of applications. The hydrotalcite-like compounds (HTLs) have been proved that could remove HCl efficiency. However, the research on impact of synthesis conditions of HTLs and SO2 on HCl removal was limited. In this study, a range of Ca-Mg-Al mixed oxide sorbents was synthesized by calcining HTLs, with variations in crystallization temperature, solution pH, and the Ca/Mg molar ratio. These sorbents were examined for their effectiveness in removing HCl at medium-high temperatures under diverse conditions. The adsorption performance of selected sorbents for the removal of HCl, SO2, and HCl-SO2 mixed gas at temperature of 350 °C, 450 °C, and 550 °C, respectively, was evaluated using thermogravimetric analysis (TGA). It was observed that the HTL synthesis parameters significantly influenced the HCl adsorption capacity of Ca-Mg-Al mixed oxides. Notably, HTLs synthesized at 60 °C, a solution pH of 10-11, and a Ca/Mg ratio of 4 exhibited superior crystallinity and optimal adsorption characteristics. For individual HCl and SO2 removal, temperature had a minor effect on HCl adsorption but significantly impacted SO2 adsorption rates. At temperatures above 550 °C, SO2 removal efficiency substantially decreased. When exposed to a mixed gas, the Ca-Mg-Al mixed oxides could efficiently remove both HCl and SO2 at temperatures below 550 °C, with HCl dominating the adsorption process at higher temperatures. This dual-action capability is attributed to several mechanisms through which HTL sorbents interacted with HCl, including pore filling, ion exchange, and cation exchange. Initially, HCl absorbed onto specific sites created by water and CO2 removal due to the surface's polarity. Subsequently, HCl reacted with CaCO3 and CaO formed during HTL decomposition.

Facile use of coal combustion fly ash (CCFA) as Ni-Re bimetallic catalyst support for high-performance CO2 methanation.

The industrial waste coal combustion fly ash (CCFA) was used as a cheap catalyst support and by facile co-impregnation method, the active component Ni and promoter Re was loaded to form a bimetallic catalyst for high-performance CO2 methanation. The physico-chemical properties of the prepared catalyst were further measured by a series of characterizations such as X-ray fluorescence (XRF), N2 isothermal adsorption-desorption, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) et al. The effect of reaction temperature and gas hourly space velocity (GHSV) on the catalytic performance was carefully investigated on a continuous fixed-bed reactor. The results showed that in comparison with the non-promoted monometallic Ni/CCFA catalyst, the bimetallic Ni-Re/CCFA catalyst displayed a superior activity, which could achieve 99.55% of CO2 conversion and 70.27% of CH4 selectivity under the condition of 400 °C, 2000 h-1, 1 atm and H2:CO2:N2 = 4:1:0.5, possibly owing to the higher Ni dispersion and more active sites in Ni-Re/CCFA. Besides, the addition of Re promoter was beneficial to enhance the catalyst anti-sintering and anti-coking abilities as reflected by the smaller Ni particle size growth and less carbon deposition amount in Ni-Re/CCFA. The in-situ diffuse reflection infrared Fourier transform spectrum (in-situ DRIFTS) was finally carried out to determine the CO2 adsorption state and its methanation intermediates, from which a loop mechanism of CO2 methanation process was proposed and depicted.

COx co-methanation over coal combustion fly ash supported Ni-Re bimetallic catalyst: Transformation from hazardous to high value-added products.

The hazardous industrial waste, coal combustion fly ash (CCFA), was creatively applied as Ni-Re bimetallic catalyst support. The expected catalyst was facilely prepared by co-impregnation method and further tested for COx co-methanation in a continuous fixed-bed reactor. The physico-chemical properties of the catalyst were examined by a series of techniques including XRF, ICP, XRD, N2 isothermal adsorption, H2-TPR, SEM and TEM. The results showed that compared to non-promoted monometallic Ni catalyst, the addition of Re promoter forming Ni-Re bimetallic catalyst was able to facilitate NiO reduction and increase Ni dispersion as well as inhibit carbon deposition and Ni sintering during reaction. The performance tests revealed that Ni15Re1.0 presented superior COx co-methanation activity over Ni15Re0, Ni15Re0.5 and Ni15Re1.5 due to its better anti-coking and anti-sintering ability. Based on in-situ DRIFTS analysis, a possible cycle reaction mechanism of COx co-methanation was reasonably proposed in the end. The reaction pathway for CO and CO2 methanation differed from each other, where CO was linearly adsorbed on Ni metals followed by stepwise hydrogenation while CO2 was first immobilized by the surface hydroxyl group and then gradually reacted with H2 to form CH4.