Use of La-Co@NPC for Sulfite Oxidation and Arsenic Detoxification Removal for High-Quality Sulfur Resources Recovery in Desulfurization Process.

Ammonia desulfurization is a typical resource-recovery-type wet desulfurization process that is widely used in coal-fired industrial boilers. However, the sulfur recovery is limited by the low oxidation rate of byproduct (ammonium sulfite), leading to secondary SO2 pollution due to its easy decomposability. In addition, the high toxic arsenic trace substances coexisting in desulfurization liquids also reduce the quality of the final sulfate product, facing with high environmental toxicity. In this study, nitrogen-doped porous carbon coembedded with lanthanum and cobalt (La-Co@NPC) was fabricated with heterologous catalytic active sites (Co0) and adsorption sites (LaOCl) to achieve sulfite oxidation and the efficient removal of high toxic trace arsenic for the recovery of high-value ammonium sulfate from the desulfurization liquid. The La-Co@NPC/S(IV) catalytic system can generate numerous strongly oxidizing free radicals (·SO5- and ·O2-) for the sulfite oxidation on the Co0 site, as well as oxidative detoxification of As(III) into As(V). Subsequently, arsenic can be removed through chemical adsorption on LaOCl adsorption sites. By using the dual-functional La-Co@NPC at a concentration of 0.25 g/L, the rate of ammonium sulfite oxidation reached 0.107 mmol/L·s-1, the arsenic (1 mg/L) removal efficiency reached 92%, and the maximum adsorption capacity of As reached up to 123 mg/g. This study can give certain guiding significance to the functional material design and the coordinated control of multiple coal-fired pollutants in desulfurization for high-value recovery of sulfur resources.

In Situ Reconstruction of Active Catalysis Sites Triggered by Chromium Immobilization for Sulfite Oxidation.

Hexavalent chromium (Cr(VI)) is a highly toxic substance in wastewater, triggering grievous detriment to aquatic life and human health. Magnesium sulfite is spawned along with the desulfurization process in coal-fired power plants, which is usually disposed of as solid waste. Here, a "waste control by waste" method was proposed upon the redox of Cr(VI)-sulfite, in which highly toxic Cr(VI) is detoxicated and sequent enriched on a novel biochar-induced cobalt-based silica composite (BISC) due to the forced electron transfer from chromium to surface hydroxyl. The immobilized Cr on BISC gave rise to the reconstruction of catalytic active sites "Cr-O-Co", which further enhance its performance in sulfite oxidation by elevating O2 adsorption. As a result, the sulfite oxidation rate increased by 10 times compared with the non-catalysis benchmark together with the maximum chromium adsorption capacity being 120.3 mg/g. Therefore, this study provides a promising strategy to simultaneously control highly toxic Cr(VI) and sulfite, achieving high-grade sulfur resource recovery for wet magnesia desulfurization.

TiO2 Coating Strategy for Robust Catalysis of the Metal-Organic Framework toward Energy-Efficient CO2 Capture.

High energy duty restricts the application of amine-based absorption in CO2 capture and limits the achievement of carbon neutrality. Although regenerating the amine solvent with solid acid catalysts can increase energy efficiency, inactivation of the catalyst must be addressed. Here, we report a robust metal-organic framework (MOF)-derived hybrid solid acid catalyst (SO42-/ZIF-67-C@TiO2) with improved acidity for promoting amine regeneration. The TiO2 coating effectively prevented the active components stripping from the surface of the catalyst, thus prolonging its lifespan. The well-protected Co-Nx sites and protonated groups introduced onto the TiO2 surface increased the amount and rate of CO2 desorption by more than 64.5 and 153%, respectively. Consequently, the energy consumption decreased by approximately 36%. The catalyzed N-C bond rupture and proton transfer mechanisms are proposed. This work provides an effective protection strategy for robust acid catalysts, thus advancing the CO2 capture with less energy duty.