Novel ultra-low NOx coal combustion technologies based on local microenvironment targeted regulation. Part 1. Selective oxygenation

•Effect of the local microenvironment on the nitrogen transformation and NO evolution is revealed.•Targeted regulation of local microenvironment around fuel-N is realized by selective oxidation.•Attack of free radicals on nitrogen-containing heterocycles promotes the conversion of fuel-N to HCN.•PAA selective oxidation can reduce NO emission from air combustion by 31.72% – 34.30%. Developing a novel high-efficiency coal combustion technology with ultra-low NOx emission is urgently needed to sustain the good ecological environment. Here, the targeted regulation of local microenvironment around fuel-N, such as functional groups, radicals, molecular configurations, and reaction atmosphere, is realized by the selective oxidation. The molecular configurations, including pore networks and microcrystalline structure in coal, are well characterized through synchrotron radiation-induced SAXS (small angle X-ray scattering) and WAXS (wide angle X-ray scattering) simultaneously. Furthermore, by combining density functional theory (DFT) and experiments, the effects of the local microenvironment on the nitrogen transformation and NO evolution during the thermal conversion are focused on. The results indicate that for the PPA oxidation, the H radicals attack the adjacent carbon to pyrrole/pyridine nitrogen, promoting the conversion of fuel-N to HCN. On the other hand, for the H2O2 oxidation, disrupting the π bond electron cloud by the CO and C = O on the ortho carbon of pyrrole/pyridine dominates the NH3 generation. Additionally, the increased La (average graphene layer extent), a3 (average interlayer spacing), σ3 (standard deviation of interlayer spacing) and σ1 (standard deviation of the first-neighbor distribution) induce massive smaller pores, promoting the generation of abundant reaction defects inside the particles. Importantly, the intensified adsorption on abundant active sites lead to the decreased HCN and increased NH3 evolution, which is adverse for the interaction between homogeneous and heterogeneous NO reduction. Interestingly, the PAA selective oxidation can reduce NO emission by 31.72 % - 34.30 % during the air combustion, which is far better than the H2O2 oxidation. Overall, the attack of free radicals on nitrogen-containing heterocycles promotes the conversion of fuel-N to HCN, the adsorption of which on char surfaces can further enhance the heterogeneous reduction in a lean oxygen atmosphere. The work here provides a novel route for developing high-eff