Investigations of NO reduction by coal-based activated carbon with KOH activation: Performance and mechanism.

Selective catalytic reduction of ammonia is the most widely used technology for NOx removal, but there have been serious ammonia leaks and a narrow reaction temperature window. To overcome these limitations, a coal-based activated carbon (CAC) approach using KOH activation for the ammonia-free reduction of NO was investigated in this work. A preparation process was investigated by evaluating the De-NOx performance at different mass ratios (KOH:coal = 0-3:1), and activation temperatures (700-900 °C). The optimum conditions were an activation temperature of 700 °C and a 1:1 ratio of KOH/coal, named CAC-1:1-700. Between 330 and 500 °C, the NO conversion efficiency is maintained at 100% within 90 min. The CAC-1:1-700 showed excellent denitrification performance and SO2 resistance. Based on BET, SEM, XRD, Raman, FT-IR, and XPS characterization analysis, it was found showed that KOH activation could increase the amorphous carbon, pore structure, and C(O) functional groups in CAC, which had positive effects on the denitrification performance. Furthermore, the evolution of char structures and surface species before and after the Char-NO-O2 reaction was evaluated by Raman and XPS, and the possible reaction mechanisms was proposed. Aliphatic structures and small aromatic rings can play the same role in De-NOx, O2 is adsorbed on the carbon to form an oxygen-containing functional group, generating more C-O groups and creating reactive sites C*. NO then interacts with these reactive sites and is reduced to N2. This research prepared CAC as a promising potential alternative to ammonia reductants due to its excellent denitration performance over a medium temperature range and complex flue gas environments, while providing the high-value utilization of coal resources.

Three-dimensional porous CuO-modified CeO2-Al2O3 catalysts with chlorine resistance for simultaneous catalytic oxidation of chlorobenzene and mercury: Cu-Ce interaction and structure.

Chlorine poisoning effects are still challenging to develop efficient catalysts for applications in chlorobenzene (CB) and mercury (Hg0) oxidation. Herein, three-dimensional porous CuO-modified CeO2-Al2O3 catalysts with macroporous framework and mesoporous walls prepared via a dual template method were employed to study simultaneous oxidation of CB and Hg0. CuO-modified CeO2-Al2O3 catalysts with three-dimensional porous structure exhibited outstanding activity and stability for simultaneous catalytic oxidation of CB and Hg0. The results demonstrated that the addition of CuO into CeO2-Al2O3 can simultaneously enhance the acid sites and redox properties through the electronic inductive effect between CuO and CeO2 (Cu2++Ce3+↔Cu++Ce4+). Importantly, the synergistic effect between Cu and Ce species can induce abundant oxygen vacancies formation, produce more reactive oxygen species and facilitate oxygen migration, which is beneficial for the deep oxidation of chlorinated intermediates. Moreover, macroporous framework and mesoporous nanostructure dramatically improved the specific surface area for enhancing the contact efficiency between reactants and active sites, leading to a remarkable decrease of byproducts deposition. CB and Hg0 had function of mutual promotion in this reaction system. In tune with the experimental results, the possible mechanistic pathways for simultaneous catalytic oxidation of CB and Hg0 were proposed.

Highly efficient simultaneous removal of HCHO and elemental mercury over Mn-Co oxides promoted Zr-AC samples.

MnxCoy/Zrz-AC prepared by impregnation method was investigated on the simultaneous removal of HCHO and Hg0. The samples were characterized by BET, SEM, XRD, H2 pulse chemisorption, H2-TPR, XPS, Hg-TPD and in-situ DRIFTS. Thereinto, the optimal Mn2/3Co8/Zr10-AC achieved 99.87% HCHO removal efficiency and 82.41% Hg0 removal efficiency at 240 °C, respectively. With increased surface area and pore volume, Zr-AC support facilitated higher dispersion of MnOx-CoOx. Moreover, the co-doping of MnOx-CoOx endowed the sample with more active oxygen species and higher reducibility, which further facilitated the removal of HCHO and Hg0. Chemisorption was proved to predominate in Hg0 removal, and oxidation also worked as Hg2+ was detected in outlet gas. Besides, HCHO predominated in the competition of active oxygen species, especially for lattice oxygen, thus suppressed the Hg0 removal. According to in-situ DRIFTS, HCHO removal proceeded as HCHOads → DOM → formate species → CO2 + H2O, and was boosted by active oxygen species. Furthermore, Mn2/3Co8/Zr10-AC was proved with excellent regeneration performance, indicating its potential in practical application.

The synthetic evaluation of CuO-MnOx-modified pinecone biochar for simultaneous removal formaldehyde and elemental mercury from simulated flue gas.

A series of low-cost Cu-Mn-mixed oxides supported on biochar (CuMn/HBC) synthesized by an impregnation method were applied to study the simultaneous removal of formaldehyde (HCHO) and elemental mercury (Hg0) at 100-300° C from simulated flue gas. The metal loading value, Cu/Mn molar ratio, flue gas components, reaction mechanism, and interrelationship between HCHO removal and Hg0 removal were also investigated. Results suggested that 12%CuMn/HBC showed the highest removal efficiency of HCHO and Hg0 at 175° C corresponding to 89%and 83%, respectively. The addition of NO and SO2 exhibited inhibitive influence on HCHO removal. For the removal of Hg0, NO showed slightly positive influence and SO2 had an inhibitive effect. Meanwhile, O2 had positive impact on the removal of HCHO and Hg0. The samples were characterized by SEM, XRD, BET, XPS, ICP-AES, FTIR, and H2-TPR. The sample characterization illustrated that CuMn/HBC possessed the high pore volume and specific surface area. The chemisorbed oxygen (Oß) and the lattice oxygen (Oα) which took part in the removal reaction largely existed in CuMn/HBC. What is more, MnO2 and CuO (or Cu2O) were highly dispersed on the CuMn/HBC surface. The strong synergistic effect between Cu-Mn mixed oxides was critical to the removal reaction of HCHO and Hg0 via the redox equilibrium of Mn4+ + Cu+ ↔ Mn3+ + Cu2+.

Oxidation of elemental mercury by modified spent TiO2-based SCR-DeNOx catalysts in simulated coal-fired flue gas.

In order to reduce the costs, the recycle of spent TiO2-based SCR-DeNOx catalysts were employed as a potential catalytic support material for elemental mercury (Hg(0)) oxidation in simulated coal-fired flue gas. The catalytic mechanism for simultaneous removal of Hg(0) and NO was also investigated. The catalysts were characterized by Brunauer-Emmett-Teller (BET), scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) method. Results indicated that spent TiO2-based SCR-DeNOx catalyst supported Ce-Mn mixed oxides catalyst (CeMn/SCR1) was highly active for Hg(0) oxidation at low temperatures. The Ce1.00Mn/SCR1 performed the best catalytic activities, and approximately 92.80% mercury oxidation efficiency was obtained at 150 °C. The inhibition effect of NH3 on Hg(0) oxidation was confirmed in that NH3 consumed the surface oxygen. Moreover, H2O inhibited Hg(0) oxidation while SO2 had a promotional effect with the aid of O2. The XPS results illustrated that the surface oxygen was responsible for Hg(0) oxidation and NO conversion. Besides, the Hg(0) oxidation and NO conversion were thought to be aided by synergistic effect between the manganese and cerium oxides.

Study on the removal of elemental mercury from simulated flue gas by Fe2O3-CeO2/AC at low temperature.

Fe2O3 and CeO2 modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg(0)) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe2O3 and CeO2, reaction temperature, and individual flue gas components including O2, NO, SO2, and H2O (g) on Hg(0) removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe2O3 and 3 % CeO2 on Fe3Ce3/AC, the Hg(0) removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O2 and NO exhibited a promotional effect on Hg(0) removal, H2O (g) exerted a suppressive effect, and SO2 showed an insignificant inhibition without O2 to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg(0) removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg(0) oxidation.