Abstract:
Nitrogen oxides (NO
x) are major air pollutants produced by fuel combustion that cause adverse effects on the environment and human health. The deep purification of NO
x from flue gases has become a worldwide issue. In China, a rigorous ultra-low emission standard (ULES) of NO
x ≤ 50 mg·m
–3 has been implemented in the power and steel industries in recent years. NO
2 is a valuable chemical feedstock that is worthy of being recycled from flue gas. Adsorption is a promising technology that can achieve deep purification and resource recovery of NO
x from industrial flue gas, in which a high-performance NO
x adsorbent plays a key role. However, a systematic understanding of NO
x adsorbents for practical applications is still lacking. This study compares and analyzes the NO
x adsorption and desorption performances of typical practical adsorbents including zeolites, metal oxides, and silica-alumina gels based on the practical need for both NO
x purification efficacy and material thermal stability. NO
x adsorption capacities, breakthrough curves, uptake curves, and temperature-programmed desorption (TPD) curves were also measured. Results show that compared to Fe–Mn–Ce and 13X as competitive adsorbents, H-ZSM-5_25 showed NO
x deep purification (purification efficiency close to 100% before adsorption breakthrough), great NO
x adsorption capacity (0.206 mmol·g
–1), and high NO
2 concentration ratio in desorption, which are likely due to its high NO catalytic oxidation rate and comparable NO
2 physical adsorption rate. Regarding the desorption characteristics, H-ZSM-5_25 showed a bimodal TPD desorption peak with a lower desorption temperature (400–470 K) in the low-temperature region. Meanwhile, NO
2 is the primary NO
x component in the desorbed gas (adsorption-desorption enrichment ratio of NO
2 being up to 57), which can easily be recovered using the liquefaction method. Furthermore, by comparing the adsorption performances on the H-ZSM-5 with different silica-to-alumina ratios, the NO
x adsorption was found to decrease (from 0.706 to 0.206 mmol·g
–1 for H-ZSM-5_25 and from 0.454 to 0.127 mmol·g
–1 for H-ZSM-5_38) with increasing temperature (298–398 K). The dependence of the NO
2 adsorption on the temperature was more significant for H-ZSM-5_25 compared to H-ZSM-5_38. Compared to H-ZSM-5_38, H-ZSM-5_25 with a lower silica-to-alumina ratio (consequently, more cation sites) rendered greater NO oxidation performance, a potentially higher NO
2 adsorption capacity, and a greater decreasing trend of the adsorption capacity with increasing temperature. Results of adsorption kinetic experiments showed that the NO
x mass transfer parameters on H-ZSM-5_25 were lower than those on H-ZSM-5_38 with a smaller primary micro pore channel. Results of the current work can provide technical references for economic flue gas denitrification.