Abstract:
Nitrogen oxides (NO
x) emissions resulting from the burning of fossil fuels have detrimental effects on both human health and the environment. Therefore, it is necessary to reduce the release of NO
x into the atmosphere. Selective catalytic reduction of NO with C
3H
6 (C
3H
6-SCR) shows great potential because C
3H
6, as a reducing gas, not only reduces the expenses, but also offers enhanced safety and convenience, as compared to NH
3. Low-temperature denitrification process is considered to be cost-saving and energy-efficient. Improving the low-temperature denitrification activity of the catalyst is the key point and a hot topic. Cu-BTC catalyst has the advantages of an adjustable metal site, uniform pore structure and high specific surface area and shows excellent low-temperature catalytic activity in SCR of NO using NH
3 (NH
3-SCR), however, it has poor low-temperature activity when applied to C
3H
6-SCR. To overcome this limitation, in the present study, an additional metal, Ni, was introduced to Cu-BTC to enhance its low-temperature denitrification activity through intermetallic synergies effect. One -step hydrothermal technique was used to synthesize the Ni-doped Cu-Ni
x-BTC catalyst. The basic chemical physical properties of the catalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), N
2 adsorption-desorption, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction of hydrogen (H
2-TPR) and pyridine adsorption-Fourier transform infrared spectroscopy (Py-FTIR), etc. The C
3H
6-SCR reactivity was evaluated in a fixed bed reactor with flue gas consisting 0.05% NO, 0.1% C
3H
6, 5% O
2. The results demonstrated that the introduction of Ni improved the catalytic activity of Cu-BTC. The Cu-Ni
1/2-BTC catalyst achieved a NO conversion rate of 100% and N
2 selectivity of 98.3% at 250−275 ℃, and the C
3H
6 conversion rate of Cu-Ni
1/2-BTC is higher at the same temperature, and the C
3H
6 conversion temperature moves to low temperature. The resistance to SO
2 of Cu-Ni
1/2-BTC catalyst was tested. Results showed, when there was 0.02% SO
2 in the simulated flue gas, the NO conversion rate of Cu-Ni
1/2-BTC decreased to 89.2% at 275 ℃ because of the formation of sulfate on the catalyst surface. Characterization results demonstrated that Ni was effectively doped into the catalyst framework structure and evenly distributed over the catalyst surface. Results from XRD patterns and SEM images demonstrated that Cu-Ni
x-BTC retained the characteristics peaks and basic morphology of Cu-BTC. The XPS spectra showed that the doped Ni existed as Ni
2+ and Ni
3+, and that once Ni was doped, the Cu
+ content in the catalysts increased, suggesting that there was strong electron transfer between Ni and Cu. As the Ni content increased, the specific surface area and pore volume of the catalysts progressively decreased, while the pore size initially increased and then decreased. The H
2-TPR data proved that when Ni was doped, the reduction peaks of the catalysts shifted to a lower temperature and exhibited a higher reduction capacity. Results showed that Cu-Ni
x-BTC possessed better redox properties at low temperatures, more surface-adsorbed oxygen, more Cu
+ ions, and more Lewis acid than Cu-BTC, all of which contributed to its increased catalytic activity.