Effects of different methods of introducing Mo on denitration performance and anti-SO2 poisoning performance of CeO2

doi:10.1016/S1872-2067(20)63778-0

Abstract

Abstract:

Cerium-based catalysts are very attractive for the catalytic abatement of nitrogen oxides (NO_x) emitted from stationary sources. However, the main challenge is still achieving satisfactory catalytic activity in the low-temperature range and tolerance to SO₂ poisoning. In the present work, two series of Mo-modified CeO₂ catalysts were respectively obtained through a wet impregnation method (Mo-CeO₂) and a co-precipitation method (MoCe-cp), and the roles of the Mo species were systematically investigated. Activity tests showed that the Mo-CeO₂ catalyst displayed much higher NO conversion at low temperature and anti-SO₂ ability than MoCe-cp. The optimal Mo-CeO₂ catalyst displayed over 80% NO elimination efficiency even at 150 °C and remarkable SO₂ resistance at 250 °C (nearly no activity loss after 40 h test). The characterization results indicated that the introduced Mo species were highly dispersed on the Mo-CeO₂ catalyst surface, thereby providing more Brønsted acid sites and inhibiting the formation of stable adsorbed NO_x species. These factors synergistically promote the selective catalytic reduction (SCR) reaction in accordance with the Eley-Rideal (E-R) reaction path on the Mo-CeO₂ catalyst. Additionally, the molybdenum surface could protect CeO₂ from SO₂poisoning; thus, the reducibility of the Mo-CeO₂ catalyst declined slightly to an adequate level after sulfation. The results in this work indicate that surface modification with Mo species may be a simple method of developing highly efficient cerium-based SCR catalysts with superior SO₂ durability.

Key words: Surface modification, MoO₃-CeO₂, NH₃-SCR, Br?nsted acid sites, SO₂ resistance

Lulu Li, Chengyan Ge, Jiawei Ji, Wei Tan, Xin Wang, Xiaoqian Wei, Kai Guo, Changjin Tang, Lin Dong. Effects of different methods of introducing Mo on denitration performance and anti-SO₂ poisoning performance of CeO₂[J]. Chinese Journal of Catalysis, 2021, 42(9): 1488-1499.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63778-0

https://www.cjcatal.com/EN/Y2021/V42/I9/1488

Figures/Tables 16

Fig. 1. The NO conversions of the synthesized catalysts.

Fig. 2. The H2O and SO2 durability of these catalysts at 250 °C. (a) SO2 durability over Mo-CeO2, MoCe-cp and CeO2 catalysts; (b) H2O+SO2 durability over Mo-CeO2 and MoCe-cp.

Fig. 3. The XRD (a) and Raman (b) patterns of these synthesized catalysts.

Fig. 4. The TEM images of CeO2 (a), Mo-CeO2 (b), and MoCe-cp (c); the HRTEM images of CeO2 (d), Mo-CeO2 (e), and MoCe-cp (f).

Table 1 The results of BET, pore diameter and the peak area of NH3-TPD curves and NOx-TPD curves over these samples.

Sample	S_BET (m²·g^‒1)	Pore diameter (nm)	peak area of NH₃-TPD curves/a.u.	peak area of NO_x-TPD curves/a.u.
CeO₂	88.1	2.9	—	—
Mo-CeO₂	66.4	8.7	5711	9641
MoCe-cp	119.6	8.9	6219	28130

Fig. 5. N2 adsorption-desorption isotherms (a) and BJH pore distribution curves (b) of these catalysts.

Fig. 6. XPS results of these synthesized catalysts. (a) Mo 3d; (b) S 2p; (c) Ce 3d; (d,e) O 1s.

Table 2 The fitting data of XPS over these samples.

Sample	Ce³⁺/ (Ce³⁺+Ce⁴⁺)/%	O_α/ (O_α+O_β)/%	Atomic concentration of Mo	Atomic concentration of S
CeO₂	17	22	—	—
Mo-CeO₂	18	12	3.42	—
MoCe-cp	22	28	0.49	—
CeO₂-U	38	47	—	3.07
Mo-CeO₂-U	22	29	3.04	1.65
MoCe-cp-U	33	48	0.49	2.71

Fig. 7. H2-TPR results of different catalysts.

Fig. 8. NH3-TPD (a) and NOx-TPD (b) results of different catalysts.

Fig. 9. NH3 adsorption in situ DRIFTS of the Mo-CeO2 (a) and MoCe-cp (b) catalysts at 150 °C.

Fig. 10. NO+O2 adsorption in situ DRIFTS of the Mo-CeO2 (a) and MoCe-cp (b) catalysts at 150 °C.

Fig. 11. NO+O2 adsorption in situ DRIFTS of Mo-CeO2 (a) and MoCe-cp (b) pre-adsorbed NH3 at 150 °C.

Fig. 12. NH3 adsorption in situ DRIFTS of Mo-CeO2 (a) and MoCe-cp (b) pre-adsorbed NO+O2 at 150 °C.

Fig. 13. TG curves of CeO2-U, Mo-CeO2-U and MoCe-cp-U catalysts.

Fig. 14. SO2+O2 adsorption in situ DRIFTS of CeO2 (a), Mo-CeO2 (b) and MoCe-cp (c) catalysts at 250 °C.

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Effects of different methods of introducing Mo on denitration performance and anti-SO₂ poisoning performance of CeO₂

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