Ba、Co共掺MnOx复合氧化物低温选择性催化还原NO研究

doi:10.11949/0438-1157.20191520

摘要/Abstract

摘要：

利用柠檬酸络合法制备了一系列Ba、Co掺入MnO_x脱硝催化剂，研究了Ba、Co掺入对MnO_x低温NH₃-SCR性能的影响。测试结果表明：Ba单独掺入时抑制了MnO_x的催化性能，Co单独掺入时促进了MnO_x的催化性能；而当Ba、Co共掺时，催化剂性能出现了最大的提升，其中3BaMnCoO_x表现出了优异的脱硝活性，反应温度高于180℃时其脱硝性能在99%以上，且表现出了良好的抗水硫性能。采用XRD、SEM、NO-TPD、NH₃-TPD、H₂-TPR和NO吸附原位红外等表征手段对催化剂进行了表征。结果表明，Co掺杂后形成了MnCo₂O_4.5固溶体，赋予了催化剂优异的氧化还原性能；Ba掺杂为催化剂提供了新的NO吸附位点，导致了新的活性硝酸盐吸附物种形成，显著促进了催化剂的NO吸附性能。这些特性使得BaMnCoO_x低温脱硝催化剂展现出了优异的脱硝性能。

关键词: 吸附, 选择性催化还原, 实验验证, 钡掺杂

Abstract:

A series of Ba and Co doped MnO_x doping catalysts were prepared by citric acid complex method. The effects of Ba and Co doping on the performance of MnO_x low temperature NH₃-SCR were studied. The test results showed that the addition of Ba inhibited the catalytic performance of MnO_x. The Co addition promoted the catalytic performance of MnO_x. When Ba and Co are co-doped, the performance of the catalyst increased obviously. 3BaMnCoO_x showed the most excellent catalytic performance, and the catalytic activity was above 99% when the reaction temperature was higher than 180°C. It showed good water and sulfur resistance. The catalysts were characterized by XRD, SEM, NO-TPD, NH₃-TPD, H₂-TPR and NO adsorption in situ infrared spectroscopy. The results showed that MnCo₂O_4.5 solid solution was formed after Co doping, which guaranteed excellent redox performance. Ba doping provided a new NO adsorption site for the catalyst, which led to the formation of new active nitrate adsorption species. The NO adsorption performance of the catalyst was promoted. These characteristics make BaMnCoO_x low-temperature denitration catalysts show excellent denitration performance.

Key words: adsorption, SCR, experimental validation, Ba addition

中图分类号:

O 643

刘涛, 张书廷. Ba、Co共掺MnO_x复合氧化物低温选择性催化还原NO研究[J]. 化工学报, 2020, 71(7): 3106-3113.

Tao LIU, Shuting ZHANG. Study on low temperature selective catalytic reduction of NO by Ba and Co co-doped MnO_x[J]. CIESC Journal, 2020, 71(7): 3106-3113.

图/表 8

图1 不同催化剂脱硝性能随温度的变化

Fig.1 Catalytic performance of different catalysts with different temperature

图2 不同催化剂抗水硫脱硝性能（200℃）

Fig.2 Catalytic performance of different catalysts with water and sulfur dioxide（200℃）

图3 不同催化剂的XRD谱图

Fig.3 XRD patterns of various catalysts

图4 催化剂MnCoOx和3BaMnCoOx的SEM图像和Mn、Co元素分布图

Fig.4 SEM photographs of various catalysts（MnCoOx,3BaMnCoOx） and mapping photographs of Mn and Co elements

图5 不同催化剂的NH3-TPD曲线

Fig.5 NH3-TPD curves of different catalysts

图6 不同催化剂的NO-TPD曲线

Fig.6 NO-TPD curves of different catalysts

图7 不同催化剂的H2-TPR曲线

Fig.7 H2-TPR curves of different catalysts

图8 不同催化剂的NO+O2吸附原位红外谱图

Fig.8 In situ FTIR spectra of MnCoOxand3BaMnCoOx in a stream of 1339 mg/m3 NO + 10%O2 and N2

参考文献 34

1	Zi Z H, Zhu B L, Sun Y L, et al. Low-temperature selective catalytic reduction of NO_x with ammonia over MnO_x/Al₂O₃ catalysts[J]. Journal of Molecular Catalysis, 2018, 32(3): 249-260.
2	Xia F T, Song Z X, Liu X, et al. Improved catalytic activity and N₂ selectivity of Fe-Mn-O_xcatalyst for selective catalytic reduction of NO by NH₃ at low temperature[J]. Research on Chemical Intermediates, 2018, 44(4): 2703-2717.
3	Sheng Z Y, Ma D R, Yu D Q, et al. Synthesis of novel MnO_x@TiO₂ core-shell nanorod catalyst for low-temperature NH₃-selective catalytic reduction of NO_x with enhanced SO₂ tolerance[J]. Chinese Journal of Catalysis, 2018, 39(4): 821-830.
4	Kwon D W, Park K H, Hong S C. Enhancement of SCR activity and SO₂ resistance on VO_x/TiO₂ catalyst by addition of molybdenum[J]. Chemical Engineering Journal, 2016, 284: 315-324.
5	Li W, Guo R T, Wang S X, et al. The enhanced Zn resistance of Mn/TiO₂ catalyst for NH₃-SCR reaction by the modification with Nb[J]. Fuel Processing Technology, 2016, 154: 235-242.
6	Putluru S S R, Schill L, Jensen A D, et al. Mn/TiO₂ and Mn-Fe/TiO₂ catalysts synthesized by deposition precipitation-promising for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Applied Catalysis B-Environmental, 2015, 165: 628-635.
7	Choi H, Jeong Y E, Kumar P A, et al. Sb modified Fe-Mn/TiO₂ catalyst for the reduction of NO_xwith NH₃ at low temperatures[J]. Research on Chemical Intermediates, 2018, 44(6): 3737-3751.
8	Ma A Z, Muhler M, Grunert W. Selective catalytic reduction of NO by ammonia over Raney-Ni supported Cu-ZSM-5 (I): Catalyst activity and stability[J]. Chemical Engineering & Technology, 2000, 23(3): 273-278.
9	Pietrogiacomi D, Magliano A, Ciambelli P, et al.The effect of sulphation on the catalytic activity of CoO_x/ZrO₂for NO reduction with NH₃ in the presence of O₂[J]. Applied Catalysis B-Environmental, 2009, 89(1/2): 33-40.
10	Qu W Y, Chen Y X, Huang Z W, et al. Active tetrahedral iron sites of gamma-Fe₂O₃ catalyzing NO reduction by NH₃[J]. Environmental Science & Technology Letters, 2017, 4(6): 246-250.
11	Si Z C, Weng D, Wu X D, et al. Structure, acidity and activity of CuO_x/WO_x-ZrO₂ catalyst for selective catalytic reduction of NO by NH₃[J]. Journal of Catalysis, 2010, 271(1): 43-51.
12	金奇杰, 陶兴军, 潘有春, 等. Y³⁺和La³⁺改性对CeO₂(ZrO₂)/TiO₂催化剂脱硝性能的影响[J]. 热力发电, 2018, 47(2): 71-77.
	Jin Q J, Tao X J, Pan Y C, et al. Effect of Y³⁺ and La³⁺ on catalytic performance of CeO₂(ZrO₂)/TiO₂ catalyst during selective catalytic reduction of NO_x[J]. Thermal Power Generation, 2018, 47(2): 71-77.
13	Jin Q J, Shen Y S, Chu L, et al. Resource utilization of waste CeO₂-based deNO_x composite catalysts for hydrogen production via steam reforming[J]. Composites Part B: Engineering, 2019, 178: 107483.
14	Liu Z, Liu Y, Li Y, et al. WO₃ promoted Mn-Zr mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Chemical Engineering Journal, 2016, 283: 1044-1050.
15	Zhang D, Zhang L, Shi L, et al. In situ supported MnO_x-CeO_x on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH₃[J]. Nanoscale, 2013, 5(3): 1127-1136.
16	Jin Q J, Shen Y S, Sui G R, et al. Synergistic catalytic removals of NO, CO and HC over CeO₂ modified Mn-Mo-W-O_x/TiO₂-SiO₂ catalyst [J]. Journal of Rare Earths, 2018, 36(2): 148-155.
17	Meng D M, Zhan W C, Guo Y, et al. A highly effective catalyst of Sm-MnO_x for the NH₃-SCR of NO_x at low temperature: promotional role of Sm and its catalytic performance[J]. ACS Catalysis, 2015, 5(10): 5973-5983.
18	Yang S J, Wang C Z, Li J H, et al. Low temperature selective catalytic reduction of NO with NH₃ over Mn-Fe spinel: performance, mechanism and kinetic study[J]. Applied Catalysis B-Environmental, 2011, 110: 71-80.
19	Liu Z M, Liu Y X, Li Y, et al. WO₃ promoted Mn-Zr mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Chemical Engineering Journal, 2016, 283: 1044-1050.
20	Pan Y C, Shen Y S, Jin Q J, et al. Promotional effect of Ba additives on MnCeO_x/TiO₂ catalysts for NH₃-SCR of NO at low temperature[J]. Journal of Materials Research, 2018, 33(16): 2414-2422.
21	Zhou C, Feng Z J, Zhang Y X, et al. Enhanced catalytic activity for NO oxidation over Ba doped LaCoO₃ catalyst[J]. RSC Advances, 2015, 5(36): 28054-28059.
22	Castoldi L, Lietti L, Nova I, et al. Alkaline- and alkaline-earth oxides based Lean NO_xtraps: effect of the storage component on the catalytic reactivity[J]. Chemical Engineering Journal, 2010, 161(3): 416-423.
23	Li Y, Li Y P, Shi Q, et al. Novel hollow microspheres Mn_xCo_3-_xO₄ (x=1, 2) with remarkable performance for low-temperature selective catalytic reduction of NO with NH₃[J]. Journal of Sol-Gel Science and Technology, 2017, 81(2): 576-585.
24	Zhang L, Zhang D, Zhang J, et al. Design of meso-TiO₂@MnO_x-CeO_x/CNTs with a core-shell structure as DeNO_x catalysts: promotion of activity, stability and SO₂-tolerance[J]. Nanoscale, 2013, 5(20): 9821-9829.
25	Shen Y S, Zong Y H, Ma Y F, et al. Synergistic catalytic removals of NO, CO and C₃H₈ over CeSn_0.8W_0.6O_x/TiAl_0.2Si_0.1O_x[J]. Fuel, 2016, 180: 727-736.
26	Jin Q J, Chen M M, Tao X J, et al. Component synergistic catalysis of Ce-Sn-W-Ba-O_x/TiO₂ in selective catalytic reduction of NO with ammonia[J]. Applied Surface Science, 2020, 512: 145757.
27	Wang X M, Li X Y, Zhao Q D, et al. Improved activity of W-modified MnO_x-TiO₂ catalysts for the selective catalytic reduction of NO with NH₃[J]. Chemical Engineering Journal, 2016, 288: 216-222.
28	Deng S C, Zhang K, Xu B L, et al. Promotional effect of iron oxide on the catalytic properties of Fe-MnO_x/TiO₂ (anatase) catalysts for the SCR reaction at low temperatures[J]. Catalysis Science & Technology, 2016, 6(6): 1772-1778.
29	Cai T, Huang H, Deng W, et al. Catalytic combustion of 1, 2-dichlorobenzene at low temperature over Mn-modified Co₃O₄catalysts[J]. Applied Catalysis B-Environmental, 2015, 166: 393-405.
30	阚侃, 王珏, 付东, 等. Co₃O₄中空纳米球的可控制备及气敏性能[J]. 材料工程, 2019, 47(1): 50-57.
	Kan K, Wang J, Fu D, et al. Preparation of Co₃O₄ hollow nanospheres and gas sensing properties[J]. Journal of Materials Engineering, 2019, 47(1): 50-57.
31	Li Y, Wan Y, Li Y P, et al. Low-temperature selective catalytic reduction of NO with NH₃ over Mn₂O₃-doped Fe₂O₃ hexagonal microsheets[J]. ACS Applied Materials & Interfaces, 2016, 8(8): 5224-5233.
32	Chen Q, Guo R, Wang Q, et al. The catalytic performance of Mn/TiWO_x catalyst for selective catalytic reduction of NO_x with NH₃[J]. Fuel, 2016, 181: 852-858.
33	Gao G, Shi J W, Liu C, et al. Mn/CeO₂ catalysts for SCR of NO_x with NH₃: comparative study on the effect of supports on low-temperature catalytic activity[J]. Applied Surface Science, 2017, 411: 338-346.
34	Jin Q J, Shen Y S, Zhu S M, et al. Novel TiO₂ catalyst carriers with high thermostability for selective catalytic reduction of NO by NH₃[J]. Catalysis Today, 2019, 327: 279-287.

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