Preparation of monolithic cordierite supported Cu-SSZ-13 catalyst and its performance in the selective catalytic reduction of NOx with NH3
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摘要: 以聚乙烯醇（PVA）或拟薄水铝石（SB粉）为涂覆助剂，采用超声波辅助分散法将Cu-SSZ-13分子筛涂覆于蜂窝状堇青石（Cordierite）上，制备了整体式堇青石负载的Cu-SSZ-13分子筛催化剂（Cu-SSZ-13/Cordierite），用于氨选择性催化还原（NH3-SCR）脱硝，并结合XRD、氮气吸附、SEM及H2-TPR等表征手段，研究了涂覆助剂对该催化剂的Cu-SSZ-13涂层稳定性、NH3-SCR脱硝活性、水热稳定性和抗SO2毒化能力的影响。结果表明，以PVA为涂覆助剂制备的整体式Cu-SSZ-13（PVA）/Cordierite催化剂，其Cu-SSZ-13涂层稳定、脱落率低，选择性催化还原脱硝活性与Cu-SSZ-13原粉基本相当；同时，该Cu-SSZ-13（PVA）/Cordierite催化剂也具有较好的耐高温水热稳定性和抗硫中毒能力，在移动源和固定源脱硝方面有较好应用前景。Abstract: A series of monolithic cordierite supported Cu-SSZ-13 catalysts (Cu-SSZ-13/Cordierite) was prepared by coating the Cu-SSZ-13 molecular sieves on the cellular cordierite through ultrasonic dispersion with polyvinyl alcohol (PVA) or pseudo boehmite powder (SB) as assisting agent and used in the selective catalytic reduction of NOx with NH3 (NH3-SCR). With the help of XRD, nitrogen sorption, SEM and H2-TPR characterization techniques, the influence of coating assistant agent on the firmness of the Cu-SSZ-13 layer, catalytic activity in the NH3-SCR of NO, hydrothermal stability and resistance against SO2 poisoning was then investigated. The results indicate that by using PVA as the coating assistant agent, a firm layer of Cu-SSZ-13 can be formed on the surface of monolithic Cu-SSZ-13/Cordierite catalyst. Moreover, the Cu-SSZ-13(PVA)/Cordierite exhibits high catalytic activity in the NH3-SCR of NOx (close to that of the pristine Cu-SSZ-13 molecular sieve), high hydrothermal stability and good tolerance to SO2, displaying great potential as a practicable catalyst for the removal of NOx from exhausts of both the mobile and the stationary sources.
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图 1 堇青石载体和Cu-SSZ-13/Cordierite催化剂的图片和SEM照片
Figure 1 Photographs of the original cordierite support (a), Cu-SSZ-13(PVA)/Cordierite catalyst (b), and Cu-SSZ-13(SB)/Cordierite catalyst (c); SEM images of the Cu-SSZ-13 molecular sieve (d), the original cordierite (e), the acid-treated cordierite (f), the Cu-SSZ-13(PVA)/Cordierite catalyst (g), and the Cu-SSZ-13(SB)/Cordierite catalyst (h)
图 2 堇青石载体、Cu-SSZ-13分子筛和Cu-SSZ-13/Cordierite催化剂的XRD谱图
Figure 2 XRD patterns of the cordierite support (a), Cu-SSZ-13(PVA)/Cordierite catalyst (b), Cu-SSZ-13(SB)/Cordierite catalyst (c), and Cu-SSZ-13 molecular sieve (d)
图 3 Cu-SSZ-13分子筛和Cu-SSZ-13/Cordierite催化剂的H2-TPR谱图
Figure 3 H2-TPR profiles of the Cu-SSZ-13 molecular sieve (a), Cu-SSZ-13(PVA)/Cordierite catalyst (b), and Cu-SSZ-13(SB)/Cordierite catalyst (c)
图 4 Cu-SSZ-13分子筛和Cu-SSZ-13/Cordierite催化剂的NH3-SCR活性比较
Figure 4 A comparison of the pristine Cu-SSZ-13 molecular [JP2]sieve (a), Cu-SSZ-13 (20%) + quartz sand (b); Cu-SSZ-13[JP](PVA)/Cordierite catalyst (c), Cu-SSZ-13(SB)/Cordierite catalyst (d), Cu-SSZ-13(PVA)/Cordierite catalyst subjected to hydrothermal treatment at 800 ℃ for 12 h (e), and Cu-SSZ-13(SB)/Cordierite catalyst subjected to hydrothermal treatment at 800 ℃ for 12 h (f), in their activity for the selective catalytic reduction (SCR) of NO by NH3 (0.05% NH3, 0.05% NO, 6% O2 and balanced N2, with a space velocity of 20000 h-1)
图 5 Cu-SSZ-13/Cordierite催化剂用于NH3-SCR脱硝时的抗水和耐SO2性能
Figure 5 NO conversion for the NH3-SCR over the Cu-SSZ-13(PVA)/Cordierite (a) and Cu-SSZ-13(SB)/Cordierite (b), for the NH3-SCR in the presence of 5% water over the Cu-SSZ-13(PVA)/Cordierite (c) and Cu-SSZ-13(SB)/Cordierite (d), and for the NH3-SCR in the presence of 0.01%SO2 over the Cu-SSZ-13(PVA)/Cordierite (e) and Cu-SSZ-13(SB)/Cordierite (f)
图 6 新鲜、150 ℃下SO2处理及300 ℃下SO2处理的Cu-SSZ-13分子筛的S 2p XPS谱图
Figure 6 S 2p XPS spectra of the fresh Cu-SSZ-13 (a), Cu-SSZ-13 treated in 0.01%SO2 at 150 ℃ for 30 min (b), and the sulfated Cu-SSZ-13 heated at 300 ℃ (c)
表 1 涂覆助剂及涂覆次数对堇青石上Cu-SSZ-13涂层增量及涂层稳定性的影响
Table 1 Influence of coating assistant agent and coating times on the weight increment of coating and the stability of Cu-SSZ-13 layer on the cordierite support
Coating
assistant agentCoating weight increment /% Cu-SSZ-13
content /%Coating exfoliation rate /% 1st 2nd 3rd total 1st 2nd 3rd overall PVA 6.2 6.9 7.6 20.7 20.7 4.9 0.7 0.1 5.7 SB 14.0 15.2 - 29.2 20.1 7.7 2.3 0.7 10.7 
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表 2 堇青石载体和Cu-SSZ-13/Cordierite催化剂的比表面积及孔体积
Table 2 Surface area and pore volume of the cordierite support and the Cu-SSZ-13/Cordierite catalysts
Sample Surface area
A/(m2·g-1)Pore volume
v/(cm3·g-1)Cordierite, raw ＜1 - Cordierite, acid treated 10 0. 041 Cu-SSZ-13 500 0. 324 Cu-SSZ-13(PVA) / Cordierite 79 0. 062 Cu-SSZ-13(SB) / Cordierite 76 0. 080
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