Research progress on NH3-SCR mechanism of metal-supported zeolite catalysts
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摘要: 在NH3选择性催化还原(NH3-SCR)反应中,由于具有宽温度窗口和良好的水热稳定性,金属负载型分子筛是具有广泛应用潜力的脱硝催化剂。本文综述了Cu基和Fe基分子筛催化剂在NH3-SCR领域的研究进展,总结了催化剂的结构特征和NH3-SCR性能指标,并对相应的金属活性位点和反应机理进行了归纳。此外,系统介绍了密度泛函理论(DFT)计算在NH3-SCR反应机理中的应用及反应动力学的研究方法,并对比了不同催化剂体系下的表观动力学参数,为进一步研究金属负载型分子筛催化剂的NH3-SCR反应机理提供方法与思路。Abstract: Metal-supported zeolite catalysts have been widely used in the NH3 selective catalytic reduction (NH3-SCR) reactions due to their wide temperature window and good hydrothermal stability. In this review, the research progress in the structural characteristics, catalytic performance and reaction mechanism of Cu- and Fe-based zeolite catalysts in NH3-SCR was summarized. In addition, the application of density functional theory (DFT) calculation in clarifying the reaction mechanism of NH3-SCR was introduced. Finally, the reaction kinetics and the apparent kinetic parameters of different metal-based zeolite catalysts in NH3-SCR were compared and discussed. We hope this review could provide new ideas for the study of NH3-SCR reaction mechanism over metal-supported zeolite catalysts.
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Key words:
- NH3-SCR /
- zeolite /
- reaction mechanism /
- reaction kinetics
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表 1 代表性的铁基NH3-SCR分子筛催化剂
Table 1 Summary of representative Fe-based NH3-SCR zeolites catalysts
Catalyst Topology Channel system Preparation method Metal content
w/%Reaction condition Temperature window/℃ NOx conversion Ref. Fe/ZSM-5 MFI 3-dimensiona l10-MR IEa 1.9 0.1% NO,0.1% NH3,5% O2,6% H2O,balance of He,GHSV =
1.9 × 105 h−1300−550 > 80% [59] Fe/Beta BEA 3-dimensiona l12-MR CVDb 4.7 0.1% NO,0.12% NH3,8% O2,8% H2O,10%CO2,balance of N2,GHSV = 2.1 × 105 h−1 300−500 > 90% [60] Fe/Mordenite MOR 1-dimensiona l12-MR IE 2.3 0.05% NO,0.05% NH3,5% O2,balance of N2,GHSV =
1.6 × 104 h−1350−500 100% [61] Fe/SSZ-13 CHA 3-dimensiona l8-MR IE 1.37 0.035% NO,0.035% NH3,14% O2,2.5% H2O,balance of N2,GHSV = 2 × 105 h−1 320−550 > 80% [50] Fe-SAPO-34 CHA 3-dimensiona l8-MR OPc 1.0 0.035% NO,0.035% NH3,14% O2,5%CO2,balance of Ar,GHSV = 3.0 × 104 h−1 300−600 > 80% [51] Fe/Ferrierite FER 2-dimensiona l10-MR CVD 4.7 0.1% NO,0.12% NH3,8% O2,8% H2O,10%CO2,balance of N2,GHSV = 2.1 × 105 h−1 250−500 > 90% [60] Fe-SSZ-39 AEI 3-dimensiona l8-MR OP 1.01 0.005% NO,0.006% NH3,10% O2,10% H2O,balance of N2,GHSV = 4.5 × 105 h−1 300−550 > 90% [57] Fe/L LTL 1-dimensiona l12-MR CVD 5.1 0.1% NO,0.12% NH3,8% O2,8% H2O,10%CO2,balance of N2,GHSV = 2.1 × 105 h−1 300−500 > 80% [60] Fe-ERI ERI 3-dimensiona l8-MR OP 1.03 0.05% NO,0.06% NH3,10% O2,10% H2O,balance of N2,GHSV = 1 × 105 h−1 450−550 > 60% [62] Fe-SSZ-16 AFX 3-dimensiona l8-MR OP 0.95 0.05% NO,0.05% NH3,5% O2,10% H2O,balance of N2,GHSV = 1 × 105 h−1 400−550 > 80% [62] Fe-MCM-22 MWW 2-dimensiona l10-MR OP 4.8 0.05% NO,0.05% NH3,5% O2,balance of N2,GHSV = 6 × 104 h−1 190−490 > 80% [23] Fe/LTA LTA 3-dimensiona l8-MR IE 1.8 0.05% NO,0.05% NH3,5% O2,10% H2O,balance of N2,GHSV = 1 × 105 h−1 370−580 > 90% [58] Fe/UZM-35 MSE 3-dimensiona l12-MR IE 1.9 0.05% NO,0.05% NH3,5% O2,10% H2O,balance of N2,GHSV = 1 × 105 h−1 250−570 > 90% [56] a: ion-exchange; b: chemical vapor deposition; c: one-pot 表 2 代表性的铜基NH3-SCR分子筛催化剂总结
Table 2 Summary of representative Cu-based NH3-SCR zeolites catalysts
Catalyst Topology Channel system Preparation method Metal content
w/%Reaction condition Temperature window/℃ NOx conversion Ref. Cu/ZSM-5 MFI 3-dimensiona l10-MR IEa 4.7 0.05% NO,0.05% NH3,5% O2, 10%H2O,balance of N2,GHSV = 1.0 × 105 h−1 150−450 > 80% [89] Cu/Beta BEA 3-dimensiona l12-MR IE 2.1 0.075% NO,0.075% NH3,9.5% O2,balance of Ar,GHSV = 9 × 104 h−1 280−520 > 70% [90] Cu/SSZ-13 CHA 3-dimensiona
l8-MRIE 3.6 0.05% NO,0.05% NH3,5% O2, 10% H2O,balance of N2,GHSV = 4.0 × 105 h−1 200−550 > 85% [91] Cu/SAPO-34 CHA 3-dimensiona
l8-MRIE 1.89 0.05% NO,0.05% NH3,5% O2,balance of N2,GHSV = 6.0 × 103 h−1 190−540 > 80% [52] Cu/SAPO STA-7 SAV 3-dimensiona
l8-MRIE 3.3 0.05% NO,0.05% NH3,5% O2,balance of N2,GHSV = 1 × 105 h−1 250−350 > 80% [84] Cu/SAPO STA-7 SAV 3-dimensiona
l8-MRDSb 4.2 0.05% NO,0.05% NH3,5% O2,balance of N2,GHSV = 1 × 105 h−1 200−400 > 80% [84] Cu/SSZ-16 AFX 3-dimensiona
l8-MRIE 5.65 0.05% NO,0.05% NH3,10% O2,balance of N2,GHSV = 4.25 × 104 h−1 200−500 > 90% [52] Cu/Nu-3 LEV 2-dimensiona
l8-MRIE 0.79 0.05% NO,0.05% NH3,10% O2,balance of N2,GHSV = 4.25 × 104 h−1 270−420 > 90% [52] Cu/Sigma-1 DDR 2-dimensiona
l8-MRIE 0.82 0.05% NO,0.05% NH3,10% O2,balance of N2,GHSV = 4.25 × 104 h−1 230−450 > 90% [52] Cu/SSZ-39 AEI 3-dimensiona
l8-MRIE 0.52 0.05% NO,0.05% NH3,7% O2,balance of N2,GHSV = 2.7 × 105h−1 220−550 > 90% [92] Cu/ERI ERI 3-dimensiona
l8-MRIE 2.2 0.05% NO,0.053% NH3,7% O2,5% H2O,balance of N2,GHSV = 1 × 105 h−1 250−500 > 80% [62] Cu/SSZ-16 AFX 3-dimensiona
l8-MRIE 3.0 0.05% NO,0.053% NH3,7% O2,5% H2O,balance of N2,GHSV = 1 × 105 h−1 270−550 > 90% [62] Cu/SAPO-18 AEI 3-dimensiona
l8-MRIE 5.6 0.05% NO,0.053% NH3,7% O2,5% H2O,balance of N2,GHSV = 4.5 × 105 h−1 240−460 > 90% [82] Cu/KFI KFI 3-dimensiona
l8-MRIE 4.7 0.05% NO,0.05% NH3,8% O2,5% H2O,balance of N2,GHSV = 1.2 × 105 h−1 250−500 > 90% [93] Cu/RHO RHO 3-dimensiona
l8-MRIE 2.4 0.05% NO,0.05% NH3,5% O2, 10% H2O,balance of N2,GHSV = 1 × 105 h−1 250−500 > 90% [94] Cu/SAPO-44 CHA 3-dimensiona
l8-MRIE 1.59 0.05% NO,0.05% NH3,5.3% O2,balance of He,GHSV = 1 × 105h−1 180−550 > 90% [83] Cu/LTA LTA 3-dimensiona
l8-MRIE 2.7 0.05% NO,0.05% NH3,5% O2, 10% H2O,balance of N2,GHSV = 1 × 105 h−1 220−600 > 90% [85] Cu/UZM-35 MSE 3-dimensiona
l12-MRIE 3.3 0.05% NO,0.05% NH3,5% O2, 10% H2O,balance of N2,GHSV = 1 × 105 h−1 200−550 > 90% [88] a: ion-exchange, b: directly synthesised 表 3 各铁基和铜基分子筛催化剂上标准NH3-SCR反应的表观反应活化能
Table 3 Apparent activation energy values of standard NH3-SCR reactions over Fe- and Cu-based zeolite catalysts
Catalyst Temperature range t/℃ Ea/(kJ·mol−1) Ref. Cu/ZSM-5 150−240 42 [120] Fe/ZSM-5 200−250 46 [121] Cu/BEA 100−140 58.9 [122] Fe/BEA 350−400 48 [56] Cu/MOR 200−250 35 [123] Fe/MOR 220−320 58 [124] Cu/SSZ-13 100−200 43 [125] Fe/SSZ-13 220−270 48 [76] Cu/SAPO-34 100−200 33.6 [101] Cu/SAPO-18 150−180 58.3 [126] Cu/KFI 140−180 53 [93] Cu/FAU 190−240 29 [127] Cu/SAPO-44 150−200 38.2 [83] Cu/LTA 170-200 43 [86] Fe/LTA 350−400 49 [56] Fe/UZM-35 350−400 48 [56] -
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