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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2020, Vol. 14 Issue (4): 471-491   https://doi.org/10.1007/s11705-019-1847-7
  本期目录
Selective catalytic reduction of NOx with ethanol and other C1-4 oxygenates over Ag/Al2O3 catalysts: A review
Pavlo I. Kyriienko()
L.V. Pisarzhevskii Institute of Physical Chemistry of the NAS of Ukraine, Kyiv 03028, Ukraine
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Abstract

Research results regarding selective catalytic reduction (SCR) of NOx with ethanol and other C1-4 oxygenates as reductants over silver-alumina catalysts are summarized. The aspects of the process mechanism, nature of active sites, role of alumina and silver (especially in the formation of bifunctional active sites), effects of reductants and reaction conditions are discussed. It has been determined that key stages of the process include formation of reactive enolic species, their interaction with NOx and formation of nitroorganic compounds which transform to NCOads species and further to N2. The results obtained over various silver-alumina catalysts demonstrate the perspectives of their application for reducing the level of nitrogen oxides in engine emissions, including in the presence of water vapor and sulfur oxides. Ways to improve the catalysts for the SCR of NOx with C1-4 oxygenates are outlined.

Key wordsSCR    nitrogen oxides    silver-alumina catalyst    silver species    ethanol    oxygenates
收稿日期: 2018-12-08      出版日期: 2020-05-22
Corresponding Author(s): Pavlo I. Kyriienko   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2020, 14(4): 471-491.
Pavlo I. Kyriienko. Selective catalytic reduction of NOx with ethanol and other C1-4 oxygenates over Ag/Al2O3 catalysts: A review. Front. Chem. Sci. Eng., 2020, 14(4): 471-491.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-019-1847-7
https://academic.hep.com.cn/fcse/CN/Y2020/V14/I4/471
Catalyst Reductant XNOmax (%)/TNOmax (K) a) Δ2/3 (K) b) Ref.
3% Ag/Al2O3 ethanol 83/573 518–698 [35]
3% Fe/Al2O3 27/573 473–798
3% Cu/Al2O3 20/573 553–633
3% Al2O3 20/573 573–798
1% Ag/Al2O3 DME 87/573 260–653 [36]
1% Pd/Al2O3 79/523 [53] c) 220–573
1% Rh/Al2O3 74/573 [29] c) 230–593
1%Pt/Al2O3 53/523 [46] c) 200–623 d)
Al2O3 93/673 330–673 d)
3% Ag/Al2O3/cordierite methanol 40/673 643–723 [163]
3% Ag/MOR/cordierite 18/673 633–723
3% Ag/ZSM-5/cordierite 18/673 623–723
2% Ag/Al2O3 ethanol 82/623 533–733 [37]
2% Ag/TiO2 67/723 633–648
2% Ag/SiO2 2/623
2.5% Ag/Al2O3 ethanol 90/673 548–698 [38]
3% Ag/ceria–zirconia 52/623 573–773
3% Ag/sulphated ceria–zirconia 32/623 573–698
4% Ag/H-MFI 30/573 423–773
Tab.1  
Catalyst Reaction mixture Reductant XNOmax (%)/TNOmax (°C)a) Ref.
2% Ag/Al2O3 1000 ppm NO, 10% O2; 10000 h−1 900 ppm of ethanol 86/623−673 [30]
1500 ppm of methanol 23/523
1000 ppm of propene 70/723
5% Ag/Al2O3 800 ppm NO, 10% O2, 10% H2O; 50000 h−1 1565 ppm of ethanol 99/623 [70]
1565 ppm of acetaldehyde 99/623
1714 ppm of propene 90/753
1565 ppm of acetic acid 57/633
4% Ag/Al2O3 500 ppm NO, 10% O2, 5% H2O; 50000 h−1 3000 ppm C1 (ethanol) 99/613 [79]
3000 ppm C1 (750 ppm of ethanol+ 500 ppm of C3H6) 82/613
3000 ppm C1 (85% of ethanol+ 15% of gasoline) 97/613
3000 ppm C1 (50% of ethanol+ 50% of gasoline) 95/643
2% Ag/Al2O3 500 ppm NO, 15% O2, 10% H2O; 200000 h−1 1200 ppm of ethanol 100 [88]b)/623 [74]
400 ppm of C8H18 96 [85]b)/673
Ag/Al2O3 200 ppm NO, 6% O2, 2.5% H2O; 14000 h−1 400 ppm of ethanol, 67 ppm of dodecane (C1/NOx = 8) 100 [65]b)/623 [142]
133 ppm of dodecane (C1/NOx = 8) 100 [90]b)/673
2% Ag/Al2O3 720 ppm NO, 4.3% O2, 7.2% CO2, 7.2% H2O; 60000 h−1 4340 ppm C1 (n-octane), 4340 ppm of methanol 95/548 [143]
4340 ppm C1 (toluene), 4340 ppm of methanol 95/573
4340 ppm C1 (n-octane) 90/673
4340 ppm C1 (toluene) 85/773
4340 ppm of methanol 10/523
2% Ag/Al2O3 400 ppm NO, 500 ppm CO, 167 ppm H2, 8% O2, 10% H2O, 10% CO2; 150000 h−1 1200 ppm of ethanol 100/623 [64]
1200 ppm of acetaldehyde 100/723
1200 ppm of ethylene 30/823
0.3% Ag/46%Al2O3/
cordierite
500 ppm NO, 10% O2, 2% H2O; 50000 h−1 1000 ppm of ethanol 95/623 [25]
1000 ppm of acetaldehyde 99/673
1000 ppm of ethylene 60/773
Tab.2  
Fig.1  
Fig.2  
Fig.3  
Fig.4  
Fig.5  
Fig.6  
Fig.7  
Fig.8  
Fig.9  
Fig.10  
Reductant Conversion NO to N2/% (without/with H2)
523 K 573 K 623 K
Diethyl ether 28/100 91/100 90/97
Ethyl tert-butyl ether 20/73 72/77 72/78
Ethanol 7/47 52/60 67/76
2-Propanol 34/56 58/58 62/73
1-Propanol 17/34 44/50 73/78
t-Butanol 22/43 38/90 89/86
Ethyl acetate 5/41 27/73 77/78
Acetone 0/13 9/76 57/72
1-Propanal 9/6 45/45 72/93
Propane (for comparison) 0/51 0/69 48/97
Tab.3  
Reaction mixture H2O/% T50/K* XNOmax/%/TNOmax/K** Ref.
800 ppm NO, 2400 ppm ethanol, 10% O2; 40000 h−1 583 95/653 [154]
10 633 95/753
800 ppm NO, 1565 ppm ethanol, 10% O2; 300000 h−1 598 90/723 [153]
0.5 603 90/773
1.0 673 90/773
10 723 75/773
500 ppm NO, 1000 ppm ethanol, 10% O2; 30000 h−1 97/523 [108]
6 94/598
500 ppm NO, 1000 ppm 1-butanol, 10% O2; 30000 h−1 503 97/553
6 483 88/573
Tab.4  
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