Hydrolysis of isocyanic acid on SCR catalysts

被引:137
作者
Kleemann, M [1 ]
Elsener, M [1 ]
Koebel, M [1 ]
Wokaun, A [1 ]
机构
[1] Paul Scherrer Inst, CH-5232 Villigen, Switzerland
关键词
D O I
10.1021/ie9906161
中图分类号
TQ [化学工业];
学科分类号
0817 ;
摘要
The hydrolysis of isocyanic acid (HNCO) was investigated on various oxidic catalysts, including TiO2, V2O5/TiO2, and V2O5-WO3/TiO2. The kinetics were studied using powdered samples in a microreactor. The conversions of HNCO are high even at the high space velocities (10(6) h(-1)) and low temperatures (150 degreesC) used in the tests. The highest rate for the hydrolysis of HNCO was found on pure TiO2 powder, while the addition of vanadia and tungsta decreased the activity slightly. To compare the rate of HNCO hydrolysis with the rate of the SCR reaction, uncorrected first-order rate constants were calculated for both reactions using the integral equation for a plug flow reactor. For a catalyst sample containing both WO3 and V2O5, the rate constant for hydrolysis of HNCO at low temperatures is about 2 orders of magnitude higher than the respective rate constant for the SCR reaction, whereas at high temperatures, the rate constants are of comparable magnitude. The apparent activation energy of the hydrolysis reaction amounts to similar to 13 kJ/mol, thus suggesting that the overall reaction rate is mainly limited by external and internal mass transfer. Experiments using a coated monolithic SCR catalyst containing V2O5-WO3/TiO2 showed that the conversion of HNCO is not complete at the high space velocities necessary for mobile applications. Additionally, experiments were performed on a diesel engine test stand using a coated monolithic SCR catalyst and various reducing agents. The use of urea strongly affected the NOx conversion, especially at the highest catalyst temperature of 455 degreesC, leading to a substantially increased slip of (NH3 + HNCO).
引用
收藏
页码:4120 / 4126
页数:7
相关论文
共 10 条
[1]   VIBRATION-ROTATION SPECTRUM OF HNCO BETWEEN 1200-450 CM-1 [J].
ASHBY, RA ;
WERNER, RL .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1965, 18 (02) :184-+
[2]  
Bosch H., 1986, CATAL TODAY, V2, P369, DOI DOI 10.1016/0920-5861(88)80002-6
[3]  
BOWMAN CT, 1992, P 24 S INT COMB COMB, P859
[4]   Physico-chemical study of selective catalytic reduction vanadia-titania catalysts prepared by the equilibrium adsorption method [J].
Ciambelli, P ;
Lisi, L ;
Russo, G ;
Volta, JC .
APPLIED CATALYSIS B-ENVIRONMENTAL, 1995, 7 (1-2) :1-18
[5]   ALKYL CYANATES .V. EXISTENCE OF CYANIC ACID HOCN [J].
GROVING, N ;
HOLM, A .
ACTA CHEMICA SCANDINAVICA, 1965, 19 (07) :1768-+
[6]   INFRA-RED SPECTRUM AND STRUCTURE OF THE HNCO MOLECULE [J].
HERZBERG, G ;
REID, C .
DISCUSSIONS OF THE FARADAY SOCIETY, 1950, (09) :92-99
[7]  
JACOB E, 1994, Patent No. 0487886
[8]   Selective catalytic reduction of NO over commercial DeNOx-catalysts:: experimental determination of kinetic and thermodynamic parameters [J].
Koebel, M ;
Elsener, M .
CHEMICAL ENGINEERING SCIENCE, 1998, 53 (04) :657-669
[9]  
KOEBEL M, 1996, COMBUST SCI TECHNOL, V121, P67
[10]  
WELTZIEN C, 1858, LIEBIGS ANN CHEM, V107, P219