Vanadia on sulphated-ZrO2, a promising catalyst for NO abatement with ammonia in alkali containing flue gases

被引:67
作者
Kustov, AL
Kustova, MY
Fehrmann, R [1 ]
Simonsen, P
机构
[1] Tech Univ Denmark, Dept Chem, DK-2800 Lyngby, Denmark
[2] Tech Univ Denmark, ICAT Interdisciplinary Res Ctr Catalysis, DK-2800 Lyngby, Denmark
[3] ENERGI E2 AS, DK-2450 Copenhagen, Denmark
关键词
NOSCR with ammonia; potassium poisonings deactivation; V2O5-based catalysts; sulphated-ZrO2; NH3-TPD;
D O I
10.1016/j.apcatb.2004.11.016
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Vanadia supported on TiO2, ZrO2, and sulphated-ZrO2 have been prepared. These catalysts were characterized by elemental analysis, N-2-BET, XRD, FTIR, and NH3-TPD methods. The stability of surface sulphated groups, studied by FTIR- spectroscopy, was found to depend dramatically on the temperature of the calcination of the samples. No considerable decomposition of surface sulphates was observed below 350 degrees C. The influence of potassium oxide additives on the acidity and activity in NO SCR with ammonia was studied. It was found that the introduction of small amounts of potassium (K/V molar ratio < 0.5) led to almost complete depression of the samples acidity and considerable weakening of the remaining acid sites for TiO2 and ZrO2 based systems. For the sulphated system, surface sulphur groups, due to their strong acidity, represent attractive sites for the localization of potassium oxide and the decrease in the total acidity is less pronounced in this case. The results of NO SCR with ammonia reveal a noticeable shift of the maximum catalytic activity towards higher temperatures in going from the conventional catalyst to vanadia supported on sulphated zirconia. The loading of the catalysts with potassium leads to considerable decrease of their catalytic activity, and to a shift of the maximum catalytic activity towards lower temperatures. Among all the catalysts, V2O5/sulphated-ZrO2 reveals the highest resistance towards alkali poisoning. The presence Of SO2 in the reaction mixture was found to enhance stability and activity of the V2O5/sulphated-ZrO2 probably due to regeneration of surface sulphated groups at the reaction conditions. The potassium-doped V2O5/sulphated-ZrO2 catalyst reveal high activity and stability at 300 degrees C, comparable with unpoisoned catalysts. At 400 degrees C the presence of potassium compounds seems to enhance the deactivation of the catalyst under reaction conditions during 30 h, possibly due to formation of potassium sulphate-pyrosulphate species reacting with vanadium oxide. (c) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:97 / 104
页数:8
相关论文
共 28 条
[1]   Preparation of superacids by metal oxides for reactions of butanes and pentanes [J].
Arata, K .
APPLIED CATALYSIS A-GENERAL, 1996, 146 (01) :3-32
[2]   Influence of potassium doping on the formation of vanadia species in V/Ti oxide catalysts [J].
Bulushev, DA ;
Rainone, F ;
Kiwi-Minsker, L ;
Renken, A .
LANGMUIR, 2001, 17 (17) :5276-5282
[3]   FT-IR STUDY OF THE SURFACE-PROPERTIES OF POLYCRYSTALLINE VANADIA [J].
BUSCA, G ;
RAMIS, G ;
LORENZELLI, V .
JOURNAL OF MOLECULAR CATALYSIS, 1989, 50 (02) :231-240
[4]   MECHANISM OF POISONING OF THE V2O5 TIO2 CATALYST FOR THE REDUCTION OF NO BY NH3 [J].
CHEN, JP ;
YANG, RT .
JOURNAL OF CATALYSIS, 1990, 125 (02) :411-420
[5]   SELECTIVE CATALYTIC REDUCTION OF NO WITH NH3 ON SO4(-2)/TIO2 SUPERACID CATALYST [J].
CHEN, JP ;
YANG, RT .
JOURNAL OF CATALYSIS, 1993, 139 (01) :277-288
[6]   Effect of promoters includingWO3 and BaO on the activity and durability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3 [J].
Choo, ST ;
Yim, SD ;
Nam, IS ;
Ham, SW ;
Lee, JB .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2003, 44 (03) :237-252
[7]   ACIDIC PROPERTIES OF SUPPORTED NIOBIUM OXIDE CATALYSTS - AN INFRARED-SPECTROSCOPY INVESTIGATION [J].
DATKA, J ;
TUREK, AM ;
JEHNG, JM ;
WACHS, IE .
JOURNAL OF CATALYSIS, 1992, 135 (01) :186-199
[8]   DEACTIVATION AND COMPOUND FORMATION IN SULFURIC-ACID CATALYSTS AND MODEL SYSTEMS [J].
ERIKSEN, KM ;
KARYDIS, DA ;
BOGHOSIAN, S ;
FEHRMANN, R .
JOURNAL OF CATALYSIS, 1995, 155 (01) :32-42
[9]   Conductivity, NMR measurements, and phase diagram of the K2S2O7-V2O5 system [J].
Folkmann, GE ;
Eriksen, KM ;
Fehrmann, R ;
Gaune-Escard, M ;
Hatem, G ;
Lapina, OB ;
Terskikh, V .
JOURNAL OF PHYSICAL CHEMISTRY B, 1998, 102 (01) :24-28
[10]   In situ UV-vis-NIR diffuse reflectance and Raman spectroscopic studies of propane oxidation over ZrO2-supported vanadium oxide catalysts [J].
Gao, XT ;
Jehng, JM ;
Wachs, IE .
JOURNAL OF CATALYSIS, 2002, 209 (01) :43-50