Characterization of chromium species in catalysts for dehydrogenation and polymerization

被引:114
作者
Gaspar, AB [1 ]
Brito, JLF [1 ]
Dieguez, LC [1 ]
机构
[1] Univ Fed Rio de Janeiro, COPPE, PEQ, NUCAT, BR-21945970 Rio De Janeiro, Brazil
关键词
Cr/SiO2; Cr/Al2O3; chemisorption; XRD; DRS; FT-IR; DRIFTS; TPR;
D O I
10.1016/S1381-1169(03)00381-9
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
Chromium catalysts, prepared with different chromium contents, supports and precursor compounds, were characterized by O-2 and CO chemisorption, in order to quantify the Cr3+ and Cr2+ sites, active species to dehydrogenation and ethylene polymerization reactions. Both probe molecules, O-2, and CO, showed to be selective to the chromium active species, Cr3+ and Cr2+, respectively, and a valid method to quantify these sites. Distinct chromium species, Cr6+, amorphous Cr3+, crystalline Cr3+ and Cr2+, were characterized by XRD, DRS, TPR, FT-IR and DRIFTS in the calcined and reduced catalysts. The distribution of chromium species, which depends on the content, precursor compound and support, was related to the catalytic activity in the dehydrogenation and polymerization reactions. The catalytic activity to cyclohexane dehydrogenation depends on the dispersion of amorphous Cr3+ species. The activity in the ethylene polymerization is related to the amount of Cr-A(2+) and Cr-B(2+) species. Both sites showed similar activities. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:251 / 266
页数:16
相关论文
共 49 条
[1]   Thermal transformations of chromium acetylacetonate on silica surface [J].
Babich, IV ;
Plyuto, YV ;
VanderVoort, P ;
Vansant, EF .
JOURNAL OF COLLOID AND INTERFACE SCIENCE, 1997, 189 (01) :144-150
[2]  
BAIKER A, 1985, INT CHEM ENG, V25, P16
[3]   BISTRIPHENYLSILYL CHROMATE - OXIDATION OF OLEFINS AND USE IN ETHYLENE POLYMERIZATION [J].
BAKER, LM ;
CARRICK, WL .
JOURNAL OF ORGANIC CHEMISTRY, 1970, 35 (03) :774-&
[4]  
Boudart M., 1969, ADV CATAL, V20, P153, DOI DOI 10.1016/S0360-0564(08)60271-0
[5]   Chemical and physical characterization of alumina-supported chromia-based catalysts and their activity in dehydrogenation of isobutane [J].
Cavani, F ;
Koutyrev, M ;
Trifiro, F ;
Bartolini, A ;
Ghisletti, D ;
Iezzi, R ;
Santucci, A ;
DelPiero, G .
JOURNAL OF CATALYSIS, 1996, 158 (01) :236-250
[6]   Chromia/zirconia catalysts with Cr content exceeding the monolayer. A comparison with chromia/alumina and chromia/silica for isobutane dehydrogenation [J].
De Rossi, S ;
Casaletto, MP ;
Ferraris, G ;
Cimino, A ;
Minelli, G .
APPLIED CATALYSIS A-GENERAL, 1998, 167 (02) :257-270
[7]  
DEROSSI S, 1992, APPL CATAL A-GEN, V81, P113
[8]  
EINARSON MD, 2001, ENVIRON SCI TECHNOL, V35, P67
[9]   Alumina-supported chromium-based mixed-oxide catalysts in oxidative dehydrogenation of isobutane to isobutene [J].
Elbashir, NO ;
Al-Zahrani, SM ;
Abasaeed, AE ;
Abdulwahed, M .
CHEMICAL ENGINEERING AND PROCESSING-PROCESS INTENSIFICATION, 2003, 42 (10) :817-823
[10]   CHARACTERIZATION OF CR SILICA POLYMERIZATION CATALYSTS [J].
ELLISON, A ;
OVERTON, TL ;
BENCZE, L .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1993, 89 (05) :843-849