Cobalt-catalyzed amination of 1,3-propanediol:: Effects of catalyst promotion and use of supercritical ammonia as solvent and reactant

被引:69
作者
Fischer, A [1 ]
Maciejewski, M [1 ]
Bürgi, T [1 ]
Mallat, T [1 ]
Baiker, A [1 ]
机构
[1] ETH Zentrum, Swiss Fed Inst Technol, Tech Chem Lab, CH-8092 Zurich, Switzerland
关键词
amination; alpha-cobalt; beta-cobalt; 1,3-diaminopropane; 1,3-propanediol; supercritical ammonia; effect of iron and lanthanum promotion;
D O I
10.1006/jcat.1999.2408
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
The catalytic synthesis of 1,3-diaminopropane from 1,3-propanediol and ammonia was studied in a continuous fixed-bed reactor in the pressure range 50 to 150 bar. The unsupported Co-based catalysts applied were characterized by N-2 physisorption, XRD, XPS, TPR, and ammonia adsorption using pulse thermal analysis and DRIFT spectroscopy. The latter investigations revealed that the best catalyst, 95 wt% Co-5 wt% Fe, contained only very weak acidic sites, unable to chemisorb ammonia. The absence of strong acidic and basic sites was crucial to suppress the various acid/base-catalyzed side reactions (retro-aldol reaction, hydrogenolysis, alkylation, disproportionation, dimerization, oligomerization). Other important requirements for improved diaminopropane formation were the use of excess ammonia (molar ratio NH3/diol > 20) and the presence of the metastable beta-Co phase. A small amount of Fe additive could efficiently hinder the transformation of this phase into the thermodynamically stable alpha-Co phase and thus prevent catalyst deactivation up to 10 days on stream. Application of supercritical ammonia almost doubled the selectivity to amino alcohol and diamine. The selectivity enhancement in the near-critical region is attributed to elimination of the interphase mass transport limitations and to the resulting higher surface ammonia concentration. (C) 1999 Academic Press.
引用
收藏
页码:373 / 383
页数:11
相关论文
共 50 条
[1]  
ADAM K, 1970, Patent No. 3520933
[2]  
ALLAMAGNY P, 1976, ENCY GAZ, P951
[3]  
AMINI B, 1992, KIRKOTHMER ENCY CHEM, V2, P426
[4]   Supercritical fluids in heterogeneous catalysis [J].
Baiker, A .
CHEMICAL REVIEWS, 1999, 99 (02) :453-473
[5]   CATALYTIC SYNTHESIS OF HIGHER ALIPHATIC-AMINES FROM THE CORRESPONDING ALCOHOLS [J].
BAIKER, A ;
KIJENSKI, J .
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING, 1985, 27 (04) :653-697
[6]  
BAIKER A, 1994, CHEM INDUST, V53, P91
[7]   DEACTIVATION OF COPPER, NICKEL, AND COBALT CATALYSTS BY INTERACTION WITH ALIPHATIC-AMINES [J].
BAIKER, A ;
MONTI, D ;
FAN, YS .
JOURNAL OF CATALYSIS, 1984, 88 (01) :81-88
[8]  
BAIKER A, 1983, IND ENG CHEM PROD RD, V22, P217
[9]  
BEST DC, 1978, Patent No. 4123462
[10]  
BEST DC, 1978, Patent No. 4111840