Synthesis, characterization and reactivity of transition metal containing zeolites

Transition metal containing zeolites (zeolite A and ZSM-5) were prepared by addition of various transition metal containing substrates to zeolite synthesis gels. Crystal growth data were recorded in order to determine the influence of the transition metal species on the rate of crystal growth. X-ray diffraction, oxygen adsorption, FTIR and SEM were utilized to evaluate crystal purity. X-ray photoelectron spectroscopy (XPS), chemical analysis and electron microprobe analysis were performed in order to ascertain the position (intrazeolitic versus surface) and homogeneity of the transition metal. It was concluded that intrazeolitic transition metals were produced by the novel procedure presented in this work. 1-Hexene hydroformylation by rhodium zeolite A showed intrazeolitic rhodium to migrate to the external surface of the zeolite. However, in the presence of a solution and surface rhodium poison, intrazeolitic rhodium was found to hydroformylate 1-hexene exclusively to heptanal. Ruthenium containing zeolite A was evaluated under CO-hydrogenation conditions. No migration of intrazeolitic ruthenium to the external surface of the zeolite was observed over the course of the reaction. The product distribution obtained for this catalyst did not follow a log normal behavior. Also, loss of zeolite crystallinity was observed following the reaction. Cobalt ZSM-5 was evaluated under CO-hydrogenation conditions. No migration of cobalt to the external surface of the zeolite occurred. XPS analysis of the catalyst following various stages of the reaction indicated that intrazeolitic cobalt was not reduced to the zero valent state. Consequently, the non-zero valent cobalt was not capable of hydrogenating carbon monoxide.

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemical Engineering

Department dc:contributor.department

Chemical Engineering

Grantor dc:publisher

Virginia Polytechnic Institute and State University

Year dc:date.issued

1986

Author dc:creator

• Rossin, Joseph A.

Chair dc:contributor.committeechair

• Davis, Mark E.

Committee members dc:contributor.committeemember

• Gibbs, Gerald
• Hanson, Brian E.
• Squires, A.M.
• Wills, George B.

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en_US

Handle dc:identifier.uri

http://hdl.handle.net/10919/76271

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/76271