Catalysts for the Positional Isomerization of Internal, Long-Chain Olefins

Double-bond isomerization of internal C16-C18 olefins is a necessary step in the production of paper sizing agents. In this work, the properties that enable long-lasting solid acid catalysts (both commercial and lab-synthesized) were identified, the efficacy of regenerated solid acid catalysts was tested, and the feasibility of organometallic chain-walking catalysts (both homogeneous and polymer-supported) for olefin isomerization was evaluated. Hexadecene isomerization was investigated using perfluorinated ion exchange resins (Nafion®) supported on SiO2 or Al2O3, sulfonated poly(styrene-co-divinylbenzene) resins (PS-DVBs), tungstated zirconias, and acidic zeolites. Selected catalysts underwent lifetime studies. Oversulfonated PS-DVBs (e.g., Amberlyst 35) were reasonably selective with long lifetimes, only gradually deactivating due to poisoning by surface oligomers. Amberlyst® 70, Amberlyst® XN1010, ZSM-35 and SAPO-11 were evaluated because of their lower acid site densities and degree of crosslinking (for the PS-DVBs). None of these catalysts were optimal for various reasons. Both beneficial and harmful effects arising from the cooperativity of acid sites in close proximity were observed. Enhanced acid strength was associated with multiple adjacent sites, but at the expense of more rapid deactivation due to olefin oligomerization. Used SAC-13 catalysts were regenerated by solvent extraction. Nonpolar m-xylene was the most effective in reopening pore volume. The catalysts regenerated by ethanol were active in octadecene isomerization, but deactivation was relatively rapid. Small pores volumes and a small fraction of surface sites resulted in both a diffusion limitation within the catalyst and enhanced deactivation from fewer oligomerization events. Homogeneous Fe(CO)5 was an extremely effective catalyst capable of highly selective double bond isomerization (100% selective) with a high (80%) conversion of alpha olefins to internal olefins. The optimal batch reactor conditions to isomerize 2 L of 1-hexadecene were 500 ppm of Fe(CO)5 at 180°C for 1-4 h. Iron pentacarbonyl was also immobilized on a functionalized PS-DVB. Iron carbonyls were detected on the surface, though it was unclear whether they were physisorbed or bonded to surface groups. The catalyzed reactions of octadecenes were slow with a very low conversion and internal olefins were being removed from the product. Therefore, the heterogeneous iron carbonyls synthesized here were ineffective for generating internal double bonds.

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemical Engineering

Grantor

Chemical Engineering

Year dc:date.available

2015

Author dc:creator

• Bruno, James Edward

• lifetime studies
• organometallic catalysis
• perfluorinated ion exchange resins
• solid acid catalysis
• olefin isomerization

Statement dc:rights

• withheld
• Secure the entire work for patent and/or proprietary purposes for a period of one year. Student has submitted appropriate documentation which states: During this period the copyright owner also agrees not to exercise her/his ownership rights, including public use in works, without prior authorization from LSU. At the end of the one year period, either we or LSU may request an automatic extension for one additional year. At the end of the one year secure period (or its extension, if such is requested), the work will be released for access worldwide.

Identifier

etd-07102015-165945
https://repository.lsu.edu/gradschool_dissertations/278

OAI identifier oai:identifier

oai:repository.lsu.edu:gradschool_dissertations-1277