John Frederick Knifton

OLEFIN OLIGOMERIZATION VIA ZEOLITE CATALYSIS

Oligomerization of terminal and internal long-chain, linear olefins has been successfully demonstrated using large pore zeolites with high silica-to-alumina ratios as catalysts. Both reactant and product selectivities have been demonstrated using 12-membered ring zeolites for the oligomerization of C12–C18 olefins. The catalytic activity of these zeolites decreases in the order faujasite > mordenite > pentasil; the activity of the Y-zeolites depends primarily upon the silica-to-alumina molar ratio, but not on the total acidity. 1-tetradecene oligomerization, followed by oligomer hydrogenation, yields synthetic lubricant base stocks with excellent physical characteristics.

Phenol/acetone cogeneration via solid acid catalysis

Abstract Phenol/acetone cogeneration via cumene hydroperoxide (CHP) cleavage has been demonstrated using various classes of novel solid acid catalysts. Mineral acid-treated montmorillonite silica-alumina clays, heteropoly acids impregnated into Group IV oxide supports, fluorophosphoric acid and HF-treated oxides, as well as montmorillonite clays modified with heteropoly acids or certain Lewis acids, are each effective. The influence of solid acid structure upon phenol yields has been examined while minimizing by-product acetophenone, 2-methylstyrene, 2-phenyl-2-propanol, mesityl oxide formation, etc. For the more promising candidates, decomposition of 80% CHP solutions in continuous, plug-flow reactor systems, under mild conditions (ca. 60°C at LHSVs≈10) has been realized.

A new, improved, solid-acid catalyzed process for generating linear alkylbenzenes (LABs)

Linear alkylbenzenes (LABs) comprising >80% 2-phenyl isomer content, have been prepared in high yields from detergent-range linear olefins via regioselective benzene alkylation. HF-treated mordenites, acidic Beta-zeolites, and fluorided montmorillonite clays, each provide enhanced shape-selective alkylation performance when employed as heterogeneous catalysts in the subject syntheses. Both individual C8–C12 α-olefins, as well as mixed, commercial plant-derived, C10 through C14 paraffin dehydrogenate feedstocks containing ca. 8.5% internal olefins, have been successfully alkylated for extended periods using reactive distillation technology.

The dicarbonylation and hydrodimerization of unsaturated hydrocarbons via heterogeneous palladium catalysis

Graphite and polymer-supported palladium catalysts, coupled with copper/lithium cocatalysts, have been found very effective for the oxidative carbonylation of unsaturated hydrocarbons. Hex-3-ene-1,6-dioate has been generated in 85% selectivity from 1,3-butadiene,α-olefins yield dimethyl succinate derivatives. Butadiene hydrodimerization via analogous platinum catalysis selectively provides 1,6-octadiene, or 2,7-octadienyl formate. Mechanisms for the product selectivity are described.

Detergent-range alcohol alkoxylates via vicinal glycol additions to α-olefins

Abstract The synthesis of detergent-range, secondary alcohol alkoxylates via vicinal glycol addition to C 8 –C 14 linear α-olefins has been demonstrated using both homogeneous, heteropoly acids and solid strong-acid catalysis — acidified montmorillonite clays. 1-Tetradecene reaction with ethylene glycol yields 2-(2-tetradecyloxy)ethanol as the principal glycol ether product. 1,2-Propylene glycol addition to typical linear α-olefins (e.g. 1-octene and 1-tetradecene) gives the corresponding secondary alkyl alcohol propoxylates. Both batch and continuous preparations of C 8 –C 14 secondary alcohol 1-and 2-alkoxylates are described.

Cobalt-catalyzed carbonylation of phenylacetaldehyde to N-acetyl-beta-phenylalanine

N-acetyl-beta-phenylalanine has been produced by the reaction of phenylacetaldehyde, acetamide and CO/H2 in the presence of cobalt carbonyl catalyst. N- acetyl-beta-phenylalanine yields of 72-82 mol% and cobalt recoveries of 98% had been achieved under the conditions of 2000 psi of 3 : 1 CO/H2 and 80°C in a batch process. The presence of a suitable ligand, 1,2-bis(diphenylphosphino)ethane, was essential for maintaining cobalt in homogeneous solution. The feasibility of using a continuous phase reactor with a dual feed stream system was demonstrated. N-acetyl-beta-phenylalanine is proposed to be the precursor to L-phenylalanine, the key intermediate for aspartame sweetener.