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Selective oxidation of n-butane and butenes over vanadium-containing catalysts  

Science.gov (United States)

The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg-Al mixed oxides with Mg/(Al + Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C{sub 4}-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reaction with the selective way, i.e., the oxydehydrogenation process by a redox mechanism. ...

2000-01-01

2

High octane ethers from synthesis gas-derived alcohols  

Science.gov (United States)

Catalytic testing of inorganic catalysts was continued with the highly active sulfate-modified zirconia catalyst prepared here. Using isobutanol as the only reactant over this catalyst, it was demonstrated that high conversion and selectivity to isobutene was achieved at 175[degrees]C. In addition, the high selectivity to isobutene, i.e. 79--86 mol%, was maintained at higher space velocities and higher temperatures. A high productivity of 11.35 mol isobutene was achieved at 225[degrees]C. Utilizing a methanol/isobutanol = 2/1 molar ratio reactant mixture over the ZrO[sub 2]/SO[sub 4][sup 2[minus

1992-10-01

3

Studies of the fundamental nature of catalytic acidity, sites, and intermediates: Progress report for period August 1, 1987-July 31, 1988  

Energy Technology Data Exchange (ETDEWEB)

Neopentane, because of its unique structural features, was found to be a useful probe for the assay of the acidity of various zeolites. The C-C bond was attacked by catalyst protons yielding CH/sub 4/ and the isobutyl carbenium ion in equal quantities. The latter either decomposed to produce isobutene or underwent secondary reactions. New avenues for reaction were opened with isobutane. The reaction of the Bronsted protons with the tertiary CH bonds produced H/sub 2/ and the same isobutyl carbenium ion. Hydride ion transfer of the same tertiary hydrogen to existing carbenium ions also occurred and the results showed that about half of the reaction was carried by this pathway. As with Neopentane, the C-C bond could also be attacked yielding the sec-propyl carbenium ion. These tools are being further developed.

1988-06-01

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Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts  

Energy Technology Data Exchange (ETDEWEB)

The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The ...

2002-05-27