Epoxidation of Lower Olefins with Hydrogen Peroxide and Titanium Silicalite

Clerici, Mario G.; Ingallina, Patrizia

doi:10.1006/jcat.1993.1069

Cited by 713 publications

(395 citation statements)

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“…For both the open and closed structures, the extra equivalent of hydroperoxide lowers the transition-state energy via hydrogen-bond-donating interactions to the hydroperoxide involved in oxygen transfer, as described previously (29), and this additional transition-state energy lowering corresponds to ∼0.6-1.0 kcal/mol. We note that the hydrogen bond donor within this context can in principle be either organic hydroperoxide, alcohol byproduct of organic hydroperoxide that is formed following oxygen transfer, or silanol (30)(31)(32)(33). Previous comparisons of trimethylsilyl (TMS)-capped and native silanolcontaining Ti-on-silica olefin epoxidation catalysts show a lack of appreciable activity or selectivity difference under dry conditions, when using organic hydroperoxide as oxidant (45).…”

Section: Resultsmentioning

confidence: 98%

Catalytic consequences of open and closed grafted Al(III)-calix[4]arene complexes for hydride and oxo transfer reactions

Nandi

Tang

Okrut

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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Section: Resultsmentioning

confidence: 98%

Catalytic consequences of open and closed grafted Al(III)-calix[4]arene complexes for hydride and oxo transfer reactions

Nandi

Tang

Okrut

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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“…[10,15] The structure of the zeolite (MFI, BEA, MEL) [16][17][18] and the nature of the solvent [19,20] influence oxidation rates. Hulea et al [21] reported that H 2 O 2 reacts with ethylsulfide on Ti-BEA and TS-1 (Ti-MFI), but only Ti-BEA catalyzed the oxidation of larger thiophenic molecules, because of difussional constraints prevalent in TS-1.…”

Section: Introductionmentioning

confidence: 99%

Selective Catalytic Oxidation of Organosulfur Compounds with tert‐Butyl Hydroperoxide

Chica¹,

Gatti²,

Modén³

et al. 2006

Chemistry A European J

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Rates and selectivities for the oxidation of various organosulfur compounds with tert-butyl hydroperoxide were measured on CoAPO-5 (APO = aluminophosphate; Co/P = 0.05), Co/H-Y (Co/Al = 0.15), and MoO(x)/Al2O3 (15 % wt MoO3). Rates increased with increasing electron density at the sulfur atom (methyl phenyl sulfide>diphenyl sulfide>4-methyldibenzothiophene>2,5-dimethyl thiophene). Rates (per metal atom) were significantly higher on CoAPO-5 than on Co/H-Y, MoO(x)/Al2O3, or homogeneous Co acetate catalysts. Small amounts of sulfoxides (1-oxide) were detected on all catalysts at low reactant conversions, together with their corresponding sulfones; at higher conversions, only sulfones (1,1-dioxide) were detected, indicating that the oxidation of sulfoxides is much faster than for organosulfur reactants in the sequential oxidation pathways prevalent on these catalysts. Framework Co cations were not leached from CoAPO-5 during the oxidation of 4-methyldibenzothiophene, but most exchanged Co cations in H-Y and >20 % of Mo cations in MoO(x)/Al2O3 were extracted during these reactions. The fraction of redox-active Co cations in CoAPO-5 and Co/H-Y was measured by reduction-oxidation cycles using H2 and O2 and by UV-visible spectroscopy. This fraction was much larger in CoAPO-5 (0.35) than in Co/H-Y (0.01), consistent with the higher oxidation rates measured on CoAPO-5 and with the involvement of redox-active species in kinetically-relevant steps in catalytic oxidation sequences. Redox-active Co cations at framework positions within accessible channels are required for catalytic activity and structural stability during oxidative desulfurization, whether hydroperoxides are used as reactants or as intermediates (when O2 is used as the oxidant).

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“…The zeolite titanium silicalite-1 (TS-1) is able to very selectively epoxidize propene using diluted hydrogen peroxide. 6,42 For this reaction, many other catalysts also are possible, and an excellent overview of these is given by Lane and Burgess. 43 A cost-saving feature in this process is that, instead of separating the hydrogen peroxide produced, it can be used directly in the epoxidation of propene.…”

Section: Hydrogen Peroxide Combination Processmentioning

confidence: 99%

The Production of Propene Oxide: Catalytic Processes and Recent Developments

Nijhuis

Makkee

Moulijn

et al. 2006

Ind. Eng. Chem. Res.

490

405

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Propene oxide, which is one of the major commodity chemicals used in chemical industry, desperately requires a new process for its production, because of the disadvantages that are encountered with the currently available processes. This paper discusses the existing processes used for the production of propene oxidesthe chlorohydrin and hydroperoxide processessand their advantages and disadvantages. Furthermore, the new processes and catalysts under development for the propene oxide production are discussed, as well as the challenges that are still limiting the applications of some of those prospects. The most important new developments for the production of propene oxide discussed in this paper are: the hydrogen peroxide combination process, the ethene oxide alike silver catalysts, the molten salt systems, and the gold-titania catalyst systems.

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Epoxidation of Lower Olefins with Hydrogen Peroxide and Titanium Silicalite

Cited by 713 publications

References 0 publications

Catalytic consequences of open and closed grafted Al(III)-calix[4]arene complexes for hydride and oxo transfer reactions

Catalytic consequences of open and closed grafted Al(III)-calix[4]arene complexes for hydride and oxo transfer reactions

Selective Catalytic Oxidation of Organosulfur Compounds with tert‐Butyl Hydroperoxide

The Production of Propene Oxide: Catalytic Processes and Recent Developments

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