Hydrogen peroxide based propylene oxide

HPPO hydrogen peroxide-based propylene oxide mCPBA meta-chloroperbenzoic acid MTA metric tons per annum... 

ChemSystems PERP Report Hydrogen Peroxide-Based Propylene Oxide 06/07S2 Nexant s ChemSystems PERP report, 06/07S2, Hydrogen Peroxide-Based Propylene Oxide, 2007. 

In 2008, BASF and Dow Chemical successfully started the first commercial production plant based on the novel hydrogen peroxide to propylene oxide (HPPO) process. The plant is located in Antwerp, Belgium and the initial annual capacity is around 300 000 tons. A second plant based on this technology will start production in 2011 in Map Ta Phut, Thailand. 

In 2008, Dow and BASF successfully started up the first commercial-scale production plant based on the novel BASF/Dow-developed HPPO (hydrogen peroxide for propylene oxide) technology at BASF s Antwerp, Belgium, facility. A second plant based on this technology was scheduled to begin production in Map Ta Phut, Thailand, in 2011. The two companies reported that, compared with traditional technologies, the epoxidation with hydrogen peroxide has a very low environmental impact, a simpler process layout and reduced investment costs. 

A particularly interesting system for the epoxidation of propylene to propylene oxide, working under pseudo-heterogeneous conditions, was reported by Zuwei and coworkers [61]. The catalyst, which was based on the Venturello anion combined with long-chained alkylpyridinium cations, showed unique solubility properties. I11 the presence of hydrogen peroxide the catalyst was fully soluble in the solvent, a 4 3 mixture of toluene and tributyl phosphate, but when no more oxidant was left, the tungsten catalyst precipitated and could simply be removed from the... 

This technology could also be applied for the oxidation of methane (70 °C, 5 Mpa) to formic acid (46% selectivity based on hydrogen peroxide). Another catalyst which can be applied for the direct oxidation of benzene with H202 is the TS-1 catalyst, as described above for propylene epoxidation [41]. Conversion is generally kept low, because introduction of a hydroxy group activates the aromatic nucleus to further oxidation to hydroquinone, catechol and eventually to tarry products [137]. 

The key to the success of the oxidation examples cited above is the ability of the catalysts used to exert proper kinetic control on the possible side reactions. Without it, thermodynamically favorable but undesired products such as CO2 and H2O are made instead. Controlling oxidation kinetics to stop at the desired oxygenated products is quite difficult, and has yet to be solved for many other systems. For instance, although many attempts have been made to develop a commercial process for the oxidation of propylene to propylene oxide, both the activity and the selectivity of the systems proposed to date, mostly based on silver catalysts, are still too low to be of industrial interest " propylene oxide is presently manufactured by processes based on chlorohydrin or hydrogen peroxide instead. In spite of these difficulties, though, recent advances in selective liquid phase oxidation of fine chemicals on supported metal catalysts have shown some promise, offering high yields (close to 100%) under mild reaction conditions." ... 

Key Words Ethylene oxide, Propylene oxide. Epoxybutene, Market, Isoamylene oxide. Cyclohexene oxide. Styrene oxide, Norbornene oxide. Epichlorohydrin, Epoxy resins, Carbamazepine, Terpenes, Limonene, a-Pinene, Fatty acid epoxides, Allyl epoxides, Sharpless epoxidation. Turnover frequency, Space time yield. Hydrogen peroxide, Polyoxometallates, Phase-transfer reagents, Methyltrioxorhenium (MTO), Fluorinated acetone, Alkylmetaborate esters. Alumina, Iminium salts, Porphyrins, Jacobsen-Katsuki oxidation, Salen, Peroxoacetic acid, P450 BM-3, Escherichia coli, lodosylbenzene, Oxometallacycle, DFT, Lewis acid mechanism, Metalladioxolane, Mimoun complex, Sheldon complex, Michaelis-Menten, Schiff bases. Redox mechanism. Oxygen-rebound mechanism, Spiro structure. 2008 Elsevier B.V. 

By far the most concise synthesis of 1 has arisen from the work of Schreiber in 1980 (see Scheme 1.8). The lithium enolate 28 was monoalkylated with propylene oxide in the presence of trimethyl aluminum to give keto alcohol 29 in 96% yield (based on recovered 28). The addition of hydrogen peroxide under acidic conditions then made available the hydroperoxide 30 in 99% yield. A ferrous-ion-induced fragmentation then gave the natural product 1 in 96% yield as a single olefin isomer. 

A preliminary evaliiation shows that a process based on Scheme II is advantageous with respect to the method using pinified preformed hydrogen peroxide (72). It requires, however, that both the hyckogen peroxide and the propylene oxide plants are located in close proximity to each other. 

An issue which deserves further mention is the environmentally fiiendly nature of TS-l/H Oj system. It involves the use of a safe silica based catalyst, titanium silicalite, and a reagent, hydrogen peroxide, which yields water as the coproduct. This holds for the in situ route illustrated in Scheme I and also for the epoxidation of propylene with preformed hydrogen peroxide, either used as an aqueous solution (72) or extracted by means of die epoxidation solvent (Scheme 11). Hazardous chemicals, such as chlorine, performic or other organic peracids, are not required in the process. The disposal of chlorinated salts or the recycle of brine (chloroydrin process) and any possible burden resulting from the coproduction of odier chemicals (styrene and r-butanol in the hydroperoxide route) are eliminated. The liquid phase oxidation of isobutane and ethylbenzene with air under pressure and at high temperature, to produce... 

The most widely used industrial routes to propylene oxide (PO) are based on the chlorohydrin process or hydroperoxide methods. Much attention has also been directed to processes performed in the presence of hydrogen peroxide in the liquid phase with a TS-1 molecular sieve as the catalyst, iron complexes accommodated in amorphous SBA-15 and MCM-41 modified with alkaline metal salts, and SBA-3 mesoporous molecular sieves doped with transition metal ions (Fe, V, Nb, and Ta). 

Oxirans.—A simple four-stage preparation of (5)-propylene oxide from ethyl L-( —)-maleate has been described (Scheme 2). This work is of importance for the synthesis of nonactin carboxylic acid. Another synthesis of optically-active propylene oxide involves the cyclization of OL-propylene chlorohydrin with a variety of bases in the presence of a cobalt complex the highest optical purity was 27%. Wynberg and co-workers have shown that the base-catalysed epoxidation of electron-poor alkenes is subject to catalytic asymmetric induction hydrogen peroxide and t-butyl hydroperoxide were used as oxidants in the presence of quaternary... 

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