Sumitomo hydroperoxide process

Thirty years after the invention of ENI s TS-1, new environmentally friendly processes have been commercialized for the epoxidation of propylene and the ammoximation of cyclohexanone that have no major by-products or coproducts. The BASF-Dow and Degussa-Uhde processes claim to be environmentally friendly, have low capital investment costs, and have no significant quantities of by-products when compared to either the chlorohydrin or the PO with styrene monomer processes. The Sumitomo PO process is also beneficial for the environment, because it needs only a cumene-to-cumene hydroperoxide reactivation process step. 

Finally, it is noted that the direct epoxidation of propene with molecular oxygen is potentially more economically attractive than all of the coproduct processes currently in operation. It is indeed a holy grail in oxidation chemistry. Notwithstanding the extensive research on this topic in the last three decades, an industrially viable method for the direct epoxidation of propene has not been forthcoming. Sumitomo has recently announced [67] that they will commercialize a coproduct free route to PO but this probably involves an alkyl hydroperoxide e.g. cumene) oxidant with recycling of the alcohol coproduct [68]. 

Sumitomo developed a recirculation process for manufacture of PO using CHP as oxidant (196). The company developed both a new catalyst and a new process for PO production. The production method is fundamentally similar to known methods involving organic peroxides as oxidants the major difference is that cumene is used as the reaction medium and hence the process is referred to as the cumene PO-only process. Laboratory tests started in 2000 and pilot plant testing in 2001. A plant was completed in 2002 and started up in 2003. This commercial plant was the first PO-only plant in Japan, producing PO by oxidation of propylene with cumene hydroperoxide without a significant formation of coproducts. The plant is located in the Chiba prefecture, operated by a joint venture between Nihon Oxirane Co. and Lyondell, and produces aroimd 200,000 t of PO/year. A second plant was started in May 2009 in Saudi Arabia, as a joint project of Sumitomo with Saudi Arabian Oil Co. 

Figure 1.15 Process flow diagram for the oxidation of propylene with cumene hydroperoxide as the oxidizing agent and titanium-containing mesoporous material as the heterogeneous catalyst (Sumitomo process). The process involves the following steps (1) A process for oxidation of cumene with air to obtain CMHP, (2) a process for epox-idation of propylene in the presence of a catalyst whereby o,a-dimethyl benzyl-alcohol CMA) is concomitantly obtained from CMHP, (3) a process for the hydrogenation of CMA with H2 i n the presence of a catalyst to obtain cumene, (4) a process for purification of the cumene, followed by recycle of cumene to the oxidation process, and (5) a process for the purification of PO. Adapted from Ref. (271), with permission from Wiley-VCH.

Sumitomo of Japan has developed a commercially alternative process that avoids the use of sulfuric acid and the concomitant undesired salt formation (see reaction sequence below). This alternative route is analogous to the cumene process for phenol production. Diisopropylbenzene (m-DIPB) can be manufactured by the catalytic dialkylation of benzene with two equivalents of propylene. The resulting m-DIPB is then catalytically hydroperoxidized to the corresponding dihydroperoxide (DHP). Upon acidification the dihydroperoxide (DHP) is cleaved cleanly to give resorcinol and acetone. It is worth noting that the Sumitomo process not only provides a cleaner alternative route for the production of resorcinol,... 

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