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Matthias Pascaly
Abstract The common industrial technologies for the conversion of propylene to propylene oxide have been
compared with a special focus on the direct oxidation using hydrogen peroxide. The HPPO process is an
economically and ecologically superior technology since there are no market dependencies of other coproducts and water is the
only waste product. The catalyst used in this process is a partly titanium substituted silica based zeolite called TS-1. The article
summarizes the most important information concerning the HPPO process.
system with a propylene rich phase and a solvent rich PROCESS DESIGN
phase. It is obvious that the concentration of propylene in
the liquid phase has a direct influence on the reaction The literature describes several reactor concepts for the
rate. The HPPO technology usually operates at pressures HPPO process (25-28). For laboratory and catalyst
above 15 bar (23). research purposes, batch reactors proved to be the most
The solvent used for the epoxidation of propylene has a suitable solution. Upon scale up, packed bed reactors,
fundamental impact on the reaction rate. An OH-group trickle bed reactors and heat exchanger reactors are
is mandatory for formation of the five-membered ring, commonly used. The Evonik/TKIS technology employs a
which is mechanistically necessary for the propylene trickle bed reactor operated at appropriate reaction
oxide production (29). Clerici et al. showed that using temperature (25). Besides a highly selective catalyst, an
methanol (being the smallest alcohol) results in the efficient reaction temperature control is essential to
highest activity for the epoxidation (30). suppress side reactions and to ensure a high PO
By using methanol not only higher conversion rates could selectivity.
be achieved, but also an increased selectivity towards A simplified process flow diagram with all reaction and
propylene oxide (31). Corma et al. showed that the purification steps is shown in Figure 3 (41). The reactor is
polarity of the solvent is also very important (32). While fed with H2O2, propylene and a solvent. After the
using a more hydrophilic Ti-Beta catalyst, aprotic solvents reaction the residual propylene is separated in a
like acetonitrile are superior, whereas using a consecutive flash and purge gas system. The remaining
hydrophobic TS-1, protic solvents like methanol are the product stream is lead to a preseparation unit, where
solvents of choice. However, water as the smallest protic an enriched propylene oxide containing stream is
solvent is not suitable since the solubility of propylene is separated from a water solvent mixture. The obtained
very low and the concentration of propylene at the product stream is further purified via a propylene
titanium center in the channels of TS-1 would be stripper and a distillation column. The resulting
insufficient. propylene oxide is very pure (polymer grade). The
Intense research has been carried out to use basic or remaining solvent/water mixture is purified and
non-basic additives to improve the selectivity (33-35). The recycled. The recycled propylene as well as, the
basic additives are poisoning the acid sites of the TS-1, purified solvent is lead back to the reaction mixture
moderating their activity. Furthermore unwanted side enabling integrated solvent recycling leaving only
reactions such as ring opening of propylene oxide are water as a byproduct (42).
diminished. The decomposition of hydrogen peroxide to
oxygen and water is another side reaction. Due to higher
temperatures in the catalyst bed, especially hot spots, CONCLUSION
hydrogen peroxide tends to decompose (36, 37). It has
also been reported in the literature that non-tetrahedral Propylene oxide ranges on place eleven of all organic
coordinated species of titanium enhance the chemicals produced worldwide. It is one of the most
catalytically decomposition of hydrogen peroxide (37). important epoxides currently used in industry. To serve
The deactivation of the catalyst accompanied by the loss these market needs several industrial routes to produce
of catalytic activity is a challenge in heterogeneous propylene oxide – with and without coproducts – have
catalysis. The main reason for the deactivation of the HPPO been commercially established in the past. From the
catalyst is caused by pore blockage due to side product coproduct producing processes only the PO/SM and
formation. However, the blockage of active sites is reversible PO/MTBE process yielding styrene monomer
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Lonza Inc.,
klavS JenSen
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Surface Science and Catalysis; Switzerland Technology, MA, USA
Elsevier, Vol. 84, pp. 203–210 (1994). exhibition and sponsoring opportunities offer
ShInJI haSeBe paul WattS
20. Van der Pol A. J. H. P., Verduyn A. J.; companies direct contact to conference delegates. Kyoto University, Japan Nelson Mandela
Van Hooff J. H. C., Appl. Catal. For a tailor made sponsorship package please Metropolitan University,
contact: imret13@akcongress.com South Africa
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