Direct phenol synthesis cumene

The three-step cumene process, including the liquid-phase reactions and using sulfuric acid, is energy-consuming, environmentally unfavorable and disadvantageous for practical operation the process also produces as an unnecessary byproduct acetone, stoichiometrically. Furthermore, the intermediate, cumene hydroperoxide, is explosive and cannot be concentrated in the final step, resulting in a low one-path phenol yield, ( 5%, based on the amount of benzene initially used). Thus, direct phenol synthesis from benzene in one-step reaction with high... 

In conclusion no catalysts with good performances (>5% conversion and >50% selectivity, simultaneously) have been discovered to date. New selective catalysts for direct phenol synthesis from benzene with 02 are essential for the novel industrial process replacing the cumene process - there are many problems to be resolved. 

Hence, the idea of direct use of cumene hydroperoxide as the raw material for the BPA synthesis which includes the following two steps the catalyzed cleavage of CHP and the condensation of so obtained phenol and acetone. It was found that the use of some specific combination of catalysts for the both steps provides high yields of BPA and low yields of impurities, without need for intermediate purification steps [69]. The use of an acid treated montmorillonite clay as the catalyst for the CHP cleavage, and a cross-linked cation-exchange resin with pyridyl ethyl mercaptan or... 

PROPENE The major use of propene is in the produc tion of polypropylene Two other propene derived organic chemicals acrylonitrile and propylene oxide are also starting materials for polymer synthesis Acrylonitrile is used to make acrylic fibers (see Table 6 5) and propylene oxide is one component in the preparation of polyurethane polymers Cumene itself has no direct uses but rather serves as the starting material in a process that yields two valuable indus trial chemicals acetone and phenol... 

Since zeolite catalysts are successfully introduced in the refining and petrochemical industries, it is not surprising that most of the recent advances concern incremental improvements of existing processes with the development of new generations of catalysts (e.g., dewaxing, ethylbenzene and cumene synthesis). The number of newer applications is much more limited, for example, direct synthesis of phenol from benzene and aromatization of short-chain alkanes, etc. However, both the improvement and development of processes contribute significantly to environmental advances. 

Catalysis (27-30) which allows for the direct oxidation of benzene to produce phenol. Economic analyses have shown that these are attractive only in specific instances where, for example, a cheap source of N20 is available. Nevertheless, these developments have shown that direct oxidation is possible and further innovations in this area should probably be expected. The demands for acetone and phenol have generally tended to follow each other. However, as bisphenol A becomes an even more important end use for phenol and acetone, there will be a need for a separate source of phenol. The synthesis of bisphenol A requires two moles of phenol for every one mole of acetone, while the peroxidation of cumene produces one mole of each. Still, processes such as the direct oxidation of benzene are unlikely to have a major impact on cumene demand in the short term since there are competing processes such as Mitsui s for converting acetone back to propylene. 

Co-production is still used in many relevant industrial processes. A typical example is the synthesis of phenol via the cumene process, which involves the formation of acetone as by-product. This example is discussed in a more detail later in Chapter 13. Direct oxidation of benzene to phenol using H2O2 is an attractive industrial alternative, but a main motivation is to avoid the formation of acetone, as there is actually excess acetone on the market. The process requires a single step versus three steps in the cumene process, one of which is related to the synthesis of a cumene hydroperoxide intermediate that shows significant problems of safety. There are thus various aspects that make more sustainable the direct synthesis of phenol over the cumene process, but atom economy (or related mass intensity indicators) is not the correct indicator to assess sustainability. 

With worldwide phenol consumption exceeding 5 million tons in 1995, optimizing production routes of this essential chemical becomes very important. As an alternative to the traditional cumene process, a one-step-synthesis of phenol from benzene is highly desirable. With a ZSM5 type zeolite in its acid form as catalyst and nitrous oxide as oxidant, benzene may be directly oxidized to phenol [1-4] ... 

In the synthesis of adipic acid one can start with benzene, phenol, tetrahydrofuran, butadiene, or cyclohexane. Benzene is converted to phenol (e.g., by the cumene process), this is hydrogenated to cyclohexanol, and the cyclohexanone gained by oxidation is then oxidized to adipic acid, HOOC—(CH2)4—COOH, with nitric acid. Cyclohexane can also be oxidized with air to cyclohexanol, from which adipic acid is obtained by direct nitric acid oxidation. Adipic acid can also be produced by saponification of adipodinitrile (adiponitrile), which in turn comes from tetrahydrofuran or butadiene (see below). 

Cumene hydroperoxide is produced in the second step of the Hock method in the form of 35 weight % solution. The necessary concentration of the CHP solution to 80 weight % is a potentially hazardous operation as generally is the production and handling of peroxides. Therefore, a better solution is starting the process of the BPA production directly from the synthesis of CHP from cumene, followed by direct use of so obtained CHP for the reaction with phenol [70]. Thus, a one pot synthesis of BPA from CHP and phenol, carried out at 100 C, in the presence of 20 weight % of dodecatungstenophosphoric acid supported on acidic montmoril-lonite clay (K-10), and without the CHP separation, was successfully tested. 

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