Styrene development ethylbenzene production

The alkylation of toluene with methanol has been investigated for many years as a potential alternative route to / - Qflene, ethylbenzene, and styrene. Conventional / -xylene production from petroleum reformate requires costly purification and separation from jQ lene isomers and other aromatics. A process that selectively produces /)-xylene could have a significant commercial impact by eliminating the need for p-xylene separation. Furthermore, styrene or ethylbenzene production from methanol and toluene is desired as part of the development of processes based on Cl feedstocks rather than ethylene or propylene feedstocks [48], Para- xyl ae is used primarily in terephthalic acid production, a major component of polyester manufacture. 

Central to Germany s development of polystyrene technology was Herman F. Mark (Figure 1.4). Mark worked at I. G. Farben Industrie for 6 years from 1927 to 1932, first as a research chemist (1927-28), then as Group Leader (1928-30) and finally as Assistant Research Director (1930-32). Because of the changing political climate, Mark moved to the University of Vienna, where he became Professor of Chemistry and Director of the First Chemical Institute (1932-38). While at I. G. Farben Industrie, Mark played a major role in the development of styrene monomer and PS. Mark patented a process in 1929 for the production of styrene from ethylbenzene via catalytic dehydrogenation [8]. 

When czarists became unpopular in 1921, he emigrated to the US via Latvia. As a research chemist for the US Rubber Company, he developed processes for the production of styrene from ethylbenzene and st3rrene-butadiene copolymers. His attempts to start pharmaceutical firms viz, Ostro Research and Pyridium Corp. were unsuccessful. In addition to his publications and patents in polymer science he authored a book on Scientific Basis for (Chemotherapy in 1926. 

Although the use of dehydrogenation processes to supply butadiene declined as the more economical supplies from steam cracking of naphtha were introduced, the production of styrene from ethylbenzene dehydrogenation has been continuously developed, since styrene is not available in sufficient quantities as a byproduct. 

In 1869 Berthelot- reported the production of styrene by dehydrogenation of ethylbenzene. This method is the basis of present day commercial methods. Over the year many other methods were developed, such as the decarboxylation of acids, dehydration of alcohols, pyrolysis of acetylene, pyrolysis of hydrocarbons and the chlorination and dehydrogenation of ethylbenzene." ... 

Oxidation of organic compounds by dioxygen is a phenomenon of exceptional importance in nature, technology, and life. The liquid-phase oxidation of hydrocarbons forms the basis of several efficient technological synthetic processes such as the production of phenol via cumene oxidation, cyclohexanone from cyclohexane, styrene oxide from ethylbenzene, etc. The intensive development of oxidative petrochemical processes was observed in 1950-1970. Free radicals participate in the oxidation of organic compounds. Oxidation occurs very often as a chain reaction. Hydroperoxides are formed as intermediates and accelerate oxidation. The chemistry of the liquid-phase oxidation of organic compounds is closely interwoven with free radical chemistry, chemistry of peroxides, kinetics of chain reactions, and polymer chemistry. 

Styrene, one of the world s major organic chemicals, is derived from ethylene via ethylbenzene. Several recent developments have occurred with respect to this use for ethylene. One is the production of styrene as a co-product of the propylene oxide process developed by Halcon International (12). In this process, benzene is alkylated with ethylene to ethylbenzene, and the latter is oxidized to ethylbenzene hydroperoxide. This hydroperoxide, in the presence of suitable catalysts, can convert a broad range of olefins to their corresponding oxirane compounds, of which propylene oxide presently has the greatest industrial importance. The ethylbenzene hydroperoxide is converted simultaneously to methylphenyl-carbinol which, upon dehydration, yields styrene. Commercial application of this new development in the use of ethylene will be demonstrated in a plant in Spain in the near future. 

Alkylation of benzene for the production of ethylbenzene, the raw material for making styrene and subsequently synthetic rubber, was also greatly expanded during the war because of the shortage of natural rubber. The catalyst in most of the original ethylbenzene units was aluminum chloride, but other catalysts are now preferred by many refiners. Alkylation for the production of ethylbenzene was the first large-scale alkylation process used for the production of petrochemicals. Since that time, others, such as cumene, dodecylbenzene, alkylated phenols, diisopropylbenzene, and secondary butylbenzene, have been added to the list, and others have been developed and should soon be in commercial production. 

POSM [Propylene Oxide Styrene Monomer] A process for making propylene oxide from ethylbenzene. The ethylbenzene is reacted with oxygen and propylene in the presence of a proprietary catalyst. Developed in Russia by JSC Nizkhnekamskneftkheim and licensed exclusively by Dow Chemical Company. In 2006, 36% of the world production of propylene oxide was made by this process. See also SMPO. 

Styrene is manufactured nearly entirely by the direct dehydrogenation of ethylbenzene. Smaller amounts are obtained indirectly, as a co product, from the production of propy. lene oxide by the Oxirane and Shell technologies, industrialized in the United States, the Netherlands and Spain, and whose essential intermediate step is the formation of ethylbenzene hydroperoxide, or from the production of aniline, by a technique develop jn the USSR, which combines the highly exothermic hydrogenation of nitrobenzene with the highly endothermic dehydrogenation of ethylbenzene. 

Propylene oxide (PO) is a versatile chemical intermediate used in a wide range of industrial and commercial products. Current world production is over 6 million metric torts a year. While several processes exist, the Shell Chemicals companies have derived a strong competitive advantage by using and continually developing their proprietary styrene monomer propylene oxide (SMPO) technology, a process in which propylene and ethylbenzene (EB) are converted into PO and styrene monomer (SM), respectively. Worldwide, there are now five world-scale SMPO plants based on Shell technology, the most recent one started up in 2006 in China. 

Shell subsequently developed a heterogeneous, silica-supported titania catalyst [11,12] which forms the basis of the commercial process for the epoxidation of propylene with ethylbenzene hydroperoxide. The co-product alcohol is dehydrated, in a separate step, to styrene. Ti(IV)Si02 was the first truly heterogeneous epoxidation catalyst useful for continuous operation in the liquid phase. 

We have developed an effective method for the selective autoxidation of alky-laromatic hydrocarbons to the corresponding benzylic hydroperoxides using 0.5 mol% NHPI as a catalyst and the hydroperoxide product as an initiator. Using this method we obtained high selectivities to the corresponding hydroperoxides, at commercially viable conversions, in the autoxidation of cyclohexylbenzene, cumene and ethylbenzene. The highly selective autoxidation of cyclohexylbenzene to the 1-hydroperoxide product provides the basis for a coproduct-free route to phenol and the observed inq)rovements in ethylbenzene hydroperoxide production provide a basis for in roving the selectivity of the SMPO process for styrene and propene oxide manufacture. 

By far the largest outlet for benzene (approx. 60%) is styrene (phenyl-ethene), produced by the reaction of benzene with ethylene a variety of liquid and gas phase processes, with mineral or Lewis acid catalysts, are used. The ethylbenzene is then dehydrogenated to styrene at 600-650°C over iron or other metal oxide catalysts in over 90% selectivity. Co-production with propylene oxide (section 12.8.2) also requires ethylbenzene, but a route involving the cyclodimerization of 1,3-butadiene to 4-vinyl-(ethenyl-) cyclohexene, for (oxidative) dehydrogenation to styrene, is being developed by both DSM (in Holland) and Dow. 60-70% of all styrene is used for homopolymers, the remainder for co-polymer resins. Other major uses of benzene are cumene (20%, see phenol), cyclohexane (13%) and nitrobenzene (5%). Major outlets for toluene (over 2 5 Mt per annum) are for solvent use and conversion to dinitrotoluene. 

The commercial production of styrene nowadays is carried out almost exclusively by catalytic dehydrogenation of ethylbenzene. Toray has developed a process for recovery from pyrolysis gasoline, which contains 3 to 5% styrene. The method involves hydrogenation of the aliphatic diene components of a close-cut pyrolysis gasoline (130 to 140 °C) followed by extractive distillation with dimethyl-acetamide. 

Other processes for the production of styrene, apart from dehydrogenation of ethylbenzene have been developed, but these have only limited industrial importance. 

---