An additional drawback of the use AlCl3 and hydrogen chloride is that they are corrosive.

Special materials of construction must be used in the reaction and catalyst separation systems. The zeolite Based Process Zeolite catalysts have been commercially employed in ethylbenzene processes since 1980. Their use for cumene production, however, requerid additional years of research. In 1992, dow added a zeolite transalkylation reactor to its SPA- based cumene plant at Terneuzen, the Netherlands. In the next few years, cumene processes based completely on zeolite technology started to be offered for license. Examples include the processes developed by Mobil-Badger, UOP, and CDTech (a partnership between ABB Lummus Global and Chemical Research & Licensing). Between 1996 and 1998, several cumene expansions employing zeolite technology were completed worldwide. In the United States, 7 cumene plants were retrofitted from SPA to zeolite technology, with 4 using the Mobil-Badger process and 3 using UOP tehnology. The CDTech process will be used in a grassroots plant planned for construction in Taiwan by 2000. EniChem also developed its own zeolite technology, which was employed to revamp its SPA based facilities at Porto Torres, Italy. Except for the CDTech process, which combines catalytic reaction and distillation in a single column, all zeolite based processes consist of essentially the same flowsheet configuration. The alkylation reaction is carried out in fixed-bed reactors at temperature below those used in SPA based processes. When refinery grade propylene is used as a feedstock, the effluent from alkylation is sent to a depropanizer column that removes propane overhead. A separate trasalkylation reactor converts recycled PIPB and benzene to additional cumene. The bottoms of the depropanizer are then mixed with transalkylation reactor effluent and fed to a series of three distillation columns. Benzene, product cumene, and PIPB are respectively separated in the overhead of each column, with PIPB and benzene recycled to the react ion system. A small stream of heavy aromatics is separated in the bottoms of the PIPB column. Like the AlCl3 catalyst, zeolites are sufficiently active to trasalkylte PIPB back to cumene. Overall selectivity of benzene to cumene is quite high, varying from 99.7% to almost atoichiometric, depending on the nature of the zeolite employed. Product purities as high as 99.97% can be obtained, with B/P feed ratios between 3 and 5. A particular advantage of the zeolite catalysts is that they are regenerble and an be used for several cycles. Therfor, the waste disposal problems associated with SPA and AlCl3 catalysts are greatly reduced. In addition, carbon steel can be used as the material of construction throughout the plant because of the mild operating conditions and the absence of highly corrosive compounds. One limitation of the zeolite technology is potential poisoning of the catalyst by contaminants in the feed. Depending on feedstock quality, guard beds or additional feed preteadment may thus be required. If refinery grade propylene is used, for example, its sulfur content must be closely controlled.

PROCESS ECONOMICS. This report presents conceptual designs and evaluates the economics of cumene production using SPA, AlCL3, and zeolite catalysts. The SPA based process has been updated from PEP Report 22B, Phenol (December 1977), and incorporates recent advances in the reactor technology disclosed by UOP. A versionof the process combining SPA based process is intended to resemble the improved MonsantoKellog technology, which employs a homogeneous liquid-phase reactor. Finally, the zeolite based process is a generic conceptual design based on information disclosed mainly by Mobil-Badger and UOP. Two versions of the process using refinery grade and hemical grade propylene, respectively, have been evaluated. Table 2.1 summarizes the economics for producing cumen at 595 million lb/year (270000 t/yr) by different processes. The economic evaluation reveals the following general trends: The AlCl3 based process has highest total capital investiment. This is a consequence of the additional equipment required for catalyst disposal and the use of more expensive materials of construction. Differences in capital costs between the zeolite based process (using refinery grade propylene) and the SPA based processes resemble the modern version of UOPs process, which includes an interbed propylene injection system. That feature allows for a significant reduction in the overall B/P feed ratio (5 versus about 8 in older plants), and hence in capital and operating costs. Section 5 compares the different versions of the SPA based process. Overall yield plays a dominant role in the economics of cumene production. For althe processes evaluated, raw material costs account for 86 to 96% of the net production costs. Because of its high benzene to cumene selectivity, the zeolite based process has the lowest production costs of all the processes using refinery grade propylene. The zeolite based process employing chemical grade propylene does not require a depropanizer column, and its total capital investment is about 8% lower than that for the process using refinery grade propylene. However, the higher unit price for chemical grade propylene and its lower associated liquefied petroleum gas credit result in a higher cumene product value. Differences in product value among the processes evaluated are less than 3%. Because the product value is quite sensitive to raw material costs, the zeolite based process tends to become increasingly more competitive at higher benzene and propylene prices.

As opposed to an average cumene contract price of about 21c/lb in 1997, at year-end 1998 the price was between 15.25 and 15.75 c/lb in the United States. The downward pressure on price had resulted from weak crude oil prices and riding stocks of benzene and propylene throughout 1998. Our cost analysis is based on unit prices for benzene and refinery grade propylene of 77 c/gal and 10.34 c/lb, respectively (1998 PEP Yearbook International). Appendix B discusses other general criteria for calculating capital investment and production costs.

3 INDUSTRY STATUS. The cumene industry began its development during World War II, when cumene was used as an additive for military aviation fuel. In the late 1940s, BP and Hercules introduced a commercial route to phenol and acetone via cumene peroxidation. Since the, cumene has lost its importance as a fuel additive, but has become the major feedstock fot the production of phenol. The cumene peroxidation process currently accounts for more than 90% of the phenol produced worldwide. This section reviews the status of the cumene industry and discusses market related issues. Including supply and demand, prices, and technology licensers. Our analysis is based on data from SRICs Word Petrochemicals and Chemical Economics Handbook programs, and on information from the trade literature. CUMENE MARKET GROWTH-GLOBAL ANALYSIS Table 3.1 summarizes world cumene markets by geographic region. Historical capacity, production, and consumption data from 1993 through 1998 are presented, along with SRIC forecasts for 1999, 2003, and 2008. Cumene demand is basically driven by the phenol markets. From 1993 to 1998, world cumene consumption grew at an average rate of 4.7%/yr, increasing from 5.6 million to 7. Million t/yr. over the same period, phenol consumption increased at 4.6%/yr worldwide. The forecast through 2003 indicates that cumene consumption will grow at 4.2%/yr in North America and 5.1%/yr worldwide. Asia ir expected to be main contributor to future global growth, with a rate of 8.5%/yr. In the early 1960s, because of a relatively weak economy, worldwide cumene capacity increased slowly, with no cumene additions reported in North America or Asia from 1992 through 1994. The demand for phenol and cumene started to grow more rapidly in 1994, driven by a recovery in the construction and automotive industries. Anticipating future phenol additions, the cumene industry started a period of plant expansions. The major absolute growth occurred in North America (primarily the United States), where cumene capacity increased from 2.8 million t/yr in 1994 to 3.7 million t/yr in 1998. Most of these expansions consisted of retrofitting plants based on solid phosphoric acid (SPA) with the new process using zeolite technology. The recent U.S cumene expansions affected the operating rate of the globa cumene industry, which declined from 82% in 1995 to about 74% in 1998. The additional cumene capacity was brought pnstream somewhat ahead of the corresponding phenol expansions, outpacing the growth in cumene demand for the period. Cumene operating rates, especially in the United States, are expected to recover after the planned start-up major phenol expansions in 1999 and 2000. PRODUCERS AND REGIONAL MARKETS Table 3.2 lists world producers of cumene by country and company; information, as available, on plant capacities, process technologies, and future expansion plants is included. Because many produucers

have recently completed technology upgrades, the table compares the year end situations for 1995 and 1998. A brief analysis of the most important regional markets for cumene follows. U.S CUMENE OUTLOOK. The United States has the highest concentration of merchant cumene producers, most of them using captive benzene and propylene from integrated refinery facilities. Fice companies, Georgia Gulf, JLM, Shell, Sun, and Texaco are forward-integrated into the production of phenol and acetone. Sun recently acquired AlliedSignals phenol facility, thus becoming one the worlds largest phenol producers. Sun entered the cumene business in 1994 by purchasing a plant from Chevrom in Philadelphia. As of year-end 1998, U.S cumene capacity was about 3.7 million t/yr accounting for 39.1% of world capacity. Between 1995 and 1998, a total of 965000 t/yr od additional capacity was brought onstream by Chevron, CITGO, Georgia Gulf, JLM, Koch, Marathom Ashland, and Sun. all expansions, except that of Marathon Ashland, consisted of revamping SPA based facilities with de new zeolite catalyst technology. U.S cumene consumption is projected to grow at an average rate of 4.2%/yr through 2003. Operating rates have been declining since 1996 as a result of several simultaneous capacity expansions. Cumene producers have based their new capacity on the three major phenol expansions announced by Shell, Aristech, and Phenolchemie, which are expected to come onstream between 1999 and 2000. WESTERN EUROPEAN CUMENE OUTLOOK. Western Europe is the worlds second largest regional market for cumene, with a production capacity of about 2.4 million t/yr (as of year-end 1998). Germany and Italy are the leading producers in the region. Except for Dow Benelux in the Netherlands and VEBA OEL in Germany, all the companies consume cumene captively to produce phenol and acetone. In 1992, Dow added a zeolite transakylation reactor to its SPA based plnt at Terneuzen. It was the first company in the world to use zeolite technology for the commercial production of cumene. More recently, EniChem announced the development of a cumene process based entirely on zeolite. The company used the technology to retrofit its SPA-based plant at Porto Torres, Italy, in 1996. With growing demand for phenol in Europe, other cumene producers began to announce expansion projects using zeolite technology. Two SPA based cumene plants were retrofitted in 1998 one in Germany by DOMO Caproleuna and another in Spain by Ertisa, both employing the Mobil-Badger process licensed by Raytheon. Borealis has used the same technology to retrofit its AlCl3 based cumene plant at Porvoo, Finland. These three expansion projects added a total of 420000 t/yr of cumene capacity to the region in 1998. From 1993 to 1998 cumene consumtion in Western Europe increased at an average rate of 6.7%/yr, amounting to about 2.4 million t/yr in 1998. Consumption is projected to gro at a slower rate of 4.4%/yr through 2003.

4 CHEMICAL REACTIONS AND PRODUCT IMPURITIES. As chemical intermediate, cumene (or isopropilbenzene) is obtained in a manner very similar to the manufacture of ethylbenzene. All commercial cumene is produced by alkylating benzene with propylene in the presence of an acid catalyst. This section presents the main chemical reactions involved in cumene synthesis, along with a discussion of finl product impurities and quality specifications. ALKYLATION REACTIONS The alkylation of aromatic hydrocarbons belongs to a general class of electrophilic reactions known as Friedel-Crafts reactons (639059). Common Friedel-Crafts catalysts include Lewis acids (AlCl3, BF3) Bronsted acids (H2SO4, H3PO4, HF) and acidic zeolites. In cumene production, propylene acts as the alkylating as shown in equation 4.1:

The reaction is exothermic (-23.4 kcal/ mole at 250C) rapid, and irreversible. It can take place with any of the catalysts mentioned above, although ALCL3, H3PO4, nd zeolites are preferred commercially. Propylene conversions near 100% are usually obtained. During alkylation, a small portion of cumene reacts further with propylene to form higher alkylated products as shown in equation 4.2:

The proportion of ortho, meta, and para configuarations of diisopropylbenzene (DIPB) is affected by the type of catalysts used. The ortho substitution is usually formed in smaller amounts because of sferic hindrance effects. Although DIPB is the dominant by product, its further alkylation also leads to significant amounts of triisopropylbenezene (TIPB).