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Thomas J. Stoodt and Antoine Negiz
UOP LLC Des Plaines, Illinois

The importance of benzene as an intermediate in the production of organic-based materials is exceeded only by that of ethylene. Benzene represents the basic building block for direct or indirect manufacture of well over 250 separate products or product classifications. Historically, the major consumption of benzene has been in the production of ethylbenzene (for polystyrene), cumene (for phenol and acetone), and cyclohexane (for nylon). Significant quantities of benzene are also consumed in the manufacture of aniline, detergent alkylate, and maleic anhydride. At present, approximately 92 percent of the benzene produced worldwide comes directly from petroleum sources. Catalytic reforming supplies most of the petroleumderived petrochemical benzene. However, toluene is produced in greater quantities than benzene in the reforming operation, and in many areas, low market demand for toluene can make its conversion to benzene via dealkylation economically attractive. Approximately 13 percent of the petrochemical benzene produced in the world is derived from toluene dealkylation. The thermal hydrodealkylation (THDA) process provides an efficient method for the conversion of alkylbenzenes to high-purity benzene. In addition to producing benzene, the THDA process can be economically applied to the production of quality naphthalene from suitable feedstocks.

The UOP THDA* process converts alkylbenzenes and alkylnaphthalenes to their corresponding aromatic rings, benzene and naphthalene. The relation between product distribu*Trademark and/or service mark of UOP.

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tion and operating severity is such that, for both benzene and naphthalene operations, the conversion per pass of fresh feed is maintained at somewhat less than 100 percent. A simplified process flow diagram for benzene manufacture is presented in Fig. 2.3.1. The alkyl-group side chains of the alkyl-aromatic feed as well as nonaromatics that may be present in the unit feed are converted to a light paraffinic coproduct gas consisting mainly of methane. The basic hydrodealkylation reaction enables the process to produce a high-purity benzene or naphthalene product without applying extraction or superfractionation techniques, even when charging a mixture of alkyl aromatics and nonaromatic hydrocarbons. Excessive nonaromatics in the charge significantly add to hydrogen consumption. Product yields approach stoichiometric with benzene yield from toluene approximating 99 percent on a molal basis. A small amount of heavy-aromatic material consisting of biphenyl-type compounds is coproduced. In a benzene unit, fresh toluene feedstock is mixed with recycle toluene and recycle and fresh hydrogen gases, heated by exchange in a fired heater, and then charged to the reactor. Alkyl aromatics are hydrodealkylated to benzene and nonaromatics, and paraffins and naphthalenes are hydrocracked. The effluent from the reactor is cooled and directed to the product separator, where it separates into a liquid phase and gas phase. The hydrogen-rich gas phase is recycled to the reactor, and the separator liquid is charged to a stripper for the removal of light ends. Stripper bottoms are percolated through a clay treater to the fractionation section, where high-purity benzene is obtained as an upper sidecut from a benzene fractionation column. Unconverted toluene is recycled to the reactor from the lower sidecut of the benzene column. Heavy-aromatic by-product is withdrawn from the bottom of the column to storage. The reactor-section process flow in a naphthalene THDA unit is similar to that described for the benzene unit. Fresh feed is mixed with unconverted recycle alkyl aromatics and makeup and recycle hydrogen. The mixture is then heated and charged to the reactor. Materials in the feedstock materials that boil close to naphthalene would make the

FIGURE 2.3.1 UOP THDA process for benzene production.

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recovery of high-purity product either impossible or uneconomic if they remain unconverted. Process conditions are set to ensure that these materials are hydrocracked or dealkylated, or both, to products easily separated by fractionation. In the case of naphthalene, the aromatic-splitter bottoms are charged to a naphthalene splitter, where the small amount of heavy-aromatic coproduct is rejected as a bottoms product. Naphthalene splitter overhead is directed to the naphthalene fractionator, where high-purity naphthalene is recovered as an overhead product. Naphthalene fractionator bottoms are recycled to the reactor section. In both benzene and naphthalene THDA units, clay treating of the product is generally required to meet the usual acid-wash color specifications. Several design options are available for optimizing hydrogen usage in both types of units. Coproduct light ends, primarily methane, must be removed from the reaction section to maintain hydrogen purity. When the supply of makeup hydrogen is limited, consideration also must be given to the elimination of C3 and heavier nonaromatic hydrocarbons from the makeup gas. If present, these materials hydrocrack and substantially increase hydrogen consumption. During the design stage of hydrodealkylation units, careful attention must be given to hydrogen consumption and availability as related to overall refinery operation. Depending on the application, THDA units can process a wide variety of feedstocks. For the production of benzene, feedstocks could include extracted light alkylbenzene, suitably treated coke-oven light oil, and pyrolysis coproducts. Feedstocks to produce naphthalene could include heavy reformate, extracted cycle oils from the fluid catalytic cracking (FCC) process, and coal-tar-derived materials. Benzene produced from commercial THDA units typically has a freeze point of 5.5C, which exceeds the ASTM Benzene-545 benzene specifications.

Although THDA yields are about 99 percent on a molar basis, they are considerably lower on a weight basis because of the change in molecular weight. Weight yields for the dealkylation of toluene to benzene are shown in Table 2.3.1. Investment and utility requirements are shown in Table 2.3.2.

TABLE 2.3.1

THDA Yields Feeds, wt % 2.3 17.7 0.6 83.6 100 102.3 0.4 102.3 Product, wt %

Benzene production Hydrogen (chemical consumption) Methane Ethane Benzene Toluene Heavy aromatics Total

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TABLE 2.3.2 THDA Process Investment and Utility Requirements* Estimated battery-limits erected cost Utilities Electric power, kW Fuel, 106 kcal/h (106 Btu/h) Cooling water, m3/h (gal/min) $9.5 million 620 63 (250) 112 (495)
metric tons per

*Basis: 1200 BPD of toluene feed. Note: MT/h metric tons per hour; MTA annum; BPSD barrels per stream-day.

The economics of benzene manufacture via the THDA process are very sensitive to the relative prices of benzene and toluene. As a general rule, THDA becomes economically viable when the price of benzene (per unit volume) is more than 1.25 times the price of toluene. For this reason, the THDA process has become the process used to meet benzene demand during peak periods. When benzene is in low demand, THDA units are not operated. However, a UOP-designed THDA is easily revamped at low cost to a Tatoray process unit. This flexibility greatly extends the utilization of expensive processing equipment and provides a means of generating a wider product state (for example, benzene and mixed xylenes) during periods of low benzene demand.

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