Styrene plant

The commodity nature of the product and the easy access to the Hcensed processes enable new producers, particularly in developing countries, to enter the global styrene merchant market with Htde experience in styrene technology. Access to ethylene, which caimot be easily transported by means other than pipelines, is a key factor in considering new styrene faciHties. Timing, or luck, is even more important because the supply and demand of styrene are seldom in balance and the price fluctuates broadly and rapidly as a result. Most of the time, the producers either suffer losses (1981—1985, 1991—1993) or enjoy handsome profits (1987—1990, 1994—mid-1995). Investments in styrene plants are known to have been recovered in less than a year, but prosperity encourages over-investment and lean years may foUow. 

The ethylene feedstock used in most plants is of high purity and contains 200—2000 ppm of ethane as the only significant impurity. Ethane is inert in the reactor and is rejected from the plant in the vent gas for use as fuel. Dilute gas streams, such as treated fluid-catalytic cracking (FCC) off-gas from refineries with ethylene concentrations as low as 10%, have also been used as the ethylene feedstock. The refinery FCC off-gas, which is otherwise used as fuel, can be an attractive source of ethylene even with the added costs of the treatments needed to remove undesirable impurities such as acetylene and higher olefins. Its use for ethylbenzene production, however, is limited by the quantity available. Only large refineries are capable of deUvering sufficient FCC off-gas to support an ethylbenzene—styrene plant of an economical scale. 

Figure 5 illustrates a typical distillation train in a styrene plant. Benzene and toluene by-products are recovered in the overhead of the benzene—toluene column. The bottoms from the benzene—toluene column are distilled in the ethylbenzene recycle column, where the separation of ethylbenzene and styrene is effected. The ethylbenzene, containing up to 3% styrene, is taken overhead and recycled to the dehydrogenation section. The bottoms, which contain styrene, by-products heavier than styrene, polymers, inhibitor, and up to 1000 ppm ethylbenzene, are pumped to the styrene finishing column. The overhead product from this column is purified styrene. The bottoms are further processed in a residue-finishing system to recover additional styrene from the residue, which consists of heavy by-products, polymers, and inhibitor. The residue is used as fuel. The residue-finishing system can be a flash evaporator or a small distillation column. This distillation sequence is used in the Fina-Badger process and the Dow process. 

The benzene—toluene fraction is further fractionated in a small column, not shown in Figure 5, to recover benzene for recycle to the alkylation unit and toluene for sale. This toluene can be converted to benzene by hydrodealkylation but the high selectivity catalyst has reduced the formation of toluene in the dehydrogenation reactor to the point where the cost of installing a hydrodealkylation unit is difficult to justify even in a large styrene plant. 

H. Sardina and co-workers, "New Styrene Plant Optimizer," paper presented at the AIChE Meeting, New Orleans, La., Mar. 1988. 

Figure 6.7 Schematic flowsheet of a styrene plant (Stanley and El-Halwagi, 1995, reproduced with peimission of the McGraw Hill Companies).

In the Monsanto/Lummus Crest process (Figure 10-3), fresh ethylbenzene with recycled unconverted ethylbenzene are mixed with superheated steam. The steam acts as a heating medium and as a diluent. The endothermic reaction is carried out in multiple radial bed reactors filled with proprietary catalysts. Radial beds minimize pressure drops across the reactor. A simulation and optimization of styrene plant based on the Lummus Monsanto process has been done by Sundaram et al. Yields could be predicted, and with the help of an optimizer, the best operating conditions can be found. Figure 10-4 shows the effect of steam-to-EB ratio, temperature, and pressure on the equilibrium conversion of ethylbenzene. Alternative routes for producing styrene have been sought. One approach is to dimerize butadiene to 4-vinyl-1-cyclohexene, followed by catalytic dehydrogenation to styrene ... 

Figure 10-3. Schematic diagram of the Monsanto/Lummus Crest styrene plant. ...

This is a two-step reaction. The ethylbenzene is isolated in the first step and then contacted with a different catalyst at high temperature in the second step. Ethylbenzene and styrene plants are usually built together. 

Purification of industrial oils, kerosene/jet fuel, lubricating oils Mono- dicumyldiphenylamine Mono- dioctyldiphenylamine Dimer fatty acids Purification of xylenes Improvement of bromine number of recycle cumene in phenol plants Improvement of bromine number of recycle ethylbenzene in styrene plants based on liquid pha.se oxidation Alkylation of xylenes with diisobutylenes to mono-/ rr-butyI derivatives Phenyl xylyl ethane... 

Since most of the EB is used for the manufacture of styrene, EB plants are usually found in close proximity to styrene plants. Very little EB is traded commercially or transported. A small amount of EB is used as a commercial solvent, mainly as a substitute for xylenes. 

The dominant share of styrene production comes from dehydrogenation of EB in plants like that shown in Figure 8-5. Some comes as a coproduct in propylene oxide/styrene plants. An even smaller amount is recovered from the gasoline fraction of olefins plants cracking heavy liquids. 

The steam also reacts with coke deposits on the iron oxide catalyst, forming CO2, giving the catalyst a longer, more active lifetime. The onstream factor of the styrene plant is extended by reducing the shutdown frequency for catalyst regeneration or replacement. 

The EB entering the styrene plant is generally heated to the threshold cracking temperature (about 1100°F) in a heat exchanger The counter flow in the exchanger is the effluent from the second stage reactor, as shown... 

Benzene and para-xylene are the most sought after components from reformate and pygas, followed by ortho-xylene and meta-xylene. While there is petrochemical demand for toluene and ethylbenzene, the consumption of these carmot be discussed in the same way as the other four. Toluene is used in such a large quantity in gasoline blending that its demand as a petrochemical pales in comparison. Fthylbenzene from reformate and pygas is typically dealkylated to make benzene or isomerized to make xylenes. On-purpose production of petrochemical ethylbenzene (via ethylene alkylation of benzene) is primarily for use as an intermediate in the production of another petrochemical, styrene monomer. Ethylbenzene plants are typically built close coupled with styrene plants. 

Ethylbenzene is a high volume petrochemical used as the feed stock for the production of styrene via dehydrogenation. Ethylbenzene is currently made by ethylene alkylation of benzene and can be purified to 99.9%. Ethylbenzene and styrene plants are usually built in a single location. There is very little merchant sale of ethylbenzene, and styrene production is about 30x10 t/year. For selective adsorption to be economically competitive on this scale, streams with sufficiently high concentration and volume of ethylbenzene would be required. Hence, although technology has been available for ethylbenzene extraction from mixed xylenes, potential commercial opportunities are limited to niche applications. 

Another interesting recent development in styrene technology which will affect future consumption of ethylene relates to new methods for increasing conversion in the dehydrogenation of ethylbenzene. Several years ago, Scientific Design pioneered a technique for increasing conversion in this reaction. The net result was a marked decrease in the capital investment required for styrene plants. The present trend is to-... 

Other than the reactor system, the distillation column that separates the unconverted ethylbenzene from the crude styrene is the most important and expensive equipment in a styrene plant. To minimize yield losses and to prevent equipment fouling by polymer formation, polymerization inhibitors are used in the distillation train, product storage, and in vent gas compressors. 

Most dehydrogenations do not occur readily even at high temperatures. The driving force for this reaction is the extension in conjugation that results, since the double bond on the side chain is in conjugation with the ring. Conditions must be controlled to avoid polymerization of the styrene and sulfur may be added to prevent polymerization. The crude product is a mixture of styrene, and ethylbenzene that is separated by vacuum distillation, after which the ethylbenzene is recycled. Usually a styrene plant is combined with an ethylbenzene plant when designed. 

EPA 1989d. National Emission Standards for Hazardous Air Pollutants Benzene Emissions from Maleic Anhydride Plants, Ethylbenzene/Styrene Plants, Benzene Storage Vessels, Benzene Equipment Leaks, and Coke By-Products Recovery Plants. U.S. Environmental Protection Agency. 54 FR 38044. 

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