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Appendix B Information for the Preliminary Design of Fifteen Chemical Processes

B.3.1 Process Description [1, 2]

The process flow diagram is shown in Figure B.3.1. Ethylbenzene feed is mixed with recycled ethylbenzene, heated, and then mixed with high-temperature, superheated steam.
Steam is an inert in the reaction, which drives the equilibrium shown in Equation (B.3.1) to
the right by reducing the concentrations of all components. Because styrene formation is
highly endothermic, the superheated steam also provides energy to drive the reaction.
Decomposition of ethylbenzene to benzene and ethylene, and hydrodealkylation to give
methane and toluene, are unwanted side reactions shown in Equations (B.3.2) and (B.3.3).
The reactants then enter two adiabatic packed beds with interheating. The products are
cooled, producing steam from the high-temperature reactor effluent. The cooled product
stream is sent to a three-phase separator, in which light gases (hydrogen, methane,
ethylene), organic liquid, and water exit in separate streams. The hydrogen stream is
further purified as a source of hydrogen elsewhere in the plant. The benzene/toluene
stream is currently returned as a feed stream to the petrochemical facility. The organic
stream containing the desired product is distilled once to remove the benzene and toluene
and distilled again to separate unreacted ethylbenzene for recycle from the styrene product.
CbH5C2H5^CbH5C2H3 + H2
ethylbenzene styrene hydrogen

(B.3.1)
(B.3.2)

C6H5C2H5^C6H6 + C2H4

ethylbenzene benzene ethylene

CbH5CJi5 + H2 C6H5CH3 + CH4

ethylbenzene hydrogen toluene methane

(B.3.3)

The styrene product can spontaneously polymerize at higher temperatures. Because product styrene is sent
directly to the polymerization unit, experience suggests that as long as its temperature is maintained at less than
125C, there is no spontaneous polymerization problem. Because this is less than styrene's normal boiling point, and
because low pressure pushes the equilibrium in Equation (B.3.1) to the right, much of this process is run at vacuum.
Stream tables, utility summaries, and major equipment summaries are given in Tables
B.3.1, B.3.2, and B.3.3, respectively.
B.3.2 Reaction Kinetics
The styrene reaction may be equilibrium limited, and the equilibrium constant is given as
Equation (B.3.4).
K=

In X = 15.5408 where T is in K and P is in bar.

(B.3.4)
14,852.6
T