Direct dehydrogenation of ethylbenzene to styrene accounts for 85 % of commercial production. The reaction
is carried out in the vapor phase with steam over a catalyst consisting primarily of iron oxide. The
reaction is endothermic, and can be accomplished either adiabatically or isothermally. Both methods are
used in practice.
The major reaction is the reversible, endothermic conversion of ethylbenzene to styrene and hydrogen:
C6H5CH2CH3 C6H5CH=CH2 + H2 ΔH (600 °C) = 124.9 kJ/mol
This reaction proceeds thermally with low yield and catalytically with high yield. As it is a reversible gasphase
reaction producing 2 mol of product from 1 mol of starting material, low pressure favors the forward
reaction.
Competing thermal reactions degrade ethylbenzene to benzene, and also to carbon:
C6H5CH2CH3 C6H6 + C2H4 ΔH = 101.8 kJ/mol
C6H5CH2CH3 8 C + 5 H2 ΔH = 1.72 kJ/mol
Styrene also reacts catalytically to toluene:
C6H5CH2CH3 + H2 C6H5CH3 + CH4 ΔH = – 64.5 kJ/mol
The problem with carbon production is that carbon is a catalyst poison. When potassium is incorporated
into the iron oxide catalyst, the catalyst becomes self-cleaning (through enhancement of the reaction of
carbon with steam to give carbon dioxide, which is removed in the reactor vent gas).
C + 2 H2O CO2 + 2 H2 ΔH = 99.6 kJ/mol
Typical operating conditions in commercial reactors are ca. 620 °C and as low a pressure as practicable.
The overall yield depends on the relative amounts of catalytic conversion to styrene and thermal cracking
to byproducts. At equilibrium under typical conditions, the reversible reaction results in about 80 % conversion
of ethylbenzene. However, the time and temperature necessary to achieve equilibrium give rise to
excessive thermal cracking and reduced yield, so most commercial units operate at conversion levels of
50 – 70 wt %, with yields of 88 – 95 mol %.
Dehydrogenation of ethylbenzene is carried out in the presence of steam, which has a threefold role:
1) It lowers the partial pressure of ethylbenzene, shifting the equilibrium toward styrene and minimizing
the loss to thermal cracking
2) It supplies the necessary heat of reaction
3) It cleans the catalyst by reacting with carbon to produce carbon dioxide and hydrogen.
Many catalysts have been described for this reaction. One catalyst – Shell 105, also used in this experiment
– dominated the market for many years, and was the first to include potassium as a promoter for the
water-gas reaction. This catalyst is typically 84.3 % iron as Fe2O3 , 2.4 % chromium as Cr2O3 , and 13.3 %
potassium as K2CO3 . It has good physical properties and good activity, and it gives fair yields.
In recent years, the situation has become more complex. The market has become more competitive, causing
manufacturers to seek new catalysts that produce higher yields without compromising activity or
physical properties, or catalysts that meet specific requirements. A catalyst life of ca. two years is
claimed.
2.2.2 Adiabatic Dehydrogenation
Over 75 % of all operating styrene plants carry out the dehydrogenation reaction adiabatically in multiple
reactors or reactor beds operated in series (Fig. (1)). The necessary heat of reaction is applied at the inlet
to each stage, either by injection of superheated steam or by indirect heat transfer.
Fresh ethylbenzene feed is mixed with recycled ethylbenzene and vaporized. Dilution steam must be
added to prevent the ethylbenzene from forming coke. This stream is further heated by heat exchange, superheated
steam is