Example 2 Synthesis of a styrene process.

Styrene, the monomer of polystyrene, has enjoyed strong market growth over the past
two decades. It is prepared starting with benzene and ethylene which react to form ethylbenzene;
the ethylbenzene is dehydrogenated to yield styrene. Further information about styrene
manufacture, properties, and uses is available.3 In this example, the steps involved in
synthesizing a process to produce styrene from ethylbenzene will be illustrated. The procedure
followed is analogous to that followed by the PIP program. Experience will be cited frequently in
this example for guidance of the synthesis procedure. In a computer process-synthesis program
the guidance is provided by a set of heuristics summarizing the experience. Douglas and coworkers provide information about such heuristics.ll The PIP program displays, at the request of
the user, the heuristics used in selecting processing steps.
Answer :

Step 1. Inputs and outputs.

The chemical reaction is written and balanced, as
C,Hs----C,H, + C,H,-C,H, + H, (1)
ethylbenzene styrene hydrogen

Values of $0.42/lb for styrene, $0.25/lb for ethylbenzene, and $0.30/lb for hydrogen are used (the
hydrogen value is based on its heat of combustion and a heat value of $5/million Btu). 1 lb-mol
each of styrene (104 lb) and hydrogen (2 lb) requires 1 lb-mol of ethylbenzene (106 lb); Thus, on
a basis styrene, the value of the products is 104*0.42 + 2*0.30 = $44.28 while the value of the
ethylbenzene is 106*0.25 = $26.50. The conversion of reactant to product necessarily will be less
than 100 percent.
(2) C,H,-C,H, + C,H, + C2H,
1 benzene ethylene
(3) C,H,-C,H, + H, = C,H,-CH, + CH, .
to1uene methane
Reactions (2) and (3) consume ethylbenzene without producing the desired styrene. The process
feeds are ethylbenzene and steam and the products are condensed steam, styrene, benzene,
toluene, hydrogen, methane, and ethylene. Including the steam, valued at $O.Ol/lb, adds $2.52 to
the total feed cost, raising it to $29.02 per 104 lb of styrene product.
Step 2. Recycle structure.

The values used for mass balance calculations are, Fractional extent,
reaction (1) = 0.47
reaction (2) = 0.025
reaction (3) = 0.005
Normal boiling point values (OC) for the components of this system are: hydrogen - 252.5 water
100 methane - 161.5 toluene 110.6 ethylene -104 ethylbeniene 136 benzene 80.1 styrene 145.
On the basis of 1 lb-mol(lO4 lb) of styrene product, the
calculations are:
Feed EB flowrate = (1 lb-mol styrene/h)
* (0.5 mol EB/0.47 mol styrene)
* (106 lb EB/lb mol)
= 112.8 lb/h

The EB feed rate to the reactor must be twice this, because only one-half of the
feed reacts per pass and the EB recycle rate equals the feed rate; Thus,
Reactor EB feed rate = 225.6 lb/h
The steam feed rate is then = (225.6/106 mol EB/h)
* (14 mol steam/m01 EB)
* (18 lb steam/m01 steam)
= 536 lb/h
Step 3. Separation processes.

FIGURE 4-3
Thus, a final distillation step, with styrene as the distillate product and tar (not included in
the material balances) as the bottom product, is recommended. Another complicating factor here
is that styrene polymerizes when heated. In order to avoid significant polymerization, styrene
distillation temperatures are lowered by operating under vacuum. Separation processes in reality
do not achieve perfect separation as we have assumed in the mass balances. Actual separationproduct stream compositions must be specified if the separations are to be designed in more
detail.
Step 4. Heat integration.
Both heating and cooling are needed in this process. Required temperatures are specified;
for example, a reactor outlet temperature of 600C (1112F) is needed.

FIGURE 4-4
Styrene-process separation sequence for Example 2.
The reactor-inlet temperature required to achieve the specified outlet temperature is
calculated from a reactor energy balance,
Enthalpy of products = enthalpy of reactants - heat of reaction
Enthalpies of reactants and products are expressed with respect to a reference temperature
of 25C (77F)
the heat of reaction is available at 25C: [m*C*(1112-77)],= [m*C*(T-77)],-m*AH,
m is the mass flow rate (lb/h)
C is the heat capacity (Btu/lb-F), m * AH, is the total heat of reaction (Btu/h), and
fixes the heated feed temperature at 590C (1094F).
An energy balance for the heated feed and steam mixture establishes the required steam
temperature: [m*C*(T- 1237)], + [m*C*(1094 - 1237)],, = 0
the subscripts s and EB signify steam and ethylbenzene, respectively. Using C, = 0.5, C,, = 0.6
Btu/lb-F
the flow rates calculated above gives T(of superheated steam) = 1309F (709C)
An energy balance around the feed-effluent heat exchanger, [m*C*(1112 - T)]erauet =
[m*C*(1094 - 140)],,, gives T = 792F as the outlet temperature of the effluent The reactor
effluent must reach about 40C (104F) for condensation. Thus, further cooling is required, by
cooling water or other process loads. Heating and cooling for the distillation columns represent
such possible loads.
Step 5. Economic evaluation.
Process equipment is sized and priced and total plant investment is estimated. Requirements and
costs for utilities and raw materials, other operating costs, and product values are estimated.
These values are used to evaluate the profitability of the proposed process and can provide a
sound basis for a more detailed design.