Assignment 2 (Subject: Ch.E.

401 Chemical Reactor Design)

Related to CLO1
Q1
Your design group has been asked to consider certain aspects of the preliminary design of a reactor for the
production of vinyl chloride by reacting chlorine with ethylene.

In order to minimize the production of the undesirable addition product

It is suggested that the reaction be carried out in the temperature range 320 to 380 °C. The effect of the
addition reaction is negligible in this range. In order to minimize the formation of multiple substitution
products, an ethylene/ chlorine feed ratio of 50:1 will also be used. The following values of the pseudo
first-order rate constant k1 have been reported by Subbotin, Antonov, and Etlis [Kinetics and Catalysis, 7
(183), 1966].

For your preliminary considerations, assume that the following values of product and reactant heat
capacities are constant over the temperature range of interest.

The standard enthalpy change for the reaction at 25 °C may be taken as — 23 kcal/g mole.
(a) Calculate the space time necessary to obtain 50% conversion of the chlorine in a PFR if the reactor is
maintained isothermal at 320 °C.
(b) Calculate the space time necessary to obtain 50% conversion of the chlorine in a PFR if the feed
enters at 320 °C and the reactor is operated adiabatically.
The reactor is to be designed to operate at 1 atm. Deviations from ideal gas behavior may be neglected.
Note that while the volume changes associated with changes in mole numbers are negligible, you may
wish to consider the effect of thermal expansion.
Q2
Acetic anhydride reacts with ethanol to form ethyl acetate according to the reaction

In ethanol this reaction proceeds stepwise.

Since the second reaction rate constant is orders of magnitude greater than the first at temperatures near
room temperature, the first reaction may be regarded as the rate controlling step. Since ethanol is used as
the solvent, the reaction will follow pseudo first-order kinetics. The rate of this liquid phase reaction can
be expressed as

Where T is temperature in degrees Kelvin, and where A and B refer to anhydride and alcohol,
respectively. The concentrations are expressed in kilomoles per cubic meter, and the rate in kilomoles per
cubic meter per second. On the basis of the data presented below, determine the times necessary to
achieve 20% decomposition of a 1 molal anhydride solution by isothermal operation at 20 °C and by
adiabatic operation starting from the same temperature.

The density of ethanol at 20 °C is 0.789 g/cm3, and its heat capacity is 2.85 J/g K. These properties may
be assumed to be constant over the temperature range of interest. The solution is so dilute that one may
assume that its property values are essentially equal to those of pure ethanol. Batch reactor operation is
assumed.

Q3
The decomposition of phosphine is a first order reaction that proceeds according to the following
stoichiometric equation.
Pure phosphine is to be admitted to a constant volume batch reactor and allowed to undergo
decomposition according to the above reaction. If pure phosphine enters at 672 °C and the initial pressure
is 1 atm, determine the times necessary to decompose 20% of the original phosphine for both isothermal
and adiabatic operation. The rate constant for this first-order reaction is given in the International Critical
Tables as

Where the temperature is expressed in degrees Kelvin and the time in seconds. The standard enthalpy
change for the gaseous reaction at 25 °C is approximately 5665 cal/gmole. The following values may be
used for the molal heat capacities (at constant pressure) of the species involved in the reaction.

Where
T is expressed in degrees Kelvin
Cp is expressed in calories per gram mole per degree Kelvin
For temperatures from 800 to 1000 °K the following values may be used to represent average Cp values.

Q4
Consider the reaction used as the basis for Illustrations 10.1 to 10.3. Determine the volume that would be
required to produce 2 million lb of B annually in a plug flow reactor operating isothermally at 163 °C.
Assume that 97% of the A fed to the reactor is to be converted to B and that the reactor can be operated
for 7000 hr annually. Determine the manner in which the heat transfer requirement is distributed along the
length of the reactor (i.e., what fraction of the heat evolved must be removed in the first 10% of the
reactor length, the second 10%, the third 10%, etc.?).

Q5
A reactor designer proposes to carry out a reaction with the stoichiometry

In the liquid phase in two ideal CSTR's operating in series. Since species B is very expensive, the
designer has chosen the reaction conditions so that a vast excess of species A will be present and the rate
expression becomes pseudo first order in species B.

The reaction is exothermic, and temperature control in both reactors is to be accomplished by heat
exchange with water boiling at 1 atm (T = 100 °C). The contents of the first reactor will be at 106 °C;
those of the second reactor will be at 117 °C. At these temperatures the values of the apparent rate
constant are:
For the proposed design the reactor volumes are both 0.8 m3, the input volumetric flow rate is 1.10
m3/ksec, and the overall fraction conversion of the initial B is to be 0.80. Since the reaction is carried out
in dilute liquid solution, the effective heat capacity of the liquid mixture is substantially unaffected by the
reaction and may be regarded as a constant that is equal to 3.47 J/cm3-°K. If the initial concentration of
species B is 5.6 kmole/m3 and the feed stream enters at 70 °C, determine the required heat transfer area
for each reactor.
Additional data:
AHR = —69 kJ/mole for the reaction as written.
The variation of this quantity with temperature may be neglected.
U = 68 J/ksec-cm2-K in each reactor.