LECTURE THREE

PRACTICAL-3

10/09/2020 1
 KINETIC REACTORS
• Here, the kinetic models are specified for
the reaction and the simulation calculates
the rates of reaction based on per unit
volume or unit mass of catalyst or based on
resident time in the reactor vessel.
• Kinetic reactors may not always reach
equilibrium as there may not be sufficient
time for the reactions to take place to the
point of equilibrium.
 Example
• Perform design calculations with any
kinetic reactor (PFR/CSTR) to determine
the volume required to produce 180
million kilograms of ethylene a year
(37,313 kg/h) from cracking a feed
stream of pure ethane. The reaction is
irreversible and elementary.
•  It is required to attain a 60% conversion
of ethane by operating the reactor
isothermally at 1,000 K and pressure of 5
atm. The equation of reaction is:

• Data: k = 0.072s-1 at 1,000 K; activation

energy Ea = 82 kCal/gmol
 Solution
•  The pre-exponential factor (frequency
factor) is calculated from Arrhenius
Equation:

Where: k = rate constant; ka = pre-

exponential factor (same units as rate
constant), and constant for each type of
reaction.
• It is also the frequency of collisions in
the correct orientation; Ea = activation
energy (same units as RT); T = absolute
temperature (in Kelvin); and R =
Universal gas constant (8.314 J/mol·K =
1.987 cal/mol-K.)
•  

From which:
•  The number of moles produced per hour
is (assuming 30 days off per annum):
For CSTR:
• Under parameters tab: Tolerance = 0.1%;
initial step size = 0.001 m3; maximum step
size = 0.001 m3; maximum iterations = 10
For PFR:
• The predicted volumes are between 1.0e-5
& 1.0e-6 m3;
• Under parameters tab: Tolerance = 1.0e7%;
initial step size = 1.0e8 m3; maximum step
size = 1.0e7 m3; minimum (optional) =
1.0e6; and maximum iterations = 30
 Gibbs Reactor
• This reactor model solves the complete
reaction equilibrium of all species in the
component list by minimizing the Gibbs
free energy subject to constraints of the
feed mass balance.
• It is specified with restrictions such as a
temperature approach to equilibrium or
fixed conversion of one species.
• The Gibbs reactor models high temperature
processes involving simple molecules and
that are known to come to equilibrium.
• It is not effective for complex molecules
since these have high Gibbs energy of
formation.
• The components are specified carefully
when using Gibbs reactor since it can solve
for only specified components.
• If a product component formed during
reaction is not specified, then Gibbs
reactor will not be helpful because such a
component will not be solved.
• Furthermore, if some components have
high Gibbs free energy than the other,
then their concentrations will be poorly
solved.
 Example-3
Steam Reforming of Methane
•  Hydrogen can be made by steam reforming
of methane in a highly endothermic
reaction:

• Steam reforming is usually carried out in a

fired tubular reactor with catalyst packed
inside the tubes and fuel fired on the
outside of the tubes to provide the heat of
reaction.
• The product gas mixture contains carbon
dioxide and water vapor as well as carbon
monoxide and hydrogen and is
conventionally known as synthesis gas
(syngas).
• The hydrogen can also be made by partial
oxidation of methane, which is an
exothermic process, but yields less product
per mole of methane feed:
•  

• When steam, oxygen, and methane are

combined, heat from the partial oxidation
reaction can be used to provide heat energy
for steam reforming.
• The combined process is known as auto-
thermal reforming.
•  The combined process is known as auto-
thermal reforming.
• This process has the advantage requiring less
capital investment than steam reforming
since it does not need fired heater reactor
while giving higher yields than partial
oxidation.
• The hydrogen yield can further be increased
by carrying out the water-gas shift reaction:
• The water-gas shift reaction equilibrates
rapidly at temperatures above 450°C.
• At higher temperatures this reaction favors
the formation of carbon monoxide, while at
low temperatures more hydrogen is formed.
• When hydrogen is the desired product, the
shift reaction is promoted at lower
temperatures by using an excess of steam
and providing a medium temperature to low
temperature shift catalyst.
• In an auto-thermal reforming process,
1,000 kmol/h of methane at 20°C is
compressed to 10 bar, mixed with 2,500
kmol/h of saturated steam and reacted
with pure oxygen to give 98% conversion of
the methane.
• The resulting products are cooled and
passed over a medium-temperature shift
catalyst that gives an outlet composition
corresponding to equilibrium at 350°C,
• Determine:
(i) How much heat is required to vaporize
the steam
(ii) How much oxygen is needed
(iii)The temperature at the exit of the auto-
thermal reforming reactor,
(iv)The final molar flow-rate of each
component of the syngas
 Solution
• The model must simulate the high
temperature reforming reaction and also
the re-equilibrium of the water-gas shift
reaction as the product gas is cooled.
• A Gibbs reactor can be used for the high
temperature reaction but an equilibrium
reactor must be specified for the shift
reactor, as only the water gas shift reaction
will re-equilibrate at 350°C.
• Since the methane compressor supplies
some heat to the feed, it should be
included in the model.
• Also, since the question asks how much
heat is needed to vaporize the steam, a
steam boiler should be included.
• The oxygen supply system can also be
included
• The specific requirements are:
 Methane compressor:
Methane feed flow-rate 1,000 kmol/h
Inet temperature 20°C
Outlet pressure 10 bar

Steam boiler:
Saturated steam 2,500 kmol/h
(outlet) flow-rate
Outlet temperature Same as auto-thermal
exit temperature
•  Auto-thermal reactor (Gibbs reactor)
reaction:

• The heat duty to the reforming reactor is

specified as zero.
• The oxygen flow-rate can then be adjusted
until the desired methane conversion is
achieved.
• Shift reactor (Equilibrium reactor) reaction:
PFD in Unisim Design
Component Molar flow-rate (kmol/h)
H2 2,504
H2O 1,956
CO 68
CO2 912
CH4 20
• It apparent from the model output that the
process as simulated is far from optimal.
• The oxygen consumption is larger than the
500 kmol/h that should have been needed
for partial oxidation.
• The excess oxygen is needed because the
additional steam must also be heated to
the reactor outlet temperature and this
requires more of the feed methane to be
burned.
• The corollary is that the hydrogen yield, at
roughly 2.5 moles per mole of methane, is
not much better than could have been
obtained with partial oxidation followed by
shift reaction, despite excess of steam used.
• The designer has several options that can be
examined to improve this process:
– Increase heat recovery from the product
gas to the feed streams to preheat the
reactor feed and reduce the amount of
oxygen that is needed
– Reduce the amount of steam fed with
the methane
– Bypass a part of the steam from the
reformer feed to the shift reactor feed,
so as to obtain the benefit of driving
the equilibrium in the shift reactor
without the cost of providing extra heat
to the reformer
 – Reduce the conversion of methane so
that a lower reactor conversion and
lower outlet temperature are required

• Practically all these options are

implemented to some extent to arrive at
the optimal auto-thermal reforming
conditions.