LECTURE THREE

PROCESS DESIGN

10/09/2020 1
 Modeling process units
Reactors:
• Conversion of material from one form to
another depends on what form of energy is
supplied to the reactor.
• The most common form of energy is heat
required to carry out a reaction.
• A number of reactor models common used
in simulators: stoichiometric; equilibrium;
Gibbs; CSTR; PFR and kinetic reactors
• Modeling industrial reactors is among the
most difficult steps in process simulation.
• A model is constructed to give reasonable
prediction of main product yield, outlet
composition, energy requirements, rate of
catalyst de-activation, and other design
parameters.
• Sometimes simulator models may not fully
capture all details of mass transfer, catalyst
and enzyme inhibition, etc., that often affect
design parameters.
 Modeling Conversion (Stoichiometric)
Reactor
• This reactor model requires reaction
stoichiometry and extent of reaction or
conversion of a limiting reactant to be
specified as input data.
• No reaction kinetics information is required.
• This model is important in the early stages
of process design where kinetics is not
known or when the degree of completion of
reaction is 100%.
• The reactor can handle multiple
reactions.
• The order in which equations are solved
is important if same limiting reactant is
used.
 Example-1
•  Toluene can be produced from n-heptane
by dehydrogenation over a Cr2O3 catalyst in
the reaction:

• The production process is started by heating

the n-heptane from 65°F to 800°F in a
heater.
• It is then fed to a catalytic reactor operating
isothermally.
• The reactor converts 15mol % of n-heptane
to toluene.
• The effluent from reactor is cooled to 65°F
and fed to a flash separator.
• Assuming all units operate at atmospheric
pressure:
(i) Identify the unit operations
(ii) Draw a PFD
(iii)Simulate the model to determine the
species flow-rates in every stream
Solution in UniSim Design
 Exercise-1
• If the Haber process is started by heating the n-
heptane from 60°F to 900°F in a heater.
• The reactor conversion is 25 mol% of n-heptane
to toluene and the effluent from reactor is cooled
to 60°F and fed to a flash separator. Assuming all
units operate at atmospheric pressure:
(i) Identify the unit operations
(ii) Draw a PFD
(iii) Simulate the model to determine the species
flow-rates in every stream
 Equilibrium Reactor Model
• This model determines equilibrium product
distribution and phase equilibrium for a
specified set of stoichiometric reactions.
• The outlet temperature and pressure are
required as input data and the model
calculates the duty needed to reach that
condition.
• Alternatively, the heat duty is entered and
the model predicts outlet conditions of
temperature and pressure using energy
balance equations.
• An equilibrium reactor model solves only
specified equations.
• Consequently, it is useful in circumstances
where one or more reactions attain
equilibrium rapidly while other reactions
proceed much more slowly.
• In some simulators equilibrium reactor
requires both liquid and vapor phase
products even though one stream may be
calculated to have zero flow.
 Example-2
• Ammonia is produced in the Haber process
in an equilibrium reaction.
• A mixture of gases consisting of the
following composition (mole fraction) is
heated to 300°C and 80 atm.
• It is then fed to a reactor and allowed to
equilibrate.
Component Mole fraction
Nitrogen 0.200
Hydrogen 0.778
Ammonia 0.010
Carbon monoxide 0.001
Carbon dioxide 0.001
Methane 0.010
Total 1.000
• Determine the equilibrium composition of
ammonia when the reactor temperature is:
300°C, 250°C, 200°C, 150°C, 100°C and 50°C.
• What would be the optimum temperature
assuming the process takes place at
constant pressure.
Solution in Unisim Design
 Exercise-2
• In the above example of the Haber process,
if the mixture of gases is heated to 400°C
and 85 atm, fed to a reactor and allowed to
equilibrate.
• Determine the equilibrium composition of
ammonia when the reactor temperature is:
400°C, 450°C, 500°C, 550°C, 600°C and
650°C.
• What would be the optimum temperature
assuming the process takes place at
constant pressure.
 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.
Separators
• Rarely do the reaction products have good
purity. Consequently, separators become
necessary process units for separation of
unwanted material.
• Conversion and separation constitute the
heart of chemical engineering.
• Separation is of two forms: component and
phase separation.
• In component separation, the
components in a single phase are
separated, usually by the introduction of
a second phase, and separation is based
on the difference in chemical potentials
in the two phases.
• Consequently, component separation
occurs by mass transfer.
• In phase separation amount of force acting
on one phase differs from that acting on
the other phase, usually gravitational force,
e.g., sedimentation and clarification.
• Generally, phase separation comes after
component separation, e.g., in distillation
the vapor/liquid phases mix on a tray
(component separation), then the vapor
rises and liquid descends (phase
separation).
Mixers
• The reverse of component and phase
separation is mixing.
• The mixing process requires energy, e.g., in
liquid-liquid extraction, one of the liquid
phases must be dispersed into small droplets
by mixing in order to enhance mass transfer
and increase the rate of component
separation.
• Consequently, extractors must contain a
method for dispersing one of the phases.
 Examples: Mixer & Separator

• In this simulation you will use UniSim

Design version R460-1 to study three unit
operations: mixer; heater & separator (flash
distillation). You will create a binary mixture
of ethanol and acetone using the mixer.
• The binary mixture will then be heated and
products separated using a flash distillation
unit.
• The purpose of the simulation is to study
the behavior of the stated mixture at
different physical states and using different
fluid packages.
Problem
• Ethanol is mixed with acetone at 25°C
temperature and pressure of 95 kPa.
• The feed stream flows to the mixture are
41.86 kmol/h ethanol and 38.64 kmol/h
acetone.
• The product from the mixer is then heated to
65°C and flashed into a separator which
separates the heated mixture components
basing on density differences.
• The lighter components (vapor) are the
overhead product and the heavier (liquid) to
the bottom products.
– Sketch a block flow diagram
– Determine the composition and mole flow
rates of the product streams from the
separator, use UNIQUAC fluid package
 Practice exercise-3
• Repeat the procedure with new
components: water + ethanol
• Adjust the temperature difference in the
range 40⁰C ± 5⁰C and observe changes in
composition and flow rates
• Determine the composition and mole flow
rates at the different temperatures and
different fluid Packages of:
– Non-random two-liquid model: NRTL
–Wilson
Material and Energy Transfer Operations
• Material is transferred from one process
unit to another by compression, pumping or
conveying; depending on the phase.
• These operations also require energy to
overcome frictional losses.
• Additionally, energy input is also required to
attain favorable operating conditions of
temperature and pressure.
• For example, a mixture of gases may be
compressed to achieve a reasonable conversion.
• This work done is recovered by expanding the
reacted gases in a turbine/expander when the
system pressure is eventually reduced
downstream of the reactor.
• Compression and expansion of a gas are energy
transfer operations. Compression is size
agglomeration while expansion is size reduction.
• Furthermore, gases can be transferred from
process unit to another after compression.
• This is a material transfer operation and
requires energy to overcome frictional
losses.
• Here, both the material and energy transfer
operations are combined and only one
compressor is used.
• Also, if conversion not 100% complete, a
recycle compressor transfers unreacted
gases back to the reactor after product
separation.
• Since the recycled gases are at a high
pressure, but lower than at the reactor inlet
due to frictional pressure losses, a
compressor is required to re-compress the
gases, raising pressure to the reactor inlet
pressure.
• The three process of size reduction,
agglomeration, and size separation also
common in solids handling, e.g.,
compression of powders to form tablets
(agglomeration) and screening to sort
oversized particles (size separation).
Storage
• The raw material source and delivery may
be unpredictable because of unforeseen
events such as bad weather, low supply
(shortages), etc., storage of raw materials is
a necessity.
• Similarly, the demand for products can be
unpredictable.
• Consequently, storage of materials is
necessary to maintain stable operations
 Flow sheeting exercise-1
• The catalytic dehydrogenation of propane is
carried out in a continuous packed-bed
reactor. 2000 kg/h of pure propane is
preheated to a temperature of 670ᵒC before
it passes into the reactor.
• The reactor effluent gas which includes
propane, propylene, methane, and
hydrogen is cooled from 800ᵒC to 110ᵒC and
fed to an absorber tower, where the
propane and propylene are dissolved in oil.
• The oil then goes to a stripping tower
where it is heated, releasing the dissolved
gases.
• These gases are recompressed and sent to
a distillation column in which the propane
and propylene are separated.
• The propane stream is recycled back to
join the feed to the reactor pre-heater.
• The product stream from distillation
column contains 98% propylene and
recycle stream contains 97% propane.
• The stripped oil is recycles to the absorber
tower.
– Identify the equipments
– Sketch a block diagram for the process
– Generate a PFD in UniSim Design for
the process
 Practice exercise-2
• Preliminary design work has been done on a
process to recover a valuable product,
namely ammonia, from an effluent gas
stream.
• The effluent gas will be scrubbed with a
solvent, namely water, in a packed bed
column.
• The recovered product ammonia and
solvent (water) will be separated by
distillation; and the solvent cooled and
recycled.
– Identify the process units
– Sketch a block diagram for the process
– Generate a PFD for the process in UniSim
Design