Lecture 08 - Heuristics For Process Synthesis (Part 3)

10/9/2018
Department of Chemical Engineering

College of Engineering
University of the Philippines Diliman
First Semester, AY 2018-2019
ChE 141: Chemical Process

Development and Plant Economics
LECTURE 08
Heuristics for Process
Synthesis (Part 3)
kcdeguzman/2014
Introduction
Once the input-output structure of the process
has been decided, the reactor structure of the
process can then be developed.
The objective at this stage is to determine the

most economical option among technically
feasible reaction conditions:
• Reactor model (Batch/CSTR/PFR?)

• Feed concentrations (Excess/Limiting reactant?)
• Temperature (High/Low? Adiabatic/Isothermal?)
• Pressure (High/Low?)
• Conversion
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Reaction Data
Data on reaction thermodynamics and kinetics
must be available before proceeding to this stage
of process synthesis and development.
Example: Consider the formaldehyde production via partial

oxidation of methanol. Reaction kinetic data are as follows
(rates in mol/kg-s, temperatures in K, pressures in atm).
CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
kcdeguzman/2014
Reaction Data
Data on reaction thermodynamics and kinetics
must be available before proceeding to this
stage of process synthesis and development.
Example: Consider the formaldehyde production via partial

oxidation of methanol. ∆H, ∆S, and ∆G of the main and side
reactions were calculated at different temperatures.
(Main) CH3OH + ½O2 → HCHO + H2O

(Side) HCHO + ½O2 → CO + H2O
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Reaction Data
Heat of main and side reactions as a

function of temperature. The side reaction is
more exothermic than the main reaction.
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Reaction Data
Logarithm of equilibrium constant of main and

side reactions as a function of temperature. Both
reactions can be treated as irreversible.
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Choice of Reactor Model
Batch Reactor
The reactants are charged at the beginning of
the operation. The contents are subjected to
perfect mixing for a certain period, after which
the products are discharged.
kcdeguzman/2014
Continuously-Stirred Tank Reactor

The raw materials are continuously fed and
the products are continuously withdrawn
from a perfectly stirred tank.
Maintains the reactant concentration and

the average reaction rate at a low value.
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Plug-Flow Reactor
The raw materials are continuously fed and the
products are continuously withdrawn from opposite
ends of a pipe. The concentrations vary along the
length of the pipe.
Reactant concentration is initially high. Maintains

the average reaction rate at a high value.
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Real Reactors
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Real Reactors
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Real Reactors
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When dealing with a single reaction, the
goal is usually to minimize reactor capital
cost by minimizing reactor volume for a
given conversion.
Example: What reactor model is the better choice for

the following irreversible reaction, CSTR or PFR?
A→B r = kCAa
kcdeguzman/2014

When dealing with a single reaction, the
goal is usually to minimize reactor capital
cost by minimizing reactor volume for a
given conversion.
Example: What reactor model is the better choice for

the following irreversible reaction, CSTR or PFR?
A→B r = kCAa
Answer: PFR. Highest reaction rate is achieved at

highest feed concentration. On a CSTR, feed is
immediately diluted with the vessel contents, resulting
in a reduced reaction rate.
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When dealing with multiple reactions, the goal is
usually to maximize selectivity by minimizing by-
product formation for a given conversion.
Example: What reactor model is the better choice for the

following set of reactions, CSTR or PFR?
A → B (desired) r1 = k1CAa1
A → C (undesired) r2 = k2CAa2
kcdeguzman/2014

Example: What reactor model is the better choice for the

following set of reactions, CSTR or PFR?
Answer: Selectivity can be expressed as follows:

r1 / r2 = (k1 / k2) CAa1 – a2
PFR if a1 is greater than a2. CSTR if a1 is less than a2.
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Example: What reactor model is the better choice
for the formaldehyde production via partial
oxidation of methanol, CSTR or PFR?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
kcdeguzman/2014
Feed Concentrations
Single Irreversible Reactions
When dealing with a single irreversible
reaction, the goal is usually to minimize
reactor capital cost by minimizing reactor
volume for a given conversion.
An excess of one feed component can

force another component towards
complete conversion.
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Feed Concentrations
Single Irreversible Reactions
The usual choice of excess reactant is to
eliminate the component that is more
difficult to separate in the downstream
system. Economics and safety are also
considered (i.e., if the limiting reactant is
expensive and/or hazardous).
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Feed Concentrations
Single Reversible Reactions
An excess of one feed can be used to shift
the equilibrium towards the forward
reaction, at the expense of higher capital
due to higher equipment capacities.
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Feed Concentrations
Multiple Reactions
Example: For the following set of reactions, what feed

component should be put in excess, A or B?
A + B → C (desired) r1 = k1CAa1CBb1
A + B → D (undesired) r2 = k2CAa2CBb2
kcdeguzman/2014
Feed Concentrations
Multiple Reactions
Example: For the following set of reactions, what feed

component should be put in excess, A or B?
A + B → C (desired) r1 = k1CAa1CBb1
A + B → D (undesired) r2 = k2CAa2CBb2

r1 / r2 = (k1 / k2) CAa1 – a2 CBb1 – b2
Excess A if (a1 – a2) is greater than (b1 – b2).
Excess B if (a1 – a2) is less than (b1 – b2).
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Feed Concentrations
Process Heuristics
1. Higher concentrations in feed will lead to
higher reaction rates, which may be
dangerous for highly exothermic reactions.
An excess of the other feed or the addition of
an inert material reduces this possibility.
2. For feeds with impurities/inerts, eliminate

the inert species before reaction to if
separation is easily accomplished or when
the a catalyst is adversely affected by the
inert. For highly exothermic reactions,
reconsider.
kcdeguzman/2014
Feed Concentrations
Process Heuristics
3. Provide purge streams as exits for feed
impurities or for those formed as products of
irreversible side reactions ONLY when these
species are in trace quantities or will require
difficult separation. Lighter species leave in
vapor purge streams, and heavier specie exit
in liquid purge streams.
4. Do not purge valuable/toxic/hazardous

species, even in small concentrations. Add
separators to recover valuable species. Add
reactors to eliminate hazardous ones.
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Feed Concentrations
Process Heuristics
5. By-products produced in reversible reactions
and in small quantities are usually just
recycled to extinction.
6. Inert species reduce the rate of reaction, and

can be used to control and improve the
selectivity of the reaction.
7. Inert diluents allow operation outside the

flammability envelope.
kcdeguzman/2014
Feed Concentrations
Example: What should be the limiting and excess
reactants for the formaldehyde production via
partial oxidation of methanol, methanol or
oxygen?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
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Reaction Temperature
Example: What temperature is the better choice for the
following irreversible reaction, high or low?
A→B r = kCAa
kcdeguzman/2014
following irreversible reaction, high or low?
A→B r = kCAa
Answer: Operate at high temperatures, regardless of

whether the reaction is exothermic or endothermic.
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When dealing with multiple irreversible
reactions, the goal is usually to maximize
selectivity by minimizing by-product formation
for a given conversion.

following set of irreversible reactions, high or low?
kcdeguzman/2014
When dealing with multiple irreversible
reactions, the goal is usually to maximize
selectivity by minimizing by-product formation
for a given conversion.

following set of irreversible reactions, high or low?

r1 / r2 = (k1 / k2) CAa1 – a2
Operate at high temperatures if k1 increases faster than k2.
Operate at low temperatures if k2 increases faster than k1.
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For reversible reactions, consider the heat of
reaction in choosing the reaction temperature
(Le Chatelier’s principle).
Feed ↔ Product + Heat

Operate exothermic reversible
reactions at low temperatures.
Feed + Heat ↔ Product

Operate endothermic reversible
reactions at high temperatures.
kcdeguzman/2014
Process Heuristics
1. If heat of reaction is small, a small change of
temperature across the reactor may be
acceptable and heating/cooling can be
avoided. Operate in adiabatic mode.
2. Adding an inert diluent to control the reaction

temperature can enable adiabatic operation.
3. Staged addition of hot/cold feed can additional

heat/quench to an endothermic/exothermic
reaction operated in adiabatic mode.
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Feed Concentrations
Process Heuristics
4. Operating at very high temperatures will lead
to higher reactor cost. Operating conditions
above 400°C must be justified and must have
proper selection for materials of
construction.
kcdeguzman/2014
Feed Concentrations
Process Heuristics
5. The objective in heating or cooling reactor
contents is to achieve uniform temperature
throughout the unit and eliminate hot/cold
spots.
• Indirect heat transfer
• Direct heat transfer
• Interstage heating/cooling
• Heat-exchange devices as reactors
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Example: What temperature is the better choice
oxidation of methanol, high or low?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
kcdeguzman/2014
Example: Should formaldehyde production via
partial oxidation of methanol be performed in
an adiabatic reactor or an isothermal reactor?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
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Reaction Pressure
Reactor pressure can shift the equilibrium of
gas-phase reversible reactions based on the
change on the number of moles (∆N).
Any change in pressure will lead to the system

counteracting this change. An increase in P
will favor the reaction side with the fewer
number of moles.
The effects of pressure is less pronounced for

liquid-phase reactions. In this case, the
pressure is selected mainly to prevent
vaporization of the products.
kcdeguzman/2014
Reaction Pressure
Example: What pressure is the better choice for
the formaldehyde production via partial oxidation
of methanol, high or low?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
kcdeguzman/2014
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Example: What reactor model is the better choice
oxidation of methanol, CSTR or PFR?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
Answer: PFR. At the inlet of the PFR, the main reaction rate is
heavily promoted by high methanol partial pressure and the
side reaction rate is heavily inhibited by low formaldehyde
partial pressure.
kcdeguzman/2014
Feed Concentrations
Example: What should be the limiting reactant for
of methanol, methanol or oxygen?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
Answer: Methanol. The absence of oxygen in the rate equations

signify that it is supplied in a large excess (partial pressure of
oxygen is almost constant). The amount of excess oxygen is
determined with due consideration on economics and safety
(flammability limits).
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Example: What temperature is the better choice
oxidation of methanol, high or low?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
Answer: Operate at low temperatures since k2 increases faster

than k1 with temperature (i.e., activation energy of side reaction
is larger than that of main reaction).
kcdeguzman/2014
Example: Should formaldehyde production via
partial oxidation of methanol be performed in
an adiabatic reactor or an isothermal reactor?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
Answer: Isothermal. If the reactor were operated adiabatically,

the temperature will increase due to heat generation as the
reactions proceed. The side reaction is promoted at high
temperatures.
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Reaction Pressure
Example: What pressure is the better choice for
of methanol, high or low?

-r1 = k1P0.75yM0.75/(1 + yM0.5)0.5 -r2 = k2PyF
k1 = 292 exp(–36,786/T) k2 = 3,000 exp(–66,413/T)
Answer: Operate at low pressure since the selectivity (r1/r2) is

inversely proportional to P0.25.
kcdeguzman/2014
Establishing Reactor Conditions

Consider the formaldehyde production via
partial oxidation of methanol. So far, the
following have been established:
• Reactor model PFR (Isothermal)

• Feed concentrations Air in excess
• Temperature Low
• Pressure Low
• Conversion (To be decided)
What combination of feed concentrations,

temperature, pressure, and conversion will be
an optimum?
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1. Select a design objective:
1. Maximum yield/selectivity/conversion
2. Minimum waste generation
3. Most economic reactor conditions
2. Choose a maximum of 6 design parameters

that will affect your design objective.
3. Perform case studies on the effect of these

design parameters.
4. Select the two (2) parameters in which the

design objective is most sensitive to.
5. Determine the optimum values of the two

kcdeguzman/2014
parameters.

Preliminary mass and energy balances,
equipment sizing, and cost estimation will be
performed in order to determine the most
economical reactor conditions.
Hence, a preliminary process flow diagram

from feed storage to reactor must also be
ready before proceeding to this stage of
process synthesis and development. The
recycle of unreacted reactants must be
included.
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Establish the limits first prior the start of
determination of most economical reactor
conditions:
Excess Air
Min The air flowrate that will yield a methanol-air
mixture at LEL. Below this minimum flowrate, the
gas mixture becomes explosive.
Max The air flowrate that can be handled by the largest

commercially available air blower or compressor.
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conditions:
Temperature
Min 234°C
Below this temperature, HP steam can be used as
heating medium instead of fuel gas. The use of a
shell-and-tube heat exchanger instead of a furnace
will change the entire calculation and will not be
explored due to time constraints.
Max 400°C
The thermal stability of Dowtherm A, the heat
transfer fluid circulated to maintain the reactor
temperature, is only up to 400°C.
kcdeguzman/2014

conditions:
Pressure
Min 0 kPag
Lowest possible pressure inside reactor.
Max 2,300 kPag

Strength of materials decreases at increasing
temperatures. For type 304 stainless steel,
maximum pressures are ~3,800 kPag at 65 and
~2,300 kPag at 430°C.
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conditions:
Conversion
Since the range of residence time cannot be defined,
establish the limits on conversion instead.
Min The conversion which will require the largest

commercially available pump.
Max ~98%
The formalin solution can have at most 1 wt%
unreacted methanol based on the product
specifications. At this conversion, methanol recycle
rate is zero.
kcdeguzman/2014

Four reactor conditions need to be optimized.
Limit the optimization study to one to two
variables due to time constraints:
• Reactor model PFR (Isothermal)

• Feed concentrations Feed at LEL (min)
• Temperature (To be decided)
• Pressure 0 kPag (min)
• Conversion (To be decided)
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Steps in selecting the economically optimum
reactor conditions:
1. Select temperature and conversion. Complete the HMB
based on these two information.
2. Perform preliminary equipment sizing.
3. Estimate the capital costs of equipment and annual

costs of raw materials, products, and utilities. Then
determine the annualized operating costs (assuming an
interest rate of 15% and a service life of 15 years).
4. Select the reactor conditions with the lowest annualized

operating cost.
kcdeguzman/2014
Annual profit at different temperatures and

conversions. Highest annual profit (15.38
million dollars) is achieved at 400°C and 88%.
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10/9/2018

Department of Chemical Engineering

ChE 141: Chemical Process

The objective at this stage is to determine the

• Reactor model (Batch/CSTR/PFR?)

Example: Consider the formaldehyde production via partial

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

Example: Consider the formaldehyde production via partial

(Main) CH3OH + ½O2 → HCHO + H2O

Heat of main and side reactions as a

Logarithm of equilibrium constant of main and

Choice of Reactor Model

Choice of Reactor Model

Continuously-Stirred Tank Reactor

Maintains the reactant concentration and

Choice of Reactor Model

Reactant concentration is initially high. Maintains

Choice of Reactor Model

Example: What reactor model is the better choice for

Choice of Reactor Model

Example: What reactor model is the better choice for

Answer: PFR. Highest reaction rate is achieved at

Choice of Reactor Model

Example: What reactor model is the better choice for the

Choice of Reactor Model

Example: What reactor model is the better choice for the

Answer: Selectivity can be expressed as follows:

Choice of Reactor Model

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

An excess of one feed component can

Example: For the following set of reactions, what feed

Example: For the following set of reactions, what feed

Answer: Selectivity can be expressed as follows:

2. For feeds with impurities/inerts, eliminate

4. Do not purge valuable/toxic/hazardous

6. Inert species reduce the rate of reaction, and

7. Inert diluents allow operation outside the

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

Answer: Operate at high temperatures, regardless of

Example: What temperature is the better choice for the

Example: What temperature is the better choice for the

Answer: Selectivity can be expressed as follows:

Feed ↔ Product + Heat

Feed + Heat ↔ Product

2. Adding an inert diluent to control the reaction

3. Staged addition of hot/cold feed can additional

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

Any change in pressure will lead to the system

The effects of pressure is less pronounced for

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

Choice of Reactor Model

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

Answer: Methanol. The absence of oxygen in the rate equations

CH3OH + ½O2 → HCHO + H2O HCHO + ½O2 → CO + H2O

Answer: Operate at low temperatures since k2 increases faster