EP426

Chemical Process Design and Optimization

Chapter 2 - Synthesis of process flow diagram
Jan – Apr 2017
Student attainment
CLO2: Propose a chemical process flow diagram using
the hierarchy of process design.
C5 – Identify component concept and use component skill
to solve a problem.
A3 – Proposed a plan for improvement.

PLO3 -Design/Development of Solutions.

Design solutions for flowsheet diagram, which the components or
processes that meet specified needs with appropriate consideration for
public health and safety, cultural, societal, and environmental
considerations

Note:
Teaching method - Lecture & Group Project
Assessment - Test, Final Exam and report presentation.
 Chapter 2
Synthesis of process flow
diagram (PFD)

Steps in Designing
Rule of thumb for Examples &
Chemical
process synthesis Group Exercise
Processes
Class revision
List 3 Design Approaches for Safety consideration
(3 marks)
Design Approaches for Safety
1. Techniques to Prevent Fires and Explosions
• Inerting - addition of inert dilutant to reduce the fuel
concentration below the LFL
• Installation of grounding devices and anti-static devices to avoid
the buildup of static electricity
• Use of explosion proof equipment
• Ensure ventilation - install sprinkler systems
2. Relief Devices
3. Hazard Identification and Risk Assessment
• the plant is carefully scrutinized to identify all sources of accidents
or hazards.
• Hazard and Operability (HAZOP) study is carried out, in which all
of the possible paths to an accident are identified.
• when sufficient probability data are available, a fault tree is
created and the probability of the occurrence for each potential
accident computed.
 EP426
Chemical Process Design and Optimization
Chapter 2a – Synthesis of process flow diagram (PFD).
Rule of thumb for process synthesis.
(Process Design Heuristics)
What You should Know?
1. Understand the importance of selecting reaction paths
2. Be able to distribute the chemicals in a process
flowsheet
3. Be able to apply heuristics.
4. Be able to remove the exothermic heats of reaction.
5. Understand the advantages of pumping a liquid rather
than compressing a vapor.
 Introduction
 The heuristic rules is to expedite the selection and
positioning of processing operations as flow-sheets
are assembled.

 These rules are based on experience and hold in

general.

Note: However, it should be tested to ensure that

they apply in the specific application.
Raw Materials and Chemical Reactions
Heuristic 1: Avoid, or reduce, the handling and storage of
hazardous and toxic chemicals.

Example: Manufacture of Ethylene Glycol (EG).

O
1
C2H 4 + -2 O 2  CH 2 - CH 2 (R.1)
O OH OH

CH2 - CH2 + H2O  CH2 - CH2 (R.2)

Since both reactions are highly exothermic, they need to be
controlled carefully. But a water spill into an ethylene-oxide storage
tank could lead to an accident similar to the Bhopal incident.

Often such processes are designed with two reaction steps, with
storage of the intermediate, to enable continuous production.
Alternatives to the two-step EG
process
Use chlorine and caustic in a single reaction step, to avoid the
intermediate:
OH OH
CH2=CH2 + Cl2 + 2NaOH(aq)  CH2CH2 + 2NaCl (R.3)

 As ethylene-oxide is formed, react it with carbon dioxide

to form ethylene-carbonate, a much less active
intermediate that can be stored safely and hydrolyzed,
to form the ethylene-glycol product, as needed:
O
O C
CH2 - CH2 + CO2  O O (R.4)
CH2 CH2
Distribution of Chemicals
Heuristic 2: Use an excess of one chemical reactant in a reaction
operation to completely consume chemical reactant.

Example: Consider using excess ethylene in DCE production

Distribution of Chemicals (Cont’d)
Heuristic 3: When nearly pure products are required,
eliminate inert species before the reaction
operations.
Note:
 Do not do this when a large exothermic heat of reaction
must be removed.
 Do when the separations are easily accomplished,
 Do when the catalyst is adversely affected by the inert

Example:
Distribution of Chemicals (Cont’d)
Need to decide whether to
remove inerts before reaction...

… or after reaction...

Clearly, the ease and cost of the separations must be assessed. This can be
accomplished by examining the physical properties upon which the
separations are based, and implies the use of simulation
Distribution of Chemicals (Cont’d)
Heuristic 4: Introduce liquid or vapor purge streams to provide
exits for species.
The species such as
– impurities in the feed
– produced by irreversible side-reactions
Note: when these species are in trace quantities and/or are
difficult to separate from the other chemicals.

Example: NH3 Synthesis Loop.

What are the

configuration?

Purge flow rate selection depends on economics!

Distribution of Chemicals (Cont’d)
Heuristic 5: Do not purge valuable species or species that
are toxic and hazardous, even in small
concentrations.
• Add separators to recover valuable species.
• Add reactors to eliminate toxic and hazardous species.

Example: Catalytic converter in car exhaust system.

Distribution of Chemicals (Cont’d)
Heuristic 6: Recycled to extinction.
By-products that are produced in reversible
reactions, in small quantities, are usually not
recovered in separators or purged but it being
recycled back to the process until its fully converted.

However, for irreversible reactions,

small quantities of by-products must be
purged, otherwise they will buildup.
Distribution of Chemicals (Cont’d)
Heuristic 7: For competing series or parallel reactions,
adjust the temperature, pressure, and catalyst
to obtain high yields of the desired products.
In the initial distribution of chemicals, assume that
these conditions can be satisfied
- obtain kinetics data and check this assumption
before developing a base-case design.

Example: Manufacture of allyl-chloride.

Allyl Chloride Manufacture (Cont’d)
Example: Manufacture of allyl-chloride.

Kinetic data
HR ko
Reaction 3 2
E/R (oR)
Btu/lbmole lbmole/(hr ft atm )
1 -4,800 206,000 13,600
2 -79,200 11.7 3,430
3 -91,800 4.6 x 108 21,300
Exercise
The operating limit for the following reaction is within 50 oC to
250 oC. 𝑘 𝑘
1 3
𝐴+𝐵 →𝐶+𝐴→𝐸
𝑘2
𝐷+𝐴 𝑘4

The pre-exponential factor and activation energy for the

reaction are tabulated as follows:
Reaction 𝐤 𝟎 (𝐦𝟔 /𝐤𝐦𝐨𝐥𝟐 . 𝐬) 𝐄 (𝐤𝐉/𝐤𝐦𝐨𝐥)
1 1.01 × 105 54500
2 3.6 × 107 63100
3 0.1 × 104 51654
4 1.1 × 106 70400

Q. Select the operating temperature that favours the

production of C. Discuss your finding.
Distribution of Chemicals (Cont’d)
Heuristic 8: For reversible reactions, consider conducting the
reaction in a separation device capable of removing
the products. Hence, driving the reactions to the right.
Such reaction-separation operations lead to very
different distributions of chemicals.

Example: Manufacture of Ethyl-acetate using reactive

distillation.
Conventionally, this would call for reaction:
MeOH + HOAc 
 MeOAc + H2O,
followed by separation of products using a sequence
of separation towers.
MeOAc Manufacture using Reactive
Distillation
MeOAc

HOAc
Reaction
zone
MeOH

H2O

MeOH + HOAc  MeOAc + H2O
Separations
Heuristic 9: Separate liquid mixtures using distillation and
stripping towers, and liquid-liquid extractors, among
similar operations.

Ref: Douglas (1988)

Select from distillation,

enhanced distillation,
stripping towers, liquid-
liquid extraction, etc.
Separations (Cont’d)
Heuristic 10: Attempt to condense vapor mixtures with
cooling water. Then, use Heuristic 9.
Ref: Douglas (1988) Select from partial
condensation, cryogenic
distillation, absorption,
adsorption, membrane
separation, etc.

Select from distillation,

enhanced distillation,
stripping towers, liquid-
liquid extraction, etc.

Attempt to cool
reactor products
using cooling water
Separations (Cont’d)
Heuristic 11: Separate vapor mixtures using partial
condensers, cryogenic distillation, absorption
towers, adsorbers, and/or membrane devices.

Ref: Douglas (1988)

Heat Transfer in Reactors

Although heat transfer in reactors is better

discussed in the context of heat and power
integration (Chapter 5),

Heat transfer in reactors affect the

distribution of chemicals.
Heat Transfer in Reactors (Cont’d)
Heuristic 12: Treat exothermic reactors first.
To remove a highly-exothermic heat of reaction, consider
the use of…

excess reactant

an inert diluent

cold shots.
Heat Transfer in Reactors (Cont’d)
Heuristic 13: For less exothermic heats of reaction,
circulate reactor fluid to an external cooler,
or use a jacketed vessel or cooling coils. Also,
consider the use of intercoolers.
Heat Transfer in Reactors (Cont’d)
Example: TVA design for NH3 synthesis converters

• Feed gases pass up the

reactor through tubes.

• The reaction take place

at the catalyst chamber.
Heat Transfer in Reactors (Cont’d)
Endothermic reactors are treated similarly:

Heuristic 14: To control temperature for a highly-endothermic heat

of reaction, consider the use of excess reactant an
inert diluent, and hot shots. These affect the
distribution of chemicals and should be inserted early
in process synthesis.

Heuristic 15: For less endothermic heats of reaction,

circulate reactor fluid to an external heater,
or use a jacketed vessel or heating coils. Also,
consider the use of interheaters.
Pumping and Compression
Heuristic 16: To increase the pressure of a stream, pump a liquid
rather than compress a gas;
that is, condense a vapor, as long as refrigeration (and
compression) is not needed, before pumping.

Since work done by pumping or compressions is given by:

  P2V dP
W  P1
It follows that it is more
efficient to pump a liquid than
to compress a gas. Thus, it is
almost always preferable to
condense a vapor, pump it, and
vaporize it, rather than
compress it.
Exception: if condensation requires
refrigeration.
 H1 - avoid or reduce
H12 –Treat H13 – usage of hazardous/toxic
heat from Intercooler chemical
Exo. reactor
1st
(↓ ∆Hexo)
Raw
H15 – Materials &
External Chemical H2 -
heater Heat Reactions excess
reactant
(↓ ∆Hendo) H3 - Remove
Transfer inert before
H8 - reaction
Reactive-
separator
(↔ 𝑟𝑥𝑛)
H14 - Use
excess
reactant/hot Distribution
shots (Endo. H4 - purge
reactor) of Chemical stream to
remove
HEURISTIC impurities

H7 - Adjust
T, P, or Cat
X%
H6 - Recycle H5 - Do not
purge
to extinction valuable
(small) species/toxic
Pumping & H9 –
Compression Distillation/
Stripping
(liquid)

H16 - Pump a liquid Separations

rather than
compress a gas H10 – Use
H11 –
• Partial condenser cooling water
Separate (vapour
• cryogenic distillation vapour condensation)
• absorption tower mixtures
• Adsorbers
• membrane
What You should?
• Understand the importance of selecting reaction paths that do not
involve toxic or hazardous chemicals, and when unavoidable, to
reduce their presence by shortening residence times in the process
units and avoiding their storage in large quantities.
• Be able to distribute the chemicals in a process flowsheet, to account
for the presence of inert species, to purge species that would
otherwise build up to unacceptable concentrations, to achieve a high
selectivity to the desired products.
• Be able to apply heuristics in selecting separation processes to
separate liquids, vapors, and vapor-liquid mixtures.
• Be able to distribute the chemicals, by using excess reactants, inert
diluents, and cold shots, to remove the exothermic heats of reaction.
• Understand the advantages of pumping a liquid rather than
compressing a vapor.
To be continued…
Chapter 2b - Synthesis of process flow diagram (PFD).
Steps in Designing Chemical Processes