ChE 405: Process Design I

Process Flowsheet Development

Dr. Syeda Sultana Razia

Professor
Department of Chemical Engineering, BUET

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 Key Learning Objectives

• Read and draw PFD

• Batch or continuous process

• Synthesize flowsheet for a new process

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 Process Block Diagram

• Simple form of flow diagram. Each block represents a

complete stage in the process or a single piece of
equipment

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 PBD

• Single piece of equipment

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 Process Flow Diagram

• PFD symbols
• Information to be included
• Layout
• Equipment identification
• Utilities
• Precision of data
• Basis of calculation
• Batch processes
• Flow sheet drafting

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PFD Typical Symbols

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PFD Typical Symbols

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PFD Typical Symbols

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 Information
• The amount of information shown on a flowsheet will depend
on the custom and practice of the particular design office.
• All process equipment, feed and product storage and
equipment used for transpiration of fluid and solids
• Indicate location of process control valve
• Stream composition, either
– the flow rate of each individual component, kg/h, which is
preferred or
– the stream composition as a weight fraction
• Stream Total stream flow rate, kg/h
• temperature, degrees Celsius preferred;
• Nominal operating pressure (the required operating
pressure);
• Stream enthalpy, kJ/h.
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Hand Drawn PFD

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Simplified nitric acid process

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Chemical Engineering Design
 PFD continues

• Layout:
– stream line: left to right and consecutive, all steam lines should
be numbered, different numbers for different sections, 100 for
feed preparation; 200 for reaction; 300 for separation, 400 for
purification
• Equipment identification:
– each equipment should have a name and a code number.
– Initial letter for the type of equimwnt folloed by digits, H-heat
exchanges, C- Columns, R-reactos
• Utilities: to avoid cluttering utilities lines and headers are
not shown in the PFD

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 PFD continues
• Basis of calculation:
– good practice to show basis of the calculation, i.e. operating
hours, yields, datum temperature for energy balance etc
• Batch processes:
– quantities required to produce one batch are shown in PFD
• Flow sheet drafting:
– most design company has their own drafting software with
standard symbols
– Final flowsheet usually prepared by professional draftsman
– Simulation programs has graphical interfaces that created the
drawings that resemble PFD, this should not be used as PFD

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Anatomy of a Chemical Manufacturing
Process
• Raw material storage • Purification
• Feed preparation • Product storage
• Reaction • Ancillary processes
• Product separation

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 Continuous and Batch Processes

• Continuous: 24 hours a day, 7 days a week with

downtime for maintenance, catalyst regeneration etc.

– Continuous process is economical for large scale production

• Batch processes: operate intermittently with some/all

process units shut down and startup frequently,
combination of batch reactor with continuous separation
– Batch processes are used for flexibility

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 Batch Processes: Advantages

• Allows multiple products in the same equipment

• Integrity of a batch is preserved, good for quality control

• Production rate is flexible

• Easier to clean and maintain sterile operation

• Easier to scale up

• Low capital for small scale production volumes

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 Batch Processes: Disadvantages

• Scale of production is limited

• Difficult to reach high production rate for achieving

economies

• Batch to batch quality varies

• Recycle and heat recovery are harder

• Asset utilization is lower

• More labor intensive

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 When to Chose Batch?

With high value small scale products

• Food products

• Pharmaceuticals products

• Personal care product

• Blended products with multiple grade

• Specialty chemicals

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 Conversion

• Conversion is a measure of the fraction of the reagent

that reacts. To optimize reactor design and minimize
byproduct formation, the conversion of a particular
reagent is often less than 100%.

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 Selectivity

• Selectivity is a measure of the efficiency of the reactor in

converting reagent to the desired product. It is the
fraction of the reacted material that was converted into
the desired product. If no byproducts are formed, then
the selectivity is 100%

• Selectivity is usually improved by operating the reactor at

low conversion

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 Yield

• Yield is a measure of the performance of a reactor or

plant.

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 Yield

• Plant yield is a measure of the overall performance of

the plant and includes all chemical and physical losses..

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 Use of Excess Reagent

• In industrial reactions the components are seldom fed to

the reactor in exact stoichiometric proportions. A reagent
may be supplied in excess to promote the desired
reaction; to maximize the use of an expensive reagent;
or to ensure complete reaction of a reagent, as in
combustion.

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 Recycles and Purges

• Processes in which a flow stream is returned (recycled)

to an earlier stage in the processing sequence are
common. If the conversion of a valuable reagent in a
reaction process is appreciably less than 100%, the un-
reacted material is usually separated and recycled.

• It is usually necessary to bleed off a portion of a recycle

stream to prevent the buildup of unwanted material.
Some portion of the stream must be purged to keep the
inert level within acceptable limits. A continuous purge
would normally be used. Under steady-state conditions:
– Loss of inert in the purge = Rate of feed of inerts into the system

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 Bypass
• A flow stream may be divided and some part diverted
(bypassed) around some units. This procedure is
often used to control stream composition or
temperature. Material balance calculations on
processes with bypass streams are similar to those
involving recycle, except that the stream is fed
forward instead of backward. This usually makes the
calculations easier than with recycle.

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 Selection, Modification, and Improvement of
Commercially--proven Processes
Commercially
Factors a design team should consider when developing a
flowsheet based on a commercially-proven technology
• Sources of Information on Manufacturing Processes
– Encyclopedia of Chemical Technology edited by Kirk & Othmer
(2001, 2003),
– Encyclopedia covering manufacturing processes is that edited by
McKetta (2001)
– Shreve’s book on the chemical process industries, now updated
by Austin and Basta (1998)
– The journal Hydrocarbon Processing publishes an annual review
of petrochemical processes

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 Factors Considered in Process
Selection
• Patents Patents can be a useful source of information,
– Patents can be downloaded for free from the web site of the U.S.
patent office, www.uspto.gov

• Consultants Engineers in industry often hire specialist

consulting firms to prepare analyses of commercial
technology.

• Vendors Technology suppliers and contractors make

design information available to a client in the hope of
securing a sale

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 Factors Considered in Process
Selection
• Freedom to Practice Freedom to practice is a legal
concept that arises from patent law. If a process,
catalyst, enzyme, genetically modified organism, or
chemical route is patented, it can only legally be used
under license from the patent holder.

• Safety and Environmental Performance All

commercially-practiced technologies should meet or
exceed the minimum legally acceptable safety
standards, but some older processes may no longer
have acceptable environmental performance

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 Factors Considered in Process
Selection
Government and International Restrictions

• It is fairly common for nationally owned companies in

developing countries to be required to maximize use of
indigenous technology, equipment, and parts, so as to
stimulate the development of local engineering industries
and reduce hard currency outflows.

• This may lead a company to develop its own version of

an older technology rather than working with a
technology vendor or major international company that
can supply the latest technology.

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 Factors Considered in Process
Selection
• Experience and Reliability

• If a process has been widely adopted and proven in

many locations by different operating companies then it
is likely to be easy to apply in a new plant.

• A technology that has only been built once or twice may

still experience “teething troubles” and be more difficult
to implement.

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 Modification and Improvement of
Established Processes
• Modifications to Improve Process Economics
• Improve reactor selectivity and process yield.
– Feedstock costs are usually more than 80% of the cost of
production,
– Improved yields usually require the development of more
selective catalysts, enzymes, or organisms, or a more effective
reactor design, a more efficient separation scheme or better
purification of a feed or recycle.

• Improve process energy efficiency. Energy costs can

be reduced by improving process energy efficiency.

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 Modification and Improvement of
Established Processes
• Improve process fixed costs by making the process
more continuous and less labor intensive, and by
increasing the plant attainment of batch processes

• Reduce capital investment.

– Design engineers look for pieces of equipment that can be
combined or eliminated to reduce capital cost.
– for example, the feed can be charged to a reactor, heated in the
reactor, reacted, cooled down, and the product crystallized
before pumping out the product as a slurry and repeating the
process

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 Modification and Improvement of
Established Processes
• Reduce working capital.
– Working capital can be reduced by decreasing inventories of raw
materials, work in progress, and consumables.
– Making a process more continuous or using fewer different
solvents in a process both lead to a reduction in working capital.

• Modifications to Improve Plant Safety :Plants can be

made more inherently safe

• Modifications to Improve Plant Reliability

• Modifications to Improve Environmental Impact

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Synthesis of Novel Flowsheets

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Procedure for Process Synthesis

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Use of Targets in Process Synthesis
• The cost of production is compared to a price target set
by the marketing organization at steps 1, 3, and 7
• The design team sets yield and selectivity targets for the
research team at step 2
• Hot and cold utility targets calculated by pinch analysis
are used for initial estimates of process energy
consumption
• The preliminary economic analysis sets targets for
capital cost and the components of cost of production
that the design team must confirm as they refine the
process structure and fill in the PFD

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Preliminary Economic Assessment

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PROCESS CREATION

Ref: Seider, Seader and Lewin (2009), Chapter 4

Process Creation
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 Schedule - Process Creation
• Preliminary Database Creation
– to assemble data to support the design.

• Experiments
– often necessary to supply missing database items or verify
crucial data.

• Preliminary Process Synthesis

– top
top--down approach.
– to generate a “synthesis tree” of design alternatives.
– illustrated by the synthesis of processes for the manufacture of
VCM.

• Development of Base-
Base-case Design
– focusing on the most promising alternative(s) from the synthesis
tree.

Process Creation
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 Preliminary Database Creation
• Thermophysical property data
– physical properties
– phase equilibria (VLE, LLE, VLLE data)
– Property prediction methods

• Environmental and safety data

– toxicity data
– flammability data

• Chemical Prices
– e.g. as published in the Chemical Marketing Reporter

• Experiments
– to check on crucial items above

Process Creation
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 Preliminary Process Synthesis
Synthesis of chemical processes involves:
 Selection of processing mode:
mode: continuous or batch
 Fixing the chemical state of raw materials, products, and by-
by-
products, noting the differences between them.
 Synthesis steps -
1. Chemical reaction
2. Separation of chemical mixtures
3. Phase separation
4. Change of temperature
5. Change of pressure
6. Change of phase
7. Mixing and splitting of streams or batches 8.
8. Operations on solids, such as size reduction and
enlargement

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Continuous or batch processing?

Continuous

Batch

Fed-batch

Batch-product removal

Process Creation
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 The Chemical State

• Decide on the raw material and product specifications ((states

states):
):
 Mass (flow rate)
 Composition (mole or mass fraction of each chemical species
having a unique molecular type)
 Phase (solid, liquid, or gas)
 Form (e.g., particle-
particle-size distribution and particle shape)
 Temperature
 Pressure

Process Creation
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 Synthesis Steps

Synthesis Step Process Operation

 Eliminate differences in Chemical reaction
molecular types
 Distribute chemicals by Mixing
matching sources and sinks
 Eliminate differences in Separation
composition
 Eliminate differences in Temperature, pressure and
temperature, pressure and phase change
phase
 Integrate tasks (combine
tasks into unit operations)
operations)

Process Creation
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 Process Creation

Example :

Vinyl Chloride Manufacture

Process Creation
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  Eliminate differences in molecular types
Chemicals participating in VC Manufacture:
Molecular Chemical Chemical
Chemical weight formula structure

Acetylene 26.04 C2H2 H- CC- H

Chlorine 70.91 Cl2 Cl-Cl

Cl Cl
| |
H-C-C-H
1,2-Dichloroethane 98.96 C2H4Cl2 | |
H H
H H
C=C
Ethylene 28.05 C2H4 H H

Hydrogen chloride 36.46 HCl H-Cl

H Cl
C=C
Vinyl chloride 62.50 C2H3Cl H H

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (1
(1)
 Direct chlorination of ethylene:
C2H4  Cl2  C2H3Cl  HCl (1)
Advantages:
– Attractive solution to the specific problem denoted as Alternative 2 in
analysis of primitive problem.
– Occurs spontaneously at a few hundred oC.
Disadvantages:
– Does not give a high yield of VC without simultaneously producing large
amounts of by-products such as dichloroethylene
– Half of the expensive chlorine is consumed to produce HCl by-product,
which may not be sold easily.

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (2
(2)
 Hydrochlorination of acetylene:

C2H2  HCl  C2H3Cl (2)

Advantages:
– This exothermic reaction is a potential solution for the specific problem
denoted as Alternative 3. It provides a good conversion (98%) of C2H2
VC in the presence of HgCl2 catalyst impregnated in activated carbon at
atmospheric pressure.
– These are fairly moderate reaction conditions, and hence, this reaction
deserves further study.
Disadvantages:
– Flammability limits of C2H2 (2.5 100%)

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (3)
 Thermal cracking of C2H4Cl2 from chlorination of C2H4:
C2H4  Cl2  C2H4Cl2 (3)
C2H4Cl2  C2H3Cl  HCl (4)
C2H4  Cl2  C2H3Cl  HCl (1)
Advantages:
– Conversion of ethylene to 1,2-dichloroethane in exothermic reaction (3.3) is
98% at 90 oC and 1 atm with a Friedel-Crafts catalyst such as FeCl3. This
intermediate is converted to vinyl chloride by thermal cracking according to
the endothermic reaction (3.4), which occurs spontaneously at 500 oC with
conversions as high as 65% (Alternative 2).
Disadvantage:
– Half of the expensive chlorine is consumed to produce HCl by-product,
which may not be sold easily.

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (4
(4)
 Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
C2H4  2HCl  21 O2  C2H4Cl2  H2O (5)
C2H4Cl2  C2H3Cl  HCl (4)
C2H4  HCl  21 O2  C2H3Cl  H2O (6)
Advantages:
– Highly exothermic reaction (5) achieves a 95% conversion to C2H4Cl2 in
the presence of CuCl2 catalyst, followed by pyrolysis step (4) as Reaction
Path 3.
– Excellent candidate when cost of HCl is low
– Solution for specific problem denoted as Alternative 3.
Disadvantages:
– Economics dependent on cost of HCl

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (5
(5)
 Balanced Process for Chlorination of Ethylene
Ethylene::
C2H4  Cl2  C2H4Cl2 (3)
C2H4  2HCl  21 O2  C2H4Cl2  H2O (5)
2C2H4Cl2  2C2H3Cl  2HCl (4)
2C2H4  Cl2  21O2  2C2H3Cl  H2O (3.7)
Advantages:
– Combination of Reaction Paths 3 and 4 - addresses Alternative 2.
– All Cl2 converted to VC
– No by-products!

Process Creation
Chemical Engineering Design
 Evaluation of Alternative Pathways

 Reaction Path  is eliminated due its low selectivity.

 This leaves four alternative paths, to be compared first in terms of
Gross Profit.
Chemical Bulk Prices
Chemical Cost (cents/lb)
Ethylene 18
Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0

Process Creation
Chemical Engineering Design
 Computing Gross Profit
Reaction path  C2 H4 + Cl2 = C2H3Cl + HCl
lb-mole 1 1 1 1
Molecular weight 28.05 70.91 62.50 36.46
lb 28.05 70.91 62.50 36.46
lb/lb of vinyl chloride 0.449 1.134 1 0.583
cents/lb 18 11 22 18

Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC

Reaction Gross Profit
Overall Reaction
Path (cents/lb of VC)
 C2H2 + HCl = C2H3Cl -9.33

 C2H4 +Cl2 = C2H3Cl + HCl 11.94

 C2H4 + HCl + O2 = C2H3Cl + H2O 3.42

 2C2H4 + Cl2 + O2 = 2C2H3Cl + H2O 7.68

Process Creation
Chemical Engineering Design
 Preliminary Flowsheet for Path 

Raw Materials Products

Process Flowsheet?
C2H4, Cl2 C2H3Cl, HCl

• 800 MM lb/year @ 330 days/y  100

100,,000 lb/hr VC

• On the basis of this principal sink

sink,, the HCl sink and reagent
sources can be computed (each flow is 1,600 lbmol lbmol/h)
/h)

Process Creation
Chemical Engineering Design
 Preliminary Flowsheet for Path 
Cl2 HCl
113,400 lb/hr 58,300 lb/hr
C2H4Cl2
Direct HCl
Pyrolysis
Chlorination
C2H3Cl
C2H4Cl2
C2H3Cl
C2H4 C2H4 + Cl2 C2H4Cl2 C2H4Cl2  C2H3Cl + HCl
100,000 lb/hr
44,900 lb/hr

• 800 MM lb/year @ 330 days/y  100

100,,000 lb/hr VC

• On the basis of this principal sink

sink,, the HCl sink and reagent
sources can be computed (each flow is 1,600 lbmol lbmol/h)
/h)

Process Creation
Chemical Engineering Design
  Distribute the chemicals
• A conversion of 100
100%
% of the C2H4 is assumed in the chlorination
reaction.

Process Creation
Chemical Engineering Design
  Distribute the chemicals
• Only 60%
60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct
of HCl, according to Eqn.
Eqn. (3.4).

• To satisfy the overall material balance, 158

158,,300 lb/h of C2H4Cl
must produce 100,
100,000 lb/h of C2H3Cl and 58,
58,300 lb/h of HCl.
HCl.

• But a 60
60%
% conversion only produces 60,
60,000 lb/h of VC
VC..

• The additional C2H4Cl2 needed is computed by mass balance to

equal::
equal
[(1
[( 1 - 0.6)/
)/0
0.6] x 158,
158,300 or 105,
105,500 lb/h.
lb/h.

• Its source is a recycle stream from the separation of C2H3Cl from

unreacted C2H4Cl2, from a mixing operation, inserted to combine
the two sources, to give a total 263,
263,800 lb/h.
lb/h.

Process Creation
Chemical Engineering Design
  Distribute the chemicals
• The effluent stream from the pyrolysis operation is the source for the
C2H3Cl product, the HCl by-
by-product, and the C2H4Cl2 recycle.

Process Creation
Chemical Engineering Design
  Distribute the chemicals
• Reactor pressure levels:
– Chlorination reaction: 1.5 atm is recommended, to eliminate the
possibility of an air leak into the reactor containing ethylene.
– Pyrolysis reaction: 26 atm is recommended by the B.F. Goodrich
patent (1963
(1963)) without any justification. Since the reaction is
irreversible, the elevated pressure does not adversely affect the
conversion. Most likely, the patent recommends this pressure to
reduce the size of the pyrolysis furnace, although the tube walls
must be considerably thicker and many precautions are necessary
for operation at elevated pressures.
– The pressure level is also an important consideration in selecting
the separation operations, as will be discussed in the next synthesis
step.

Process Creation
Chemical Engineering Design
  Eliminate Differences in Composition
• The product of the chlorination reaction is nearly pure C2H4Cl2,
and requires no purification.
purification.

• In contrast, the pyrolysis reactor conversion is only 60

60%
%, and one
or more separation operations are required to match the required
purities in the C2H3Cl and HCl sinks.

• One possible arrangement is given in the next slide. The data

below explains the design decisions made. Critical constants
Boiling point (oC)

Chemical 1 atm 4.8 atm 12 atm 26 atm Tc,C Pc, atm

HCl -84.8 -51.7 -26.2 0 51.4 82.1

C2H3Cl -13.8 33.1 70.5 110 159 56

C2H4Cl2 83.7 146 193 242 250 50

Process Creation
Chemical Engineering Design
  Eliminate Differences
Boiling point (oC) in Composition
Critical constants

Chemical 1 atm 4.8 atm 12 atm 26 atm Tc,C Pc, atm

HCl -84.8 -51.7 -26.2 0 51.4 82.1

C 2H 3Cl -13.8 33.1 70.5 110 159 56

C 2H 4Cl2 83.7 146 193 242 250 50

There may be other, possibly better alternative configurations

Process Creation
Chemical Engineering Design
 Eliminate differences in T, P and phase

Process Creation
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 Integrate tasks (tasks
(tasks  unit operations)
operations)

Process Creation
Chemical Engineering Design
 Assembly of synthesis tree
Reaction Distribution of Separations T, P and Task
path chemicals phase integration
changes




Process Creation
Chemical Engineering Design
 Development of Base-
Base-case Design
Develop one or two of the more promising flowsheets from the
synthesis tree for more detailed consideration.

Process Creation
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 Process Creation - Summary
• Preliminary Database Creation
– needed to provide data to support the design.

• Experiments
– often necessary to supply missing database items or verify
crucial data.

• Preliminary Process Synthesis

– top
top--down approach.
– generates a “synthesis tree” of design alternatives.
– illustrated by the synthesis of the VCM .

• Development of Base-
Base-case Design
– focusing on the most promising alternative(s) from the
synthesis tree.

Process Creation
Chemical Engineering Design
Onion Model

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Foo et al., (2005) Process Simulation, CEPwww.cepmagazine.org October 2005
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 Separation

Chemical Boiling point at 1 atm

ethylene -103.70C
i-butane -11.70C
n-octane 1250C

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Chemical Engineering Design
 Preliminary Flowsheet

• Flash
ΔP= 2 psi

• Distillation

• Purge Stream

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Flowsheet with Heat Integration

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 What Else can be Done?
• Where is the heat duty for the Flash vessel coming
from?
– Heat Exchanger coupling reactor feed to reactor product.

• Do we really need the flash vessel?

– Let distillation column do all the separation.

• Reactor heat duty

– Exo or Endo reaction?
– Where does it come from?

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