Structure & Synthesis

of Process Flow Diagram

Chapter 2

The Structure & Synthesis of Process Flow

Diagram
2.1 Hierarchy of process Design
2.2 Step 1 : Batch process vs. Continuous
process
2.3 Step 2 : Input / output structure of the process
2.3.1 Process concept diagram
2.3.2 I/O structure of PFD
2.3.3 I/O structure & other features of generic BFD
2.3.4 Other consideration for I/O structure of PFD
2.3.5 Information determined using I/O diagram:
2

2.4 Step 3 The recycle structure of the

process
2.4.1 Efficiency of raw materials usage
2.4.2 Identification & definition of recycle
structure of process
2.4.3 Other issues affecting recycle structure

2.1 Hierarchy of process Design

Choose between alternatives according to
( raw material, complexity, environment,
byproducts..etc.)
New process decide whether :
1.Batch or continuous ?
2.Identify I/O structure of process
3.Identify recycle structure of process
4.Identify & design structure of separation
system
5.Identify & design heat exchangers & heat

2.2 Step 1 : Batch process vs. Continuous

process
1. Batch process finite quantity of product
( batch ) is produced during a time period
Different products are made from the same
facility
2. Continuous process raw materials are fed
continuously & products , wastes , by products
are removed continuously.
There is a batch process and batch unit
6

Batch vs Continuous
1.Size or economy of scale favors continuous
Batch < 500 t / y , Continuous > 5000 t /y
2. Product Quality: Batch is better for
verification of each batch of products ( as
required by FDA regulation)
3. If off quality product can be dumped , stored or
reprocessed then continuous is preferred
4. Flexibility : Batch can use same equipment
for many operations , while continuous is built for
a fixed product.

5. Process efficiency : batch requires

scheduling , not optimized & utility usage is
higher
6. Maintenance / Labor : Cost of labor for
batch is higher
7. Feedstock availability : Batch favors
seasonal products such as wineries. Continuous
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8. Rate of reaction : Batch favors reactions with

long reaction rate e.g. fermentation , aerobic ,
anaerobic
9.Fouling : Batch is favored for big fouling since
cleaning is easy . for continuous Process use
two units in parallel
10. Safety : batch safety is less , less
automation , training of workers is essential
9

2.3 Step 2 - Input /output structure of

the process
2.3.1 Process concept diagram
Balanced chemical reaction forms basis for
process concept diagram as in Fig 2.1
Steps to create diagram are :
1. Cloud around chemical reaction with
stoichiometry
2. Reactants Streams with names entering cloud
from left
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11

2.3.2 I/O structure of PFD

Inputs enters from left & products leaves at

right
PFD contains stream No , utilities , recycle
streams
Fig 2.1 & Fig 2.2 have same I/O structure
12

 Products either enter with feed or produced

by reaction
Utility streams rarely interact with process
stream Fig 2.3 .
Utilities to add or remove thermal energy or
work
Other utilities :
13

14

15

2.3.3 I/O structure & other features of

generic BFD
Generic BFD is intermediate between
concept diagram & BFD
BFD contains I/O & all logical building blocks
of process
Generic BFD in Fig 2.4a shows process broken
to 6 blocks:
1. Reactor feed preparation : change feed
from storage to reaction conditions (T , P,

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3. Separation feed preparation ( T , P , Conc )

for separation
4. Separator ( unit operation for separation )
5. Recycle ( unreacted inert , pump or heat
exchanger )
6. Environmental control (dispose of gas ,
liquid ,solid waste)
Environmental treatment is not included in
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18

1.Reactor feed Preparation block :

Prepare feed from storage to reactor conditions
2. Reactor Block:
Reaction to give products , by-products ,
unreacted raw materials , inert
3. Separation Feed preparation Block:
Prepare for conditions required in effective
separation
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4. Separator Block:
Separation of products , by-products , unreacted
Raw materials , inert
5. Recycle Block:
recycle unreacted raw materials after separation
back to reactor
Environmental Control Block:
Gas , liquid , solid wastes treated before
discharge

20

2.3.4 Other consideration for I/O structure

of PFD
1. Feed purity and trace components :
a. If in small quantities & inert do not
separate
e.g. H2 feed contains 5% CH4 ( inert) so do not
remove CH4
b. If separation of impurities is difficult Do not
separate
Liquids form Azeotrope which are difficult to

21

c. If impurities foul or poison catalyst then

separate
e.g. Sulfur poison Group VIII Metals (Pt , Pd ,
Ru , Rh)
d. If impurity reacts to form difficult-toseparate material or hazardous product then
separate
E.g. Phosgene COCl2 : H2 in CO produce HCl
which is corrosive & affects isocyanate product
If impurity is in large quantities then purify.
22

2- Addition of feeds to stabilize product or

enable separation
Product quality often met by single train of
operations
If product reactive or unstable chemicals are
added to stabilize it.
The same for feeding solvents & catalyst to
process.
23

4- Inert feed material to control exothermic

reaction
High exothermic reactions such as partial
oxidation of H/C
Steam is fed to absorb heat, dilute H/C &
prevent explosion in partial oxidation of
propylene

Steam is regarded as a feed and leaves as a

24

3- Inert feed to control equilibrium reaction

e.g. ethyl benzene to styrene
C6H5CH2CH3

C6H5CH = CH2 + H2

Reaction at equilibrium, T = 600-750 0C,

endothermic & at P < 1 bar .
Super heated Steam is added to provide
heat , dilute feed
It shifts equilibrium to the right by Le
Chateliers principle
25

2.3.5 Information determined from using I/O

diagram
1. Carry Basic economic analysis based on profit
margin
2. What chemicals enter with feed & what leave
with product
3. All reactions desired & undesired
Profit margin = value of products cost of

 Profit margin should be averaged over many

years
Profit margin for HDA process is negative
Disproportionation reaction to produce
benzene & mix of xylenes from toluene is
unprofitable but better than HAD
So cost of raw material decides which
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28

Example 2.1
Evaluate profit margin for HDA process. From
Tab 8.3 & 8.4, the following prices for raw
materials & products are found:
Benzene = $ 0.919/ kg

Toluene = $ 1.033/ kg ,

Natural gas ( methane and ethane, MW = (18)

= $ 11.10/ GJ = $ 11.89/ 1000 std. ft3 = $
0.302/ kg,
Hydrogen = $ 1.000/ kg ( based on the same
equivalent energy cost as natural gas)

29

 1 kmol of toluene feed as a basis Cost of Raw

Materials

92 kg of Toluene = ( 92 kg)($ 1.033/ kg) = $

95.04

2kg of Hydrogen = ( 2 kg)($ 1.000/ kg) = $

2.00

Value of Products

Benzene = ( 78 kg)($ 0.919/ kg) = $ 71.68

Methane = ( 16 kg)($ 0.302/ kg) = $ 4.83

So
Profit Margin = (71.68 + 4.83) (95.04 + .
30

 Based on this result, it is concluded that further

investigation of this process is definitely not
warranted.
Despite the results illustrated in Example 2.1,
benzene has been produced for the last 50
years and is a viable starting material for a
host of petrochemical products.
So try another route by dispropotionation
31

Example 2.2
Evaluate profit margin for toluene
disproportionation process
2C7H8 = C6H6 + C8H10
Toluene

Benzene

Xylene

From Table 8.4: Price Mixed Xylenes = 0.820 $/kg

Using 2 kmols of toluene feed as a basis:
184 kg of Toluene = (184 kg)($1.033/kg)=
$190.07
78 kg of Benzene = (78 kg)($0.919/kg) = $71.68
106 kg of Xylene = (106 kg)($0.820/kg) = $86.92
Profit Margin = 86.92 +71.68 190.07=

32

 Benzene via disproportionation of toluene

unprofitable but better than by HDA process
purified xylenes more valuable than mixed
xylene
Addition of purification to disproportionation is
profitable
Toluene disproportionation is the preferred
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2.4 Step 3

The recycle structure of the

process

1 Efficiency of raw materials usage

Cost of raw materials constitute 20-75% of
operating cost, so unreacted materials are
recovered and recycled
Recycle if recovery & recycle is easy &
economic
1. Single pass conversion = reactant
consumed in reactor / reactant fed to reactor
2. Overall conversion = reactant consumed in
34

HDA : single pass=75% , overall= 99.3%, yield

= 99.95%

35

1. High single pass conversion reduces recycle

and cost of equipment
2. Overall conversion is usually high in
chemical processes because of recycle
3. Yield is high if no side reactions exist
4. H2 conversion = 11.3% which is low because
Excess H2 is needed to prevent deposits of
coke on catalyst

36

2. Identification & definition of recycle

structure of process
3 possibilities of recycle structure :
1. Separate & purify unreacted raw materials
from product
2. Recycle feed & product together and use a
purge system
3.Recycle feed & product together but

37

38

1. Separate products & purify :

. Choice of Unit Operation to separate depends
on conditions such as T , P
. Also it depends on differing physical or
chemical properties of materials to be
separated
. E.g. benzene from toluene Economic to
choose distillation
. H2 from CH4 can be separated by distillation ,
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Example 2.3
Separation of methane and hydrogen
1-distillation:
Normal boiling point of CH4 = - 161 C , H2 = 252 C Separation by distillation easy due to
large difference in boiling points of two
components

However, in order to obtain a liquid phase, a

combination of high pressure & low
40

2- Absorption :
Possible to absorb or scrub methane from
Streams 8 &17 into a hydrocarbon liquid

In order to determine which liquids are

suitable for this process, solubility parameters
for CH4 & H2 in different liquids must be
determined

Because of the low boiling point of CH4 it would

require a low temperature & high pressure
41

3-Pressure Swing Adsorption :

Adsorption affinity of mole to adhere to a solid
material
In pressure- swing adsorption, preferential
adsorption of one species from gas phase at
given P & desorption is facilitated by reducing P
& allowing the solid to de- gas.

2 beds operate in parallel, one adsorbing ,

other desorbing

H2 in gaseous H/C separated by P- swing

42

4- Membrane Separation :
Commercial membrane processes are available
to purify H2 from H/C
H2 pass more readily through certain
membranes than CH4
Process occurs at moderate P, consistent with
HDA process
However, H2 recovered is at low P & it have to
be recompressed prior to recycling

This separation could be applied to the

43

Example 2.4
What process should be used in the separation
of toluene and benzene?
Distillation Normal boiling point of benzene =
79.8 C Normal boiling point of toluene = 110
C
Separation should be easy using distillation,
and neither excessive temperatures nor
pressures will be needed
This is a viable operation for this separation of
44

2. Recycle feed & product together with

purge system
Separation not easy: recycle product &
unreacted raw material
Purge when product does not react to avoid
accumulation

Recycles in HDA : CH4 product & unused H2

There is a purge in this system
This is represented by Fig 2.5
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46

3. Recycle Feed & Product Together without

a Purge Stream
Feasible only when product can react further in
a reactor
If product does not react & leaves it would
accumulate
C7H8 + H2

C6H6 + CH4

1. Small amount of Toluene reacts to form light

H/C
. does not affect separation . They are flashed
with H2& CH4

47

48

49

How does excess reactant affect recycle

structure ?

Decide which reactant in excess in reaction for

recycle .
In HAD : H2/ Toluene is 5:1 to prevent coking

so H2 recycle is large requiring large circuit &

large turbine
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How many reactors are required ?

1. Equilibrium :
Many reactors are required for the reaction
N2 + H2

NH3

. Stage packed bed with feed of reactants

. This lower T & increase concentration thus shift
equilibrium to right
2. Temperature control :
.

Mild exothermic or endothermic

. Add cold or hot shots between stages to

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3. Concentration control :
If one reactant forms a by-products , keep its
concentration low by using multiple feeds
/reactants.
4. Optimization for multi-reactions:
Series reactions

If T is desired product use multi-stage reactor

52

Do unreacted RM need to be purified prior

to recycling ?
If in distillation relative volatilities are each
near to each other there is no need to separate
Is recycling of an inert warranted ?
1. Depends on process .
2. May be worth to recycle
3. E.g. water to absorber in acetone production
4. Water was purified and recycled to prevent
53

2.4.3 Other issues affecting recycle

structure
1- How many potential recycle stream are
there ?
All processes with single pass conversion < 90
- 99% are potential for recycling
This Depends on :
1. cost of raw materials
2. cost to separate & recycle
3. cost of disposal as waste
54

2. Can recycle shift equilibrium to produce

less unwanted product ?
Recycle unwanted product or inert to change
conversion or selectivity of equilibrium
reaction
Recycle CO2 in water gas shift reaction to
produce synthesis gas ( CO + H2) shifts
equilibrium to left & produce more CO
55

3. Recycle of unwanted product or inert to

control reactor operation

Inert added in partial oxidation of H/C to

absorb heat & move mixture outside explosive
limit .
Steam is most often used material, so any
available inert
Steam is added to moderate T in coal
gasification
Recycle CO in partial oxidation of coal to

56

4. What is the phase of the recycle stream ?

Phase of recycle determine separation &
recycle
1. For liquids problem of azeotropic mixtures
2. For gas problem of high P or low T for
separation , both options are expensive
. Avoid gas separation unless necessary
because of cost & difficulty .

57

Summary
First choice is whether to use batch or
continuous
Continuous chemical processes have a
general structure:
1. Input-output
2. Recycle
3. Separation
I/O structure of a continuous chemical process
consists of:
4. Reactor feed preparation
5. Reactor
6. Separation feed preparation
7. Separation
58

SHORT ANSWER QUESTIONS

1. What are the five elements of the hierarchy of process
design?
2. What are the three types of recycle structures possible
in a chemical process ? Explain when each is used.
3. Give three criteria for choosing a batch process as
opposed to a continuous process.
4. When would one purposely add an inert material to a
feed stream? Illustrate this strategy with an example, and
explain the advantages (and disadvantages) of doing this.
5. In general, when would one purify a material prior to
feeding it to a process unit ? Give at least one example
59

Example 2.5
Consider the following two process alternatives
for the HDA process when side reaction of
benzene to form diphenyl occurs.
Alternative B

shown in Figure E2.5( b)

Additional separator is required, as a second

distillation column T- 102 along with associated
equipment (not shown) & extra utilities to carry
out separation
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61

Alternative A

Fig E2.5( a)

Cost of additional equipment is avoided

but recycle stream ( S 11) will be larger
because it now contains toluene & diphenyl &
utilities and equipment through which this
stream passes ( H- 101, E- 101, R- 101, E- 102,
V- 102, V- 103, T- 101, E- 106) will all be larger

Which is the economically preferable

alternative?
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63

 Answer depends upon value of equilibrium

constant for benzene- diphenyl reaction

If equilibrium conversion of benzene is high,

then there will be a large amount of diphenyl
in recycle & costs to recycle will be high & vice
versa

Equilibrium constant :

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 Exit conditions of reactor estimated by

assuming that benzene - diphenyl reaction has
reached equilibrium
Using this assumption & data from Table 1.5
for Stream 9, if x kmol/ h of diphenyl is present
in reactor effluent, then:
Solving for the only unknown gives x = 1.36
kmol/ h
Thus, toluene recycle, Stream 11, will be
increased from 35.7 to 37.06 kmol/ h, an
increase of 4%, while increases in S4 & S6 will
65