INDG1030

Chemical Plant Design

II Term 2019

The Structure and Synthesis of

Process Flow Diagrams

Santiago D. Salas, Ph.D. Lecture 5

Table of Contents

1. Hierarchy of process design.

2. STEP 1: batch vs continuous process.
3. STEP 2: the input/output structure of the process.
4. STEP 3: the recycle structure of the process.
5. STEP 4: general structure of the separation system.
6. STEP 5: heat-exchanger network.

2
Hierarchy of process design

3
Hierarchy of process design

The most important decision in the evolution of a

process is the choice of which chemical syntheses or
routes should be investigated to produce a desired
product.

The identification of alternative process chemistries

should be done at the very beginning of any
conceptual design. The conceptual design and
subsequent optimization of a process are “necessary
conditions” for any successful new process.

4
Hierarchy of process design

At least two viable ways to produce a given

chemical. These alternative routes may require
different raw materials and may produce
different by-products. The cost of the raw
materials, the value of the by-products, the
complexity of the synthesis, and the
environmental impact of any waste materials and
pollutants produced must be taken into account
when evaluating alternative synthesis routes.

5
Decisions and steps

1. Decide whether the process will be batch or

continuous.
2. Identify the input/output structure of the
process.
3. Identify and define the recycle structure of
the process.
4. Identify and design the general structure of
the separation system.
5. Identify and design the heat-exchanger
network or process energy recovery system.

6
Step 1: batch or continuous

7
Batch process

It is one in which a finite quantity (batch) of

product is made during a period of time. It
consists of metering feed(s) into a vessel followed
by a series of unit operations (mixing, heating,
reaction, distillation, etc.) taking place at discrete
scheduled intervals. Followed by the removal
and storage of the products, by-product, and
waste streams. The equipment is then cleaned
and made ready for the next process. Up to 100
different products from the same facility has
been reported.
8
Continuous process

The feed is sent continuously to a series of

equipment, with each piece usually performing a
single unit operation. Products, by-products, and
waste steams leave the process continuously and
are sent to storage or for further processing.

9
Batch vs continuous process

10
Batch vs continuous process

Many things to consider when batch vs continuous:

- Size and flexibility.
- Batch vs to equivalent continuous process, the
capital investment is much lower because the
same equipment can be used for multiple
operations and reconfigured easily for other
feeds/ products. However, operating labor costs
and utility costs is much higher.
- Modular approach to the sequencing of batch
operations can improve productivity and ease
the scheduling of different events in the process.
11
Step 2: input/ output
structure of the process

12
Process Concept Diagram
The first step in evaluating a process route is to construct a
process concept diagram. The diagram uses the stoichiometry
of the main pathway to identify feed(s) and product(s).
The chemical reaction(s) taking place within the process have
to be identified. The balanced chemical reaction(s) form the
basis for the overall process concept diagram.
Output Structure of the Process Concept Diagram for the
Toluene Hydrodealkylation Process.

13
The Input/Output Structure of the PFD

If the process concept diagram represents the most

basic or rudimentary representation of a process,
then the process flow diagram (PFD) represents the
other extreme. However, the same input/output
structure is seen in both diagrams.

14
The Input/Output Structure of the PFD
16
1

3 15

15
Example:
The input streams (toluene and hydrogen) contain the
reactant chemicals plus other chemicals that are in the
raw feed materials. These streams are identified as 1
and 3. Likewise, the output streams, which contain
benzene and methane, must appear on the right. The
benzene leaving the process (15) is labeled, but it is no
clear identification for the methane. By looking at the
entry for stream 16, it can be seen that it contains a
considerable amount of methane. From the
stoichiometry of the reaction, the amount of methane
and benzene produced in the process should be equal
(on a mole basis).
16
Example:

17
Example:

18
Example:

Benzene produced in process = benzene leaving –

benzene entering

Amount of methane produced = methane leaving –

methane entering

19
Factors to consider in input/output structures

1. Chemicals entering the PFD from the left that are not
consumed / reacted are either required to operate a
piece of equipment or are inert material that simply
passes through the process.
2. Any chemical leaving a process must either have
entered in one of the feed streams or have been
produced by a chemical reaction.
3. Utility streams, such as cooling water, steam, fuel, and
electricity, rarely directly contact the process streams,
and are treated different from the process.

20
Utility Streams on the Toluene Hydrodealkylation PFD

21
What else can be determined?

✓ Basic economic analysis on profit margin,

✓ What chemical components must enter with the feed
and leave as products,
✓ All the reactions, both desired and undesired, that take
place.

22
Example:

Evaluate the profit margin considering:

• Benzene = $0.657/kg
• Toluene = $0.648/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)

Using 1 kmol of toluene feed as a basis

23
Example:
Cost of Raw Materials
92 kg of Toluene = (92 kg)($ 0.648/kg) = $ 59.62
2 kg of Hydrogen = (2 kg)($ 1.000/kg) = $ 2.00

Value of Products
78 kg of Benzene = (78 kg)($ 0.657/kg) = $ 51.25
16 kg of Methane = (16 kg)($ 0.302/kg) = $ 4.83

Profit Margin
Profit Margin = (51.25 + 4.83) – (59.62 + 2.00) =
-$ 5.54 or -$ 0.060/kg toluene
Based on this result, we conclude that further investigation of
this process is definitely not warranted.

24
Step 3: the recycle
structure of the process

25
Hydrodealkylation process

16

1
6

9
15

26
Let’s check the toluene

27
Let’s check the toluene

28
Recycle structure of the process

✓ It is important to understand the difference between

single-pass conversion in the reactor, the overall
conversion in the process, and the yield.
𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏
𝑆𝑖𝑛𝑔𝑙𝑒 − 𝑝𝑎𝑠𝑠 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 =
𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒇𝒆𝒅 𝑡𝑜 𝑡ℎ𝑒 𝒓𝒆𝒂𝒄𝒕𝒐𝒓
𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝒑𝒓𝒐𝒄𝒆𝒔𝒔
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 =
𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒇𝒆𝒅 𝑡𝑜 𝑡ℎ𝑒 𝒑𝒓𝒐𝒄𝒆𝒔𝒔
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 ∙ 𝑠𝑡𝑜𝑖𝑐ℎ. 𝑓𝑎𝑐𝑡𝑜𝑟
𝑌𝑖𝑒𝑙𝑑 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒓𝒆𝒂𝒄𝒕𝒆𝒅
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝒅𝒆𝒔𝒊𝒓𝒆𝒅 𝒑𝒓𝒐𝒅𝒖𝒄𝒕 𝒇𝒐𝒓𝒎𝒆𝒅
𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝒖𝒏𝒅𝒆𝒔𝒊𝒓𝒆𝒅 𝒑𝒓𝒐𝒅𝒖𝒄𝒕 𝒇𝒐𝒓𝒎𝒆𝒅

29
Hydrodealkylation process

The following values are obtained for the most costly

reactant (toluene):

𝟏𝟒𝟒 − 𝟑𝟔, 𝟎
𝑆𝑖𝑛𝑔𝑙𝑒 − 𝑝𝑎𝑠𝑠 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = = 𝟎, 𝟕𝟓 𝐨𝐫 𝟕𝟓%
𝟏𝟒𝟒

(𝟏𝟎𝟖, 𝟕 − 𝟎, 𝟒 − 𝟎, 𝟑𝟏)
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = = 𝟎, 𝟗𝟗𝟑𝟓 𝒐𝒓 𝟗𝟗, 𝟑𝟓%
𝟏𝟎𝟖, 𝟕

(𝟏𝟎𝟓, 𝟐 + 𝟐, 𝟖𝟓 − ? ? )
𝑌𝑖𝑒𝑙𝑑 = = 𝟎, 𝟗𝟗𝟗𝟓 𝒐𝒓 𝟗𝟗, 𝟗𝟓%
(𝟏𝟎𝟖, 𝟕 − 𝟎, 𝟒 − 𝟎, 𝟑𝟏)

30
Hydrodealkylation process

The single-pass conversion tells us how much of the

toluene that enters the reactor is converted to benzene.
The lower the single-pass conversion is, the greater the
recycle must be.

The overall conversion tells us what fraction of toluene in

the feed is converted to products. The hydrodealkylation
process shows a high (99.3%) overall conversion.

The yield tells us what fraction of the reacted toluene ends

up in our desired product: benzene.

31
Let’s check the hydrogen

32
Let’s check the hydrogen

33
Hydrodealkylation process

The following values are obtained for the hydrogen:

𝟕𝟑𝟓, 𝟒 − 𝟔𝟓𝟐, 𝟔
𝑆𝑖𝑛𝑔𝑙𝑒 − 𝑝𝑎𝑠𝑠 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = = 𝟎, 𝟏𝟏𝟑 𝐨𝐫 𝟏𝟏, 𝟑%
𝟕𝟑𝟓, 𝟒
(𝟐𝟖𝟔 − 𝟏𝟕𝟖)
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = = 𝟎, 𝟑𝟕𝟖 𝒐𝒓 𝟑𝟕, 𝟖%
𝟐𝟖𝟔

These conversions are much lower than for toluene.

The single-pass conversion is kept low because a high
hydrogen-to-hydrocarbon ratio is desired in the reactor to
avoid or reduce coking of the catalyst. But, the low overall
conversion indicates poor raw material usage.

34
Questions to ask:

✓ Why is the material usage for toluene so much better than

that of hydrogen?
✓ How can the hydrogen usage be improved?

These questions can be answered by looking at the ease of

separation of hydrogen and toluene from their respective
streams and leads us to investigate the recycle structure of the
process.

35
Identification and Definition of the Recycle
Structure of the Process

There are basically three ways that unreacted raw materials

can be recycled in continuous processes:

1. Separate and purify unreacted feed material from products

and then recycle.
2. Recycle feed and product together and use a purge stream.
3. Recycle feed and product together and do not use a purge
stream.

36
(1) Separate and Purify

Mixtures of nearly all commercially chemicals have technically

feasible separation paths.
To separate the unreacted raw materials is made purely from
economic considerations. Consider:

- First, for the separation process (unit operation) considered,

what operating conditions (temperature and pressure) are
necessary?
- Second, for the chemical species requiring separation, are
the differences in physical or chemical properties large or
small?

37
Example for the hydrodealkylation
The reactor effluent,
Stream 9, is cooled
and separated in a
two-stage flash
operation. The liquid,
Stream 18, contains
essentially benzene
and toluene. The
combined vapor
stream, Streams 8
and 17, contain
essentially methane
and hydrogen.

38
Separation of methane and hydrogen
Distillation

Normal boiling point of methane = –161°C

Normal boiling point of hydrogen = –252°C

Separation should be easy 😊 using distillation due to the

large difference in boiling points of the two components.
However, in order to get a liquid phase, we will have to use a
combination of high pressure and low temperature. This will
be very costly 😧 and suggests that distillation is not the best
operation for this separation.

39
Separation of methane and hydrogen
Absorption

It might be possible to absorb or scrub the methane from

Streams 8 and 17 into a hydrocarbon liquid. In order to
determine which liquids, if any, are suitable for this process, we
must compare the solubility parameters for both methane and
hydrogen in the different liquids. However, because of the low
boiling point of methane, again it would require a low
temperature and high pressure for effective absorption.

40
Separation of methane and hydrogen
Pressure-Swing Adsorption 😊
The affinity of a molecule to adhere (either chemically or
physically) to a solid material is the basis of adsorption. In
pressure-swing adsorption, the preferential adsorption of one
species from the gas phase occurs at a given pressure, and the
desorption of the adsorbed species is facilitated by reducing
the pressure and allowing the solid to “de-gas.” Two (or more)
beds operate in parallel, with one bed adsorbing and the other
desorbing. The separation and purification of hydrogen
contained in gaseous hydrocarbon streams could be carried out
using pressure-swing adsorption. In this case, the methane
would be preferentially adsorbed on to the surface of a
sorbent. This separation could be applied to the HDA process.
41
Separation of methane and hydrogen
Membrane Separation 😊
Commercial membrane processes are available to purify
hydrogen from hydrocarbon streams. This separation is
facilitated because hydrogen passes more readily through
certain membranes than does methane. This process occurs at
moderate pressures, consistent with the operation of the HDA
process.

However, the hydrogen is recovered at a fairly low pressure and

would have to be recompressed prior to recycling. This
separation could be applied to the HDA process.

42
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 benzene and toluene in
the HDA process.
Economic considerations often make distillation the separation
method of choice. The separation of benzene and toluene is
routinely practiced through distillation and is the preferred
method in the preliminary PFD for this process.

43
(2) Recycle feed + product + purge stream

If separation of unreacted feed and products is not

accomplished easily, the recycling of feed and product should
be considered. In the HDA process, the methane product will
act as an inert because it will not react with toluene. The
reaction of methane and benzene to give toluene and
hydrogen (the undesired path for this reaction), under the
conditions used in this process, is not significant.
When a product is recycled with an unused reactant and the
product does not react further, then a purge stream must be
used to avoid the accumulation of product in the process. For
the HDA process, the purge is the fuel gas containing the
methane product and unused hydrogen, Stream 16, leaving the
process.
44
Recycle Structure of Hydrogen Stream in
Toluene Hydrodealkylation Process

45
(3) Recycle feed + product + no purge stream

This recycle scheme is feasible only when the product can react
further in the reactor and therefore there is no need to purge it
from the process.

If the product does not react and it does not leave the system
with the other products, then it would accumulate in the
process, and steady state operations could not be achieved. In
the previous case, with hydrogen and methane, we saw that
the methane did not react further and that we had to purge
some of the methane and hydrogen in Stream 16 in order to
prevent accumulation of methane in the system.

46
Example

Main reaction

Side reaction

The bottoms product from T-101 will now contain toluene and
essentially all the diphenyl because it has a much higher
boiling point than toluene. It is known that the benzene/
diphenyl reaction is equilibrium limited at the conditions used
in the reactor. If the diphenyl is recycled with the toluene, it will
simply build up in the recycle loop until it reaches its
equilibrium value. At SS, the amount of diphenyl entering the
reactor will equal the diphenyl in the reactor effluent.
47
PFD for Alternative A

48
PFD for Alternative B

49
Which alternative is better?

Depends on the value of the equilibrium constant for the

benzene-diphenyl reaction.

50
Which alternative is better?

Solving for the only unknown gives x = 1.36 kmol/h.

Thus, the toluene recycle, Stream 11, will be
increased from 35.7 to 37.06 kmol/h, an increase of
4%, while the increases in Streams 4 and 6 will be
approximately 0.1%.

Based on this result, Alternative A will probably be

less expensive than Alternative B.

51
Step 4: general structure of
the separation system.

52
General guidelines

✓ Use distillation as a first choice for separation

of fluids when purity of both products is
required.
✓ Use gas absorption to remove one trace
component from a gas stream.
✓ Consider adsorption to remove trace
impurities from gas or liquid streams.
✓ Consider pressure-swing adsorption to purify
gas streams, especially when one of the
components has a cryogenic boiling point.

53
General guidelines

✓ Consider membranes to separate gases of cryogenic

boiling point and relatively low flowrates.
✓ Choose an alternative to distillation if the boiling
points are very close or if the heats of vaporization
are very high.
✓ Consider extraction as a choice to purify a liquid
from another liquid.
✓ Use crystallization to separate two solids or to purify
a solid from a liquid solution.
✓ Use evaporation to concentrate a solution of a solid
in a liquid.
54
General guidelines

✓ Centrifugation to concentrate a solid from a slurry.

✓ Filtration to remove a solid in almost dry form from
a slurry.
✓ Use screening to separate solids of different
particle size.
✓ Use float/sink to separate solids of different
density from a mixture of pure particles.
✓ Consider reverse osmosis to purify a liquid from a
solution of dissolved solids.

55
Step 5: Identify and design
the heat-exchanger
network or process energy
recovery system.

56
Heat exchanger network

The main objective of process energy recovery is

to optimize the energy that a process exchanges
with the utilities. At the expense of capital
investment, the utility usage can be decreased by
exchanging energy between process streams.
The amount of energy integration is a function of
the relative costs of the utilities. In addition, the
process becomes more complex and more
difficult to control. This loss in flexibility must be
weighed against the savings in operating costs.

57
Take Home Ideas!
✓ It is helpful to follow a systematic methodology to develop a
process.

✓ Batch = discrete, continuous process.

✓ In = out, principle of mass conservation.

✓ Recycle to improve.

✓ Separation following the needs.

✓ Enhance energy consumption.

Lecture 5