CHE 425

CHAPTER 2

The Structure and Synthesis of Process

Flow Diagrams

1
The evolution of every process follows a similar path.
The resulting processes will often be quite different,
but the series of steps that have been followed to
produce the final processes are similar.

2
 Generic Structure of Process Flow Diagrams

Factors determining choice of alternative route

• Cost of raw materials

• Value of by-products
• Complexity of the synthesis
• Environmental impact of waste materials

3
Hierarchy of Conceptual Process Design
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.
Designing new processes: [1-2-3-4-5]
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Analyzing existing processes: [5-4-3-2-1]
Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

• Batch process is one in which a finite quantity (batch) of

product is made during a period of a few hours or days.

• Continuous process is one in which feed is sent

continuously to a series of equipment, with each piece
usually performing a single unit operation.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes (< 500 t/y) Continuous Processes (> 5000 t/y)
Size Smaller throughput favors batch Economies of scale favor
operations. As throughput continuous processes for large
increases, the required size of throughput.
the process equipment increases,
and the technical difficulties
of moving large amounts of
chemicals from equipment to
equipment rapidly increase.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Batch When the product quality of Continuous or periodic testing of
Accountability/ each batch of material must product quality is carried out, but
Product be verified and certified, batch some potentially large quantities
Quality operations are preferred. This is of off-specification product can
especially true for pharmaceutical be produced. If off-specification
and food products. If reworking material may be blended or stored
(reprocessing) of off-specification in dump/slop tanks and reworked
product is not permitted, small through the process when the
batches are favored. schedule permits, continuous
processes are favored.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Operational Often the same equipment can Operational flexibility can be
Flexibility be used for multiple operations, built in to continuous processes
for example, a stirred tank can be but often leads to inefficient use
used as a mixer, then a reactor, of capital. Equipment not
then as a stage of a mixer-settler required for one process but
for liquid-liquid extraction. needed for another may sit idle
for months. Often continuous
processes are designed to
produce a fixed suite of
products from a well-defined
feed material. If market
forces change the feed/product
availability/demand, then the
plant will often be “retrofitted”
to accommodate the change.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Standardized Often batch processes can The product suite or slate
Equipment– be easily modified to produce produced from continuous
Multiple several different products using processes is usually fixed.
Products essentially the same equipment. Equipment tends to be designed
Examples of batch plants that and optimized for a single
can produce 100 different or small number of operating
products are known [3]. For such conditions.
processes the optimal control
and sequencing of operations are
critical to the success of such a
plant.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Processing Operation of batch processes requires Generally, as throughput
Efficiency strict scheduling and control. Because increases, continuous processes
different products are scheduled back- become more efficient. For
to-back, changes in schedules have a example, fugitive energy
ripple effect and may cause serious losses are reduced, and
problems with product availability for rotating equipment (pumps,
customers. If the same equipment is compressors, etc.) operate
used to produce many different with higher efficiency. Recycle
products, then this equipment will not of unused reactants and the
be optimized for any one product. integration of energy within
Energy integration is usually not the process or plant is standard
possible, so utility usage tends to be practice and relatively easy to
higher than for continuous processes. achieve.
Separation and reuse of raw materials
is more difficult than for continuous
processes.
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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Maintenance There are higher operating labor For the same process, operating
and costs in standard batch plants labor will be lower for continuous
Operating due to equipment cleaning and processes.
Labor preparation time. These costs
have been shown to be reduced
for the so-called “pipeless batch
plants” [4].

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Feedstock Batch operations are favored Continuous plants tend to be
Availability when feedstock availability is large and need to operate
limited, for example, seasonally. throughout the year to be
Canneries and wineries are profitable. The only way that
examples of batch processing seasonal variations in feeds can
facilities that often operate for be accommodated is through the
only part of the year. use of massive storage facilities
that are very expensive.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Product Seasonal demand for products Difficult to make other products
Demand such as fertilizers, gas-line during the “offseason.” However,
antifreeze, deicing chips for roads similar but different products, for
and pavements, and so on, can be example, a family of solvents,
easily accommodated. Because can be produced using the same
batch plants are flexible, other processes through a series of
products can be made during the “campaigns” at different times
“off-season.” during the year. Each campaign
may last several months.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Rate of Batch operations favor processes Very slow reactions require very
Reaction that have very slow reaction large equipment. The flow
to Produce rates and subsequently require through this equipment will be
Products long residence times. Examples slow and dispersion can be a
include fermentation, aerobic and problem if very high conversion is
anaerobic wastewater treatment, desired and plug flow is required.
and many other biological
reactions.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Equipment When there is significant Significant fouling in continuous
Fouling equipment fouling, batch operations is a serious problem
operations are favored because and is difficult to handle.
cleaning of equipment is always Operating identical units in
a standard operating procedure parallel, one on-line and theother
in a batch process and can be off-line for cleaning, can solve
accommodated easily in the this problem. However, capital
scheduling of the process. investment is higher, additional
labor is required, and safety
problems are more likely.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Safety Generally, worker exposure to Large chemical plants operating
chemicals and operator error continuously have excellent
will be higher (per pound of safety records, [6], and safety
product) than for continuous procedures are well established.
processes. Operator training in Operator training is still of great
chemical exposure and importance, but many of the
equipment operation is critical. risks associated with opening
equipment containing chemicals
are eliminated.

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 Hierarchy of Conceptual Process Design
Step 1 — Batch vs. Continuous Process

Factor Batch Processes Continuous Processes

Controllability This problem arises because Generally, continuous processes
batch processes often use the are easier to control. Also, more
same equipment for different unit work/research has been done for
operations and sometimes to these processes. For complicated
produce different products. The and highly integrated (energy
efficient scheduling of equipment and/or raw materials) plants, the
becomes very important. The control becomes complex, and
control used for this scheduling is operational flexiblity is greatly
complicated, [3]. reduced.

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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Process Concept Diagram
A diagram uses the stoichiometry of the main reaction pathway to
identify the feed and product chemicals.

The toluene hydrodealkylation process

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 Input- Output Structure of the PFD

Important factors to consider in analyzing the overall input output

structure of a PFD:

1. Chemicals not consumed are either required to operate a piece

of equipment or are inert material.
2. Any chemical leaving a process must have either entered in
one of the feed streams or have been produced by a chemical
reaction within the process.
3. Utility streams are treated differently from process streams.
Utility streams rarely directly contact the process streams.
They usually provide or remove thermal energy or work.
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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Generic Block Flow Process Diagram
This chemical process broken down into six basic areas or blocks
Each block provides a function necessary for the operation of the
process.

GBFPD for toluene hydrodealkylation process

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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Generic Block Flow Process Diagram
Each of the process blocks may contain several unit operation.
Several process blocks may be required in a given process, e.g,
multiple process blocks in a single process.
Each unit operation can be placed into one of these blocks.

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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Process Flow Diagram
The PFD, by convention, shows the process feed stream(s) entering
from the left and the process product stream(s) leaving to the right.
Toluene hydrodealkylation process

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Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Utility Streams
Utility streams, such as cooling water, steam, fuel, and electricity,
rarely directly contact the process streams. They usually provide or
remove thermal energy or work.
Utility streams for Toluene hydrodealkylation process

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Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Other Considerations: Feed Purity and Trace Components
➢ In general, the feed streams entering a process do not contain pure
chemicals. The option always exists to purify further the feed to
the process. (Purification before feeding ?)
➢ The question of whether this purification step should be performed
can only be answered by a detailed economic analysis.
➢ However, some common-sense heuristics may be used to choose a
good base case or starting point. The following heuristics are
modified from Douglas [1].

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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Heuristics: Feed Purity and Trace Components
➢ If the impurities are not present in large quantities (say < 10 ∼
20%) and these impurities do not react to form by-products, then
do not separate them prior to feeding to the process.
For example, the hydrogen fed to the toluene HDA process contains a small
amount of methane (5 mol%–see “Stream 3 in Table 1.5”). Since the methane
does not react (it is inert) and it is present as a small quantity, it is probably not
worth considering separating it from the hydrogen.
➢ If the separation of the impurities is difficult (for example, an
impurity forms an azeotrope with the feed or the feed is a gas at
the feed conditions), then do not separate them prior to feeding to
the process.
For example, again consider the methane in Stream 3. The separation of
methane and hydrogen is relatively expensive (see “Example 2.3”) because it
involves low temperature and/or high pressure. This fact, coupled with the
reasons given above, means that separation of the feed would not normally be
attempted.

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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Heuristics: Feed Purity and Trace Components
➢ If the impurities foul or poison the catalyst, then purify the feed.
For example, one of the most common catalyst poisons is sulfur. This is
especially true for catalysts containing Group VIII metals such as iron, cobalt,
nickel, palladium, and platinum [7]. In the steam reformation of natural gas
(methane) to produce hydrogen, the catalyst is rapidly poisoned by the small
amounts of sulfur in the feed. A guard bed of activated carbon (or zinc oxide)
is placed upstream of the reactor to reduce the sulfur level in the natural gas to
the low ppm level.
➢ If the impurity reacts to form difficult-to-separate or hazardous
products, then purify the feed.
For example, in the manufacture of isocyanates for use in the production
of polyurethanes, the most common synthesis path involves the reaction of
phosgene with the appropriate amine [8]. Because phosgene is a highly toxic
chemical, all phosgene is manufactured on-site via the reaction of chlorine and
carbon monoxide.
C O + Cl 2 −→ C OC l 2 (phosgene)
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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Heuristics: Feed Purity and Trace Components
If carbon monoxide is not readily available (by pipeline), then it must be
manufactured via the steam reformation of natural gas. The following equation
shows the overall main reaction (carbon dioxide may also be formed in the
process but it is not considered here):

CH 4 + H 2 O → C O + 3H2

The question to ask is, at what purity must the carbon monoxide be fed to the
phosgene unit? The answer depends on what happens to the impurities in the
CO . The main impurity is hydrogen. The hydrogen reacts with the chlorine to
form hydrogen chloride that is difficult to remove from the phosgene, is highly
corrosive, and is detrimental to the isocyanate product. With this information, it
makes more sense to remove the hydrogen to the desired level in the carbon
monoxide stream rather than send it through with the C O and cause more
separation problems in the phosgene unit and further downstream. Acceptable
hydrogen levels in carbon monoxide feeds to phosgene units are less than 1%.
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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Heuristics: Feed Purity and Trace Components

➢ If the impurity is present in large quantities, then purify the feed.

This heuristic is fairly obvious as significant additional work and heating/cooling
duties are required to process the large amount of impurity. Nevertheless, if the
separation is difficult and the impurity acts as an inert, then separation may still
not be warranted. An obvious example is the use of air, rather than pure oxygen,
as a reactant. Because nitrogen often acts as an inert compound, the extra cost
of purifying the air is not justified compared with the lesser expense of processing
the nitrogen through the process. An added advantage of using air, as opposed
to pure oxygen, is the heat absorbing capacity of nitrogen, which helps moderate
the temperature rise of many highly exothermic oxidation reactions.

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Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Addition of Feeds Required to Stabilize Products or Enable Separations
➢ Generally, product specifications are given as a series of characteristics that the
product stream must meet or exceed. Clearly, the purity of the main chemical in
the product is the major concern. However, other specifications such as color,
density or specific gravity, turbidity, and so on, may also be specified.
➢ Often many of these specifications can be met in a single piece or train of
separation equipment. However, if the product stream is, for example, reactive
or unstable, then additional stabilizing chemicals may need to be added to the
product prior to it going to storage. These stabilizing chemicals are additional
feed streams to the process.
➢ The same argument can be made for other chemicals such as solvent or catalyst
that are effectively consumed in the process. If a solvent such as water or an
organic chemical is required to make a separation take place, for example,
absorption of a solvent-soluble chemical from a gas stream, then this solvent is
an additional feed to the process. Accounting for these chemicals both in feed
costs and in the overall material balance (in the product streams) is very
important. 29
Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Inert Feed Material to Control Exothermic Reactions
➢ In some cases, it may be necessary to add additional inert feed streams to the
process in order to control the reactions taking place. Common examples of this
are partial oxidation reactions of hydrocarbons.
➢ For example, consider the partial oxidation of propylene to give acrylic acid, an
important chemical in the production of acrylic polymers. The feeds consist of
nearly pure propylene, air, and steam. The basic reactions that take place are:

3O
C 3H 6 + 2 2 → C3H4O2 + H2O Reaction 1
5O
C 3H 6 + 2 2 → C2H4O2 + H2O + CO 2 Reaction 2
9O
C 3H 6 + 2 2 → 3H2O + CO 2 Reaction 3

All these reactions are highly exothermic, not limited by equilibrium, and
potentially explosive. In order to eliminate or reduce the potential for explosion,
steam is fed to the reactor to dilute the feed and provide thermal ballast to
absorb the heat of reaction and make control easier.
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 Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Inert Feed Material to Control Exothermic Reactions

➢ In some processes, enough steam (or other inert stream) is added to move the
reaction mixture out of the flammability limits, thus eliminating the potential for
explosion. The steam (or other inert stream) is considered a feed to the process,
must be separated, and leaves as a product, by-product, or waste stream.

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Hierarchy of Conceptual Process Design
Step 2 — Process Input-Output Structure
Inert Feed Material to Control Equilibrium Reactions

➢ Sometimes it is necessary to add an inert material to shift the

equilibrium of the desired reaction.
Consider the production of styrene via the catalytic dehydrogenation of
ethyl benzene:
C6H5CH2CH3  C 6 H 5 CH = CH 2 + H2
ethyl benzene styrene
This reaction takes place at high temperature (600 ∼ 750oC) and low
pressure (< 1 bar) and is limited by equilibrium. The ethyl benzene is co-
fed to the reactor with superheated steam. The steam acts as an inert in
the reaction and both provides the thermal energy required to preheat
the ethyl benzene and dilutes the feed. As the steam to ethyl benzene
ratio increases, the equilibrium shifts to the right (LeChatelier’s
principle) and the singlepass conversion increases. The optimum steam-
to-ethyl benzene feed ratio is based on the overall process economics.

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Information Obtained From Input-Output Diagram

• 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.

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Profit Margin (PM)

PM = Value of products – Cost of raw materials

If PM < 0, then don’t bother to pursue this process but start

looking for an alternate route
Toluene HDA vs. Toluene Disproportionation
C6H5CH3 + H2  C6H6 + CH4 Toluene used
Toluene benzene
more
efficiently
2C6H5CH3  C6H6 + C6H4(CH3)2
Toluene benzene xylene

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Profit Margin (PM)

• Some processes are more sensitive to product and feed

prices than others.

• Average cost data over a period of several years should

be used in evaluating PM.

• Cost of raw materials play a role in deciding which

chemical path to choose to produce a given product.

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Example 2.1

Evaluate the profit margin for the HDA process.

From Tables 8.3 and 8.4, we get the following prices for raw
materials and products:

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

Using 1 kmol of toluene feed as a basis

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Example 2.1 (cont.)

Cost of Raw Materials

92 kg of Toluene = (92 kg)($ 1.033/kg) = $ 95.04
2 kg of Hydrogen = (2 kg)($ 1.000/kg) = $ 2.00
Value of Products
78 kg of Benzene = (78 kg)($ 0.919/kg) = $ 71.68
16 kg of Methane = (16 kg)($ 0.302/kg) = $ 4.83
Profit Margin
Profit Margin = (71.68 + 4.83) - (95.04 + 2.00) = - $ 20.53
or - $ 0.223/kg toluene
Conclusion
Based on this result, further investigation of this process
is definitely not warranted.

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Despite the results illustrated in Example 2.1, benzene has
been produced for the last 50 years and is a viable raw
material for a host of petrochemical products. How is this
possible?
Benzene can be produced via at least one other route that is
less sensitive to changes in the price of toluene, benzene, and
natural gas.
One such commercial process is the disproportionation or
transalkylation of toluene to benzene and a mixture of para-,
ortho-,and meta-xylene by the following reaction:
2C7H8 C6H6 + C8H10

The profit margin for this process is given in Example 2.2

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Example 2.2

Evaluate the profit margin for the toluene

disproportionation
process.

From Tables 8.4, we have

Mixed Xylenes = 0.82 $/kg
Using 2 kmols of toluene feed as a basis

Cost of Raw Materials

184 kg of Toluene = (184 kg)($1.033/kg) = $ 190.07

Value of Products
78 kg of Benzene = (78 kg)($0.919/kg)= $ 71.68
106 kg of xylene = (106 kg)($0.82/kg) = $ 86.92
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Example 2.2

Margin
Profit Margin = 86.92 + 71.68– 190.07= -$ 31.47 or -$0.171/kg
toluene feed
Based on the results of Example 2.2, the production of benzene via the
disproportionation of toluene is better than the toluene HDA process but
is still unprofitable.
However, a closer look at the cost of purified xylenes (from Table 8.4)
shows that these purified xylenes are considerably more valuable ($1.235
to $2.91) than the mixed xylene stream
($0.82/kg).
Therefore, the addition of a xylene purification section to the
disproportionation process might well yield a potentially profitably
process that is worth further, more-detailed analysis.

40
 Hierarchy of Conceptual Process Design
Step 3 — The Recycle Structure of the Process
➢ This step basically involves the recovery of materials and energy
from the process. It may be instructive to break down the operating
costs for a typical chemical process.
➢ Peters and Timmerhaus suggest that raw materials make up
between 10% and 50% of the total operating costs for processing
plants; however, due to increasing conservation and waste
minimization techniques this estimate may be low, and an upper
limit of 75% is more realistic.
➢ Because these raw materials are so valuable, it is imperative that
we be able to separate and recycle unused reactants.
➢ The extent of recycling of unused reactants depends largely on the
ease with which these unreacted raw materials can be separated
(and purified) from the products that are formed within thereactor.
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 Hierarchy of Conceptual Process Design
Step 3 — The Recycle Structure of the Process
Efficiency of Raw Material Usage

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
Yield =
moles of limiting reactant reacted

Benzene Process: (for the most costly reactant, toluene)

144.0 − 36.0
Single-pass Conversion = = 0.75 or 75%
144.0
108.7 − 0.4 −0.31 = 0.993 or 99.3%
Overall Conversion =
108.7
105.2 + 2.85 = 0.9995 or 99.95%
Yield =
108.7 − 0.4 −0.31
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43
Efficiency of Raw Material Usage

Single-pass Conversion (SPC)

• SPC tells us how much of the reactant that enters the reactor is
reacted.

• The lower the SPC the greater the amount of recycle.

• SPC affects equipment size and utility flows.

• Raw material costs are not changed significantly by SPC.

• SPC of hydrogen in HDA process is kept low to reduce coking of the

catalyst.

44
Efficiency of Raw Material Usage

Overall Conversion (OC)

• OC tells us tells us what fraction of the reactant in the feed
to the process is converted to product.

• High OC (e.g 99.3 %) is typical for chemical processes.

• High OC shows that unreacted raw materials are not being

lost from the process.

• Low OC of hydrogen in the HDA process indicates poor raw

material usage.

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Efficiency of Raw Material Usage

Yield

• Yield tells us what fraction of the limiting reactant

ends up in our desired product.

• Competing or side reactions may reduce the yield.

• Yields for hydrodealkylation process are generally

high (e.g 98-99 % for DETOL, Lummus).

46
3 Basic Recycle Structures

Separate and purify un-reacted feed from products and

then recycle, e.g., Toluene

Recycle feed and products together and use a purge

stream, e.g., hydrogen with purge as fuel gas

Recycle feed and products together but do not use a

purge stream - must come to Equilibrium

2C6H6 C12H10 + H2

47
Separate and purify

Ease of separation depends on:

• What conditions (T and P) are necessary to operate

the process?

• Are the differences in physical and chemical

properties for the species to be separated large or
small?

48
Example 2.3
For the separation of methane and hydrogen, first look at 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.

49
Other Separation Techniques
• Absorption
It might be possible to absorb or scrub the methane from
streams 8 and 17 into a hydrocarbon liquid. However, suitable liquids
have to be identified considering the solubility parameters for both
methane and hydrogen in the different liquids.

• Pressure-Swing Adsorption
Using a pressure-swing adsorption, the methane would be
preferentially adsorbed on to the surface of a sorbent, and the stream
leaving the unit would contain a higher proportion of hydrogen than the
feed. This could be applied to the HDA process

• Membrane Separation
Hydrogen passes more readily through certain membranes than
does methane. This could be applied to the HDA process

50
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 benzene and toluene in
the HDA process.

51
 Hierarchy of Conceptual Process Design
Step 3 — The Recycle Structure of the Process
Recycle Feed and Product Together with a Purge Stream
If separation of unreacted feed and products is not accomplished easily, then
recycling both feed and product should be considered.
Recycle structure of hydrogen stream.
Methane is purged via stream 16.

52
Hierarchy of Conceptual Process Design
Step 3 — The Recycle Structure of the Process
Recycle Feed and Product Together with a Purge Stream

53
 Hierarchy of Conceptual Process Design
Step 3 — The Recycle Structure of the Process
Recycle Feed and Product Together without a Purge Stream
This recycle scheme is only feasible when product can react further in reactor and
therefore there is no need to purge it from the process. (2 C6H6 = C12H10 + H 2 )
Because diphenyl reacts back to benzene, it can
be recycled without purging it from the system.

54
Example 2.5
Consider the following two process alternatives for the toluene
HDA process when the side reaction of benzene to form diphenyl
occurs.
Alternative A

As recycle
increases,
Equip and
Op costs
increases

2C6H6 C12H10 + H2

55
Example 2.5 (cont.)

Alternative B 2C6H6 C12H10 + H2

Extra
tower with
associated
operating
costs

56
Example 2.5 (cont.)

Clearly for Alternative B, we require an additional separator,

shown here as a second distillation column T-102, along with the
associated equipment (not shown) and extra utilities to carry out
the separation. For Alternative A, we avoid the cost of additional
equipment, but the recycle stream (Stream 11) will be larger
(because it now contains toluene and Diphenyl), and the utilities
and equipment through which this stream pass (H-101, E-101, R-
101, E-102, V-102, V-103, T-101, E-106) will all be greater. Which
is the better (economically preferable) alternative?

The answer depends on the value of Keq

57
 Hierarchy of Conceptual Process Design
Step 3 — The Recycle Structure of the Process
Other Issues Affecting the Recycle Structure

➢ How many potential recycle streams are there?

 Consider valuable reactant species (except air and water).
 If SPC < 99 %, then consider recycling.
 99% can be relaxed and use lower number for the criteria
depending on the cost of raw material, separation process,
and disposal of waste materials.
➢ How does excess reactant affect recycle structure?
 Size of Recycle Loop
 H2 : Toluene = 5 : 1

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 Other Issues Affecting the Recycle Structure

➢ How many reactors are required?

 Approach to equilibrium
 Temperature control
 Concentration control
 Optimization of conditions for multiple reactions.

➢ Do unreacted raw material streams need to be purified prior to

recycling?

59
Other Issues Affecting the Recycle Structure

➢Is recycling of an inert warranted?

60
 Other Issues Affecting the Recycle Structure

➢ Can recycling an unwanted product or an inert shift the reaction

equilibrium to produce less of an unwanted product?
 Gasification of coal

➢ Is recycling of an unwanted product or an inert warranted for the control

of reactor operation?
 CO2 in Gasifier

➢ What phase is the recycle stream?

 For liquids: concerns about azeotropes.
 For gases: concerns about temperature and pressure.
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Example 2.6

Illustrative Example Showing the Input/Output and Recycle Structure

Decisions Leading to the Generation of Flowsheet Alternatives for a
Process.

Consider the conversion of a mixed feed stream of methanol (88 mol%),

ethanol (11 mol%), and water (1 mol%) via the following dehydration
reactions:

62
Example 2.6 (cont.)
Components in reactor effluent listed in order of decreasing volatility

• Ethylene (C2H4)

• Dimethyl ether (DME)

• Diethyl ether (DEE)

• Methanol (MeOH)

• Ethanol (EtOH)

• Water (H2O)

63
Example 2.6 (cont.)
Azeotropes

• DME - H2O (but not with significant alcohol present)

• DME – EtOH
• DEE - EtOH
• DEE - H2O
• EtOH - H2O

The mixed alcohol stream is available at a relatively low price from a local source
($0.75/kg). However, pure methanol ($0.672/kg) and/or ethanol
($1.138/kg) streams may be purchased if necessary. The selling price for
DME, DEE, and ethylene are $0.841/kg, $1.75/kg, and $1.488/kg,
respectively. Preliminary market surveys indicate that we can sell up to
15,000 tonne/y of DEE and up to 10,000 tonne/y of ethylene.

For a proposed process to produce 50,000 tonnes/y of DME, determine what are
the viable process alternatives?

64
Example 2.6 (cont.)

65
Example 2.6 (cont.)

66
Example 2.6 (cont.)

Important Points
Because making ethylene is far less profitable. In
addition, the maximum amount of DEE that the market
can support is not currently being produced. Therefore,
supplementing the feed with ethanol should be
considered.
Since the main feed stream contains both reactants
and an impurity (water), separation or purification
of the feed prior to processing should be
considered.
In order to minimize the production of by-products
(ethylene), the selectivity of the DEE reaction should
be optimized.

67
Example 2.6 (cont.)

68
Example 2.6 (cont.)

69
Example 2.6 (cont.)

70
Example 2.6 (cont.)

71
 Hierarchy of Conceptual Process Design

Step 4 — General Structure of Separation System

Chapter 12
Step 5 — HEN or Process Energy Recovery
System
Chapter 15

72