Process Synthesis and Integration

CONTENT
• FLOW SHEETS
• FINANCIAL OUTLOOK
• ENERGY INTERGRATION
Process Synthesis and Integration
ASSESSMENT

COURSE WORK (CW) 40%

FINAL EXAMINATION 60%

Test 1 15 % of CW
Mid Semester 20% of CW
Test 2 15% of CW
Design Assignment 50% CW
 FLOW SHEETING
• Visual information is the clearest way to present
material and is least likely to be misinterpreted.
• For these reasons, it is essential that chemical
engineers be able to formulate appropriate process
diagrams and be skilled in analyzing and interpreting
diagrams prepared by others.
• The most effective way of communicating information
about a process is through the use of flow diagrams
PROCESS DESIGN CONCEPT
Based on information derived from these block flow diagrams, a
decision can be either to proceed or not with a process.
(Financial analysis)
They allow the detailed process calculations, material and energy
balances, equipment sizing, etc.
This leads to production of PFDs (Process Flow Diagrams) for the
process.
After PFD the next step is to prepare the P&IDs (Piping and
Instrumentation Diagrams)
After all approvals can the process be put in place.
 Block Flow Diagram (BFD)
• This diagram consisted of a series of blocks representing
different equipment or unit operations that were connected
by input and output streams.
• Important information such as operating temperatures,
pressures, conversions, and yield are included on the diagram
along with flowrates and some chemical compositions.
• However, the diagram does not include any details of
equipment within any of the blocks.
The Structure and Synthesis of
Process Flow Diagrams
• 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.
Block Flow Diagram (BFD)
Block Flow Diagram (BFD)
Process Flow Diagram (BFD)
• The process flow diagram (PFD) represents a quantum step up
from the BFD in terms of the amount of information that it
contains.
• The PFD contains the bulk of the chemical engineering data
necessary for the design of a chemical process.
• A typical commercial PFD will contain the following
information:
1. All the major pieces of equipment in the process will be
represented on the diagram along with a description of the
equipment. Each piece of equipment will have assigned a unique
equipment number and a descriptive name.
Process Flow Diagram (BFD)
2. All process flow streams will be shown and identified by a
number. A description of the process conditions and chemical
composition of each stream will be included. These data will be
either displayed directly on the PFD or included in an
accompanying flow summary table.
3. All utility streams supplied to major equipment that provides a
process function will be shown.
4. Basic control loops, illustrating the control strategy used to
operate the process during normal operations, will be shown.
Process Flow Diagram (BFD)
The basic information provided by a PFD can be categorized into
one of the following:
1. Process topology

2. Stream information

3. Equipment information
Process Flow Diagram (BFD)
Process Flow Diagram (BFD)
Process Flow Diagram Alternative
Routes
• Most often, there are at least two viable ways to produce a
given chemical. These alternative routes may require different
raw materials and may produce different byproducts.
• 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.
Hierarchical Approach to Process
Synthesis
There are 5 ways to this approach

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.
1. The following guidelines can assist for
selecting the processing mode:

Continuous Batch
• Production rate • Production rate less
greater than 5 x 106 than 5 x 106 kg/h
kg/h • A range of products
• Single product or product
• No severe fouling specifications
• Good catalyst life • Severe fouling
• Proven processes • Short catalyst life
design • New product
• Established market • Uncertain design
2. Identify the input/output structure of the
process.

• The first step in evaluating a process route is to construct a

process concept diagram.
• Such a diagram uses the stoichiometry of the main reaction
pathway to identify the feed and product chemicals.
• The first step to construct such a diagram is to identify the
chemical reaction or reactions taking place within the process.
• The balanced chemical reaction(s) form the basis for the
overall process concept e.g. toluene hydrodealkylation
process discussed should be noted that only chemicals taking
place in the reaction are identified on this diagram.
2. Identify the input/output structure of the
process.

1. A single “cloud” is drawn to represent the concept of the

process. Within this cloud the stoichiometry for all reactions that
take place in the process is written. The normal convention of
the reactants on the left and products on the right is used.
2. The reactant chemicals are drawn as streams entering from the
left. The number of streams corresponds to the number of
reactants (two). Each stream is labeled with the name of the
reactant (toluene and hydrogen).
3. Product chemicals are drawn as streams leaving to the right.
The number of streams corresponds to the number of products
(two). Each stream is labeled with the name of the product
(benzene and methane).
.
2. Identify the input/output structure of the
process.

4. Seldom does a single reaction occur, and unwanted side

reactions must be considered. All reactions that take place and
the reaction stoichiometry must be included. The unwanted
products are treated as by-products and must leave along with
the product streams shown on the right of the diagram
2. Identify the input/output structure of the
process.
 The Input/Output Structure of the Process Flow Diagram

The generic block flow diagram is intermediate between the

process concept diagram and the PFD.
This diagram illustrates features, in addition to the basic
input/output structure, that are common to all chemical
processes. Moreover, in discussing the elements of new processes
it is convenient to refer to this diagram because it contains the
logical building blocks for all processes.
The blocks must include as a minimum the following
1. Reactor feed preparation , 2. Reactor, 3. Separator feed
preparation, 4. Separator, 5. Recycle, 6. Environmental control
2. Identify the input/output structure of the
process.
2. Identify the input/output structure of the
process.
2. Identify the input/output structure of the
process.

1. Reactor Feed Preparation Block: In most cases, the feed

chemicals entering a process come from storage. These chemicals
are most often not at a suitable concentration, temperature, and
pressure for optimal performance in the reactor. The purpose of
the reactor feed preparation section is to change the conditions
of these process feed streams as required in the reactor.
2. Reactor Block: All chemical reactions take place in this block.
The streams leaving this block contain the desired product(s), any
unused reactants, and a variety of undesired by-products
produced by competing reactions.
3. Separator Feed Preparation Block: The output stream from the
reactor, in general, is not at a condition suitable for the effective
separation of products, by-products, waste streams, and
2. Identify the input/output structure of the
process.

unused feed materials. The units contained in the separator feed

preparation block alter the temperature and pressure of the
reactor output stream to provide the conditions required for the
effective separation of these chemicals.
4. Separator Block: The separation of products, by-products,
waste streams, and unused feed materials is accomplished via a
wide variety of physical processes. The most common of these
techniques are typically taught in unit operations and/or
separations classes—for example, distillation, absorption, and
extraction
2. Identify the input/output structure of the
process.

5. Recycle Block: The recycle block represents the return of

unreacted feed chemicals, separated from the reactor effluent,
back to the reactor for further reaction. Because the feed
chemicals are not free, it most often makes economic sense to
separate the unreacted reactants and recycle them back to the
reactor feed preparation block. Normally, the only equipment in
this block is apump or compressor and perhaps a heat exchanger.
.
2. Identify the input/output structure of the
process.

6. Environmental Control Block: Virtually all chemical processes

produce waste streams. These include gases, liquids, and solids
that must be treated prior to being discharged into the
atmosphere, sequestered in landfills, and so on. These waste
streams may contain unreacted materials, chemicals produced by
side reactions, fugitive emissions, and impurities coming in with
the feed chemicals and the reaction products of these chemicals.
Not all of the unwanted emissions come directly from the process
streams. An example of an indirect source of pollution results
when the energy needs of the plant are met by burning high
sulfur oil. The products of this combustion include the pollutant
sulfur dioxide, which must be removed before the gaseous
combustion products can be vented to the atmosphere. The
purpose of the environmental control block is to reduce
significantly the waste emissions from a process and to render all
nonproduct streams harmless to the environment.
Other Considerations for the Input/Output Structure of the
Process Flowsheet: Impurities considerations

Feed Purity and Trace Components

1. 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.
2. 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.
3. If the impurities foul or poison the catalyst, then purify the
feed
Other Considerations for the Input/Output Structure of the
Process Flowsheet

5. If the impurity reacts to form difficult-to-separate or

hazardous products, then purify the feed
6. If the impurity is present in large quantities, then purify the
feed
Other Considerations for the Input/Output Structure of the
Process Flowsheet : Feeds

1. 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
2. Addition of Inert Feed Material to Control Equilibrium
Reactions. Sometimes it is necessary to add an inert material
to shift the equilibrium of the desired reaction.
What Information Can Be Determined Using the
Input/Output Diagram for a Process?

The following basic information, obtained from the input/output

diagram, is limited but nevertheless
very important:
• 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
 Economic potential

Evaluate the profit margin for the HDA process. 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)
 Economic potential

Using 1 kmol of toluene feed as a basis

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 = (71.68 + 4.83) – (95.04 + 2.00) = –$20.53 or –
$0.223/kg toluene
Based on this result, it is concluded that further investigation of
this process is definitely not.
 Step 3—The Recycle Structure of the Process

It may be instructive to break down the operating costs for a

typical chemical process. Peters and Timmerhaus suggest that
1. 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.
2. Because these raw materials are so valuable, it is imperative
that unused reactants are separated and recycled. Indeed, high
efficiency for raw material usage is a requirement of the vast
majority of chemical processes.
3. However, 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 the reactor
Step Conversions
Example
Step Conversions
Step Conversions
 Step 3—The Recycle Structure of the 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, the greater the recycle must be,
assuming that the unreacted toluene can be separated and
recycled.
• In terms of the overall economics of the process, the single-
pass conversion will affect equipment size and utility flows,
because both of these are directly affected by the amount of
recycle.
• However, the raw material costs are not changed significantly,
assuming that the unreacted toluene is separated and recycled.
 Step 3—The Recycle Structure of the Process

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
 Step 3—The Recycle Structure of the Process

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
Step 3—The Recycle Structure of the Process
 Step 3—The Recycle Structure of the Process

1. Ethylene (C2H4)
2. 2. Dimethyl Ether (DME)
3. 3. Diethyl Ether (DEE)
4. 4. Methanol (MeOH)
5. 5. Ethanol (EtOH)
6. 6. Water (H2O)
 Step 3—The Recycle Structure of the Process

Moreover, because these are all polar compounds, with varying

degrees of hydrogen bonding, it is not surprising that these
compounds are highly non-ideal and form a variety of azeotropes
with each other.
These azeotropes are as follows:
• DME – H2O (but no azeotrope with significant presence of
alcohol)
• DME – EtOH
• DEE – EtOH
• DEE – H2O
• EtOH – H2O
 Step 3—The Recycle Structure of the Process

For this problem, it is assumed that 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 prices for
DME, DEE, and ethylene are $0.841/kg,
$1.75/kg, and $1.488/kg, respectively. Preliminary market
surveys indicate that up to 15,000 tonne/y
of DEE and up to 10,000 tonne/y of ethylene can be sold.
For a proposed process to produce 50,000 tonne/y of DME,
determine the viable process alternatives.
 Answer

Step 1: Batch versus Continuous

For a plant of this magnitude, a continuous process would
probably be chosen. However, this issue will be reviewed after
considering some process alternatives and it will be seen that a
hybrid batch/continuous process should also be considered
Answer
Answer
Answer
Answer
 Answer

Important Points
From this margin analysis, it is clear that the amount of DEE
produced should be optimized, 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.
Because 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
Answer
 Answer

In this option, shown in Figure E2.6(b), the mixed alcohol feed is

not separated, but feed is supplemented with ethanol. One
reactor is used for both reactions. The disadvantages of this case
are that the separations are complicated and the reactor for both
DME and DEE production cannot be
optimized easily
Answer
 Answer

In this option, shown in Figure E2.6(c), feed is supplemented with

ethanol and is separated into separate methanol and ethanol
streams. Two reaction trains are used: one for DME and the other
for DEE production. This allows the production of DME and DEE
to be optimized separately and eliminates problems associated
with the DME-ethanol azeotrope. However, there are two
reactors and at least one more separation (column).
 Answer

In this option, shown in Figure E2.6(c), feed is supplemented with ethanol and is
separated into
separate methanol and ethanol streams. Two reaction trains are used: one for DME
and the other for
DEE production. This allows the production of DME and DEE to be optimized
separately and
eliminates problems associated with the DME-ethanol azeotrope. However, there are
two reactors and
at least one more separation (column).
 Answer

In
 Answer

Separation and heat exchanger processes will be dealt with in more detail later.