LQI3122/LQI4031

Process Engineering
Unit 1
1.6 Disciplines in process engineering: analysis, synthesis and evaluation

Ernestina Moreno Rodriguez, Ph.D.

Steps
in a
process
design

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Steps
in a
process
design

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Steps in a process design
Part I Development of Base case
Part II Detailed Process Synthesis
Part III Design, equip, sizing and optimization
Part IV Plantwide Controllability Assessment
Part V Written Design Report and oral presentation
Process Synthesis
Characteristics
• Involves the selection of processing operations to convert the raw
materials to products.
• Each operation can be viewed as having a role in eliminating one or
more of the property differences the raw materials and the desired
products.
• When additional separations are needed, additional operations to
change the temperature, pressure, and phase, fewer differences
remain. The operations are inserted with the goal of reducing the
diffrences until the streams leaving the last operations are identical in
state to the required products.
Synthesis Steps

Synthesis Step Process Operation

1.Eliminate differences in molecular types Chemical reaction
2. Distribute chemicals by matching sources Mixing
and sinks
3. Eliminate differences in composition Separation
4. Eliminate differences in temperature, Temperature, pressure and phase
pressure and phase change
5. Integrate tasks (combine tasks into unit
operations)

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
 Synthesis Tree
As the synthesis proceed, note that many
alternatives should be considered in the
application of each step, many of which cannot be
eliminated before proceeding to the next steps.
The result is that, at each step, a new set of
candidate flowsheets is born. These are organized
into synthesis trees as the steps are applied to
create a chemical product.
As you can see, approaches are needed to
eliminate the least promising branches as soon as
possible, to simplify the selection of a near-optimal
process flowsheet.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Identify several promising chemical reactions, chemicals, products,
subproducts.
For newer substances, the design team often begins to carry out
process synthesis as the data are emerging from the laboratory.
Identifying those reaction paths that lead to processes that are costly
to build and operate, and to arrive at design as quickly as possible, in
time to capture the marker before a competitive process or chemical is
developed by another Company.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 2
2. Distribute chemicals by matching sources and sinks
Where possible, the sources and sinks for each of the chemical species are
matched so that the total mass flow into a reactor equals the total mass flow out.
This often entails the introduction of mixing operations to eliminate differences in
flow rates when a single sink is supplied by two or more sources. In others cases, a
single source is divided among several sinks.
When a stoichiometric ratio of 1:1 is set in a reaction, no differences exist between
flow rates of the sources and sinks, and hence, no mixers are needed.
When it is desired to have an excess of one chemical in relation to the others so as
to completely consume the others chemicals, which may be toxic or very expensive,
the other raw material is mixed with recycle and fed to the reactor in excess.
Synthesis Steps. Step 3
3. Eliminate differences in composition
When a stream is a mixture that needs to be separated into nearly pure
species, a separation process becomes obvious.
Separation process:
Distillation is possible because of the large differences among the
species.
Synthesis Steps. Step 4
4. Eliminate differences in temperature, pressure and phase
When the reaction and separations are positioned, the states of their feed and
product streams are selected. This is accomplished usually by adjusting the
temperature and pressure levels to achieve the desired reaction conversions and
separations factors.
Subsequently, after the flowsheets have been created, these are often adjusted
toward the economic optimum, often using the optimizers in the process
simulators.
In this synthesis step, however, the states are assumed to be fixed and operations
are inserted to eliminate the temperature, pressure, and phase differences
between the feed sources, the product sinks, and the reaction and separation
operations.
Synthesis Steps. Step 5
5. Integrate tasks (tasks  unit operations)
At the completion of step 4, each of the candidate flowsheets has a complete set of
operations that eliminates the differences between the raw materials and
products.
The selection of the processing units, often referred to as unit operations, in which
one or more of the basic operations are carried out, is known as task integration.
Example:
Vinyl Chloride Manufacturing
To satisfy the need for an additional 800 Mlb/yr of VCM, the following
plausible alternatives might be generated:
• Alternative 1. A competitor’s plant, which produces 2 Mlb/yr of VCM and is located about 100 miles
away, might be expanded to produce the required amount, which would be shipped. In this case, the
design team projects the purchase price and designs storage facilities.

• Alternative 2. Purchase and ship, by pipeline from a nearby plant, chlorine from the electrolysis of NaCl
solution. React the chlorine with ethylene to produce the monomer and HCl as a byproduct.

• Alternative 3. Since the existing company produces HCl as a byproduct in large quantities, HCl is
normally available at low prices. Reactions of HCl with acetylene, or ethylene and oxygen, could
produce 1,2-dichloroethane, an intermediate that can be cracked to produce vinyl chloride.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Chemicals participating in VC Manufacture:

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Reactions Pathways: 1) Direct chlorination of ethylene

• Advantages:
 Attractive solution to the specific problem denoted as Alternative 2 in analysis of primitive
problem.
 Occurs spontaneously at a few hundred °C
• 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.
Ref: Product and Process Design Principles, Seider,
Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Reactions Pathways: 2) Hydrochlorination of acetylene:

• 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%)

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Reactions Pathways: 3) Thermal cracking of C2H4Cl2 from chlorination of C2H4

• Advantages:
 Conversion of ethylene to 1,2-dichloroethane in exothermic reaction is aprox. 98% at 90°C 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, which occurs
spontaneously at 500 °C with conversions as high as 65% (Alternative 2).
• Disadvantages:
 Half of the expensive chlorine is consumed to produce HCl by-product, which may not be sold
easily.
Ref: Product and Process Design Principles, Seider,
Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Reactions Pathways: 4) Thermal Cracking of C2H4Cl2 from Oxychlorination
of C2H4:

• Advantages:
 Highly exothermic reaction (2.5) achieves a 95% conversion to C2H4Cl2 in the presence of
CuCl2 catalyst, followed by pyrolysis step 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.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 1
1. Eliminate differences in molecular types
Reactions Pathways: 5) Balanced Process for Chlorination of Ethylene

• Advantages:
 Combination of Reaction Paths 3 and 4 - addresses Alternative 2.
 All Cl2 converted to VC
 No by-products!

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Evaluation of Alternative Pathways
• Reaction Path 1 is eliminated due its low selectivity.
• This leaves four alternative paths, to be compared first in terms of
Gross Profit.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Evaluation of Alternative Pathways
Gross Profit
Its too early to estimate the cost of the equipment and its operation,
before the remaining process operations are in place, the design team
normally computes the gross profit (excluding the costs of equipment
and the operation costs) for each reaction path and uses it as a vehicle
for screening out those that cannot be profitable.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Reaction Path 3
Thermal cracking of C2H4Cl2 from chlorination of C2H4
Reaction Path 3
Thermal cracking of C2H4Cl2 from chlorination of C2H4

Progress of reaction (𝜀𝑗 )

𝑛𝑖 = 𝑛𝑖,0 + ෍ 𝜈𝑖𝑗 ∗ 𝜀𝑗
𝑗

Equations:
𝑛𝐶2𝐻4 = 𝑛𝐶2𝐻4,0 − 𝜀1 ; 0 = 𝑛𝐶2𝐻4,0 − 𝜀1
𝑛𝐶𝑙2 = 𝑛𝐶𝑙2,0 − 𝜀1 ; 0 = 𝑛𝐶𝑙2,0 − 𝜀1
𝑛𝐶2𝐻3𝐶𝑙 = 𝑛𝐶2𝐻3𝐶𝑙,0 + 𝜀1 ; 𝑛𝐶2𝐻3𝐶𝑙 = 0 + 𝜀1 (Main Product)
𝑛𝐻𝐶𝑙 = 𝑛𝐻𝐶𝑙,0 + 𝜀1 ; 𝑛𝐻𝐶𝑙 = 0 + 𝜀1
Reaction Path 3
Thermal cracking of C2H4Cl2 from chlorination of C2H4
Evaluation of Alternative Pathways
Even without the capital costs (for construction of the plant, purchase of land,
etc.) and the operating cost (for labor, steam, electricity, etc.), the gross profit
for reaction path 2 is negative, whereas the gross profits for the other reaction
paths are positive.
Synthesis Tree
Reaction Path 1  Low selectivity
Reaction Path 2  Negative gross profit
Preliminary flowsheet for reaction path 3

• 800 M lb/year @ 330 days/y  100,000 lb/hr VC

• On the basis of this principal sink, the HCl sink and reagent sources can be computed (each flow is
58300 lb/h)
• Next step involves distributing the chemicals by matching sources and sinks.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 2
2. Distribute chemicals by matching sources and sinks
A conversion of 100% of the C2H4 is assumed in the chlorination reaction.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 2
2. Distribute chemicals by matching sources and sinks
IDEAL: A conversion of 100% of the C2H4 is assumed in the chlorination reaction.
REAL:
• Only 60% of the C2H4Cl2 is converted to C2H3Cl with a
byproduct of HCl, according to second equation.
• To satisfy the overall material balance, 158,300 lb/h of C2H4Cl
must produce 100,000 lb/h of C2H3Cl and 58,300 lb/h of HCl.
• But a 60% conversion only produces 60,000 lb/h of VC.
• The additional C2H4Cl2 needed is computed by mass balance to
equal: [(1 - 0.6)/0.6] x 158,300 or 105,500 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.
Ref: Product and Process Design Principles, Seider,
Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 2
2. Distribute chemicals by matching sources and sinks
The effluent stream from the pyrolysis operation is the source for the C2H3Cl
product, the HCl by-product, and the C2H4Cl2 recycle.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 3
3. Eliminate differences in composition
• The product of the chlorination reaction is nearly pure C2H4Cl2, and requires no
purification.
• In contrast, the pyrolysis reactor conversion is only 60%, and one or more separation
operations are required to match the required purities in the C2H3Cl and HCl sinks.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 3

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 4
4. Eliminate differences in temperature, pressure and phase

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Synthesis Steps. Step 5
5. Integrate tasks (tasks  unit operations)

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Development of Base-case Design
Develop one or two of the more promising flowsheets from the synthesis
tree for more detailed consideration.

Ref: Product and Process Design Principles, Seider,

Seader and Lewin, Chapter 3 in 2nd Ed, 4 in 3rd Ed.
Doubts?