Plant Design and Economics

Saeed Eini
Department of Chemical and Petroleum Engineering
Sharif University of Technology

1401 ‫پاییز‬
http://che.sharif.edu/~ProSET
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology

Introduction to Process Design

and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Chemical Products
• The chemical industry is a vast industry with a wide variety of more than 70,000
products, including agrichemicals, ceramics, elastomers, electronic materials, explosives,
foods, flavors, …
• Three classes of chemical products:
o Commodity or bulk chemicals
o produced in large volumes
o purchased on the basis of chemical composition, purity and price
o Methanol, sulfuric acid, …
o Fine chemicals
o produced in small volumes
o purchased on the basis of chemical composition, purity and price
o Methionine, dimethyl formamide, …
o Specialty or effect or functional chemicals
o purchased because of their effect (or function)
o Perfumes, pharmaceuticals, …
• When considering the design of processes for the manufacture of chemical products,
the market into which they are being sold fundamentally influences the objectives and
priorities in the design.
Chemical Process: Design and Integration, 2nd edition, Smith, 2016.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Chemical Products

Product and Process Design Principles Synthesis, 4th Ed.

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Chemical Products

Gary et al., Petroleum Refining_ Technology and Economics, 5th Edition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Chemical Products
Kellogg process

Product and Process Design Principles Synthesis, 4th Ed.

Kirk-Othmer Encyclopedia of Chemical Technology
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Chemical Products
Haber-Bosch process

Kirk-Othmer Encyclopedia of Chemical Technology

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Synthesis and Simulation
• In a chemical process, the transformation of raw materials into desired chemical
products is carried out through reaction, separation, mixing, heating, cooling, pressure
change, particle size reduction or enlargement for solids

• Synthesis
Activity 1: individual transformation steps are selected
Activity 2: these individual transformations are interconnected to form a complete
process that achieves the required overall transformation

• Simulation
a mathematical model of the process that attempts to predict how the process would
behave if it was constructed

Chemical Process: Design and Integration, 2nd edition, Smith, 2016.

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Process Design Considerations:

o Accuracy of design calculations

o Physical properties in process design

o Evaluation of performance

o Materials of construction

o Process safety

o Optimization

o Keeping design options open

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Accuracy of design calculations:

o The design calculations for this will most often be carried out in a general purpose
simulation software package and solved to a high level of precision.

o The plant will almost never work precisely at its original design flowrates,
temperatures, pressures and compositions.

o Different operating conditions, instrumentation malfunction, fouling problems, …

o High precision and reasonable assumptions, might be required in the calculations for
certain specific parts of the design

o Because of all the uncertainties in carrying out a design, the specifications are
often increased beyond those indicated by the design calculations and the plant is
overdesigned, or contingency is added, through the application of safety factors to
the design.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Physical properties in process design:

o Physical properties can be critical to obtaining meaningful, economic and safe

designs.

o If poor decisions are made by the designer regarding physical properties, the
design calculations can be meaningless or even dangerous, even though the
calculations have been performed to a high level of precision

o Using physical property correlations outside the ranges of conditions for which they
were intended can be an equally serious problem

o Adequate property estimation package must be selected

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Evaluation of performance:

o Good economic performance is an obvious first criterion, but it is certainly not the
only one.

o Industrial systems should strive to satisfy human needs in an economically viable,

environmentally benign and socially beneficial way; sustainability

o The boundary of consideration should go beyond the immediate boundary of the

manufacturing facility to maximize the benefit to society to avoid adverse health
effects, unnecessarily high burdens on transportation, odour, noise nuisances, …

o Health and safety Criteria, flexibility, ease of control (controllability), availability,

uncertainty, …
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Materials of construction:

o Choice of materials of construction affects both the mechanical design and the
capital cost of equipment

o Many factors enter into the choice of the materials of construction:

 mechanical properties (particularly yield and tensile strength, compressive
strength, ductility, toughness, hardness, fatigue limit and creep resistance)
 effect of temperature on mechanical properties (both low and high
temperatures)
 ease of fabrication (machining, welding, and so on)
 corrosion resistance
 availability of standard equipment in the material
 cost
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Process safety:

o Safety considerations must not be left until the design has been completed

o Safety systems need to be added to the design later for the relief of overpressure,
to trip the process under dangerous conditions

o The largest impact on process safety can be made early in the design through
measures to make the design inherently safer
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process Design Considerations
• Optimization:

o Once the basic performance of the design has been evaluated, changes can be made
to improve the performance; the process is optimized
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration

What is the design hierarchy?

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
The Hierarchy of Chemical Process Design and Integration

Onion Diagram
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Continuous and Batch Processes

• Not all processes operate continuously

• In a batch process, the main steps operate discontinuously

• A batch process delivers its product in discrete amounts (heat, mass, temperature,
concentration and other properties vary with time)

• Batch processes are made up of series of batch and semi-continuous steps

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Continuous and Batch Processes
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Continuous and Batch Processes

What is the design hierarchy

for batch processes?

What about equipment design?

Optimization?
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Continuous and Batch Processes

• The application of batch processes:

o are economical for small volumes

o are flexible in accommodating changes in product formulation

o are flexible in changing production rate

o allow easily maintenance/cleaning/sterilization

o easy to be multi-product

o allow product identification

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Retrofitting an revamping

• Two design situations:

(1) new plant or grassroot
(2) retrofit or revamp

• Retrofit purposes:
• Increase plant capacity
• allow for different feed/product specifications
• reduce operating costs
• improve safety
• reduce environmental emissions
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Availability, Reliability, and Maintainability

• Availability measures the portion of the total time that the process meets its
production

• Reliability is the probability of survival after the unit/system operates for a certain
period of time. It defines the failure frequency and determines the uptime patterns

• Maintainability describes how long it takes for the unit/system to be repaired, which
determines the downtime patterns

• Availability is related to reliability and maintainability

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Availability, Reliability, and Maintainability

• Availability can be improved by:

o Preventive maintenance

o Condition monitoring

o using standby (spare/redundant) components

• 2×100%
• 2×50%
• …

o Over-sizing equipment
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Approaches to Chemical Process Design and Integration

• Two [main] approaches:

o Approach 1: Creating an irreducible structure

o Approach 2: Creating and optimizing a superstructure

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Approaches to Chemical Process Design and Integration

• Approach 1: Creating an irreducible structure:

o starting the design by choosing a reactor and then moving outward by adding a
separation and recycle system, and so on
o best local decisions; decisions must be based on an incomplete picture
o based on heuristics or rules of thumb

o Drawbacks:
o Must complete the design to evaluate each option
o Completing and evaluating many options gives no guarantee of ultimately finding
the best possible design

o Advantage:
o The design team can keep control of the basic decisions and interact as the
design develops
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Approaches to Chemical Process Design and Integration
• Approach 2: Creating and optimizing a superstructure:
o a reducible structure, known as a superstructure, is first created that has
embedded within it all feasible process options and all feasible interconnections
that are candidates for an optimal design structure
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Approaches to Chemical Process Design and Integration
• Approach 2: Creating and optimizing a superstructure:
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Approaches to Chemical Process Design and Integration
• Approach 2: Creating and optimizing a superstructure:

o Disadvantages:
o the approach will fail to find the optimal structure if the initial structure does
not have the optimal structure embedded somewhere within it
o if the individual unit operations are represented accurately, the resulting
mathematical model will be extremely large
 changing the model such that the search space becomes smaller
 repeating the search many times
 exploiting mathematical transformations and bounding techniques
o the design engineer is removed from the decision making

o Advantages:
o many different design options can be considered
o the entire design procedure can be automated
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design key tasks

• Information gathering and design basis

• Experiments
• Preliminary process synthesis
• Mass/heat balances and Flowsheet development
• Mass/heat/work integration
• Equipment sizing and costing
• Economic/Environment/Sustainability/Safety evaluation
• Optimization

Product and Process Design Principles, Analysis, Synthesis and Evaluation, Fourth edition, Seider et al., 2017.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Information gathering and design basis

• Design team gathers information that is the basis for its design (General info,
Environmental and Safety Data, Chemical Prices)

o the importance?
o the applications?
o the characteristic properties?
o the producers (competitors)?
o the reaction paths?
o the principal chemical reactions?
o the raw-material alternatives?
o the byproducts and intermediates?
o the range of potential production level?
o the possible plant locations?
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Information gathering and design basis
• Vinyl Chloride Manufacturing

• VCM a monomer intermediate for the production of polyvinyl chloride

• PVC is widely used for rigid plastic piping, fittings, and similar products
• Plant production scale (worldwide) : 1 MMM lb/year

• VCM was discovered in 1835 in the laboratory of the French chemist Regnault
• The first practical method for polymerizing vinyl chloride was developed in 1917 by the
German chemists Klatte and Rollett
• VCM is an extremely toxic substance and, therefore, industrial plants that manufacture
it or process it must be designed carefully to satisfy government health and safety
regulations

• A new demand: 800 MM lb /year

Existing
VCM: 800 MM lb/year plant
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Information gathering and design basis
• Vinyl Chloride Manufacturing

• Alternative 1
o Expand an existing VCM company
o The design team must project the purchase price and design storage facilities.
o This might be the simplest solution to provide the monomer required to expand
the local PVC plant
• Alternative 2
o Chlorine from the electrolysis of NaCl solution could be processed and shipped by
pipeline from a nearby plant
o Then, chlorine could be reacted with in-house ethylene to produce the monomer
and HCl as a byproduct

• Alternative 3
o HCl is produced as a byproduct in many processes in large quantities
o Reactions of HCl with acetylene, or ethylene and oxygen, could produce 1,2-
dichloroethane, an intermediate that can be cracked to produce vinyl chloride
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Information gathering and design basis
• Vinyl Chloride Manufacturing

• Alternative 4
o Design an electrolysis plant to produce chlorine
o One possibility is to electrolyze the HCl, available from within the petrochemical
complex, to obtain H2 and Cl2
o Then, chlorine could be reacted according to alternative 2
o Hydrogen could be reacted with nitrogen to form ammonia or with CO to produce
methanol
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Information gathering and design basis
• Vinyl Chloride Manufacturing

• Thermophysical property data

• Toxicity, safety, and purchase price
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Information gathering and design basis
• Thermophysical property data:
o Required for process design and mass/energy balances
o Critical properties, property estimation models

• Environmental and Safety Data

o Design team needs toxicity data for raw materials, products, byproducts, and
intermediates incorporated in a process design
o Environmental-related data
o GWP, ODP, …
o Safety-related data
o Flammability, flash points, LC50, auto ignition temperature, …

• Chemical Prices
o Economics data are often related to supply and demand, and consequently they
fluctuate and are much more difficult to estimate
o Design team must estimate/inquire the price of raw materials and utilities and
projections
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Chemical states
o To initiate process synthesis, the chemical states of aw materials, products, and
byproducts should be specified:
 Mass (flow rate)
 Temperature
 Pressure
 Composition
 Phase (solid, liquid, or gas)
 Form, if solid phase (e.g., particle size distribution and particle shape)
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Process Operations
o There are many kinds of equipment (unit operations) which belong to one of the
one or more of these basic operations:
 Chemical reaction
 Separation of chemical mixtures
 Phase separation
 Change of temperature
 Change of pressure
 Change of phase
 Mixing and splitting of streams or batches
 Operations on solids, such as size reduction and enlargement

o These basic operations are the building blocks of nearly all chemical processes
o It is common to create flowsheets involving these basic operations as a first step
in process synthesis. Then, in a task integration step, operations are combined
where feasible
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Synthesis Steps
o Given the states of the raw-material and product streams, process synthesis
involves the selection of processing operations to convert the raw materials into
products
o Each operation can be viewed as having a role in eliminating one or more of the
property differences between the raw materials and the desired products
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Operation mode
o The production scale strongly impacts the operating mode (Continuous or Batch)
o For the production of commodity chemicals, large-scale continuous processing
units are selected
o For the production of many specialty chemicals small-scale batch processing units
are preferable
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 1 (for alternative 2)

o It occurs spontaneously at a few hundred degrees
Celsius
o Large amounts of byproducts such as dichloroethylene
o One of the two atoms of expensive chlorine is
consumed to produce the byproduct hydrogen chloride
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 2 (for alternative 3)

o It provides a good conversion (98%) of acetylene to
vinyl chloride at 150∘C in the presence of mercuric
chloride (HgCl2) catalyst impregnated in activated
carbon at atmospheric pressure
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 3 (for alternative 2)

o The sum of reactions is equal to reaction pathway 1
o This two-step reaction path has the advantage that the
conversion of ethylene to 1,2-dichloroethane in the
first reaction is about 98% at 90∘C and 1 atm with
ferric chloride (FeCl3) catalyst
o Then, the dichloroethane intermediate is converted to
vinyl chloride by thermal cracking according to the
second reaction, which occurs spontaneously at 500∘C
and has conversions as high as 65%
o This reaction path has the advantage that it does not
produce dichloroethylene in significant quantities
o Disadvantages are the same as reaction pathway 1
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 4 (for alternative 3)

o In the first reaction, HCl is the source of chlorine.
This highly exothermic reaction achieves a 95%
conversion of ethylene to dichloroethane at 250∘C in
the presence of cupric chloride (CuCl2) catalyst, and is
an excellent candidate when the cost of HCl is low
o the dichloroethane is cracked to vinyl chloride in a
pyrolysis step
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 5 (for alternative 2)

o This reaction path combines paths 3 and 4
o It has the advantage of converting both atoms of the
chlorine molecule to vinyl chloride.
o All of the HCl produced in the pyrolysis reaction is
consumed in the oxychlorination reaction.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 1 (for alternative 2)

o It occurs spontaneously at a few hundred degrees
Celsius
o Large amounts of byproducts such as dichloroethylene
o one of the two atoms of expensive chlorine is consumed
to produce the byproduct hydrogen chloride
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Reaction pathway 1 (for alternative 2)

o It occurs spontaneously at a few hundred degrees
Celsius
o Large amounts of byproducts such as dichloroethylene
o one of the two atoms of expensive chlorine is consumed
to produce the byproduct hydrogen chloride

Low selectivity
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o More screening using Economic Potential (EP)

o the sales minus the cost of raw materials, not including
the cost of utilities and operating costs

It should be noted that the price of HCl is often very

sensitive to its availability in a petrochemical complex
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o More screening using Economic Potential (EP)

o For reaction pathway 3:

o EP 3: 15.69 cents/lb vinyl chloride

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o More screening using Economic Potential (EP)

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o More screening using Economic Potential (EP)

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o More screening using Economic Potential (EP)

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Flowsheet for reaction path 3
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1: Eliminate Differences in Molecular Type

o Flowsheet for reaction path 3
o The flow rates of the external sources and sinks
are computed assuming that the ethylene and
chlorine sources are converted completely to the
vinyl chloride and hydrogen chloride sinks

operating factor
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o At reactor conditions of 90∘C and 1.5 atm, experimental data indicate that 98% of the
ethylene is converted to dichloroethane, with the remainder converted to unwanted
byproducts such as trichloroethane. This loss of yield of main product and small
fraction of byproduct is neglected at this stage in the synthesis.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o The pyrolysis operation operates at 500∘C. Here only 60% of the dichloroethane is
converted to vinyl chloride with a byproduct of HCl
158,300 lb C2H4Cl2
× 0.6 × 62.50 lb VCM/lbmol VCM = 60,000 lb VCM
98.96 lb C2H4Cl2/lbmol C2H4Cl2
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o The pyrolysis operation operates at 500∘C. Here only 60% of the dichloroethane is
converted to vinyl chloride with a byproduct of HCl
40,000 lb VCM
× 98.96 lb C2H4Cl2/lbmol C2H4Cl2= 105,500 lb C2H4Cl2
62.50 lb VCM/lbmol VCM × 0.6
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o The pyrolysis operation operates at 500∘C. Here only 60% of the dichloroethane is
converted to vinyl chloride with a byproduct of HCl
40,000 lb VCM
× 98.96 lb C2H4Cl2/lbmol C2H4Cl2= 105,500 lb C2H4Cl2
62.50 lb VCM/lbmol VCM × 0.6
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o Using the values of heat of reaction, it is possible to calculate heat load of
reactors
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o 1.5 bar pressure of the first reactor to prevent the leakage of air into the
reactor
o For the pyrolysis operation, 26 atm is recommended by the B.F. Goodrich patent
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o Since in the pyrolysis operation the reaction is irreversible, the elevated pressure does not
adversely affect the conversion. Most likely, the patent recommends this pressure to
increase the rate of reaction and, thus, reduce the size of the pyrolysis furnace, although
the tube walls must be thick and many precautions are necessary for operation at elevated
pressures. The pressure level is also an important consideration in selecting the separation
operations
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 2: Distribute the Chemicals

o More comprehensive distribution
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

o Each distribution of chemicals needs a separation system
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Sinks
Source
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

o What would be a good choice for the separation system???
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

o What would be a good choice for the separation system???
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

B.F. Goodrich patent

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

B.F. Goodrich patent

Bubble point of the bottoms product

(How to calculate?)
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

(1) away from the critical points of vinyl chloride–dichloroethane mixtures

(2) low-pressure steam
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

120 to 135 oC

-40 to -7 oC
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis

1- Information gathering

2- Preliminary process synthesis 1- Eliminate differences in molecular types

2- Distribute the chemicals by matching sources and sinks

3- Eliminate differences in composition

4- Eliminate differences in temperature, pressure, and phase

5- Integrate tasks
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 1,2,3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Temperature?
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

B.F. Goodrich patent

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

medium-pressure steam
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

o Separation alternatives :

 a single column with a side stream that is concentrated in the vinyl-chloride product

HCl

Pyrolysis products C2H3Cl

C2H4Cl2
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

o Separation alternatives :

 Absorption with water, at atmospheric pressure, can be used to remove HCl. The
resulting vapor stream, containing vinyl chloride and dichloroethane, could be dried
by adsorption and separated using distillation.

HCl C2H3Cl

Pyrolysis products

C2H4Cl2
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 3: Eliminate Differences in Composition

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

o When the reaction and separation operations are positioned, the states of their feed
and product streams are selected (to achieve the desired reaction conversions and
separation factors)

o After the flowsheets have been created, these are often adjusted toward the economic
optimum

o Operations are inserted to eliminate the temperature, pressure, and phase differences
between the feed sources, the product sinks, and the reaction and separation
operations
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Alternatives?????
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 4: Eliminate Differences in Temperature, Pressure, and Phase

a complete set of operations that eliminates the differences between

the raw materials and the products
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

o 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
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Direct Chlorination reaction:

a cylindrical reaction vessel,
containing a rectifying
section, and a condenser
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Pressure change:
pressure-change
operation of the
liquid by a pump
66 Bhp (80% eff.)
1oC temp. change
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Temperature- and phase-change :

a large kettle, with a tube bundle
inserted across the bottom
Heating to 242oC and evaporating
at this temp.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Pyrolysis reaction:
Preheating to 500oC and carrying
out the reaction
The unit is constructed of
refractory brick, with natural gas-
fired heaters, and a large bundle of
Nickel, Monel, or Inconel tubes,
within which the reaction occurs.
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Cooling the products to the dew point:

a quench tank, to rapidly quench the pyrolysis effluent to
avoid carbon deposition in a heat exchanger
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Condensation:
Transferring heat to a mild refrigerant. Then
Lowering the pressure to 12 atm across a valve
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

• Step 5: Task Integration

Recycle cooler:
To prevent vapor from entering the pump
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

Heat Integration????
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing

Decision making using Heuristics

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis

Heuristics
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary process synthesis
• Vinyl Chloride Manufacturing
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task

• Mass balances using approximate models are often carried out by

using paper and pencil, spreadsheets, and even process simulator
• Block and initial process flow diagrams are often prepared
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task

• Phase conditions are computed assuming phase equilibrium, often by

a process simulator
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task

• Energy balances require the estimation of heat capacities, latent heats,

internal energies, and enthalpies
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task

• More accurate models are inserted (models to calculate the heat to be added or
removed from a stream are replaced by models for shell-and-tube heat exchanger)
• The next task normally involves estimating key equipment sizes and costs
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Process design task
Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary flowsheet mass balances
• Process Documents

o Flow diagrams
 Block Flow Diagram
 Process flow Diagram
 Piping And Instrumentation Diagram (P&ID)

o Heat and material balances

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary flowsheet mass balances
• Process Documents

o Flow diagrams
 Block Flow Diagram
 Process flow Diagram
 Piping And Instrumentation Diagram (P&ID)

o Heat and material balances

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary flowsheet mass balances
• Process Documents

o Flow diagrams
 Block Flow Diagram
 Process flow Diagram
 Piping And Instrumentation Diagram (P&ID)

o Heat and material balances

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology
Preliminary flowsheet mass balances
• Process Documents

o Flow diagrams
 Block Flow Diagram
 Process flow Diagram
 Piping And Instrumentation Diagram (P&ID)

o Heat and material balances

Saeed Eini
Dep. of Chem. and Petrol. Eng.
Sharif Uni. of Technology

Workshop: Process Documents