ECH 158A

Economic Analysis and Design

Process Creation

HUMG 2019
Professor Palazoglu
 Preliminary Process Synthesis
GOAL: To synthesize the processing configurations
that produce chemicals in a reliable, safe, and
economical way, with high yield and no waste.
• Heuristic strategies
• Algorithmic strategies
First, a processing concept needs to be determined.
Then, a flowsheet of process operations is
constructed that would convert the raw materials to
desired product(s).
What is the chemical state of raw materials
and products?
 Chemical State
The state of a process stream is defined by
specifying the values of the following parameters:
• Mass (flow rate)
• Composition
• Phase
• Form, if solid phase Other properties may
• Temperature also have to be specified
• Pressure

Raw materials Desired products

Process

Scope of Design
 Scope of Design
 What are the products?
 What is the required
quantity?
 What is the required
purity?
 What are the storage &
shipping requirements?
 What raw materials are
required?
 What impurities are there
in raw materials?
 What are the raw material
storage requirements?
 What happens to by-
products?
 What are the waste
disposal and environmental
regulations?
 Are there any special
safety requirements?
 What utilities are present,
at what levels?
 What offsites need to be
provided?
 What is the plant location?
 Can any existing
equipment be used?
 What is the start date for
construction? Operation?
 Process Operations
GOAL: To create a process flowsheet using the
basic building blocks of process operation (unit
operations):
• Chemical reaction
• Separation of mixtures
• Phase separation
• Change of temperature
• Change of pressure
• Change of phase
• Mixing and splitting of streams
• Solids handling
 Synthesis Step: Douglas’ Approach
Hierarchy of Decisions: The design problem is
decomposed into manageable subproblems which
are less complicated and the design engineer works
his/her way back to the more detailed designs by
adding successive layers of complexity.

Douglas, J.M.
Conceptual Design of Chemical Processes
Synthesis Step: Douglas’ Approach
Energy Optimization

Separations Task

Reactor/Recycle Decisions

Input/Output Structure

Layers of Complexity
 Input/Output Decisions

 Production Rates

Batch or Continuous?  Market Forces

 Operational Constraints
Conceptual Design Strategy
 Synthesis Step: Seider’s Approach

reactions
1. Eliminate differences in molecular types
2. Distribute the chemicals by matching mixing
sources and sinks
3. Eliminate differences in composition separations
4. Eliminate differences in temperature,
pressure and phase
5. Integrate tasks heat exchangers, pumps, etc.

Combine into unit operations

Seider et al., Product and Process Design Principles, Wiley.

Case Study: Manufacture of Vinyl Chloride
Vinyl chloride (VC) is a
monomer intermediate for the
production of polyvinyl chloride
(PVC).
Global demand for PVC exceeds 10 billion kg/yr.

Patents: B.F. Goodrich, 1963; Benedict, 1960 extremely toxic

Case Study: Manufacture of Vinyl Chloride
Alternative Reaction Pathways

1. Direct chlorination of ethylene

C 2 H 4 + Cl 2 → C 2 H 3Cl + HCl

2. Hydrochlorination of acetylene

C 2 H 2 + HCl → C 2 H 3Cl

3. Thermal cracking of dichloroethane from chlorination of ethylene

C 2 H 4 + Cl 2 → C 2 H 4Cl 2
C 2 H 4Cl 2 → C 2 H 3Cl + HCl
Case Study: Manufacture of Vinyl Chloride
Alternative Reaction Pathways

4. Thermal Cracking of Dichloroethane from Oxychlorination of Ethylene

C 2 H 4 + 2 HCl + 0.5O2 → C 2 H 4Cl 2 + H 2O

C 2 H 4Cl 2 → C 2 H 3Cl + HCl

5. Balanced process for chlorination of ethylene

C 2 H 4 + Cl 2 → C 2 H 4Cl 2
C 2 H 4 + 2 HCl + 0.5O2 → C 2 H 4Cl 2 + H 2O
2C 2 H 4Cl 2 → 2C 2 H 3Cl + 2 HCl
Case Study: Manufacture of Vinyl Chloride
Calculation of Gross Profit

Reaction Path #1 C 2 H 4 + Cl 2 → C 2 H 3Cl + HCl

kgmol 1 1 1 1
MW 28.05 70.91 62.5 36.46
kg 28.05 70.91 62.5 36.46
kg/kg VC 0.449 1.134 1 0.583
cents/kg 18 11 22 18

Gross Profit = 22(1)+18(0.583)-18(0.449)-11(1.134)=11.94 cents/kg VC

What are the assumptions?

Case Study: Manufacture of Vinyl Chloride
Calculation of Gross Profit

(cents/kg VC)
Reaction Path #2 -9.33

Reaction Path #3 11.94

Reaction Path #4 3.42

Reaction Path #5 7.68

A sensitivity study is recommended with respect to the price of HCl.

 Case Study: Manufacture of Vinyl Chloride
Input/Output Flowsheet for Path #3
Cl 2 HCl
113,400 kg/hr 58,300 kg/hr
Process

C2 H 4 C 2 H 3Cl
44,900 kg/hr 100,000 kg/hr

For operating 350 days/year, and 24 hrs/day, we have the target annual production of:

840,000,000 kg/yr
Case Study: Manufacture of Vinyl Chloride
Normal Boiling Points

Ethylene -103.9 0C
Hydrogen Chloride - 85.05 0C
Chlorine - 34.6 0C
Vinyl Chloride -13.4 0C
Dichloroethane 83.70 0C
Case Study: Manufacture of Vinyl Chloride
Flowsheet for Path #3 involves two reactions:

C 2 H 4 + Cl 2 → C 2 H 4Cl 2
C 2 H 4Cl 2 → C 2 H 3Cl + HCl
Pyrolysis
Direct chlorination

Two reactors are required, given the differences in operating conditions.

C2 H 4 + Cl2 → C2 H 4Cl2 C2 H 4Cl2 → C2 H 3Cl + HCl

900C, 1.5 atm 5000C, 26 atm
exothermic endothermic
Case Study: Manufacture of Vinyl Chloride
Direct Chlorination Reactor

Cl 2
C2 H 4 + Cl2 → C2 H 4Cl2 C2 H 4Cl2
113,400 lb/hr
900C, 1.5 atm
158,300 lb/hr
exothermic
C2 H 4
44,900 lb/hr
Pyrolysis Reactor

Issues: C2 H 4Cl2 → C2 H 3Cl + HCl C2 H 3Cl

• conversion 5000C, 26 atm
endothermic
HCl
• excess reactants C2 H 4Cl2
• yield
• byproducts
• recycle
• assumptions
Case Study: Manufacture of Vinyl Chloride
Calculation of Recycle Rates

C2 H 4Cl2 M C2 H 4Cl2 → C2 H 3Cl + HCl C2 H 3Cl

5000C, 26 atm
158,300 lb/hr
endothermic
HCl
C2 H 4Cl2

Component balance around the mixing point for C2 H 4Cl2

158,300 + M (1 − x) = M x = 0.6

M = 263,833lb / hr
Case Study: Manufacture of Vinyl Chloride
Heat Effects
• Chlorination reactor releases 150 MM Btu/hr.
• Pyrolysis reactor absorbs 52 MM Btu/hr.
• How is heat of reaction calculated?
• How is the reactor operated?
• Provisions for heat supply/removal?

Pressure Effects
• Chlorination reactor is slightly above atmospheric pressure
• Pyrolysis takes place at elevated pressures
• Implications for reactor design
• How does one provide high pressures?
• Phase of recycle streams
Case Study: Manufacture of Vinyl Chloride
Eliminate Differences in Composition
Cl 2
C2 H 4 + Cl2 → C2 H 4Cl2 C2 H 4Cl2
113,400 lb/hr Pure species, does
900C, 1.5 atm not need separation
158,300 lb/hr
exothermic
C2 H 4
44,900 lb/hr

C2 H 4Cl2 → C2 H 3Cl + HCl C2 H 3Cl

Identify sinks/destinations... 5000C, 26 atm
endothermic
HCl
C2 H 4Cl2

C2 H 4Cl2
Mixture. Needs
separation
 Case Study: Manufacture of Vinyl Chloride
Separation Decisions:
• What property to use?
• What technologies available?
• Phase of the mixture?
• How many steps required?
• What is the order? “Distillation”
• What utilities required?
• Assumptions / Perfect split 12 atm 4.8 atm

HCl C2H3Cl
-26.2 0C 33 0C
Pyrolysis
Reactor

C2H4Cl2
93 0C C2H3Cl 146 0C

C2H4Cl2
 Case Study: Manufacture of Vinyl Chloride
Eliminate Differences in T, P and Phase
As the reaction and separation operations are positioned, the states of
their feed and product streams are also selected.

New operations need to be inserted to eliminate the differences in T, P

and phase.
Vapor stream from pyrolysis
Liquid dichloroethane in recycle reactor
stream • Lower temperature to 170 0C
• Increase pressure to 26 atm (d.p) at 26 atm
• Raise temperature to 242 0C (b.p.) • Condense at 6 0C and 12 atm
• Vaporize at 242 0C
• Raise temperature to 500 0C
(pyrolysis T)
Case Study: Manufacture of Vinyl Chloride
 Case Study: Manufacture of Vinyl Chloride
Task Integration 2. Pump
• Energy required
1. Chlorination Reactor
• Efficiency
• Liquid phase reaction
• Reactants bubble through
3. Evaporator
• Product is condensed
• Use steam
• Cooling water
• Kettle-type reboiler

3. Pyrolysis furnace
• Preheating 4. Spray Quench
• Brick furnace • Rapid quench / coking
• Natural gas • Presence of HCl

5. Condenser 6. Recycle cooler

• mild refrigerant • cooling water
• pressure drop across valve • pre-pump
Case Study: Manufacture of Vinyl Chloride
 Flow Diagrams
Block Flow Diagram (BFD)

Represents the main processing sections

Includes the principal flow topology

Express overall material balances

Useful for evaluating alternatives

Cl 2 HCl
113,400 lb/hr 58,300 lb/hr
Direct Separation
Pyrolysis
C2 H 4 Chlorination 5000C, 26 atm System
900C, 1.5 atm C 2 H 3Cl
44,900 lb/hr
100,000 lb/hr
C2 H 4Cl2
105,500 lb/hr
 Flow Diagrams
Process Flow Diagram (PFD)

More detailed view

Icons and naming conventions
All major processing units
Stream conventions
With the aid of process simulators

• Stream information
shown on PFDs
• Utility summary
• Equipment summary
 Flow Diagrams
Piping & Instrumentation Diagram (P&ID)

Detailed diagrams submitted for

plant construction.

Location and type of all control

and measuring instrumentation.

Size schedule of piping.

 What have we covered?

 Process creation starts with establishing a database

 Process synthesis techniques
 Douglas approach vs. Seider et al approach
 Vinyl chloride manufacture
 Flow diagrams