CHE 200 INTRODUCTION TO

EQUILIBRIUM STAGE OPERATIONS

 INSTRUCTOR
• Dr. Ariel Chan, Ph.D., P.Eng.

Office: E6-4016
Tel: (519) 888-4567 Ext. 38665
Email: ariel.chan@uwaterloo.ca

• Navid Bizmark (Teaching Assistant)

Office: E6-3106
Tel: 519-888-4567 ext. 31630
E-mail: nbizmark@uwaterloo.ca

Note: According to the University of Waterloo policy, UW E-mail

address must be used for all official correspondence (e.g.
userid@uwaterloo.ca). E-mail received from an account other than
uwaterloo.ca (e.g. gmail, hotmail, etc.) will not be responded.
 Class Schedule
Lectures:
Wednesday 2:30 - 4:20 pm in DWE 2529
Friday 12:30 - 1:20 am in DWE 2529

Tutorials:
Friday 1:30 - 2:20pm in DWE 2529

Important Dates:
• Midterm Exam: Friday, Oct 10 at 1:30-2:20 pm
• Final exams: Dec 4 - 19
 COURSE REFERENCES
 Course references are not required for this course
 Course materials will be presented using blackboard, PowerPoint
slides, and extra handout.
• Bounded notebook or binders are great for this course
• “Introduction to Equilibrium Stage Operations” (2000) U.
of Waterloo Courseware Solutions, by I. Chatzis, P.L.
Douglas, R. R. Hudgins, and P.L. Silveston
• Treybal: "Mass Transfer Operations", McGraw-Hill.
• McCabe, Smith and Harriott: "Unit Operations In Chemical
Engineering", McGraw-Hill.
 PERFORMANCE EVALUATIONS

• Assignments* 15%
• Tutorials/Quizzes 5%
• Midterm Examination 30%
• Final Examination 50%

*One group presentation assignment. Presentation begins in

week 4-12.

Notes:
• you must achieve at least 50% weighted average on the final
exam and quiz to pass the course, otherwise you receive that
average.
 GRADING PHILOSOPHY
• The homework will be hand written and legible with clarity.

• The template for HA Solutions will be like the format used

in ChE101
– Note that simply getting the “right” answer is not sufficient to
receive the marks available.
– Good problem solving methodology, including the statement of
relevant assumptions, giving the source of data, and clearly
explaining your steps, is required.

• No late assignments will be accepted!

• The homework is meant to be "Individual Effort". Copying
somebody else's solution without acknowledgement will
result in getting a zero mark for that Home Assignment.
 CHE 200 Course Overview
Course outline
– the design and analysis of separators used in many industries and
processes.
Key subject areas addressed in this course are:
• Vapour-Liquid Equilibria and Applications.

– Flash Distillation, Steam Distillation, Batch Distillation, Design of Distillation

Units for separation of Binary Mixtures and Multicomponent mixtures.

• Gas-Liquid Equilibrium Separations and Applications to the Design of

Absorbers and Strippers.

• Liquid-Liquid Equilibrium Separations

• Leaching Operations and Ion Exchange.

– Solid - Liquid Equilibrium conditions and the design of separators for
leaching and ion exchange.
 Detail course outline
1. Common separation technologies and heuristics used in industry. Review concepts of the equilibrium
stage, mass & energy balances, and liquid-liquid & vapour-liquid equilibrium.
2. Preparation of Txy, xy and Hxy diagrams for binary systems
3. Flash separation for binary system: construction and using isobaric plots for flash separation
4. Flash separation for multi-component system: bubble point calculations, dew point calculations,
approaches for estimation of feed & product compositions
5. Separation of immiscible liquids by extraction and distillation
6. Steam distillation for multi-components system
7. Batch distillation of binary and multi-component solutions. Effect of adding reflux to the separation
system
8. Continuous distillation: packed column vs trayed column. Introduction to column geometry,
condenser and reboiler, partial condensation and re-boiling
9. Mass and energy balances in continuous separation system. Deriving mathematical equations to
describe operation, feed and equilibrium of binary distillation process.
10. Graphical approaches for continuous distillation design: McCabe-Thiele method & Ponchon-Savarit
method, Murphree and overall efficiency
11. Numerical methods for continuous distillation of multicomponent system
12. Multi-stage separation for absorption and stripping & liquid-liquid extraction process. Graphical and
numerical approaches.
13. Use Aspen Plus for process simulation
 NOTE FOR STUDENTS WITH
DISABILITIES
• The Office for Persons with Disabilities (OPD), located in
Needles Hall, Room 1132, collaborates with all academic
departments to arrange appropriate accommodations for students
with disabilities without compromising the academic integrity of
the curriculum.

• If you require academic accommodations to lessen the impact of

your disability, please register with the OPD at the beginning of
each academic term.

www.studentservices.uwaterloo.ca/disabilities
 Process Synthesis

Inverted synthesis tree

Throughout the synthesis process, branches

have been added to the synthesis tree to
represent the alternative flowsheets being
considered.
 Example: Vinyl Chloride Production*
 C2H3Cl can be converted from acetylene (C2H2) or ethylene (C2H4)
 Potential synthesis routes:
1. direct chlorination of ethylene (single-step):

C2H4 + Cl2 C2H3Cl + HCl

o low conversion, large byproducts (dichloroethylene, C2H4Cl 2 )

2. Hydrochlorination of Acetylene

C2H2 + HCl C2H3Cl

o Good conversion (~98%) at 150oC

*example from Seider et al 2004

 Example: Vinyl Chloride Production
• Potential synthesis routes:
3. Thermal cracking of dichloroethane from chlorination of ethylene

C2H4 + Cl2 C2H4Cl 2 (98% conversion at 90oC and 1atm, exothermic)

C2H4Cl 2  C2H3Cl + HCl (~65% conversion at 500oC , endothermic)*
C2H4 + Cl2  C2H3Cl + HCl (overall)
*unreacted dichloroethane is recovered entirely and recycled for reaction

4. Thermal cracking of dichloroethane from oxychlorination of ethylene

C2H4 + 2HCl +1/2O2 C2H3Cl 2+ H2O (95% conversion at 250oC, exothermic)

C2H4Cl 2  C2H3Cl + HCl (500oC, endothermic, recycled)
C2H4 + Cl2 + 1/2O2  C2H3Cl + HCl (overall)
 Example: Vinyl Chloride Production
• Potential synthesis routes:
5. Balanced process for chlorination of ethylene

C2H4 + Cl2 C2H4Cl2

C2H4 + 2HCl +1/2O2 C2H3Cl 2+ H2O
2 C2H4Cl 2  2C2H3Cl +2 HCl
C2H4 + Cl2 + 1/2O2  C2H3Cl + H2O (overall)

o Convert both Cl molecules to vinyl chloride, all of HCl produced is

consumed

Synthesis route #2,3,4,5 are fine candidate for the further

consideration.
 Process creation-Vinyl Chloride
Assumed cost of chemicals purchased or sold in bulk quantities:

Chemical MW Cost (cents/Lb)

Ethylene (C2H4) 28.05 18 (505 cents/mole)
Acetylene (C2H2) 26.04 50 (1302 cents/mole)
Chlorine (Cl2) 70.91 11 (780 cents/mole)
Vinyl chloride (C2H3Cl) 62.50 22 (1375 cents/mole)
Hydrogen Chloride (HCl) 36.46 18 (656 cents/mole)
Water (H2O) 18 0
Oxygen (O2) 32 0
 Process creation-Vinyl Chloride
Gross Profit for Production of Vinyl Chloride (based on chemical
prices)
Reaction Overall reaction Gross profit
Path (cents/lb of vinyl
chloride)
2 C2H2 + HCl C2H3Cl -9.33
3 C2H4 + Cl2  C2H3Cl + HCl 11.94
4 C2H4 + Cl2 + 1/2O2  C2H3Cl + HCl 3.42
5 C2H4 + Cl2 + 1/2O2  C2H3Cl + H2O 7.68
 Example: Vinyl Chloride Production*
3. Thermal cracking of dichloroethane from chlorination of ethylene

C2H4 + Cl2 C2H4Cl 2 (98% conversion at 90oC and 1atm, exothermic)

C2H4Cl 2  C2H3Cl + HCl (~65% conversion at 500oC , endothermic)*
C2H4 + Cl2  C2H3Cl + HCl (overall)
*unreacted dichloroethane is recovered entirely and recycled for reaction
Example: Vinyl Chloride Production*
 Total mass flow into a reactor equals the total mass flow out. (recycle
of unreacted C2H4Cl2
 Block Flow Diagram
 Separation mixtures of chemicals by distillation
 Vinyl chloride product, HCl by product and dichloroethane for recycle
Separation Towers
Adjusting the temp and pressure levels to achieve the
desired reaction conversions and separation factors
 Task integration

• Task integration
Process Flow Diagram
Material’s of
construction
diagram
Key Aspects of Chemical Plant Operations

Focus of ChE 200

Chemical and phase separations involve inter-phase

& Multistage Equilibrium stage operations
• Relations to other courses in Chemical Engineering

• Fluid Mechanics taken in 2B term

• Heat and Mass Transfer taken in 3rd year
• CHE480 Process Analysis and Design taken in 4A term
• ChE 512 Separation Processes taken in 4B term
 Unit Operations: Classification
Fluid flow processes
Thermodynamic processes
- fluid transport
- solids fluidization - liquifaction
- mixing - refrigeration

Heat transfer processes Mechanical processes

- heating/cooling - crushing
- evaporation/condensation - sieving
- solid transportation
Mass transfer processes

- absorption
- distillation
- extraction
- adsorption
- drying
Introduction to Separation operations

Separation principles & Industrial Separation

process and technology
 Industrial separations
 Solubilisation from a solid matrix
• food processing: extraction of coffee and tea
• pharmaceutical: reclaiming solutes from cell mass (insulin,
enzymes)
 Concentration of dilute solution
• plastics: removal of solvent and unreacted monomer
• chemicals: production of NaCl by evaporation of sea water
 Purification
• medical: dialysis (artificial kidney)
• chemicals: manufacturer of absolute alcohol
 Fractionation
• Petrochemical: separation of crude oil (different boiling range)
• plastics: polymer of various MW
Product Rates for Industrial Separation Processes

production rate
from 100kg/h
up to a million
kg/h are
handled by
equilibrium
stage operation
 Separation technologies

Chemical separation processes

• Distillation

frequency of use
• Gas Absorption
• Crystallization
• Absorption
• Membranes
• Chromatography
 Separation Principles
 Chemical reactions do not occur in separation so a component
cannot be destroyed
– what enters the separation must leave the separation when
steady state operation is achieved
– mass transfer/diffusional operation

 Requirements for separation

– separate phases
– difference in properties
Ex. vapour pressure (distillation, absorption)
solubility (crystallization, absorption, extraction)
chemical affinity (adsorption/ion exchange)
MW and shape (membrane permeation, molecular sieves)
 Mixtures and solutions
 Mixtures and solutions:
– binary, ternary or multicomponent (# of components/species present)
 Heterogeneous (consists of more than one phase)
– Separation can be made based:
o size of particles, different phases, density differences
– Ex. Solid separation
o sedimentation
o crystallization
o sieving/membrane filtration
o magnetic separation
 Homogenous
– 2nd new phase must be created
– require the addition of an agent for separation
o energy as separation agent (ie.V-L flash separation)
o mass separation agents:
Ex. gas-stripping, liquid-absorption, L-L extraction, leaching, solid-
absorption/ion exchange
Separation process and operation units
• Separation process: batch vs continuous
• Good phase separation requires rapid and intimate mixing
• two vessels setting: mixer vessel + settler/dacanter
 Heuristics for Process Choice

 Energy is preferred to mass as a separating agent

 Fluids (liquids, gases) are preferred to solids as mass
separating agents
 Mass separating agents are preferred when one component
is to be separated from a mixture
 Processes employing gas and liquid phases are preferred
over liquid-liquid phases
 Solids are used as separating agents when the components
to be removed is present in very low concentration
 Distillation becomes expensive if boiling point differences
are less than 5oC
 Heuristics for Process Steps

 Make the easiest separation early

 Apply the difficult or most costly separations to the
smallest streams
 For example: make the highest temperature separations on
the smallest streams
 If possible, separate the most abundant component early in
the process sequence
 Make the most difficult or most expensive separation late
in the process sequence