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Today: Introduction to Separations Lecture 2: Review of equilibrium thermodynamics (not covered in class). Lecture 3: Thermodynamics of Separations
Instructor: Charles Musgrave 261 Keck 725-9176 charles@chemeng.stanford.edu http://chemeng.stanford.edu/~charles/cheme120/ Office Hour: Tuesday 3-4pm TA: Junsic Hong 03 Stauffer I 723-0980 junsic@stanford.edu Office hour: Thursday 4-5pm Book: Separation Process Principles Seader and Henley Homework Assigned on Friday/Due on Friday
Examples: Separation of blood Purification of drugs Purification of Au, Si, GaAs Refining of crude oil DNA testing Purification of organics Purification of water Smog control mixed separated
However, mixing is inherent in nature: The increase in entropy associated with the randomness of a mixture lowers the Gibbs free energy.
Therefore, to unmix a solution we must overcome the entropic driving force to mix.
Lecture 1: Introduction to Separations 2
Why Separate?
There are many reasons for wanting pure substances. Some of these reasons include: Need for pure material in engineering application (semiconductors) Preparation of raw materials into their components Need for pure material for materials processing Need to remove toxins or inactive components from solution (drugs) Need for ultrapure samples for testing Need for analysis of the components of the mixture (DNA testing) Based on these motivations for separations, we can divide separations up into three main areas: Analytical Separations small scale quantitative analysis Example: Chromatography Preparative Separations small scale materials for R&D Example: Centrifugation Industrial Separations
Example: Distillation
The list of different existing separations methods is limitless. Therefore we will emphasize the fundamentals of separations. Note: 50 to 90 percent of capital investment in chemical plant is for separations equipment.
Lecture 1: Introduction to Separations 3
The fundamentals that we will apply to study separations in this course involve: Materials and energy balances: conservation of energy and matter Thermodynamics: phase equilibrium and solution thermodynamics (Chapter 2) Transport phenomena (Chapter 3; not emphasized) Chemical reaction kinetics: rate of conversion of one species to another (not emphasized)
For the most part our analysis of various separations processes will focus on using phase equilibrium and materials and energy balances.
Process Flow Diagrams indicates processes by: Realistic symbols of process equipment Including auxiliary operations
Lecture 1: Introduction to Separations 5
Distillation
Distillation
Reflux drum Overhead vapor
F
Feed
Stripping section stages
1 2
Reflux
Distillate
Feed Stage
P2
S2
Bottoms
Example
Example: Recovery of hydrocarbons from wet natural gas (wng) These types of separations generally exploit the differences in volatility to cause a separation
C2+
ethane
C3+
C5+
propane
Notice that this process involves a train of separators: This is common in industrial processes.
Lecture 1: Introduction to Separations 7
Mechanism of Separations
UNMIXING is not a spontaneous process in nature A process requiring no external driving force Reduces randomness and thus the entropy of the system Separations involve nonspontaneous processes Usually the mixture to separate is a homogeneous, single phase: If not, then often one will phase separate first gravity centrifugation filtration.
Separator: Causes different chemical components to move to different spatial locations to be collected as more pure mixtures: Differential Transport.
Lecture 1: Introduction to Separations
Phase Creation Phase Addition Barrier Separation Solid Agent separations Separation by gradient
All five techniques rely on the ability to enhance the rate of mass transfer of certain species relative to others to effect a spatial separation of components.
Thus, all separations processes must introduce a thermodynamic driving force to overcome the decrease in the entropy of the system as the components are separated.
Thermodynamics of Separations
Remember that there is an infinite driving force associated with removing the last impurity atom from a pure substance:
SM
S A
S B
G
G' B 0 G' A 0
GA GB
XB
0 1
XB
Since the driving force to mix will eventually equal the driving force we introduced to cause the separation the extent of separation will be limited by thermodynamics equilibrium!
Lecture 1: Introduction to Separations 10
Rate of Separations
Although the extent of a separation is determined by thermodynamics, the rate of separations is limited by the differential rate at which the different species are moved. That is: The Rate of Separation is limited by Mass Transport.
Limits:
In this course we will generally focus on the thermodynamic fundamentals governing separations. Transport issues will be addressed, but not a focus.
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Thermodynamics
Next: Thermodynamics of Separations Lecture 2: Review of equilibrium thermodynamics (not covered in class). Lecture 3: Thermodynamics of Separations
Before Next lecture Read Lectures 2 and 3 (see course webpage) Review Thermodynamics (some notes available on course webpage) Equilibrium Entropy Solution Thermodynamics Activity and Activity Coefficients Equilibrium Phase Diagrams
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