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ChE351 Lecture
9/26/16
Prof. Davis

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Unit Op Selection Criteria

Depends a lot on concentration of solute / component
of interest (Dilute? Concentrated?)
T, P, and phase of feed can be changed easily (onion),
though it is expensive to vaporize heavy liquids,
condense light gases, and/or compress a vapor to
high P Why are light gases expensive?
The engineers choice of technology depends a lot on
the type of feed (Is it T sensitive? Corrosive?)
Ultimately, cost is the major factor, followed by safety
and environmental impact
Cost tends to go up to 0.6 power, i.e. $ V0.6
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Separation Sequences
More often than not, a multicomponent
separation will require multiple units / products
(one unit for each extra product) Why?
There are heuristics for determining the order
of multiple units (p. 17 of S-H):
1.
2.
3.
4.
5.
6.

Remove unstable/corrosive/reactive things first

Remove final products one by one as distillates
Remove the product of higher concentration earlier
Make the difficult separations w/out other species
Leave high SF products for later on in the sequence
Select for near-equal amounts of top/bottom products

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Activity: Separation Sequences

Time: 10 min to do, 5 min discuss
A distillation sequence produces the same four
final products from the same five components
as in Figure 1.9 on p. 17 of your book. The
molar percentages in the feed are 5%
propane, 15% isobutane, 25% normal butane,
20% isopentane, and 35% normal pentane.
The most difficult separation is between the
butanes. Use the heuristics to select the best
sequence of separation units.

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Answer: Separation Sequences

Why?
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Separator Designer Must Consider

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Selection of Feasible Sep. Units

You need to know a lot of chemistry in order to pick

the right kind of separation system
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Ease of Scale-up

We learn top ones because we know a lot about them

and they are common; they scale to high volumes well
Why dont we need parallel units for the boxed
operations?
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Activity: Separation System Design

Time: 5 min to do, 5 min discuss
Acetic acid is a very common commodity
chemical, produced from biomass
(vinegar) and from methanol. Use the
factors from table 1.12 on p. 28 to explain
in 1-2 sentences why the separation of a
stream containing 10% acid by weight
might be more economical by LLE with
ethyl acetate than by distillation.
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Answer: Separation System Design

A.
B.
C.
D.

E.

1. Dilute 2. Large 3. Low 4. Low 5. Liquid

1. Nearly pure 2. Lowish 3. Lowish 4. Liquid
1. Polar v. non-polar (organic/aqueous)
1. Pretty easy for LLE 2. Pretty easy for LLE
3. Already a liquid 4. None for LLE 5. Much less
for LLE than for distillation (boiling lots of water)
1. Probably higher for LLE, but might be similar
2. Probably lower for LLE
Since LLE uses lower temperatures, it may cost
less than distillation. Ethyl acetate probably likes
acetic acid much more than water.

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End Chapter 1
1. Role of separation processes in society
2. 5 general categories for separation units
3. Examples of equipment types for each
category
4. Specification methods (specs)
5. Selection of feasible equipment
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Ch. 2: Thermodynamics of Mixtures

I expect you to already know this, but we will do
some review and you should use this chapter
as a reference for things we do later
Objectives / skills you should have:
1. Explain phase equillibria in terms of:

Gibbs free energy Chemical potential Fugacity

Fugacity coefficients Activities Activity coefficients

2. Understand why K-values are useful

3. Explain how process simulators (Aspen, Pro/II)
compute thermodynamic properties
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Chemical Potential and Fugacity

Ch. 2 talks about exergy / availability / Gibbs
energy What is chemical potential?
Why do we need it?

fugacity of species i f i Ce
activity of species i ai
activity coefficient : iV

fi
fi

aiV

yi

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ref

i
RT

Fictitious
pressure made
using chemical
potential

aiL
or iL
xi

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Thermodynamic Equilibrium
What is true at equilibrium?
Do we need thermal equilibrium to reach
thermodynamic equilibrium?
fi

fi

i i
T

f K

T
K

P
K
i

i 1K N species

i 1K N species

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Phase #

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Activities and K-values

Activity coefficients are 1.0 for ideal mixtures;
anything non-ideal is empirically measured
ALL THESE QUANTITIES ARE EMPIRICAL
yi
K value of species i K i
f T, P
xi

VLE

Ki ?
relative volatility ij
f T , P
Kj

LLE

distibution coefficient of species i K Di

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xi

xi 2

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Finding Thermo. Parameters

Rigorously, K-values come from the
fugacities/activities of the species in the mixture
The most crude approximation (ideal
gas/Raoults law/ideal solution) is:
yi Pi sat
Ki

xi

Ptot

In order to do calculations with units where VLE

is occurring, we need K-values
This includes distillation, flash, partial
vaporization/condensation, absorption, and
stripping
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Activity: K-values
Time: 2 min to do, 2 min discuss

Use the plot on p. 45 of the book to find

the K-value of benzene at 40 psia and
200 oF.

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Process Simulators
Why do we use process simulators?
What would we have to do if we didnt have
them?
MB, EB
s, h, g, and Ki if you pick
correct EoS (not easy)
Knows all design eqn. and
unit operation models
Need thermo. to confirm simulation is correct
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