CHEE09009

Chemical Engineering Unit Operations 3

Revision Lecture

Dr. Simone Dimartino

simone.dimartino@ed.ac.uk
2.072 Faraday Building
Surgery Hour: Fri 12.00
Exams!

Aaaaah!
 xxxxday xx December 201w
xx.xx xm xx.xx xm

CHEMICAL ENGINEERING UNIT OPERATIONS 3

This paper consists of TWO questions.
All candidates should attempt ALL questions

Students should assume reasonable values for any data not given in a question nor available on a datasheet,
and should make any such assumptions clear on their script.

Students in any doubt as to the interpretation of the wording of a question, should make their own decision,
and should state it clearly on their script.

Only a calculator from the list approved by the College of Science and Engineering may
be used in this examination.

The examination paper that you are now sitting is to be marked ANONYMOUSLY.

Please write your name in the space indicated at the top right hand corner on the front cover of the answer book.

Also enter your examination number in the appropriate space on the front cover.

Write ONLY your examination number on any extra sheets,

worksheets or graph paper used and firmly attach these to the answer book(s).
Relevant supporting data and equations are bound with the examination paper.
 Exams

- Two hours, two questions

- Each question consists of several sections

- Some sections are connected to each other: i.e., to answer part b,

need something from part a

- Some sections are not related to each other: i.e. part c asks for something
completely unrelated to a or b

- READ CAREFULLY
 Exams

- Questions cover as many areas of Unit Ops as possible giving

a chance to demonstrate your knowledge of parts of the curriculum

- Questions are related to tutorial problems

- BUT THEY ARE NOT TUTORIAL PROBLEMS

- Do not search for a ready solution: think

 Exams

- Graphs: submit your graphs with the exam books

- Derivation: if you do not know how move one

- Precise answer is not expected show correct steps of solution

- Look for clues

- If asked to provide an answer in two sentences:

it really means two sentences, NOT 20 sentences!

- Several unit ops can be combined: i.e. lowering humidity via adsorption
 BASICS
- Remember units measures!

- Conversions:
- g/g -> mol/g, mol/cm3, mole fraction, mole ratio
- gas constant, Avagadro number

- Basic chemistry: molecular weight C, O, H, N, air, H2O

- Math: integration/differentiation; log average,

geometric average, trapezoidal integration technique

- Ability to draft appropriate mass and energy balances

Not just to solve them!!!
1. Fundamentals - Thermodynamic relations for mixtures
- K values and relative volatility
- Simplified models for ideal solution/ideal gas
and in Henrys law regime

2. Multi-component distillation - Bubble and dew points

- Enthalpy of multi-component mixtures
- Single stage flash separation
- Minimum number of stages (Fenske equation)
- Minimum reflux (Fenske-Underwood equations)
- Gilliland for actual number of stages
- Efficiency analysis and actual number of stages
- Further design detail: flooding analysis and
column diameter, condenser reboiler duties

3. Absorption/distillation in packed beds - Minimum L/V (absorption)

- Minimum reflux (distillation)
- Pressure drop
- Eckert generalized chart, flooding velocity etc
- Height of packing (HTU, NTU)
- Further design: condenser/reboiler duties etc
4. Humidification/Cooling towers - Humidity: absolute, relative, link to partial water
pressure, mole fraction of water in air, humid heat,
humid air enthalpy
- Psychrometric chart
- L/G ratio (minimum air flow rate requirement)
- HTU, NTU analysis
- Height of the contact zone
5. Drying - Constant drying rate regime
- Relation to psychrometric chart
6. Adsorption Batch
- Minimum S/G (equilibrium adsorbent required)
- Equilibrium number of stages

Stage-wise counter-current (purasiv)

- Minimum S/G, actual S/G
- Number of equilibrium stages (McCabe-Thiele)

Continuous contact (hypersorb)

- Minimum S/G, actual S/G
- HTU, NTU, height of contact zone

Fixed bed:
- Minimum bed requirement (S/G)
- Adsorption time (online)
1. Thermodynamic relations for mixtures:
Simplified models for ideal solution/ideal gas
Raoults law (Ideal solution/ideal gas, condensable species below critical point):

pi = xi Pi s pi is the partial pressure of component i

Daltons law (Ideal gas):

V
pi = yi P P is total pressure

K-value for ideal gas/ideal solution system: L

K i = yi / xi = Pi s / P T, P

Relative volatility for ideal gas/ideal solution system:

i , j = K i / K j = Pi s / Pjs
Antoine equation: Bi
ln Pi s (T ) = Ai
T + Ci
1. Thermodynamic relations for mixtures:
Simplified models in the Henrys law regime
Henrys law (component i is above its critical point, or non-ideal solution)

pi = H i (T )xi pi is the partial pressure of component i

Daltons law (Ideal gas):

V
pi = yi P P is total pressure

K-value in the Henrys law regime: L

K i = yi / xi = H i (T ) / P T, P

Relative volatility in the Henrys law regime:

i , j = K i / K j = H i (T ) / H j (T )
2. Calculation of Bubble point
P = const
- Model system: binary mixture A, B
T
V
x A + xB = 1
- Consider the process in the figure: we start with
a mixture of composition 1 and temperature T1
L and start increasing the temperature
1
- As we increase the temperature we are going to
reach a point where the first bubble forms

- The vapour in this bubble obeys:

y A + yB = 1 Bubble - sum of y = 1
Dew - sum of x = 1

or:

K A (T ) x A + K B (T ) xB = 1
- Thus as we increase the temperature we put new
K-values in the above equation until this condition is met
2. Calculation of Bubble point
P = const

Procedure:

a) Select T

b) Ki(T)

c) K x
i
i i

d) if K x
i
i i >1 T is too high

e) Adjust T
K i xi
g) Final composition can be corrected using yi =
K i xi
i
2. Calculation of Dew point
P = const
- Model system: binary mixture A, B
T 1
V y A + yB = 1
- Consider the process in the figure: we start with
a mixture of composition 1 and temperature T1
and start decreasing the temperature
L
- As we decrease the temperature we are going to
reach a point where the first drop of liquid forms

- The liquid in the droplet obeys:

x A + xB = 1
or:

y A / K A (T ) + y B / K B (T ) = 1
- Thus as we decrease the temperature we put new
K-values the above equation until this condition is met
2. Calculation of Dew point
P = const

Procedure:

a) Select T

b) Ki(T)
yi
c)
i K
i
y
d) if i > 1 T is too low
i Ki

e) Adjusting T
yi / K i
g) Final composition can be corrected using xi =
yi / K i
i
2. Multicomponent flash: Isothermal case
Given: P1, T1

Objective: find D, B, and their compositions D, yi

F = D+B Sum(x)-Sum(y)

important F, zi
P1 ,T1
Fzi = Dyi + Bxi

sum of x minus sum of y

B, xi
zi
derive this

xi =
1 + (K i 1) Rachford-Rice equation

zi K i zi (1 K i )
yi =
1 + (K i 1) i 1 + ( K 1) = 0
i
2. Multicomponent flash: Adiabatic case
D, yi , hD

F , zi , hF
P1 ,T1
PF , TF

B, xi , hB
Liquid feed is heated under pressure and then adiabatically flashed through
the pressure reducing valve:

P1 PF B+D = F theta = (D/F)

T1 TF Bxi + Dyi = Fzi

BhB + DhD = FhF or (1 )hB + hD hF = 0
2. Binary distillation: Complete picture

R 1
yn +1 = xn + xD
R +1 R +1
y
q zF xD = y1
y= x+
q 1 1 q
This is the intercept

L B
yn +1 = xm xB
V V zf
1
xD
R +1

xB

xB zf xD x
 2. Binary distillation: Minimum number of stages

a) Graphical method

b) Short cut methods: Fenske Equation FUG(K)

Fenske Equation Derive this

xD xB
= 1, AB 2, AB N +1, AB
1 xD 1 xB
If: 1, AB 2, AB N +1, AB AB
xD xB
= ( AB )
N min +1

1 xD 1 xB
x values are for the HK component

ln[ xD (1 xB ) / xB (1 xD )]
N min = 1 x with no subscript is always

ln AB referring to the less volatile

component
2. Binary distillation: Minimum reflux

L
R min =
D min y1 = xD

y*

zf
xD y *
Rmin =
y * x *
not a valuable use of time to remember this

xB

xB x* zf xD = x0
2. Multicomponent distillation: Short cut design:
a) Identify light and heavy key components
b) Guess splits of non-key components
c) Determine operating column pressure
d) Feed stage considerations
d) Calculate LK , HK
c) Use Fenske equation to find minimum theoretical stages, Nmin
d) Calculate splits of the non-key components and compositions
of the distillate and bottoms products
e) Use Underwood method to find minimum reflux ratio, RDm
f) Use Gilliland correlation to find actual number of ideal stages
given operating reflux
g) Use Kirkbride equation to locate the feed stage
h) Calculate condenser and reboiler duties
2. Fenske equation for multicomponent
distillations
Assumption: relative volatilities of components remain constant
throughout the column

- Determination of minimum number of stages:

LK light component
xD , LK xB , HK HK heavy component
ln
xB , LK xD , HK K LK (T )
N min = 1 LK , HK (T ) =
ln LK , HK K HK (T )

- Calculation of concentrations of all other non-key components:

x D ,i xD , HK
= ( )
i , HK
N min +1

x B ,i xB , HK
2. Estimation of relative volatilities

K i (T )
i , j (T ) = T
K j (T ) D

Choices for relative volatility:

B
1) Relative volatility at saturated feed condition

i , j = iF, j (TF )
2) Geometric mean relative volatility
why geometric mean?
i , j = iD, j (TD ) iB, j (TB )

i , j = 3 iF, j (TF ) iD, j (TD ) iB, j (TB )

 2. Minimum reflux ratio analysis:
Underwood equations

xi , F i , HK For a given q and the feed composition xi,F

= (1 q ) we are looking for a root
i , HK (usually is between LK,HK and HK,HK)

V i , HK xi , D
Rm + 1 = = Once is found, we can calculate the
D i i , HK minimum reflux ratio
Thi lies between the LK and HK
These will be provided unless asked to derive values, roots are between
relative volatilities
2. Minimum reflux ratio analysis:
Underwood equations xi , F i , HK
i , HK
=0

i , HK xF ,i
f ( ) =
i i , HK

Red lines
represent
relative volatility
values of thi
 2. Gilliland correlation:
Number of ideal plates at the operating reflux

Empirical equation,
doesnt require to be
derived.

Will be given in exam

Note: N here includes one stage 61 data point covering the ranges:

for partial reboiler and one stage

for partial condenser (if used).

R = 1.1 1.5 Rmin

2. Distillation: energy balance

Overall energy balance:

DhD + Bh B +QC = FhF + QB

D
Total condenser duty:
F

QC = D(R + 1) yi H ivap B
Condensation of distillate and reflux fed back to column
Simply an energy balance

Total reboiler duty:

QB = B xi H ivap
 3. Absorption: Design considerations

Limiting conditions: Liquid/gas ratio; straight operating line

Condition: L, V constant -> L/V constant

(mole fraction of A in V)
This is possible for dilute (< 5% mole fraction) mixtures
so change in total number of moles of L and V is negligible y equilibrium line

A) Limiting (L/V)min value: yb

Operating line is
straight only for
L * Vya - Lxa L yb y a dilate mixtures
yb = xb + = *
V V V min xb xa
Red line

B) Number of ideal stages: the actual L/V ratio is

calculated as a multiple of the limiting value ya
this gives a steeper slope of the operating line.

The number of ideal stages can be then constructed using xa xb x*b x

McCabe-Thiele method. a is top
(mole fraction of A in L)
b is bottom
 3. Absorption: Design considerations

Limiting conditions: Gas-liquid ratio; straight operating and equilibrium lines

Condition: L, V constant -> L/V constant, ye=mxe

(mole fraction of A in V)
This is possible for dilute (< 5% mole fraction) mixtures
so change in total number of moles of L and V is negligible y equilibrium line
and
the region of interest is in the Henrys law regime yb
When henrys
A) Limiting (L/V)min value: constant is the
same throughout
the system
L * Vya - Lxa
yb = xb +
V V
L y ya yb y a
= b* = ya
V min xb xa yb / m xa
y=mx*
xa xb x*b x
B) Number of ideal stages: can be calculated
Analytically (Kremser method) (mole fraction of A in L)
 3. Absorption in packed towers

This property has units of length: Change in the concentration divided by average
height of transfer units (HTU) driving force: number of transfer units (NTU)
yb
V /S dy
H Oy =
K ya
N Oy =
ya
y y*

yb
V /S dy
Z=
K ya
ya
y y*
Z = H Oy N Oy
requires logarithmic mean driving force
Derive this
In the case when the eqbm line is parallel, y-y* will be constant
 3. Generalized Pressure drop in:
in. H2O/ft of packing
pressure drop (brackets:
correlation mm H20/m of packing)

(Eckert plot)

Attention, L, V are mass flow rates!!!

 4. Air/water systems Useful definitions
1) Humidity is the measure of water content in the air:

mH 2 O M H 2O p H 2O
- Absolute humidity = =
Moisture content by mass m Air M Air ( P pH 2O )

M H 2O PHs 2O
- Saturation humidity S =
Humidity at saturation M Air ( P PHs 2O )

p H 2O
- Relative humidity R = 100
Ratio of partial pressure of moisture PHs 2O
to partial pressure of moisture at saturation

P PHs 2O
- Percentage humidity A = 100 =R
Ratio of humidity to humidity at saturation S P p H 2O
4. Air/water systems Useful definitions

- Humid heat cs = c p , Air + c p , H 2O ( g )

Specific heat of moisturegas mixture
per unit mass of moisture-free gas

- Total enthalpy H = cs (T T0 ) + H 2O
Enthalpy of moisturegas mixture
per unit mass of moisture-free gas
referred to temperature T0 (usually 0C)

RT 1
- Humid volume vH = +
P M Air M H 2O
Volume of moisturegas mixture
per unit mass of moisture-free gas
4. Air/water systems

Properties of air water systems are summarized in psychrometric charts:

 4. Temperature profiles in cooling towers

TH 2O
TAir Ti
TH 2O TH 2O TAir
TAir Tw
Ti
Ti i
Tw
i Tw
i

The main driving force for the cooling
of water is the mass transfer.
Thus latent heat cools rather than the
sensible heat that is exchanged.

Bottom: water is relatively cool. Temperature of bulk air is comparable to or can

be even higher than temperature of bulk water. Surface of water is cooled via
evaporation and the interfacial temperature is lower than the temperature of
bulk water and bulk air. This provides the driving force (TH2O-Ti) for water
cooling. There is a sensible heat flux from air to the surface, but it is insignificant
compared to evaporative cooling. The humidity at the interface is higher than in
the bulk air, providing driving force for mass transfer of water vapor (Hi-H).
 4. Temperature profiles in cooling towers

TH 2O
TAir Ti
TH 2O TH 2O TAir
TAir Tw
Ti
Ti i
Tw
i Tw
i

Top: water is hot, temperature of bulk air is lower than temperature of bulk
water. Surface of water is cooled by both evaporation (enthalpy carried away
together with moisture via Hi-H gradient) and sensible heat via Ti-TAir gradient.
The latter term is insignificant compared to the term associated with the latent
heat.
you may need to explain this in the exam
 4. Design of cooling towers

Operating line for cooling towers:

H
Equilibrium
Lwc p , H 2O (l )
( )
curve
Ha H = TH 2O ,a TH 2O
Gw H a* Lwc p , H 2O (l )
May need to derive this
Gw ,min
Minimum air flow condition: Ha

H a* H Lwc p , H 2O (l )
= Lwc p , H 2O (l )
TH 2O ,a TH 2O Gw ,min Hb
minimum flow of air required to run the system Gw

Air flow rate is usually 1.2 to 2 times the minimum. TH 2O ,b a is the top
TH 2O ,a TH 2O
b is the bottom

Self-study question:
Derive an expression for the H*-TH2O equilibrium curve using T0=0C as reference.
Draft a plot of the equilibrium curve for the water-air system between 10 and 60 C.
 4. Design of cooling towers

If overall mass transfer coefficient is employed:

H
Equilibrium
(
Gw dH = K y aM Air H * H SdZ ) curve

H a*
Gw S dH
Z=
K y aM Air H * H = H Oy N Oy Ha
H b*
May not be given this - can derive however
Where: 1 1 m Hb
= +
K y a k y a M Air hx a
dH * slope of equilibrium curve TH 2O ,b TH 2O ,a TH 2O
m=
dT

H Hb
(H H ) = (H ) (
H a H b* H b )
*
N Oy = *a ; * a
(
H H LM ) LM
H a* H a
ln * Most likely given in this
Hb Hb
 5. Adiabatic Drying: Air/water systems
The assumption of saturated air in equilibrium with liquid is not necessary.

R,2
T1, 1 , R,1 T2 , 2 , R,2

Tv
R,1

The lewis relation holds true for water/air only,

2
that is
1

Ts = Tw
T2 T1

More in general, for i) steady state drying ii) of liquid free water iii) in adiabatic
conditions, the temperature of the drying solid, Ts, is the same as the wet-bulb
temperature, Tw.
 5. Drying time under constant drying conditions

From definition of drying rate: mass of water vaporized (mv) per unit time per unit area (A):

1 dmv ms dX
R= =
Energy balance

A dt A dt
Under constant drying conditions, the heat and mass transfer are located entirely in the gas
phase, therefore:
- The wet-bulb temperature (Tw) is the steady state temperature at the solid-air interface (Ti)
and of the solid (Ts), Tw = Ti = Ts
- The humidity at the interface is at equilibrium conditions, H i = H s

The drying rate under constant drying (RC) can be expressed either in terms of heat or mass
transfer coefficients:
1 dmv h(T Tw )
Rc = = = M Air k y (H s H )
A dt H 2O
Combining the two and integrating to find the drying time:

ms (X in X fin ) ms H 2O
tc = = (X in X fin ) = ms 1
(X in X fin )
A Rc A h(T Tw ) A M Air k y (H s H )
 6. Adsorption: Conventions for the isotherm
(equilibrium line)
q [kg of adsorbate]/
Y
[kg of pure adsorbent]

(flip)

H
Y [kg of adsorbate/kg carrier gas] q
(More like in
HY absorption studies)
q=
1 + bY H, b will depend on the units
(Langmuir equation) of bulk composition
 6. Adsorption: Batch operation
Adsorbent
S, q0
Gas or liquid feed
G,Y0 G, Y1

1
Y = y/(1-y) [kg adsorbate]/ [kg carrier gas]
q=x/(1-x) [kg adsorbate]/[kg adsorbent]
S, q1
Operating line
G ' (Y0 Y1 ) = S ' (q1 q0 ) Equilibrium line
Y (Langmuir)

q0, Y0
Y1: the amount of S required -S/G
S : Y1 you can achieve
q1, Y1
If adsorption equation is available
an analytical solution is possible
q
 6. Adsorption: Stage-wise operation
Adsorbent Adsorbent
S1, q0 S1, q0 Each stage is a COLUMN

Gas or liquid feed

G,Y0 G, Y1 G, Y2

1 2

S1, q1 S1, q2
Operating line
G ' (Y0 Y1 ) = S '1 (q1 q0 )
Y
G ' (Y1 Y2 ) = S '1 (q2 q0 )
q0, Y0
-S1/G

q0, Y1
q1, Y1
q2, Y2
q
 6. Adsorption: Stage-wise operation
Adsorbent Adsorbent
S1, q0 S2, q0
Gas or liquid feed
G,Y0 G, Y1 G, Y2

1 2

S1, q1 S2, q2
Operating line
G ' (Y0 Y1 ) = S '1 (q1 q0 )
Y
G ' (Y1 Y2 ) = S '2 (q2 q0 )
q0, Y0
-S1/G
Objective: to minimize
S1 + S2
q0, Y1
Objective is to minimise solvent q1, Y1
(not in this course)
More likely to be you have this S1
-S2/G q2, Y2
and this S2, what do you get out
q
 6. Adsorption:
Countercurrent stage-wise operation

Gas or liquid feed

G,Y0 G, Y1 G, Y2 G, YN

1 2
S, q1 S, q2 S, qN+1

Operating line
G ' (Y0 YN ) = S ' (q1 q N +1 )
Y

q1, Y0
S/G

qN+1, YN

q
 6. Adsorption:
Countercurrent stage-wise operation

Gas or liquid feed

G,Y0 G, Y1 G, Y2 G, YN

1 2
S, q1 S, q2 S, qN+1

Operating line
G ' (Y0 YN ) = S ' (q1 q N +1 )
Y
Minimum adsorbent requirement:
q1, Y0
Smin/G
Design: analogy with stage-wise
absorption
qN+1, YN

q
Good luck