Application of Separation Processes

CENG
CENG221
221

Lecture
Lecture1.1.Introduction
IntroductiontotoSeparation
SeparationProcesses
Processes(2(2h)
h)
Learning Objectives:
Learning Objectives: Raw Materials
(1)
(1)Importance
Importanceofofseparation
separationprocesses
processes
(2)
(2)Popular
Popularchemical
chemicalseparation
separationprocesses
processes
(3) Physical Chemical
(3)What
Whatare
areequilibrium
equilibriumseparation
separationprocesses
processes transformation
transformation
(4)
(4)Vapor-liquid
Vapor-liquidequilibria
equilibria
Learning
LearningGuides:
Guides:
(1)
(1)Lecture
Lecturehandouts
handouts Product 1 Product 2
(2)
(2)Chapters
Chapters11and
and22ofofTextbook:
Textbook:Equilibrium-Staged
Equilibrium-Staged
Separations
Separations Examples: Examples:
(3) (1) water → distilled water (1) water → hydrogen
(3)Review
Reviewthermodynamic
thermodynamicnotes
noteson
onRaoult’s
Raoult’sLaw,
Law, (2) crude oil → gasoline (2) crude oil → polyester
Antoine
Antoineequation
equationand
andDePriestler
DePriestlerChart
Chart (3) air → nitrogen gas (3) air → ethylene glycol (antifreeze)
→ oxygen gas (4) coconut → medicinal oil
(4) coconut → cooking oil (5) limestone→ cement
(5) limestone→ gravel
Application of Separation Processes Distilled Water

Tap Water

Carbon Adsorber
Raw Material
Reactor Products

A→B

Filter Ion Exchange

Raw Material 1 Product 1

Bottled
Separator 1 Water
Separator 1
A+a↔B+b UV
Decontamination
Flash
Reactor Distillation

Separator 1 Separator 1

Raw Material 2 Product 2

Types of Separation Processes Types of Separation Processes
(1) Distillation processes: (2) Absorption/stripping processes:
* most popular chemical separation process, * popular in environmental applications,
* capable of producing pure substance from mixture, * transfer gas component from gas to liquid or vice versa,
* requires two phases: liquid and vapor, * requires two phases: liquid and gas,
* uses energy to accomplish separation. * uses the different affinity gas component for gas and liquid.
Production processes using distillation Production processes using absorber
* oil production, * scrubbing smokestacks,
* air separation, * removal of ammonia from refinery,
* distillation of wine to cognac and spirits. * remove CO2 from air.

http://lorien.ncl.ac.uk/ming/distil/distil0.htm

http://www.cheresources.com/packcolzz.shtml
Types of Separation Processes Types of Separation Processes
(3) liquid-liquid extraction: (4) solid-liquid extraction:
* used for processes that requires low temperature operation, * used liquid to extract component from a solid matrix,
* transfer soluble component from one liquid to another, * transfer soluble component from solid to liquid,
* requires two phases: two immiscible or partially miscible liquids, * requires two phases: solid and liquid,
* uses the different affinity components for separation. * uses the solubility of the component for separation.
Production processes using extraction Production processes using leaching
* food processing, * mining,
* pharmaceutical separation, * food processing,
* oil purification. * pharmaceutical.

http://www.cheresources.com/extraction.shtml
http://www.robatel.com/gb/liquide_liquide.htm
 Phase Transformation
Phase Equilibria
Phase Diagram of Water

ya, yb Tv, Pv
ya + yb = 1

xa, xb TL, PL
xa + xb = 1

http://www.lsbu.ac.uk/water/phase.html
bubble saturated dew
point vapor point
At Equilibrium:
TL = Tv (thermal equilibrium)
PL = Pv (mechanical equilibrium)
µL = µv (chemical equilibrium)

subcooled saturated superheated

liquid liquid vapor
Equilibrium-Staged Operation Equilibrium-Staged Operation

Multiple Staged Unit

Ethanol + Water
Ethanol + Water
LIQUID

LIQUID Ethanol

Water

Ethanol

Ethanol

Water
Water

VAPOR Ethanol + Water

Ethanol

Water

VAPOR
Ethanol + Water
 Antoine Equation:
Different Representation of VLE Data
(1) Ideal Solution: LnPE* (kPa) = 16.6758 – 3674.49/(T(°C) +226.45)

Raoult’s Law: LnPW* (kPa) = 16.2620 – 3799.89/(T(°C) +226.35)

PA = YAPT = PA*XA Use Antoine equation to determine the normal boiling point of
YA= (PA*/PT ) XA ethanol and water ?

Antoine Equation: Use Antoine equation to determine the bubble point

temperature of a solution containing 5 moles of ethanol and 5
LnPA* (kPa) = A - B/(T(°C) +C) moles of water.

Compound A B C

Benzene 13.8594 2773.78 220.07

Ethanol 16.6758 3674.49 226.45

n-heptane 13.8587 2991.32 216.64

Toluene 14.0098 3103.01 219.79

Water 16.262 3799.89 226.35

 Different Representation of VLE Data
Example 1: Determine the T-x-y relationship for ethanol and water
using Antoine Equation assuming that ethanol-water form
an ideal solution. Plot the resulting data. Please use
ambient pressure.

T(C) Pe* Pw* Xe Xw Ye Yw

Tmin 78.29185 101.3 44.19879 1 0 1 0

80.46185 110.315 48.2752 0.85469 0.14531 0.930752 0.069248
82.63185 119.9885 52.66227 0.722419 0.277581 0.855695 0.144305
84.80185 130.3574 57.37836 0.601839 0.398161 0.774474 0.225526
86.97185 141.4599 62.44257 0.491758 0.508242 0.686714 0.313286
89.14185 153.3356 67.87472 0.391118 0.608882 0.592027 0.407973
91.31185 166.0253 73.69541 0.298978 0.701022 0.490009 0.509991
93.48185 179.5714 79.92597 0.214501 0.785499 0.380239 0.619761
95.65185 194.0176 86.58853 0.136941 0.863059 0.26228 0.73772
Tmax 99.99131 225.7879 101.3 2.28E-16 1 5.09E-16 1
 105

100

95

T(C)
90

85

80

75
0 0.2 0.4 0.6 0.8 1
X,Y (ethanol)

What is the boiling point of pure ethanol and water?

What is the bubble point temperature of a mixture containing
0.25 mole fraction of ethanol? What is its dew point temperature?
What is the bubble and dew point temperature of a solution
containing 30 wt.% water?
Different Representation of VLE Data Different Representation of VLE Data
(2) Tabulated data: (3) Graphical representation:

X(ethanol) X(water) Y(ethanol) Y(water) T(C)

T-X-Y diagram
0 1 0 1 100
0.019 0.981 0.17 0.83 95.5
0.0721 0.9279 0.3891 0.6109 89
0.0966 0.9034 0.4375 0.5625 86.7
105
0.1238 0.8762 0.4704 0.5296 85.3
0.1661 0.8339 0.5089 0.4911 84.1
0.2377 0.7623 0.5445 0.4555 82.7 100
0.2608 0.7392 0.558 0.442 82.3
0.3273 0.6727 0.5826 0.4174 81.5
0.3965 0.6035 0.6122 0.3878 80.7
0.5079 0.4921 0.6564 0.3436 79.8 95
0.5198 0.4802 0.6599 0.3401 79.7
0.5732 0.4268 0.6841 0.3159 79.3

T(C)
0.6763 0.3237 0.7385 0.2615 78.74 90
0.7472 0.2528 0.7815 0.2185 78.41
0.8943 0.1057 0.8943 0.1057 78.15
1 0 1 0 78.3
85

The experimental VLE data are usually obtained using

special stills where the temperature, pressure and 80
concentrations of the components in liquid and vapor phases
could be accurately determined. 75
0 0.2 0.4 0.6 0.8 1
X, Y (mole fraction) → x, y (mass fraction)
for binary mixture (2-components): X,Y (ethanol)

x = X*MWA/(X *MWA + (1-X) *MWA) What is the boiling point of pure ethanol and water?
What is the bubble point temperature of a mixture containing
** derive the equations for n-component and for x → X 0.25 mole fraction of ethanol? What is its dew point temperature?
What is the bubble and dew point temperature of a solution
containing 30 wt.% water?
 Different Representation of VLE Data
Example 2:

T-x-y diagram Determine the concentration of an alcohol solution if its

bubble point temperature is 92.5 C? What should be the
ethanol content of the vapor at equilibrium with this solution?
105
What is the bubble point temperature of 78 and 95 mol.% alcohol?
100

105
95
T(C)

100
90

95
85

T(C)
90
80

85
75
0 0.2 0.4 0.6 0.8 1
80
x, y (ethanol)
75
Compare the T-X-Y and T-x-y diagrams?
What is the bubble point temperature of a mixture containing 0 0.2 0.4 0.6 0.8 1
0.25 weight fraction of ethanol? What is its dew point temperature? X,Y (ethanol)
What is the bubble and dew point temperature of a solution
containing 30 wt.% water?
 Different Representation of VLE Data Different Representation of VLE Data
(3) Graphical representation: (4) Distribution coefficient (K-value):

x-y or McCabe-Thiele diagram KA = YA/XA

1 YA = KA XA = γA(PA*/PT ) XA
K(T,P)
0.8
Y (ethanol)

T(C) Xe Ye Ke Xw Yw Kw
0.6

100 0 0 1 1 1
0.4 95.5 0.019 0.17 8.947368 0.981 0.83 0.846075
89 0.0721 0.3891 5.396671 0.9279 0.6109 0.658368
86.7 0.0966 0.4375 4.528986 0.9034 0.5625 0.622648
85.3 0.1238 0.4704 3.799677 0.8762 0.5296 0.604428
0.2 84.1 0.1661 0.5089 3.063817 0.8339 0.4911 0.58892
82.7 0.2377 0.5445 2.290703 0.7623 0.4555 0.597534
82.3 0.2608 0.558 2.139571 0.7392 0.442 0.597944
0 81.5 0.3273 0.5826 1.780018 0.6727 0.4174 0.620485
80.7 0.3965 0.6122 1.54401 0.6035 0.3878 0.642585
0 0.2 0.4 0.6 0.8 1 79.8 0.5079 0.6564 1.29238 0.4921 0.3436 0.698232
79.7 0.5198 0.6599 1.269527 0.4802 0.3401 0.708247
X (ethanol)
79.3 0.5732 0.6841 1.193475 0.4268 0.3159 0.740159
78.74 0.6763 0.7385 1.091971 0.3237 0.2615 0.807847
78.41 0.7472 0.7815 1.045905 0.2528 0.2185 0.86432
Determine the composition of the vapor at equilibrium with 78.15 0.8943 0.8943 1 0.1057 0.1057 1
an 30, 60, 80 and 90 mol.% ethanol solution. 78.3 1 1 1 0 0
Different Representation of VLE Data
(4) Distribution coefficient (K-value): DePriestler Chart
Different Representation of VLE Data
Example 3:

Determine the composition of isobutane and n-hexane solution

that boils at 50 C at a pressure of 300 kPa.

Plot T-X-Y diagram of isobutane and n-hexane solution for a P of

200 kPa.
 Different Representation of VLE Data Different Representation of VLE Data
: T(C) Kic4 KC6 alpha Example 4:

Determine the boiling point temperature of n-pentane, n-heptane

10 1.1 0.06 18.33333
20 1.5 0.095 15.78947
and n-octane which are the main components of lighter fluid.
30 2 0.15 13.33333
40 2.5 0.2 12.5 What is the liquid composition of the lighter fluid if the bubble
50 3 0.3 10 point temperature is 40 C at ambient pressure.
60 3.8 0.4 9.5
70 4.6 0.54 8.518519
80 5.5 0.7 7.857143
90 6.5 0.9 7.222222

100

80

60
T(C)

40

20

0
0 0.2 0.4 0.6 0.8 1
X,Y (i-C4)
Different Representation of VLE Data
(5) Relative Volatility (αAB)

αAB = KA/KB

YA = αAB XA/(1 + (αAB -1)XA)

T(C) Kic4 KC6 alpha

10 1.1 0.06 18.33333

20 1.5 0.095 15.78947
30 2 0.15 13.33333
40 2.5 0.2 12.5
50 3 0.3 10
60 3.8 0.4 9.5
70 4.6 0.54 8.518519
80 5.5 0.7 7.857143
90 6.5 0.9 7.222222
Different Representation of VLE Data
Example 5:

Plot X-Y diagram for isobutane-isopentane mixture if the relative

volatility is known to be 1.7
 Different Representation of VLE Data
Xic4 Yic4
:

0 0
0.1 0.158879
0.2 0.298246
0.3 0.421488
0.4 0.53125
0.5 0.62963
0.6 0.71831
0.7 0.798658
0.8 0.871795
0.9 0.93865
1 1

0.8

0.6
Y(i-C4)

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
X (i-C4)
Different Representation of VLE Data
(6) Ponchon-Savarit Diagram:

H-x-y diagram
Dew Point and Bubble Point Temperatures Different Representation of VLE Data
Example 6: (6) Ponchon-Savarit Diagram:
Using the Ponchon-Savarit diagram for ethanol-water solution, please
determine: H-x-y diagram
(1) the bubble and dew point temperatures of a solution containing
55 wt.% of ethanol.
(2) the bubble temperature of 0.2 ethanol-0.8 water solution and
the composition of the bubble at equilibrium with the liquid solution.
(3) the enthalpy of an ethanol solution (0.5-0.5) at 86 C.
(4) composition of vapor and liquid for a 0.5-0.5 ethanol-water solution
at 86 C and the V/L ratio.
(5) the enthalpy of the liquid (H) and vapor (h)
Different Representation of VLE Data
Relationships between the Ponchon-Savarit, T-x-y and y-x Diagrams:
Different Representation of VLE Data
(6) Ponchon-Savarit Diagram:
105

H-x-y
100diagram

95
T(C)

90

85

80

75
0 0.2 0.4 0.6 0.8 1
Material Balance Material Balance
Binary Equilibrium Solutions Binary Equilibrium Solutions

Overall Balance Overall Balance

Feed = (Sat. liquid) + (Sat. Vapor) Feed = (Sat. liquid) + (Sat. Vapor)
F=L+V F=L+V

Component Balance Component Balance

Fz = Lx + Vy Fz = Lx + Vy

105

100

95
T(C)

90

85

80

75
0 0.2 0.4 0.6 0.8 1
Dew Point and Bubble Point Temperatures Dew Point and Bubble Point Temperatures
(1) Bubble point temperature (Tb): (1) Dew point temperature (Td):
is the temperature at which the first bubble of vapor is formed at is the temperature at which the first dew or condensate forms
a given pressure. The composition of the vapor is at equilibrium from a vapor mixture. The composition of the dew is at equilibrium
with the liquid solution. with the vapor mixture.

(Note: One can assume that Tb is the temperature at which the (Note: One can assume that Td is the temperature at which the
distillation process starts) distillation process ends)

ya, yb ya, yb
ya + yb = 1 Tv, Pv ya + yb = 1 Tv, Pv

xa, xb TL, PL xa, xb TL, PL

xa + xb = 1 xa + xb = 1
Dew Point and Bubble Point Temperatures Dew Point and Bubble Point Temperatures
Distillation process occurs between bubble point and dew point Example 7: In a close container an alcohol solution containing
temperatures of the mixture. 0.4 mole fraction of ethanol was heated slowly from room tem-
perature to its dew point temperature. Determine the changes in
TL < Tb < T < Td < TH the liquid and vapor composition of the mixture.

Note: TL is the lowest boiling component in the solution/mixture,

Tb is the bubble point temperature of the solution with composition A,
Td is the dew point temperature of the mixture with composition A, 105
TH is the highest boiling component in the solution/mixture.
100

95

T(C)
90

ya, yb Tv, Pv 85
ya + yb = 1
80

75
TL, PL 0 0.2 0.4 0.6 0.8 1
xa, xb
xa + xb = 1 X,Y (ethanol)
Bubble Point Temperature Calculation

How
Howtotoset
setup
upaatrial
trialand
anderror
errorcalculation
calculationfor
forTTb:b:

(1)
(1)Bubble
Bubblepoint point- -allallisisliquid,
liquid,oneonebubble
bubbleofofvapor
vapor
set x = z (where z is the solution
set xi = zi (where z is the solution composition)
i i composition)
also
alsonotenotethe thepressure,
pressure,PPand andififnot
notgiven
givenset
setPPtotoambient
ambient(1(1
bar)
bar)
(2)
(2) Guessan
Guess aninitial
initialTemperature
Temperature(T (T0)0)
use
use the median temperature betweenthe
the median temperature between thehighest
highestand
andlowest
lowest
boiling components
boiling components
(3)
(3)Use
UsePPand andTT0 0totodetermine
determinethe theKiKivalues
valuesfrom
fromDePriestler
DePriestler
chart
chart
(4)
(4)Calculate
Calculateyyi i==KKi ixxi i
(5)
(5)Using
Usingmass massbalance,
balance,check checkwhether
whetherthe thesummation
summationofofyiyi==11
(6a)
(6a)IfIfnot,
not,then
thenuse usethe
themostmostvolatile
volatilecomponent
component(largest
(largestK)
K)asas
your reference and determine
your reference and determine the next T by: the next T by:
(K
(Ki)in+1
)n+1==(K (Ki)in)/Sum(y i)
n/Sum(yi)
using
usingPPand and(K (Ki)in+1
)n+1find
findthe
thenew
newTTn+1
n+1
repeat (3) to
repeat (3) to (6) (6)
(6b)
(6b)IfIfyes,
yes,TTn isisyouryourbubble
bubblepointpoint
n
Dew Point and Bubble Point Temperatures
Example 8a: Using the dePriestler chart find the bubble point
temperatures for a solution containing 0.5 mole n-pentane,
0.3 mole n-heptane and 0.7 mole n-octane at pressure of 2 bars.
Dew Point Temperature Calculation
Dew Point and Bubble Point Temperatures
How
Howtotoset
setup
upaatrial
trialand
anderror
errorcalculation
calculationfor
forTTd:d: Example 8b: Using the dePriestler chart find the dew point
temperatures for a solution containing 0.5 mole n-pentane, 0.3
(1)
(1)Dew
Dewpointpoint- -allallisisvapor,
vapor,one onedrop
dropofofliquid
liquid mole n-heptane and 0.7 mole n-octane at pressure of 2 bars.
set y = z (where z is the solution
set yi = zi (where z is the solution composition)
i i composition)
also
alsonotenotethe thepressure,
pressure,PPand andififnot
notgiven
givenset
setPPtotoambient
ambient(1(1
bar)
bar)
(2)
(2) Guessan
Guess aninitial
initialTemperature
Temperature(T (T0)0)
use
use the median temperature betweenthe
the median temperature between thehighest
highestand
andlowest
lowest
boiling components
boiling components
(3)
(3)Use
UsePPand andTT0 0totodetermine
determinethe theKiKivalues
valuesfrom
fromDePriestler
DePriestler
chart
chart
(4)
(4)Calculate
Calculatexxi i==yyi i/K /Ki i
(5)
(5)Using
Usingmass massbalance,
balance,check checkwhether
whetherthe thesummation
summationofofxixi==11
(6a)
(6a)IfIfnot,
not,then
thenuse usethethemost
mostvolatile
volatilecomponent
component(largest
(largestK)
K)asas
your reference and determine
your reference and determine the next T by: the next T by:
(K
(Ki)in+1
)n+1==(K (Ki)in)nSum(x
Sum(xi)i)
using
usingPPand and(K (Ki)in+1
)n+1find
findthe
thenew
newTTn+1
n+1
repeat (3) to
repeat (3) to (6) (6)
(6b)
(6b)IfIfyes,
yes,TTn isisyouryourdew dewpoint
point
n