11-11-02

Exam 2 graded
Hand back
Go over (briefly)
Liquid-Liquid Extraction
Leading up to extractive distillation
Exam 2 grades
66.3 average
22.7 std dev
98 high
Problem 1 Fenske, Underwood,
Gilliland calculations
FEED
I-Pentane 40 kgmol/h light key
N-Pentane 60 kgmol/h heavy key
N-Hexane 12 kgmol/h
N-Octane 12 kgmol/h
P 1.2 bar
sat'd liquid
K values:
I-Pentane 1.385 light key
N-Pentane 1.07 heavy key
N-Hexane 0.349
N-Octane 0.038
LKS 0.95
HKS 0.01
Do a preliminary column design using the Fenske,
Underwood, Gilliland method (hand, not ChemCAD) for a
column separating a mixture of isopentane, n-pentane, n-
hexane, and n-octane with the flowrates specified below fed
as a saturated liquid at 1.2 bar. The column is to operate at
1.2 bar with a light key split of 0.95 and a heavy key split of
0.01. The light key is isopentane and the heavy key is n-
pentane. Use the Molokanov version of the Gilliland
correlation and the Fenske method for determining the feed
tray. Use an R/R
min
of 1.2. Use the K-values specified
below.
Problem 1, contd
(a) N
min
as estimated using the Fenske method
29.2
(b) R
min
as estimated using the Underwood
method 8.32
(c) N for R/R
min
= 1.2 as estimated using the
Molokanov form of the Gilliland correlation
59.9
(d) N
feed
as estimated using the Fenske equation
36.2
Problem 1, grading notes
grading notes:
genl
-3 answer close but cannot find explanation in .xls
-1 answer close but cannot find explanation in .xls but is probably a 'carry over' from a previous error
nc over-rounding of ideal stage calcs - comment only
-6 missing answer (blank)
-4 wrong component as heavy key; check for cascade effect
(a)
-4 incorrect alpha (dumb mistake) - correct and see if other answers are correct, nc for other answers if yes
-5 above plus used LKS and HKS as mol fractions
(b)
-3 q incorrect
(d)
-2 NS instead of NF=NR
-5 Molokanov & wrong
-1 small formula error
-3 NS min okay, but goofed from there (not simple NS instead of NR mistake)
-3 used LKS & HKS instead of xB values in formula
-3 Molokanov & okay
Problem 2
A stream containing 75 kgmol/h methanol and 75 kgmol/h
isopropanol is to be distilled to separate the methanol and
isopropanol. The feed is available as a saturated liquid at pressures
between 1 and 12 bar. Methanol is the light key and the column is
to be designed for a light key split of 0.98; isopropanol is the heavy
key and the column is to be designed for a heavy key split of 0.01.
Using ChemCADs shortcut distillation column model with the
Unifac model for K-value estimation:

(a) determine the pressure at which the column must be
operated to have a distillate temperature of 110 degrees C.
(b) compare the column specifications for the pressure found in
part a (N, R, and heat duties in particular) with those
obtained for a column pressure of 1.2 bar. Explain the
differences between the column specifications at the two
pressures.
Problem 2, contd
(a) 4.8 bar 10
(b)
pressure found in (a) P=1.2 bar 8
Number of stages 37.5998 30.4205
Reflux ratio 3.5825 2.5791
Q, cond (MJ/h) -10755.873 -9302.6777
Q, reboiler (MJ/h) 10908.4785 9429.3418
Basically, the relative volatility is lower at the higher column pressure leading to
more stages, higher reflux, and higher exchanger duties.

Problem 2 grading notes
Grading notes
(a)
-5 simulation set up okay, but incorrect answer somehow
-5 kept' components from #1 or elsewhere
-3 set up okay, didn't converge to 110C pressure
-4 converged to a bottoms temp of 110C (nc in b for this error)
-2 incorrect feed specifications (should be sat'd liq at column pressure)
(nc for b if same mistake)
(b)
-3 superficial discussion which misses point about relative volatility difference
common : denoted with "alpha! -3"
-6 completely superficial "discussion"
-1 wrong Q units
-2 incorrect feed specifications (should be sat'd liq at column pressure)
-3 obvious error in N or other serious problem with one case
-2 somewhat superficial discussion (whole range 0 to -6 available)
Problem 3, answers
N actual 27
D actual 3.25 feet
H actual 40 feet
shell cost 675 $ $/foot
bare shell cost 27,000 $ $
installed shell cost 112,320 $ $
Condenser area 241.3782332 ft^2
bare cost 8,500 $ $
installed cost 27,200 $ $
Reboiler area 458.9966214 ft^2
bare cost 13,000 $ $
installed cost 97,760 $ $
Trays
bare trays 14,850 $ $
installed cost 17,820 $ $
Problem 3 grading notes
grading notes
12 (a)
-6 off a lot, unknown error
-3 somewhat off, unknown error
(range -2 to -6 available for this)
13 (b)
-1 not rounding diameter to 0.25 or 0.5 foot
-3 used wrong tray spacing
nc tray cost wrong if d wrong
-3 Cond area wrong
-3 Reb area wrong
-11 H calc only (+2 for shell H calc)
-2 H calc wrong (no or wrong multiplier for top & bottom)
-2 transferred diameter wrong from (a)
-3 tray costs way off
-4 used Nideal
-2 exchanger area okay, but no costing
-3 used eff wrong
Problem 4
1
1
12 2
5.5 0.5
N
R
t
t
29 2
0.99
0.01
0
AD
BD
CD
D
x
x
x
t

36 3
0.17
0.82
0.01
AP
BP
CP
P
x
x
x
t

35 3
0
0.01
0.99
AW
BW
CW
W
x
x
x
t

3
18 2 N t
100
0.35
0.30
0.35
sat'd liquid, 1.2 bar
AF
BF
CF
F
x
x
x

2
2
23 2
1.9 0.5
N
R
t
t
Grading : simply +2 for each correct fill in (adds up to 26, but okay)
Liquid-liquid extraction
Fundamentals
Kremser equations for L-L extraction
ChemCAD simulation of L-L extraction
L-L extraction terminology
Feed
F
S
R
E
Extraction
Solvent
Raffinate
Extract
Single theoretical
extraction stage
Extraction schemes:
Crosscurrent extraction
1
2
3
S
1
S
2
S
3
E
1
E
2
E
3
F
R
1
R
2
R or R
3
Extraction schemes:
Countercurrent extraction
1
E
2
R
1
2
E
3
R
2
3
S
R or R
3
E or E
1
F
Solvent selection
Based on liquid liquid equilibrium
Want a solvent which reduces the activity of the
solute in the feed and is immiscible with the
major component of the feed stream
Handy chart assembled by L.A. Robbins (in
Handbook of Separation Techniques for
Chemical Engineers; P.A. Schweitzer, ed.;
McGraw-Hill 1979)
Example:
Removal of acetone from a water stream
Acetone is a ketone (group 3 in table)
Groups 1 (acid, aromatic) and 6 (halogenated
hydrocarbons, not halogen saturated)
Can use ChemCAD to screen possible solvents
Look for phase separation (two liquid phases
present) and higher activity of the solute in the
solvent phase relative to the feed phase
Countercurrent liquid-liquid
extraction
Cautions & Caveats
Extractant selection
Preliminary design
CC5 for approximate S/F
min
Kremser equations for number of stages
Detailed performance estimates (CC5)
Cautions
Liquid-liquid extraction terminology and
working equations are very often in terms of
weight fractions even though the variables x
and y are used.
Liquid-liquid extraction practice is *way*
ahead of design principles.
Things we can make design
determinations about:
Solvent choice(s)
Approximate S/F
min
values
N
theoretical
Performance
Purity, recovery, etc. achievable
The design problem
N
F, x
f
E, y
e
R, x
r
S, y
s
Usually F and all of the
composition variables
are known )or can be
estimated) leaving S and N
to be determined
Raffinate
Feed
Solvent
Extract
Extractant selection
considerations
Selectivity
Distribution coefficient
Insolubility of extraction solvent
Recoverability
Density
Interfacial tension
Chemical reactivity, vapor pressure, flammability
Availability of thermodynamic data for LLE
Extraction solvent candidate
selection
Use interaction table to determine possible
candidate solvents
Check that thermodynamic parameters are
available for LLE prediction
In CC5 this means availability of UNIQUAC or
NRTL binary parameters for all three pairs
Solvent candidate selection, cont.
With solvent candidate as component 1,
solute as component 2, and feed major
component as component 3 in a binodal plot
Check for 2 phase region
Check selectivity of solvent candidate for solute
Check for relative insolubility of solvent
candidate and feed major component
Approximate S/F
min
determination
Build a CC5 simulation of the extractor using 10
theoretical stages
Begin with S/F=1
If this runs, systematically reduce S/F until the extractor
either will not operate or until we meet our outlet specs;
the last working S/F value is our S/F
min
estimate; refine
this estimate until we have two significant figures
If this doesnt run, systematically increase S/F until the
extractor works; the first working S/F value is our
S/F
min
estimate; refine this estimate until we have two
significant figures
Estimating N
theoretical
Choose S/F = 1.2 S/F
min
Use CC5 to estimate the slope(s) of the
equilibrium curve needed by the Kremser
equations (a VLLE flash will do this nicely)
Use appropriate form of the Kremser
equation to estimate N
Kremser equations, extraction
factor
F
S
m

Solute free
mass flow
Solute free mass
flow
Slope of
equil
curve in
mass
fractions
Kremser equations form 1

ln
1 1
1 ln
1 for
1
1
1
]
1

,
_

,
_

m
Y
X
m
Y
X
N
s
r
s
f
Here X & Y are mass fractions
Kremser equations form 2
1
1 for

m
Y
X
m
Y
X
N
s
r
s
f

Here X & Y are mass fractions

Liquid-liquid extraction example
For a stream of 20 mol% acetone in water
being extracted with 1,1,2-trichloroethane
at 25 deg C and 1 bar determine
S/F
min
m at the composition for S/F = 1.2 S/F
min
N for S/F = 1.2 S/F
min
and a mole percent of
acetone in the raffinate of 0.02% (that is a mol
fraction of 0.0002)
Binodal plot
Approximate S/F
min
determination
Build a CC5 simulation of the extractor using 10
theoretical stages
Begin with S/F=1
If this runs, systematically reduce S/F until the extractor
either will not operate or we reach the desired outlet
concentration; the last working S/F value is our S/F
min
estimate; refine this estimate until we have two
significant figures
If this doesnt run, systematically increase S/F until the
extractor works; the first working S/F value is our
S/F
min
estimate; refine this estimate until we have two
significant figures
1
1
2
3
4
S
F
E
R
Extractor Summary
Equip. No. 1
Name
No. of Stages: 10
1st feed stage 1
2nd feed stage 10
Stream No. 1 2 3 4
Stream Name S F E R
Temp C 25.0000* 25.0000* 25.0000 24.9997
Pres bar 1.0000* 1.0000* 1.0000 1.0000
Enth MJ/hr -1812.7 -7234.9 -4277.2 -4770.4
Vapor mole fraction 0.00000 0.00000 0.00000 0.00000
Total kmol/hr 10.0000 26.0000 19.2980 16.7020
Total kg/hr 1334.0401 676.7280 1708.4221 302.3460
Total std L m3/h 0.9179 0.7530 1.3691 0.3019
Total std V m3/h 224.14 582.75 432.54 374.35
Component mole fractions
Acetone 0.000000 0.200000 0.269458 0.000000
Water 0.000000 0.800000 0.213010 0.999243
1,1,2-3Cl-Ethane 1.000000 0.000000 0.517533 0.000757
( )
feed kg
solvent kg
971 . 1
feed mol
solvent mols
385 . 0
min

F
S