A Study on the Methane

A Study on the Methane

Isotope Separation Using
Isotope Separation Using
Cryogenic Distillation
Cryogenic Distillation
Jonghwan KIM
1
, Sangjin PARK
1
, Sehoon YOON
1
,
Jungho CHO
2*
, Young-Chul LEE
3
, Taek-Yong SONG
3
and Euy Soo LEE
1*
Dongguk University 1
Dong Yang University 2
LNG Technology Research Center 3
Slide 2
LNG
Synthetic Gas(CO+H
2
)
Reactor
Demethanizer
Concentration of
C13 Methane
Dehydrogenation &
Dehydration
Concentration of
C13 CO
Path I
Path II
Two Paths to Obtain
Two Paths to Obtain
13 13
CH
CH
4 4
Based on a
Based on a
Cryogenic Distillation
Cryogenic Distillation
Slide 3
Vapor Pressure Correlation of
Vapor Pressure Correlation of
12 12
CH
CH
4 4
Methane
Methane
! Antoine Vapor Pressure Equation is:
! Normal boiling temperature of
12
CH
4
methane is:
16 . 7
84 . 897
2093 . 13 ln

=
T
P
L
(P
L
in kPa and T in K)
K T 6697738 . 111
) 325 . 101 ln( 2093 . 13
84 . 897
16 . 7 =

+ =
Slide 4
Vapor Pressure Correlation of
Vapor Pressure Correlation of
13 13
CH
CH
4 4
Methane
Methane
! Correlation of
13
CH
4
methane is:
! Vapor pressure expression of
13
CH
4
methane is:
! Normal boiling temperature of
13
CH
4
methane is:
T T P
P
H
L
192 . 0 9 . 36
log
2
=
!
!
"
#
$
$
%
&
(P
L
in kPa and T in K)
T
T
T
H
P
192 . 0 9 . 36
16 . 7
84 . 897
2093 . 13 log
2
10
+
'
(
)
*
+
,

=
K T 704475 . 111 =
(0.0347K difference with
12
CH
4
methane)
Slide 5
Relative Volatilities
Relative Volatilities
btn
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12
12
CH
CH
4
4
&
&
13
13
CH
CH
4
4
! Definition of relative volatility of component i and
component j is:
( )
( )
j
i
j
i
j
i
ij
P
P
P P
P P
K
K
= = =
(component is defined as more
volatile than component j)
1.0031 79.755 80.00 108.873
1.0034 59.796 60.00 105.662
1.0036 51.812 52.00 104.139
1.0029 99.714 100.00 111.510
1.0025 149.638 150.00 116.671
1.0022 199.568 200.00 120.653
1.0018 299.46 300.00 126.784
Alpha VP of
13
CH
4
(kPa)
VP of
12
CH
4
(kPa)
Temperature (K)
Slide 6
13
13
CH
CH
4
4
Property Calculation Using PR
Property Calculation Using PR
! We used Peng-Robinson equation of state for the
modeling of methane isotope separation.
! Parameter a and b are functions of critical temperature
and pressure.
! Alpha value is functions of reduced temperature and
acentric factor.
! Acentric factor of
13
CH
4
methane was adjusted to
accurately estimate vapor pressure at a given temperature.
( ) ( ) b V b b V V
a
b V
RT
P
+ +

=

Slide 7
Comparison of
Comparison of
13 13
CH
CH
4 4
Vapor Pressure
Vapor Pressure
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Correlation & PR Equation
Correlation & PR Equation
Temperature ( K )
70 80 90 100 110 120
P
r
e
s
s
u
r
e

(

K
P
a

)
0
20
40
60
80
100
Acentric factor, was modified as
0.0108 to fit the correlated vapor
pressure vs. temperature.
Slide 8
LNG Feed Composition:
LNG Feed Composition: Supplied from KOGAS
-155.0 Temperature (
o
C)
0.0700
89.3574
0.9026
7.8100
1.3000
0.2400
0.3200
Nitrogen
12
CH
4
Methane
13
CH
4
Methane
Ethane
Propane
i-Butane
n-Butane
Mole Percent Components
Slide 9
13
13
CH
CH
4
4
Separation Procedure
Separation Procedure
! Separation of C2+ from LNG:
! Step 1: Concentration of
13
CH
4
from 1% to 9.2376%
! Step 2: Concentration of
13
CH
4
from 9.2376% to 35%
! Step 3: Concentration of
13
CH
4
from 35% to 40%
! Step 4: Concentration of
13
CH
4
from 40% to 60%
! Step 5: Concentration of
13
CH
4
from 60% to 80%
! Step 6: Concentration of
13
CH
4
from 80% to 90%
Slide 10
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
1
20
T01
1
2
3
Demethanizer
Demethanizer
Simulation Using PRO/II
Simulation Using PRO/II
File Save As: DeC1_01.prz
Slide 11
Reflux Ratio
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
T
h
e
o
r
e
t
i
c
a
l

N
u
m
b
e
r

o
f

T
r
a
y
1000
2000
3000
4000
5000
Shortcut Simulation
Shortcut Simulation
Minimum number of tray = 1,644
Minimum reflux ratio = 887
Optimum theoretical number of tray = 2,400
Slide 12
Rigorous Simulation Example:
Rigorous Simulation Example: PRO/II
File Save As: Rigorous_Small.prz
2
66
130
194
258
322
386
450
514
578
642
706
770
834
898
962
1026
1090
1154
1218
1282
1346
1410
1474
1538
1602
1666
1730
1794
1858
1922
1986
2050
2114
2178
2242
2306
2370
2399
1
2400
T01
1
2
3
Slide 13
13
13
CH
CH
4
4
Separation Step:
Separation Step: 200 stages for each column

Feed
Concentrated
13
CH
4
12
CH
4
Product
T01 T02 T03 T12
Slide 14
Case Study Results for a DeC1 & Cryogenic
Case Study Results for a DeC1 & Cryogenic
Distillation Columns
Distillation Columns
2,400 646.0 1,852 80%!90% Step 7
2,400 739.0 1,688 60%!80% Step 6
2,400 831.4 1,578 40%!60% Step 5
2,400 887.0 1,644 35%!40% Step 4
2,600 905.5 1,872 9.2376%!35% Step 3
2,000 253.0 1,417 1%!9.2376% Step 2
20 - - Demethanizer Step 1
Theoretical
Trays
Minimum Reflux
Ratio
Minimum
Trays
Role
Slide 15
Relation of a distillation column operating
Relation of a distillation column operating
time and top
time and top
13 13
CH
CH
4 4
impurities
impurities
6,209 hours - Step 1
5,158 hours 15.0 mole% Step 2
926 hours 5.0 mole% Step 3
24 hours 5.0 mole% Step 4
59 hours 2.0 mole% Step 5
31 hours 1.0 mole% Step 6
11 hours 0.5 mole% Step 7
Operating Time Top
13
CH
4
Impurities
Slide 16
Conclusions
Conclusions
!
13
CH
4
isotope separation process using a cryogenic
distillation was simulated with PRO/II with PROVISION
version 6.01. The modified Peng-Robinson modeling
equation with a newly adjusted acentric factor was suitable
to simulate the separation between methane isotope.
! It was concluded that 2,400 theoretical stages and six step
procedures were required to obtain a 90 mole% of
13
CH
4
methane product.