A Simplified Mathematical Model Of The Cryogenic

Distillation With Application To The (13C) Isotope

Separation Column
A.O. Neaga1*, C. Festila1, E.H. Dulf1, R. Both1, T. Szelitzky1 and M. Gligan2
1
Technical University of Cluj Napoca, Department of Automatic Control, Faculty of Automation and Computer
Science, 28 Memorandumului, 400114 Cluj Napoca, Romania.
2
National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293
Cluj-Napoca, Romania
*
Corresponding author: adrian.neaga@aut.utcluj.ro

Abstract. The isotope (13C) has a widespread application in many fields such as chemistry, physics, medicine, etc. To
obtain a high concentration in isotope of interest, in our case (13C), it is used the method of cryogenic distillation of
carbon monoxide (CO) which is based on the difference between the vapor pressure of (12C16O) and (13C16O) at the
temperature of liquid nitrogen. Isotopic separation plant, used to obtain the isotope (13C), is a complex installation, with
many inputs and outputs, rather difficult to control. Due to this reason, from the point of view of automation, it is needed
a simplified mathematical model. This model can be determined only with some presumption and simplification
assumptions. Using the physical laws, the hydrodynamic part of the process and the mass balance will be described by
partial differential equations. In order to design a controller for the column, it is needed a transfer function or a state-
space realization of the plant, which is the main contribution of the present work. Implementing this mathematical model
will be the key element for describing and understanding the operation of the plant and for future development of
process control strategies.
Keywords: cryogenic distillation, isotope (13C), carbon monoxide, isotopic separation column, mathematical model.
PACS: 80.

INTRODUCTION PROCESS DESCRIPTION

Long before organic chemistry was recognized as a Isotope separation columns are widely studied due
distinct branch of science, the art of distillation was to the numerous applications of an enriched isotope
practiced in the preparation of what we known as component. Several separation methods exist today,
organic substance [1]. one of them being cryogenic distillation [5].
In the case of the chemical element carbon, there The plant under study is the carbon monoxide
are two stable isotopes species: base component (12C) isotope cryogenic distillation unit, built at the National
with the natural abundance of 98.89 at.% which is the Institute for Research and Development of Isotopic
“light” isotope and the “heavier” stable isotope (13C), and Molecular Technologies Cluj-Napoca (INCDTIM-
with 1.11at.% concentration [2]. www.itim-cj.ro) [5]. In figure 1 is presented a
The isotope (13C) is used in many domains such as: simplified scheme of the isotope separation plant [6].
chemical engineering, agriculture, medicine, The main components of the plant are: condenser
environment protection, as marker in various scientific in the top of the column, the body of the column and at
researches [3]. the bottom of the column is the boiler. The condenser
Chemical processes, especial distillation have is cooled with liquid nitrogen at a temperature around
complex behavior, with a great number of inputs and (77K) witch is the boiling temperature of liquid
outputs, the functionality of the process being nitrogen at atmospheric pressure [5], figure 1. The
determined by the connections between them [4]. The body of the column is composed from a vertical pipe
goal of the present paper is to determine a with the length of 7 meters and diameter of 1.6
mathematical model which describes the functionality centimeters [3]. The column contains Helipack
of the (13C) isotope separation column. The packing which ensure a good contact between the
mathematical model will be the key element for liquid phase and gaseous phase of (CO). The body of
describing the functionality of the process and for the column is placed in a vacuum jacket where the
future development of control algorithms. vacuum level is realized using special turbo-molecular
Processes in Isotopes and Molecules (PIM 2011)
AIP Conf. Proc. 1425, 189-192 (2012); doi: 10.1063/1.3681999
© 2012 American Institute of Physics 978-0-7354-1005-3/$30.00

189
pumps. The jacket is designed to isolate the column
from the outside, for an efficient thermal insulation. In
case of this column the vacuum level reaches up to
value of 1.33·10-3 - 1.33·10-4 (Pa), figure 1 [8].
FIGURE 1. A simplified scheme of the (13C) isotope
separation plant.
In the boiler accumulates flow of liquid carbon
monoxide (CO). Variation of carbon monoxide level
in the boiler depends on the power supply that heats
the resistor and cause evaporation of liquid (CO).
The flow of the liquid (CO) is generated by the
liquid nitrogen in the condenser and the gaseous phase
of (CO) depends on the electrical power developed in
boiler, the two phases being in counter-current [7].
The principle of the method is based on the
difference between the vapor pressure of (12CO) (p1o)
and of the (13CO) (p2o), at very low temperature,
around (-193oC). The isotope separation process uses
as main parameter, the single stage separation factor
( α ), which is:
0 the column, increasing the packing hold-up. In the
α = p1 (1)
p 20
at the temperature of the liquid phase [8].
MATHEMATICAL MODEL
Before implementing the mathematical model of
the (13C) separation column, some assumptions are
necessary: (CO) gas feed is considered to be constant,
the flow of waste (CO) gas is constant and the vacuum
level in jacket is maintained at a set value.
The mathematical model of the (13C) separation
column proposed in this paper is a simplified one,
based on the representation of figure 2. In figure 2 are
190
considered as inputs for process: liquid nitrogen level
in the condenser (HnlK) and thermal power generated in
boiler (WelB). The outputs of the process are: hold-up
(gas and liquid of (CO) inside the column) (Hup) and
carbon monoxide (CO) level in the boiler (HcolB).
FIGURE 2. Model of the plant.
To determine the relationship between system
inputs and outputs shown in figure 2 is essential to
establish the mathematical equations which describe
the mass balance and the dynamic behavior of the
process.
The mass balance for the bottom side of the
column for the liquid level of CO in boiler is:
1
H colB =
S colB ∫(Q colB ( t ) − Qcov B ( t ))dt (2)
with (ScolB) the equivalent area of the boiler, depending
on the difference between the liquid flow reaching the
boiler (QcolB) and the vapor flow leaving the boiler
(QcovB) in mass unities [9].
The vapor flow leaving the boiler (QcovB) depends
on the thermal power generated in boiler (WelB) and on
the quantity of the liquid CO in boiler. The product
may be linearized using the sum [9]:
Qcov B = kcov B ⋅ HcolB ⋅WelB ≈ kelB ⋅WelB + kcolB ⋅ HcolB (3)
where kcovB, kelB, kcolB are the coefficients of the boiler.
The vapor flow reaching the condenser (QcovK)
depends on the vapor flow generated in boiler, from
which a part condenses on the packing material from
linearized approximation it is [9]:
Qcov K = Qcov B − kup ⋅ H up (4)
where kup is the specific hold-up coefficient.
The liquid phase of (CO) leaving the condenser
(QcovK) depends on the product of the gaseous inflow,
multiplied by the liquid nitrogen level in the condenser
(HnlK) and is obtained the liquid flow leaving the
condenser (QcolK) [9]:
Q colK = k cond ⋅ Q cov K + n nlK ⋅ H nlK (5)
where kcond and nnlK are the coefficients of the (Hup) and liquid nitrogen level in the condenser,
condenser. relation (10):
From the liquid carbon monoxide from the
condenser a part reaches back to the boiler, but a part K up ⋅ k elB ⋅ ( 1 + k cond )
is retained as hold-up (Hup) on the packing material H Hup / WelB (s)= (9)
T up s + 1
[9]:

QcolB = QcolK − bup ⋅ H up (6) K up ⋅ n nlK

H Hup / HnlK (s)= (10)
T up s + 1
where bup is a coefficient of packing material.
Applying Laplace-Transformation to the previous Using relation (7) can be obtained another two
equations (2-6) results [9]: transfer functions: the first one shows the time
evolution between the (CO) level in the boiler (HcolB)
 k bup + kup  and thermal power generated in boiler (WelB), relation
HcolB( s ) = − elB ⋅ WelB( s ) − ⋅ Hup( s ) ⋅ (11) and the second one present the relation between
 kcolB kcolB( 1 − kcond )  the (CO) level in the boiler (HcolB) and liquid nitrogen
(7)
1  nnlK  1 level in the condenser (HnlK), relation (12):
⋅ + ⋅ HnlK( s ) ⋅
TBs + 1  kcolB( 1 − kcond )  TBs + 1 k elB
−
Using the previous equations (3-7), is obtained the k colB
H HcolB / WelB (s)=
relation for hold-up of the column (Hup): TB s + 1
(11)

[
Hup( s ) = Kup ⋅ kelB(1 + kcond)WelB( s ) + Kup ⋅ nnlK ⋅ HnlK( s ) ⋅ ] n nlK
1 1 (8) k ( 1 − k cond )
⋅
Tups + 1
[
+ Kup ⋅ kcolB( 1 + kcond) ⋅ HcolB ⋅ ]
Tups + 1
H HcolB / HnlK ( s ) = colB (12)
TB s + 1

Based on the relation (8) can be obtained two Taking into account relations (9-12), is obtained
transfer functions: the first transfer function gives the the plant transfer function in a matrix form:
variation of the hold-up (Hup) and thermal power
generated in boiler (WelB), relation (9) and the second H (s) HHup / HnlK (s) 
transfer function shows the evolution in time of the H13C (s) =  Hup /WelB  (13)
 HHcolB /WelB (s) HHcolB/ HnlK (s)

a) b)
40 20

15
Hup/WelB

30
Hup/Hnl

10
20
5

10 0
0 200 400 600 800 0 200 400 600 800
Time(sec) Time(sec)
c) d)
-0.02 0.06

0.055
HcolB/WelB

HcolB/Hnl

-0.04
0.05
-0.06
0.045

-0.08 0.04
0 500 1000 0 500 1000
Time(sec) Time(sec)

FIGURE 3. Simulation results of the mathematical model of the (13C) isotopic separation column compared with experimental
data, “-“represent the simulated values and “x” are experimental data obtained from the real plant.

191
 Experimental data were obtained from experiments
realized at the National Institute for Research and
Development Isotopic and Molecular Technologies.
Using these data was identified the particular values of
the parameters from the process transfer function
matrix (13):
 24.2 12.9  knowledge based society-SIDOC” contract no.
 
H * 13 C ( s ) = 
125.5 s + 1 125.5 s + 1 
(14)
 − 0.049 0.061 
 
 150 s + 1 150 s + 1 
This mathematical model is tested and validated
using simulation in Matlab.
PROCESS SIMULATION
In figure 3 is presented a simulation scenario of the
process transfer function matrix (H*13C) in comparison
with the experimental data. Figure 3.a highlights the
evolution of the column hold-up for a variation of the
electrical power developed in the boiler. Figure 3.b
presents the evolution of the column hold-up for a
variation of liquid nitrogen level in the condenser.
Figure 3.c shows the evolution of the (CO) level in the
boiler when the thermal power dissipated in the boiler
is varied and the last figure (figure 3.d) presents the
variation of (CO) level in the boiler when the liquid
nitrogen level in the condenser reached a new value.
From these simulation results can be observed that
the mathematical results are close to the experimental
data, the error between these two categories being
negligible. The mathematical model can be considered
validated. This model is in proper form for further
controller design methods.
CONCLUSIONS
Obtaining a mathematical model very close to the
reality shows a good understanding of the functionality
of the process and is the basis for future
implementation of a control strategy. The resulted
model is validated by simulation, resulting a good
fitting. The advantage of this model in comparison
with other existing models is the simplicity and the
useful form for automation.
The future studies on the isotopic separation
column will attempt to implement the mathematic
model and the control algorithms on process computer.
From the possible control strategies, the authors
already implemented an ON-OFF control [3,7] and
will study an advance control: the predictive control,
192
recommended for time delay systems, such as the
studied plant.
ACKNOWLEDGMENTS
This paper was supported by the project “Doctoral
studies in engineering sciences for developing the
POSDRU/88/1.5/S/60078, project co-funded from
European Social Fund trough Sectorial Operational
Program Human Resource 2007-1013.
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