J.RADIOANAL.NUCL.CHEM.

,LETTERS 93 /5/ 309-318 /1985/

THEORETICAL AND E X P E R I M E N T A L STUDY OF THE A D S O R P T I O N

ON RADIOACTIVE GASES ON CONTINUOUS FLOW COLUMNS

V. Friedrich, I. Lux M

Institute of Isotopes of the Hungarian Academy

of Sciences,
H-1525 Budapest, P.O.B. 77, Hungary
XCentral Research Institute for Physics of the
H u n g a r i a n A c a d e m y of Sciences,
H-II21 Budapest, Konkoly Thege M. 29-33, Hungary

Received 17 September 1984

A c c e p t e d 18 O c t o b e r 1984

A b i m o l e c u l a r reaction model was used to

describe the adsorption process in continuous
flow columns filled with solid adsorbents. The
analytical solution of the model for low gas
concentrations and a cascade-type numerical
method for h i g h e r gas concentrations were
developed. An air flow apparatus using activ-
ated carbon as adsorbent and m e t h y l - i o d i d e
labelled w i t h 125I as adsorbate was constructed
for m e a s u r i n g breakthrough- and accumulation
curves.

INTRODUCTION

Industrial practice and laboratory experiments show

that the performance of continuous flow adsorption columns
has a dynamic character, i.e. the removal efficiency

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FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

changes /decreases/ in time, and this process is effected

by many parameters such as geometry of the column, tem-
perature, gas composition, relative humidity, face velocity,
etc. Investigations were performed to evaluate the de-
pendence of the removal efficiency on some of these para-
meters I-3, but most of these relations are of empirical
character. Therefore, the comparison of the results of
different laboratory tests and the e x t r a p o l a t i o n for long
term operation of the adsorbers is difficult.
The aim of our investigations is to describe the kinetics
of adsorption in continuous flow columns by the help of
suitable model containing t h e p h y s i c o - c h e m i c a l parameters
of the process /adsorption and desorption rate constants,
concentrations, specific surface of the adsorbent/ and al-
so to compare the calculated and experimental results.

THEORETICAL

Assuming that the adsorption m e c h a n i s m can be represented

by the reversible processes of adsorption and d e s o r p t i o n
Jonas and Svirbely 4 investigated the kinetics of adsorption
of carbon tetrachloride and chloroform from air mixtures
by activated carbon.
A similar model served as the starting point of our in-
vestigations:

g + a kF~ e /I/
~'kB

where g is a gas molecule, a is a free active site on the

adsorbent, e is an occupied active site, k F is the ad-
sorption rate constant and k B is the desorption rate

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 FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

constant. The rate of the'~rocess can be described by the

following Eq.:

dE/x,t/
dt
= kF.G/x,t/.A/x,t/-kB.E/x,t/ /2/
where G, A and E are the concentrations of the gas, free
active sites and occupied active sites, respectively,
that depend on time t and distance x measured from the
inlet site. Because of the conservation of /free+occupied/
active sites we have
A = A ~ - ~ /3/.

where A is the concentration of the active sites /that

o
is proportional to the specific surface of the sorbent/.
An approximate numerical solution of Eq. /2/ is obtained
in the following way. The column of a finite length X is
divided into N layers and the continuous time variable is
represented by periods of length

At = X/NV /4/

where V is the linear face velocity. /This model will be

called the cascade model./ Assuming that the inlet gas
concentration is constant, i.e. G/O,t/ = G O , and denot-
ing the values at the function in Eq. /2/ in layer i and
in period j by El, j and Gi, j a recursive solution of
Eq. /2/ is given by the equation system

k F 9A o- Gi_l ,~
Ei,j = Q /I-P/ + Ei,j_l. p 151

Gi, j = Gi_l,j-Ei, j 161

where
Q = kFGi_l, j + k B 171
P = e -Q. At 18I
and the initial conditions read GI, j = G O and Ei, O ---- O .

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FRIEDRICH, L~: ADSO~TION OF RADIOACTIVE GASES

Computing step by step theOvalues Ei, j and Gi, j

using Eqs /5/ and [6/ for i=l§ and j=O+Jma x, the Gn, j
vs. time curves will show the concentration breakthrough
and N
Ei, j
i=l

vs. time curves the adsorbate accumulation. The value

of Jmax can be d e f i n e d a s the time when the difference
between inlet and outlet concentrations is less than
some small ~ value or the increment of the accumulation
is less than E. With increasing number of layers the
accuracy increases but so does the computing time too.
When searching an analytical solution for the prob-
lem of the column of finite length, the following system
of partial differential equations is to be solved.
Again Eq. [2/ describes the rate of the process.

~E./x,t~ = kF.S/x,t/.A/x, tl _ kB.E/x,t / /9/

~t

Equation [3/ gives the active site conservation

A/x,t[ = Ao-Elx, t/

while gas conservation calls forth the relation

x[
I Ely,t/ + Gly,t[ j dy = V.Go.t-V. f G/x,t'ldt' 1101
o o

where V is the linear face velocity, x and t are variables

for distance and time. Equation /9/ describes the re-
action rate, Eq. [i0/ represents the mass balance for
the continuous flow column of finite length. This sys-
tem of partial differential equations can be solved after
introducing new variables:

~ = ~;
t xT = - ~v " Denoting F [~,r[ = F/x,t/,

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 FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

the initial conditions for Eqs /9/ and /i0/ read

to, TI = G o l ~ / ; ~ Iv,O~ = E !~,0t = 0 tv ~ 0 t .

In the analytical solution we assume that A/x,t/ in Eq.

/9/ can be replaced by its maximum value A o. It can be
seen that this assumption is equivalent to the approx-
imation

D I~,~I = kF-G Iv,T~ k B (< 1 Ill~

By the help of the Laplace-transformation the following

solutions were found:

-k B. t
/v,T/ = ~.Go.e-~V I e Io/2./~.t.v/dt /12/
o

/~,~/ = Go.e I o / 2 . ~ . ~ . ~ / + k B. I Io/2/~.t.~/dt

o
1131
where
I is the zero order Bessel-function
o

9 ~ = kF.kB.A o /14/

8 = kF.A o 1151

EXPERIMENTAL

A simplified scheme of the laboratory apparatus is

shown in Fig. i. The vapour of CH3I labelled with 125I
was produced from liquid CH3I. The concentration of
gaseous CH3I was adjusted by the temperature of the
thermostat and the air flow. The CH3I concentrations
were in the order of 0.01-0.5 mg/l. The length /bed

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FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

6 3 4 . . . . .
8 710
5! ~ / / ' 9 11
16~ , I I,~ll~_~t r"~ 17

? i1 ' ' '

L-

Fig. I. The laboratory apparatus.

1 - liquid methyl iodide, 2 - ultrathermostat,
3 - v a l v e f o r a d j u s t i n g C H q I v a p o u r flow, 4 -
m i x i n g tube, 5 - r o t a m e t e r [ 6 - v a l v e for a d -
j u s t i n g a i r flow, 7 - a d s o r p t i o n column, 8 -
gas samplers, 9 - scintillation detector, i0 -
lead shielding, ii - s a f e t y a d s o r b e r , 12 - a i r
p u m p , 13 - g a s c h r o m a t o g r a p h , 14 - i m p u l s e s c a l e r ,
15 - r e c o r d e r s , 16 - a i r f i l t e r , 17 - c e n t r a l
ventillation system

depth/ of the adsorbent /activated carbon granules/ was

3-6 cm, diameter 1 cm. Accumulation curves were observed
when measuring the 125I activity on t h e column by scintil-
lation detector and impulse-scaler, breakthrough curves
were recorded by means of a gas chromatograph /using
flame-ionization detector/. The first experiments were
carried out at a m b i e n t temperature and 25-30% relative
humidity.

RESULTS AND DISCUSSION

Figure 2. shows typical accumulation and breakthrough

curves calculated by the cascade method. The purpose of
these calculations was to test the mathematical equations

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 FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

el!V+ 3. /
o.s~, / I /
1
oi.~ d I ~ I I I
0 5 10 15 20 25
Time., rain
Fig. 2. A c c u m u l a t i o n / .... / and b r e a c k t h r o u g h / /
c u r v e s c a l c u l a t e d by the c a s c a d e m e t h o d in the
case of N = i00, DT = 0.01 s, a = 0.4, fl = 20.0,
and D O = I0.0, 5.0 and 0.i for the c u r v e s N O
i, 2 and 3, r e s p e c t i v e l y

40 ,,,,.,..,. d" ~" a" ~G0= 0.525mglt

j,p ,,,"

30 " " ..~--''~ " "-'t"

20 .,..... -," " ~ O=0.17lmg/t '
I1 1 / "1 / . ~
.,,..'"".,,.,,.-- " " . . . .Go=0.112
... "
mg/t

7///f-
eli#7 I ~ I , I , I ~ I ~ I ,
0 200 400 600 B00 1000 1200 1400
Time, rain
Fig, 3. M e a s u r e d a c c u m u l a t i o n curves at v a r i o u s inlet
c o n c e n t r a t i o n s /Go/

and the n u m e r i c a l method, therefore the v a l u e s of ~, 8,

D O were fictive. Both accumulation and b r e a k t h r o u g h curves
show inlet concentration dependence /input p a r a m e t e r s
are the same w i t h the e x c e p t i o n of Go/.
Figure 3. shows the inlet concentration dependence of
experimentally measured accumulation curves, in Fig. 4.

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FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

10 - _ -
,4

O8

J o6

O4

02

0
0 ~0 20 30 40
Time) rain
Fig. 4. S i m u l t a n e o u s l y measured accumulation and b r e a k ,
through curves

a p a i r of s i m u l t a n e o u s l y measured accumulation and b r e a k -

through curves are p l o t t e d .
In e v a l u a t i n g the c a l c u l a t i o n a l models above it is re-
markable t h a t the a n a l y t i c a l solution is p r o p o r t i o n a l to
the inlet c o n c e n t r a t i o n G b u t no o t h e r c o n c e n t r a t i o n
o
dependence appears in Eqs /12/ and /13/. On the o t h e r
hand, Eqs /5/ and /6/ show an e x p l i c i t c o n c e n t r a t i o n
dependence of E/G o 9 This c o n t r a d i c t i o n is due to the a p p r o x -
imation, Eq. /ii/ in the a n a l y t i c a l m e t h o d . In fact if
D O = k F . G o / K B ~< i, t h e n the G - d e p e n d e n c e of the c a s c a d e
method also vanishes. Dependence of the b r e a k t h r o u g h
c u r v e s on inlet c o n c e n t r a t i o n as c a l c u l a t e d by the cas-
cade m e t h o d is g i v e n in Fig. 5. It is seen t h a t w i t h de-
creasing i n l e t c o n c e n t r a t i o n the c u r v e s asymptotically
t e n d to the a n a l y t i c a l curve and at D o = 0 . O 1 the two
curves practically coincide.
It is i n t e r e s t i n g t h a t the same c o n t r o v e r s y is o b s e r v e d
b e t w e e n the r e s u l t s obtained in o u r e x p e r i m e n t s and t h o s e
resulting from reported industrial and l a b o r a t o r y experi-
ments. The r e s o l u t i o n of this apparent contradiction is

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 FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

I I I I I 9 ,,s~,"
Ill I
/ /
-"" !
Ii e ,
li' 9'
Oll,a j~/~._~,,~ 1 I I
0 5 10 15 20 25
T i m e , rain

Fig. 5. B r e a k t h r o u g h curves c a l c u l a t e d by the cascade

m e t h o d /.... / and the analytical solution / - - /
Eq. /16//. In the cascade m e t h o d N = IOO.O,
DT = 0.O1 s, and D_ = 20.0, 10.O, 5.0, I.O,
0.5, O.I, 0.05 and~ for the curves Nos i, 2,
3, 4, 5, 6, 7 and 8, respectively. For both
cascade and analytical calculations ~ = 0.4
and 8 = 20.0

again obvious, our laboratory experiments were carried

out w i t h relatively high inlet concentrations for the
reasons d i s c u s s e d below. At such high concentrations
approximation /Ii/ is not justified, i.e. the analytical
model does not apply. Industrial applications, on the
other hand, usually assume very low concentrations where
the analytical treatment is justified. The link provided
by the cascade m e t h o d between the two extreme c o n c e n t r a t i o n
cases gives us a viable strategy of experimental investi-
gations of industrial processes. Namely by numerical
/cascade-type/ r e p r o d u c t i o n of the e x p e r i m e n t a l results
the m a t e r i a l constants ~, 6 and D in Eqs /14/, /15/ and
/ii/ are d e t e r m i n e d and w i t h these constants analytical
calculations p r o g n o s t i c a t e industrial functioning.
This strategy makes h i g h - c o n c e n t r a t i o n laboratory ex-
periments possible that have the advantage that the process
of reaching dynamic saturation is significantly faster.
F r o m the obtained b r e a k t h r o u g h and/or accumulation curves

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FRIEDRICH, LUX: ADSORPTION OF RADIOACTIVE GASES

the p h y s i c o - c h e m i c a l parameters /k F, k B, Ao/ can be

calculated. The sorbent material can be better charac-
terized by these parameters since they are independent
of the experimental conditions.

REFERENCES

i. J.G. Wilhelm, Removal of Gaseous Radioiodine with Solid

Adsorbents, IAEA Seminar on Testing and Operation of
Off-Gas Cleaning Systems at Nuclear Facilities, Karls-
ruhe, 1982.

2. V.R. Deitz, Charcoal Performance Under Simulated Ac-

cident Conditions, 17th DOE Nuclear Air Cleaning Con-
ference Proceedings, Vol. 2., 1982.

3. H. Shiomi, Y. Yuasa, A. Tani, M. Ohki, T. Nakagawa,

A Parametric Study on Removal E f f i c i e n c y of Impreg-
nated A c t i v a t e d Charcoal and Silver Zeolite for Radio-
active Methyl Iodide, 17th DOE Nuclear Air Cleaning
Conference Proceedings, Vol. I., 1982.

4. L.A. Jonas, W.J. Svirbely, J. Catal., 24 /1972[ 446.

318