Kinetic Study of Carbonyl Sulphide with Aqueous Solutions of

DiEthanolAmine and MethyDiEthanolAmine.

Experiments and Modeling.
F. Amararene, C. Bouallou *

CENERG, Ecole Nationale Supérieure des Mines de Paris

60, Bd. Saint-Michel, 75006 Paris, France

Industrial field : acid gas removal by alcanolamine solutions

Applications : natural gas, petroleum refining, coal gasification, hydrogen production
Pressuretransducer T h e i n f l u e n c e o n a b s o r p t i o n k i n e t i c s o f a l l c h e m i c a l r e a c t i o n s b e t w e e n d is s o l v e d
C O S a n d r e a c t a n t s i n s o l u t io n i s u s u a l l y e x p r e s s e d b y a n " e n h a n c e m e n t f a c t o r E "
Heating o v e r p h y s i c a l a b s o r p t io n :
element
Vaccumpump
V g dP
K L EC COS ,i a  COS

Recording RT dt
unit Degassed
solution T h e p a r t i a l p r e s s u r e P C O S is r e l a t e d t o t h e c o n c e n t r a t i o n o f u n r e a c t e d d is s o l v e d C O S
b y H e n r y 's la w :

P COS
C COS ,i  P COS  P T  P I
Gascylinder
H COS

W h e r e P T is t h e t o t a l p r e s s u r e ( P a ) . P I is t h e t o t a l v a p o r p r e s s u r e o v e r t h e a q u e o u s
Micro-computer
a m i n e s o l u t io n s b e f o r e C O S lo a d i n g .
 PT  P I  K L EaRT
Ln      t  t 0 
 w h e re :  
 P T ,0  P I  VgH COS

Temperature probe
Magneticstirrer
Tube of load F o r e a c h e x p e r i m e n t , t h e e n h a n c e m e n t f a c t o r E is o b t a i n e d f r o m  a n d t h e e s t i m a t e
o f d a t a f o r t h e H e n r y 's la w c o n s t a n t H a n d t h e l iq u i d - s i d e m a s s - t r a n s f e r c o e f f i c ie n t
Flow diagram of the apparatus. K L.

RESULTS
T o d e te r m in e k in e t ic s c o n s ta n t w e c o n s id e r t h a t t h e r e a c t io n o f C O S w it h t h e By assuming the reaction order 2 for DEA, we determined Arrhenius relation:
s e c o n d a r y a m i n e D E A is d e s c r ib e d b y t h e Z W I T T E R I O N m e c h a n is m :
5199

K2.5210 exp
 
2

C O S+ D EA     D EAH C O S K 2 ,K 2
+ -  T 
D E A H + C O S - + B  K  D E A C O S - + B H b
+ Comparison with activation energies of COS absorption in aqueous DEA from
previous works.
I f t h e p s e u d o s te a d y s ta te c o n d it io n s a r e a s s u m e d f o r t h e C O S - a m in e References T (K) DEAconcentration E (kJ mol-1)
Z W I T T E R I O N c o n c e n t r a t io n , t h e fo llo w in g e x p r e s s io n c a n b e d e r iv e d fo r th e (mol m-3)
o v e r a ll fo r w a r d r e a c t io n r a te : Littel et al., 1992 283,303,333 200-2500 47.51
Hinderaker and Sandall, 293,313,333,348 476-2440 52.35
DEA COS  2000
160

R COS 
140 This work

This work 313,333,323,353 474-2400 43.22

Hinderaker and Sandall (2000)

1 1 120


H 2 O   K DEA 
100

K 2 K
Kobs(s )
-1

H 2O DEA 80

60 Considering the fact that the kinetics constant depend on the concentration. It is
W it h :
40
more interesting to determine for each studied concentration a kinetic lawof type :
  B
20

K 2K K 2K
KWi  Aexp
 
0

K 
b ,H 2 O
, K 
b , DEA 500 1000 1500 2000 2500 3000
(*)
H 2O DEA
 T 
-3

K K
CDEA(mol m )

2 2
Comparison with kinetics constant of COS absorption in aqueous DEA at 313K.
Kinetic Laws of COS absorption according to the DEA concentration (*).
K H 2 O , K D E A r e p r e s e n t r e s p e c t iv e ly t h e Z W I T T E R I O N d e p r o to n a t io n c o n s ta n t b y Without extrapolation With extrapolation
w a t e r ( m 6 m o l-2 s -1 ) a n d t h e Z W I T T E R I O N d e p r o t o n a t io n c o n s t a n t b y a m i n e ( m 6 wt %DEA A B A B
-2 -1
m o l s ). 5 6.26102 5400 31.34102 5918
2 2
15 14.0810 5773 14.6610 5786
25 10.02102 5746 36.05102 6162
350 1E-3

Hinderaker and Sandall (2000) WDEA=0.05

300 Littel and al. (1992) WDEA=0.15
This work WDEA=0.25
250

The same procedure of calculation is used for the determination of kinetics

1E-4
K(mmols )

200
-2 -1
Kobs(s )
-1

150

constant of COS absorption in MDEA aqueous solutions. The first order with
6

1E-5
100

50 respect to the MDEA concentration is tested and the Arrhenius law for the
kinetic constant KMDEA is obtained.
0 1E-6
0 500 1000 1500 2000 2500 3000 0.0028 0.0029 0.0030 0.0031 0.0032
-3 -1
CDEA(mol m ) 1/T (K )
Arrhenius law for the COS absorption in aqueous DEA.
Comparison with kinetics constant of COS absorption in aqueous DEA from
0.1 100

B y a s s u m in g th e p a r tic ip a tio n a ls o o f w a te r ( a s b a s e ) in th e d e p r o to n a tio n o f th e WMDEA=0.05

WMDEA=0.15

Z W I T T E R I O N , w e d e te r m in e d th e v a r io u s k in e tic s c o n s ta n t, b y a d ju s tin g th e 0.01

WMDEA=0.25

10

e x p e r im e n ta l c o n s ta n ts ( K ob s) w ith th o s e g iv e n b y th e r e la tio n :
KMDEA(m mols )
-1 -1

Kobs(s )
-1

DEA 
3

K obs , cal  1E-3 1

1 1
This work,T=313K
This work,T=323K


H 2 O   K DEA 
This work,T=333K
This work,T=353K

K 2 K H 2O DEA 1E-4 0.1

Al-Ghawas and al.(1989),T=313K

0.0028 0.0029 0.0030 0.0031 0.0032 500 1000 1500 2000 2500 3000 3500

C o n s ta n ts K 2 , K H 2 O a n d K D E A is o b ta in e d b y m in im iz in g th e f u n c tio n : -1
1/T (K ) CMDEA(mol m )
-3

K obs , exp  K obs , cal 2 Arrhenius plot of rate constants for COS absorption in aqueous MDEA Comparison between the observed kinetics constant of COS absorption in aqueous
MDEA at 313K.

K
i
ne
ti
csL
a
ws
of
rea
c
ti
ono
fC
OSa
cco
rd
in
gt
oth
ec
o
nc
ent
rat
i
oni
nMDEA
.
K obs , exp Wi
th
ou
t
ext
r
apo
l
at
i
on W i
the
xt
ra
po
la
t
i
on
T h is p r o c e d u r e g a v e th e fo llo w in g e q u a tio n s f o r Z W I T T E R I O N d e p r o to n a tio n wt%MD
EA A B A B
4 4
ra te c o n s ta n ts : 5 2
.
621
0 5
19
1 3 1
.8
110 5
9
86
4 4
  5773    6985  1
5 5
4
.6
91
0 6
40
21 1
7.
061
0 6
6
46
K DEA  9 . 63  10 exp  2
 K H 2O  4 . 07  10 exp  2
 2
5 1
6
.9
1
6
1
0 7
58
91 2
2.
421
06
8
2
20
 T   T 

CONCLUSION
The results of COS absorption in aqueous DEA solutions show that the limiting step in the reaction is the deprotonation of the
ZWITTERION, for witch the participation of water was highlighted. We concluded that the results of Al-Ghawas et al. (1989)
concerning the COS absorption by aqueous MDEA solutions are over-estimated. Although data treatment which involves
additional data is very dependent on the Henry’s constants and diffusion coefficients. We determined a new kinetics law by
extrapolating these parameters at high temperatures.