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Eluilbria and Kinetics of CO2 Adsorption On Hydrotalcite Adsorbent
Eluilbria and Kinetics of CO2 Adsorption On Hydrotalcite Adsorbent
Abstract
The equilibria and kinetics of high temperature CO adsorption on hydrotalcite adsorbent have been studied using semi-technical
and bench-scale elution apparatus. The former unit enabled the simulation of the adsorption, depressurisation and purge steps of
a pressure swing adsorption-based process. Conditions of measurements were chosen to depict those of the separation enhanced
steam methane reforming process, i.e. temperatures up to 753 K and in the presence of water vapour. These conditions are also
appropriate to some #ue gas CO recovery processes. At 753 K and in the presence of water vapour, adsorption saturation capacities
of &0.58 mol/kg were measured, and found to be insensitive to the actual concentration of feed water. Under dry feed conditions,
a small reduction in the capacity of the fresh adsorbent (&10%) was observed, however, both dry and wet feed cases could be
adequately described by Langmuir models. Measurements also suggest rapid and irreversible chemisorption on freshly packed
adsorbent, followed by reversible and relatively weak adsorption on the material thereafter; adsorption appears to be promoted in the
presence of water. Nevertheless, a temporal decline in the reversible adsorption capacity was also observed, which was particularly
severe for dry feed operation. For example, at 673 K, a steady-state capacity 30% to 40% less than that of the fresh adsorbent was
measured. A steam purge was found to partially reactivate the adsorbent, but some irreversible loss in capacity was indicated for very
long times-on-stream (e.g. '90 d at 673 K). A mathematical model based on a linear driving force description of mass transfer, but in
which the non-linearity of the isotherm is accounted for, was found to give a good description of the adsorption, depressurisation and
purge steps of operation. The model also accounts for non-isobaric and non-isothermal adsorption/desorption, and is thus suitable for
the purposes of large-scale design and process analysis. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Adsorption isotherms; Desorption kinetics; Carbon dioxide; Hydrotalcite; Mass transfer; Mathematical modelling; Steam methane
reforming
1. Introduction
The equilibria and kinetics of CO adsorption over
various adsorbents have been studied extensively since
the early 1950s. Except for a few cases, most studies have
been limited to low temperatures (273}400 K) and low
partial pressures (0}1 bar) of operation, and in which
CO is the only adsorbate rather than the multicompo
nent systems which are of industrial importance; see
Valenzuela and Myers (1989), and Ritter and Yang
(1987). Recent interest in CO recovery from #ue and
other process e%uent gases (see Suzuki, Sakoda, Suzuki
& Izumi, 1997a, b), and in the use of CO adsorbents for
0009-2509/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 5 9 6 - 5
3462
2. Experimental
The adsorbent pellets were of cylindrical shape of
1.6 mm diameter and 5.5 mm length. These were used in
their original form in the semi-technical scale unit, whereas both original and crushed pellets (average diameter of
0.36 and 0.5 mm) were used in the bench-scale unit.
Cylinder supply of two premixed gases, 5.81% (v/v) CO
in N and 19.93% (v/v) CO in N , and pure oxygen-free
N were used to give the desired feed concentrations of
CO .
A schematic diagram of the semi-technical scale adsorption unit is given in Fig. 1. The unit consists of
a stainless steel adsorption column of internal diameter
38.4 mm and length 607 mm. The column was divided
into 3 sections: preheat, adsorbent and exit. The preheat
and exit sections were packed with dense alumina balls of
12 mm diameter, which aided in the temperature control
of the adsorbent section, as well as the steady modulation
of gas #ow. The length of the adsorption section was
approximately 318 mm and consisted of 350 g of adsorbent. The vessel was "tted with inlet ports for introducing
feed gas (premixed CO /N , N and H O) and purge gas
(N and H O). Switching from one feed stream to an
other was via a manually operated 3-way valve. The inlet
#ow rates of premixed CO /N gases and N were
controlled by Brooks 5850E mass#ow controllers. An
HPLC pump and an electrically heated vaporisation
system were used to supply steam to the vessel. Surge
(mixing) vessels enabled the constant supply of a desired
steam concentration. Feed CO and water partial
pressures in the range of 0}4 bar could be achieved, with
a maximum total operating pressure of 20 bar. Typically,
a CO partial pressure in the range of 0}0.6 bar was used
3463
3. Mathematical model
3.1. Governing equations
A dynamic model was developed to describe adsorption and desorption of CO under a semi-technical scale
of operation, i.e. non-isothermal, non-adiabatic, and
non-isobaric operation, and adsorbent in its original
(pelletized) form. For computational and design convenience, linear driving force (LDF) models were used to
describe intraparticle mass transfer processes (see
Glueckauf & Coates, 1947; Liow & Kenney, 1990; Karger & Ruthven, 1992). These involved a driving force
based on the linear di!erence between the equilibrium
adsorption amount and the actual (volume-averaged)
adsorption amount, and a constant of proportionality
accounting for the intraparticle di!usional resistance of
the adsorbent. An adsorption model based on instantaneous local adsorption equilibrium (ILE) between the
gas and adsorbed phases was also developed to further
assess the importance of intraparticle mass transfer during di!erent steps of operation. Several adsorption isotherm models could be readily employed, e.g. linear,
Langmuir and Toth. As will be shown later, the Langmuir model was found to give an adequate description of
CO adsorption on the hydrotalcite, and will be de
scribed here. Other principal model assumptions can be
3464
*
*C
*(uC )
*
G !
G
(e C #o q )"
D
R
G
@
G
X
*t
*z
*z
*z
(2)
(2a)
j (1!e )o
@ E.
K "1.75 Q
4
d e
. @
(2b)
P
*
C e
#o C
NE R R
@ NQ *t
(3)
(3a)
k
E
k
Q
(3b)
where the void}void and solid}solid radiative heat transfer coe$cients, h and h respectively, are given as
PT
PQ
h " 0.1952
PT
e
1!e
@
1#
)
2(1!e )
e
@
(/100),
e
h " 0.1952
(/100).
PQ
2!e
(3c)
(3d)
; D
6d
M P "1.26Re
exp ! N (cylindrical packing,
N
k
D
E
P
Re "20!800, d /D "0.03!0.2)
N
N P
; D
6d
M P "2.03Re
exp ! N (spherical packing,
N
D
k
E
P
Re "20!7600, d /D "0.05!0.3)
N
N P
(3e)
*P
*
*
P *
"e
#
K
!uC
R *t
NE R *z
*z X *z
*q
4;
G # ( !).
!o H
@
?BG *t
U
D
P
G
b (1!e )
@
1
#c
d h
1
N
PQ
#
U
k
E
K
h d
X "e 1#b PT N #
@
k
k
E
E
(1)
(3f)
(4)
(5a)
(5b)
" ,
(6d)
C" C "P/(R ).
(6e)
G
The initial conditions for the depressurisation and purge
steps are taken as the conditions at the end of the adsorption and depressurisation steps, respectively. The following boundary conditions were used to simulate the
adsorption and desorption steps in the semi-technical
scale unit:
Adsorption step
(i) Inlet conditions (z"0)
!D (*C /*z)"u(C !C ),
X
G
DG
G
!K (*/*z)"uo C ( !),
X
E NE D
P"P ,
D
*C /*z"0,
G
*/*z"0,
u"(Q /A)(1!y
)/(1!y ),
D
D !-
!Depressurisation step
(7d)
(7e)
(7f)
(7h)
(7i)
(7g)
(7j)
(7k)
/A! e "dP/dt"/P.
(7l)
Eq. (7l) is derived from the mass balance of the exit zone
under the assumption that the spatial pressure drop in
this zone is negligible. Note that Q in Eq. (7f) and Q in
D
Eq. (7l) are volumetric #ow rates measured under local
conditions.
Purge step
(i) Inlet conditions (z"0)
*P/*t"0,
u"Q
q "0,
G
*P
"!K u !K u ,
"
T
*z
3465
(7a)
(7b)
(7c)
!D (*C /*z)"u(C !C ),
X
G
NG
G
!K (*/*z)"uo C ( !),
X
E NE N
P"P ,
N
(ii) Outlet conditions (z")
*C /*z"0,
G
*/*z"0,
(8a)
(8b)
(8c)
(8d)
(8e)
(8f)
u"(Q /A)/(1!y ).
N
!In this work, Eqs. (1), (2), (2a), (2b), (3a)}(3f), (4), (4a),
(5a) and (5b), with the appropriate boundary conditions,
were solved in the gPROMS modelling environment
(Process Systems Enterprises Ltd.). The spatial discretisation method of orthogonal collocation on "nite elements
was employed; second-order collocation on 100 elements
was found to give a converged solution in which component balance errors (associated with the numerical
integration) did not exceed 1%. The above model is, of
course, equally applicable to the simulation of the adsorption step in the bench-scale unit, except that the
outlet pressure and inlet velocity are known for this case,
and replace boundary conditions (7c) and (7f), respectively. A summary of "xed design parameters used in the
simulations is given in Table 1.
3466
Table 1
Parameters (constants) used in the simulations
Parameters (constants)
Value
Unit
d (original, equivalent)
N
D
P
C
NE
C
NQ
e
K
E
K
Q
b
e
@
e
e
N
e
R
U
c
j (original pellet)
Q
k
E
o
@
o
N
2.75
38.4
35
850
0.35
0.05
0.3
150
0.95
0.48
0.4
0.24
0.61
0.2
0.667
1.32
3;10\
811
1563
mm
mm
J/mol K
J/kg K
*
J/m K
J/m K
mm
*
*
*
*
*
*
*
*
Pa s
kg/m
kg/m
(i.e. 10 to 20 K). This observation suggests the rehydration of the hydrotalcite following heat treatment.
Fig. 4 shows the time dependence of the CO adsorp
tion capacity under a dry nitrogen purge. Capacities after
each purge period were measured at 673 K, with a feed
CO partial pressure of 0.1 bar (2.4 mol%). The average
CO contact time was 2 hr/d. It is seen that the adsorp
tion capacity decreases rapidly in the "rst 200 h of operation and tends to a constant value of 0.2 mol/kg. The
adsorption isotherm of the degraded adsorbent can also
be described by the Langmuir model, in which the Langmuir model parameter, b , is approximately the same
!as that of the fresh adsorbent. The reversibility of the
deactivation was investigated by the steam treatment of
the deactivated adsorbent. In speci"c, this involved the
low pressure (1.3}3 bar) purge of the adsorbent with
10 mol% steam for 2 h, whilst maintaining the adsorbent
bed at a temperature of 673 K, followed by dry N purge
for 12 h to remove all traces of water. With reference to
Fig. 5, it is seen that after steam treatment, there is almost
complete recovery of the adsorbent capacity, i.e. to values
measured in experiments directly proceeding the "rst
12 h purge period. It has also been observed (data not
shown), that adsorbent regeneration is particularly
3467
steam
treatment;
3468
D
K r
N
Fig. 7. Breakthrough curves at high bed pressures: comparison between experiments and mathematical model (ILE and simple LDF
models): (a) dry feed conditions: 673 K, 17.26 bar, 4.63 SLM
1.62%CO /N , (b) wet feed conditions: 673 K, 18.7 bar, 3.69 SLM
1.51%CO /21%H O/N .
(9)
Fig. 8. Breakthrough curve with crushed adsorbent: comparison between experiments and mathematical model (ILE and simple LDF
models): 0.5 mm mean particle diameter, 673 K, 4.4 bar,
6.68%CO /66.5%H O/N .
3469
3470
Fig. 12. Desorption percentage as function of purge gas amount (dry basis) at 673 K.
e D #o D (*q /*C )
1 *
*C
*C
N N
N Q G
G
G"
r G .
e #(1!e )o (*q /*C ) r *r
*r
*t
N
N N
G
G
(10a)
e D #o D (*q /*C )
N Q G
G .
D" N N
C e #(1!e )o (*q /*C )
G
N
N N G
(11)
1 *
*C
1 *
*q
"
e D r G #
o D r G
r *r N N *r
r *r N Q *r
(10)
k e D #o D (*q /*C )
G
N Q G
k" K N N
r e #(1!e )o (*q /*C )
N N
N N G
G
(12)
(12a)
Fig. 14. Desorption by purge with dry N at 673 K and 1.14 bar
(2 psig): comparison between experiments and model (simple LDF
model).
k D
o (*q /*C )
N G
G
k" K Q
(1!h).
(12c)
r e #(1!e )o (*q /*C )
N
N
N N G
G
Since *q /*C and h can be evaluated from the isotherm,
G
G
then if k "k D/r is used as a "tting parameter, Eq.
QM
K Q N
(12c) can be used directly in the simulations. Fig. 15
shows the modelling results of a run under dry feed
conditions at 673 K and 1.14 bar (2 psig) with the
bench-scale unit. Only adsorption and purge steps were
conducted in this run. With reference to Fig. 15(b), it can
be seen that the "t of the experimental date is much better
than that by the simple LDF model (Fig. 14(b)). Fig. 16
shows the pro"les of e%uent CO molar fraction, which
again shows the improved "t. However, the k value in
QM
the adsorption step (&0.0075) is still about 15 times that
3471
(12d)
3472
Fig. 16. E%uent molar fraction pro"les: comparison between experiment with simulations using simple LDF, low surface di!usivity and
high surface di!usivity models: bench-scale apparatus.
Fig. 17. Comparison between experiment and model assuming a relatively low surface di!usivity contribution to overall #ux; 1.14 bar,
673 K bench-scale apparatus.
5. Conclusions
Under conditions depicting the separation enhanced
steam-methane reforming process, experimental data for
the adsorption and desorption of CO on potassium
promoted hydrotalcite adsorbent have been measured.
In this work, adsorption saturation capacities of 0.65 and
0.58 mol/kg were measured at 673 and 753 K, respectively, under wet feed conditions. Under dry feed conditions,
an &10% reduction of the saturation capacity was observed. In both cases, a Langmuir model was found to
adequately describe the adsorption isotherm. Experimental data indicated the relatively rapid degradation of
Notation
a
h
PT
H
?BG
k
k
E
k
K
k
NM
k
QM
k
Q
K
"
K
4
K
X
K
X
m
G
M
P
P
D
P
G
P
N
q
G
qH
G
q
G
Q
Q
D
Q
.
r
r
A
r
N
r
r
Q
R
t
U
u
u
;
y
DG
y
G
3473
Greek letters
b
e
@
e
e
N
e
R
U
c
3474
j
j
Q
k
E
h
o
@
o
E
o
N
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