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Kinetics of Sodium Bircarbonate-Sulfur Dioxide Reaction

Article in Chemical Engineering Science · August 1993

DOI: 10.1016/0009-2509(93)80032-L

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Chemical Engineering Science. Vol. 48. No. 16. pp. 2859-2865,1993. CHlO%2509,93 S6.M + 0.00
Printed in Great Etritain. Q 1993 R@mon Rsa Ltd

KINETICS OF THE SODIUM BICARBONATE-SULFUR

DIOXIDE REACTION

TIM C. KEENER’ and SOON-JAI KHANG*

Civil and Environmental Engineering Department, and ‘Chemical Engineering Department, University of
Cincinnati, Cincinnati, OH 45221, U.S.A.

(First received 21 April 1992; accepted in revised form 27 January 1993)

Abstmct-A parallel reaction path model has been developed to explain the reaction between sodium
bicarbonate (NaHCO,) particles and sulfur dioxide (SO,) gas. This reaction is atypical compared to other
alkali and alkaline compounds with SOi in that the optimum reaction temperature occurs where thermal
decomposition of the parent particles is pronounced. The model accounts for the concomitant thermal
decomposition reaction which occurs at the temperatures where this reaction is industrially significant. The
subsequent reaction between the product of the thermal decomposition, micro-grains of sodium carbonate
(Na,CO,) and SO2 is considered in the reaction path by the use of a pore plugging model. The model has
been applied to published kinetic data for the NaHCOs-SO2 reaction in order to obtain the reaction rate
constants which are shielded from observation by the thermal decomposition reaction and the subsequent
reaction between Na,CO, and SOz. An expression for the reaction rate constant for the reaction of
NaHCO, with SO1 has been found and is of the form
k, = 2.2625 x 106e-*3*5’2/RT.
The model has been applied to conversion of the bicarbonate particles for up to 600s reaction time, with
good agreement with the data. This model can be used to predict the reactivity of NaHCOI with SO1 in
typical gas-solid reactors.

INTRODUCTION AND BACKGROUND KINETIC MODEL

Recently passed provisions of the Clean Air Act
Amendments (1990) will require extensive scrubbing
of sulfur dioxide (SO,) from waste combustion gases.
The use of sodium bicarbonate (NaHCO,) as a solid
sorbent for the removal of SO2 has many attractive
features, including a high degree of conversion and
process simplicity when coupled with a fabric filter.
The Electric Power Research Institute (EPRI) has
been studying dry sodium injection since 1977 and has
evaluated this material as a solid sorbent with full-
scale demonstration tests (Bland, 1990). The results of
their extensive testing indicate that 70-90% reduc-
tions of SOz may be obtained for subbituminous coals
with a variety of sodium based sorbents, all of which
contain a significant proportion of sodium bicarbon-
ate.
The influence of thermal decomposition of
NaHCO, to Na,COs (sodium carbonate) on the de-
gree of reactivity with SO2 has been well established.
A variety of reports and studies (Bland, 1990; Carson,
1980; Erdos, 1989; Knight, 1977) indicate that the
sodium sorbcnt has its greatest utilization for SO2
scrubbing at gas temperatures between 120 and 175°C
(250 and 350°F) when the initial material injected into
the duct is sodium bicarbonate. A summary of the
results from a pilot plant scrubbing study is given in
Fig. 1, which indicates the superiority of the use of
NaHCOo as a sorbent over that of Na2C03. This
difference in reactivity has been described as being the
result of an “activation” of the sodium compounds
produced by the thermal decomposition of NaHCO,
(Erdos, 1989).
decomposition of NaHCOj
Thermal
The reaction between NaHCOJ and SOP is com-
plicated and involves the interaction of two solids
with the gas at the temperatures of interest. When
NaHCOj is exposed to flue gases at temperatures
between 120 and 175”C, thermal decomposition of the
solid commences according to the reaction producing
the micro-grain structure of Na,COJ:
2NaHCO,(s) -, NaXO&) + CO&) + H,O(g) (1)
The temperature at which decomposition occurs will
depend on the partial pressures of carbon dioxide and
water vapor present, which arc generally well below
equilibrium values at stack gas conditions (Church
and Dwight, 1982).
The solid sodium carbonate formed in eq. (1) is
known to have a high specific surface area. The man-
ner in which sodium bicarbonate decomposes (i.e. the
gas temperature) has been shown to influence greatly
the degree of surface area production (Howatson,
1980; Knight, 1977; Stern, 1978) which would influ-
ence the reactivity of Na2COJ with S02.
Thermal decomposition of sodium bicarbonate has
been studied by a number of investigators. Hu et al.
(1986) studied the thermal decomposition of 125/rm
sodium bicarbonate particles in a thermal gravimetric
analyzer. They assumed the reaction to be first order
with respect to the mass of unreacted bicarbonate.
Their results indicated an activation energy of 24,370
Cal/g mol. Subramanian et al. (1972) studied pul-
verized sodium bicarbonate particles (14-350 m)
mixed with alumina in a differential thermographic

CES 48:16-C 2859

2860 TIM C. KEENERand SOON-JAIKHANG

analyzer. The measured activation energy from this gas has the following form (Erdos, 1989):
study was between 20,000 and 24,000 Cal/g mol.
2NaHCOJ + SO1 + 40, --, Na2S04
Keener et al. (1985) studied the thermal decomposi-
tion reaction of sodium bicarbonate particles ranging + 2COr + H20. (2)
in size from 51 to 140pm in a thin differential-bed
However, it has been assumed by previous researchers
reactor. The reaction was found to follow a first-order
that sodium bicarbonate does not react directly with
dependency with the remaining surface area of un-
SOz, but that the product of thermal decomposition,
reacted NaHCO, and could be well represented by
sodium carbonate, does. The generally accepted reac-
a shrinking core reaction model. The activation en-
tion scheme assumes that eq. (1) is followed by the
ergy for the reaction was determined to be 20,500
reaction between Na,CO, and SO?,
Cal/g mol.
Na,COJ + SO2 + ?O, + Na2S04 + CO1. (3)
REACTION OF SO, WITH NaHCO,
It has been shown (Keener, 1982) that sodium bicar-
A limited amount of kinetic data concerning the bonate reacts directly with SO2 at temperatures below
reaction of NaHC03 and SO2 exist in the literature. which any detectable thermal decomposition was in-
No models for this reaction have been proposed be- itiated ( < 340°K). This gives rise to a multipath reac-
cause of the influence of thermal decomposition on tion scheme between SO2 and the two solids which
may be represented as follows:

(W
2NaHC0, + 2C02 + H20 ---- path 1
[Nonporous]

2 3 + CO1 + Hz0 ---- path Id

[Micro-grain] (4)
~ + so2 (R) ----- path 2

the degree of sulfur uptake. Typical sulfation models
do not account for porosity development due to ther-
mal decomposition, only pore closure resulting from
sulfation.
The overall reaction of NaHCO, with SO2 in a flue
Na2S03 + CO2
In this proposed reaction scheme, the sodium bicar-
bonate may either react directly with SO1 (path 1) or
thermally decompose and form micro-grains of so-
dium carbonate via the parallel reaction path id.
Sodium carbonate may then react directly with SO*
to form the final product, which is sodium sulfite.
Sodium sulfite will then react with oxygen according
to the reaction
Na2S03 + fl, + Na$IO+ (5)
The overall reaction as expressed by eqs (4) and (5) is
the same as that given by eqs (l-(3) except that it is
arranged in a logical sequence of the individual reac-
tions.

MODEL DEVELOPMENT
In the overall development of the model, the so-
dium bicarbonate particle is considered to be nonpor-
ous having low specific surface area. As reaction pro-
gresses, a shrinking boundary of NaHCO, exists and
at the boundary, micro-grains of reaction products
ma&O3 and Na2S03 from paths 1 and Id of eq. (4)]
are produced, as illustrated in Fig. 2. Due to the low
Stoithiometric Ratio specific volume of the reaction products, these grains
NaHCO, NGO,
MMO. 32”rn B n. Temp.=3007 d MMD=Z?um create large outside channels that provide easy mass
MMD=
MMD=
32”rn
32”rn
B.“. Tednpl25w
(1978 Data)
transfer within the grain region. Each micro-grain
MMD=52 urn
8.H. Temp=3Oo=F
6 H. Temp=ZSCfF
I MMD=42”rn
MMD42Urn
contains micro-pores providing a high specific surface

P area of the decomposed material. This model is a vari-

MMD=119urn B.H. Temp=MO’F MMD=o4”m
MMD-154urn B.H. Tem~=3oo‘F MMD=lO1um
MMD=lO3 urn E.H. Temp=JW MMD-180um ation of the crackling core model originally proposed
MMD-(93 urn 6.H. Temp-2WF MMD=t80um
%
by Park (1975).
Fig. 1. Results of a pilot plant dry scrubbing demonstration The total conversion of NaHCOj to Na,SOa is the
study using NaHCO, (Carson, 1980). summation of the fractional conversion of each com-
 Kinetics of the sodium bicarbonat+sulfur dioxide reaction 2861

t seconds from the beginning of thermal decomposition

Freshly formed N&CO,

/ Exposure time (age) = 0

,/ Oldest Na$O,
. Exposure time (age) = t seconds

) NqCO, formed between

u and u+du seconds.
Exposure time (age) = t-u seconds.

Volume fraction = ‘$a (1 -IL! Z, )du

Micro-grains containing
micro-pores,
/ Pore-plugging model applied
for each grain

Fig. 2. Shrinkingcore of NaHCO, and varying exposure times (or ages) of NazCOl in a pelletcomposed of
micro-grains.

ponent reaction path as given by eq. (4). The fractional and the concentration of SO1:
conversion of path 1 and path 2 can be derived by the
separate reaction kinetics associated with each reac- (10)
tion path.
For reaction path 1 (the reaction of NaHCO, with or
SO*), a first-order reaction rate with respect to SO, is
assumed. Since the original NaHCO, pellet is non-
PBRO
(11)
porous, the reaction should take place at the surface
” = 2k, C,, + kd'
of its unreacted core of NaHCO,. Therefore, The fraction of NazCOl formed between time u and
u + du is obtained by differentiating eq. (9) and multi-
= 2klCso,. (6) plying by the rate fraction of path Id:

The thermal decomposition reaction of NaHCOJ (12)

produces a product (Na2COp) with a higher density,
and thus produces micro porous grains with large The reaction of Na,CO, and SOz (path 2) has been
outside channels. This reaction is also assumed to shown to approach an asymptotic level with time and
take place at the surface of the unreacted core of to exhibit the behavior of other gas-solid reactions

dNit
NaHCOJ : where product deposits plug pore passages within the

-411rf
dt
1Id=
dm
micro-grains (Keener, 1982). A simplified semiempiri-
1
k cal pore plugging model has been shown to describe
[ this type of reaction behavior by assuming that the
Therefore, the fractional amount of NaHCOs which reaction rate approaches zero after a period of reac-
decomposes is attributed to path id and may be tion (Lee et al., 198 1). This model can be applied to the
expressed as Na,CO,-SO, reaction in the following manner:

p= kd Production rate of Na2SOs using pure Na2COB

2klCsc,, + kd' = k2Cso I e-f/rp (13)
After u of reaction, the total fraction of decomposition where
of NaHC03 as expressed by a shrinking unreacted
core model has been shown to occur according to the t is the period during which the reactant,
following formula (Levenspiel, 1972): Na,CO,, is exposed to SO,,
3 zc is the pore plugging time constant, s, and
X,(u) = 1 -
( >1- ;

where zB is the time for the complete decomposition of

kz is the reaction rate constant, SK’
The pore plugging time constant has been found to
NaHCOo, which is dependent on the pellet diameter be inversely proportional to the concentration of SO1
2862 TIM C. KEENER and SOON-JAI KHANG

for reaction with sodium carbonate (Keener, 1982). The moles of Na,SO, produced by reaction path
We can express rP in terms of a pore plugging con- 1 can be obtained from the following expression:
stant, P*, as
P* NRl=$(1-;)‘](1-8). (18)
zp=-. (14)
C so2
Therefore, the total moles of Na2SOs produced will
Let us consider a partially reacted pellet which con- be the sum of eqs (16)(17 (18) or
tains an unreacted core of NaHCO,, as shown in Fig.
2. At the shrinking boundary of NaHCO,, both sulfa- NR,= NR, + N,c2. for t c Z*
tion reaction (path 1) and thermal decomposition (19)
(path Id) are taking place. The product of path id is NR, = NR~ + NRI_ + N,,, for t > zB
Na2COJ, which further reacts with SO2 according to We can express the total moles of NatSO produced
reaction path 2. The reaction rate of path 2 declines in terms of conversion of NaHC03 as follows:
exponentially with its exposure time to SO1 according
x = 2(Total moles of Na2SOJ produced) 2Ne,
to eq. (13). The shell region, shown in Fig. 2, has been R =-*
exposed to SO2 for z - us and the fraction, expressed (Initial moles of NaHCO,) PS
by eq. (12) is attributed to reaction path 2. Therefore,
(20)
the local production rate of Na2S03 attributed to
reaction path 2 may be found from eqs (12) and (13): The expression for conversion of NaHCO, to
Na2S03 can be written as
Local production rate of Na,SOa in the shell region
For t < zB:
= k2CS02 e-(f-Y)‘7p q%(u)du
x /&o,B A(t - rp + rpe-t’rn)
R
PEZB

The overall production rate of Na,SOJ may be found

by integrating the above local reaction rate with re-
spect to I( between 0 and t. which is equivalent to
(21)
averaging between the core boundary and the pellet For t 2 TV:

surface:
B
Overall production rate of NaZSOS in the pellet
x, = 6kz Go,B A@ - Tp + 7&9 - - 7;
PSTB 2

= k2CSOle-“-“““r [$ (1 - :>‘I du. (15)

where
In eq. (15), the current time, t, is the total time of the
reaction and the time difference, t - II, is a varying A=7,+($;+($)r: (23)
“age” of an incremental amount of Na&03, during
which the reactant was exposed to SO2 after its g++%
formation according to the reaction path Id.
The total moles of Na2SOs produced by reaction
path 2 may be calculated by integrating eq. (5) with
(25)
respect to the total reaction time and multiplying the
result by the pellet volume. Since reaction path 1 stops
when thermal decomposition is complete (t = ~a), eq.
(15) must be integrated over two different time per-
iods, before and after me, as follows: (26)
For t d zB:
RESULTS AND DISCUSSION
It has been shown that NaHCOJ directly feacts
with SOa at temperatures above which thermal de-
composition has been found to commence (Keener,
e-(t’-u)/r~ dudt’ 1982). However, from eq. (4) it can be seen that rate
(16)
constant kl is intrinsically hidden from observation at
For t > 7#:
these temperatures. Therefore, it seems more prudent
to use eqs (21) and (22) to evaluate the constant kl by
the use of kinetic data,
Figures 3-5 are examples obtained where eqs (21)
x e-(“-Y)‘r~ dudt’ + (NR1_, at t = 7s). (17) and (22) were applied to published kinetic data for the
 Kinetics of the sodium bicarbonatesulfur dioxide reaction 2863
Table 1. Values of model parmters llsed for simulation

Model
parameters Values

.p-JJ@-Je-ww-
_._____-_m_______
584 e- *0.000,RT 0.8

a(T) - b( 2”) + c(Z’) + d

o = 5.82 x 10-S(l/d,) + 9.2 x 10-s
b = 1.52 x lo-‘(l/d,) + 3.02 x lo-‘O
c = 1.21 x lo-“(l/d& - 2.565 x lo-”
d = - 7.66 x lO-3(l/d,) + 2.454 x 1O-4
[where d, is the particle diameter]
6.64 x IO-‘mol/cm’
0.0263 mol&m3

Fig. 4. Model predictions and data for 450 K [data reference

Keener (1982)].

Fig. 3. Model prediction and data for 394 K [data reference

Keener (1982)].

NaHCOs-SOa reaction. The values of the other kin-

etic expressions and constants are independently
measured and are given in Table 1. These equations
were visually best fit to the data by adjusting the
reaction rate constant, k,, for the model predictions
and the data for the 87pm particles at each temper-
ature. The predictions for the other two particle sixes
were then obtained by making model predictions
based solely on a change in particle size, as indicated
by eq. (11). Owing to the nature of experimental and
analytical techniques, the data show significant scat-
tering. Nonetheless, the model is in general agreement
with the data except for the case shown in Fig.
3 (where the model predicts higher conversion for
smaller particle size while the data indicate otherwise)
and does indicate the anomalous behavior of the data
with respect to conversion as a function of temper-
ature and particle size. The data indicate that in
general, smaller particle sizes do not necessarily result
.in higher degrees of conversion at a given temper-
ature, as shewn in Figs 4 and 5. The model indicates
that the extent of conversion increases with particle
size at temperatures greater than 394K (250°F) and
that this effect is greatest at 450K (350°F).
Fig. 5. Model predictions and data for 505 K [data reference
Keener (1982)].
The values of kl obtained by the method described
above have been were plotted against reciprocal tem-
perature and the results are shown in Fig 6. The
Arrhenius functional form of kl was obtained by lin-
ear regression of the best fit values and is of the
following form:
k, = 2.2625 x lo6 e-13.5’2’RT
The best fit values are seen to deviate from a linear
relationship at reaction temperatures above 505 K
(450°F). This is attributed to particle sintering, which
has been reported (Stern, 1978) to occur in these
materials above this value but is not accounted for in
our present model. The value of the activation energy
for this reaction (13,512 cal/mol) is greater than that
found for reaction of SO2 with Na2C03 (7324
cal/mol) (Keener, i982), indicating the high degree of
temperature-sensitivity of this gas-solid reaction in
comparison to that of the decomposition solid prod-
uct.
2864 TIM C. KEENER and SOON-JAI KHANG

pore blockage of the resulting carbonate. The model

has been used in conjunction with published kinetic
data for this reaction in order to derive the reaction
rate constant as a function of temperature and the
activation energy for the reaction of NaHCOs with
SOz. The value of the activation energy, 13,512
cal/mol, indicates the high degree of temperature-
sensitivity of this reaction compared to reaction of
SO2 with other sodium cornpour&. This model can
be used to predict the behavior of these particles when
used as a sorbent for the removal of SO2 from stack

NOTATION
SOz concentration in the bulk gas, mol/cm’
reaction rate constant for the thermal de-
composition of NaHCO, to Na,COS,
mol/cm* s
reaction rate constant for the reaction of
NaHCO, with SO*, cm/s
reaction rate constant for the reaction of
Na2C03 with SOz, s-l
moles of NaHCO,, mol
moles of Na,SOS, mol
pore plugging constant, mol/cm3
thermal decomposition reaction front radial
position, cm
particle radius, cm
time of exposure of Na2C03 to SO*, s
total reaction time, s
conversion of NaHCO,
conversion to Na2SOa

Greek letters
B fractional amount of NaHC03 decom-
posing to Na#O, as given by eq. (8)
TEMPERATURE, OF
PB molar density of NaHCO,, mol/cm,
Fig. 7. Model predictions for conversion of 87~m particles rn time for the complete decomposition of
at 600s. NaHCO,, s
pore plugging time constant, s
differential fraction of formation of Na2C03
The value of this kinetic expression is that it allows
for the prediction of conversion values at longer reac-
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