Petroleum 3 (2017) 51e55

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Petroleum
journal homepage: www.keaipublishing.com/en/journals/petlm

A novel rate of the reaction between NaOH with CO2 at low

temperature in spray dryer
Yadollah Tavan a, b, *, Seyyed Hossein Hosseini b
a
National Iranian Gas Company (NIGC), Tehran, Iran
b
Chemical Engineering Department, Faculty of Engineering, Ilam University, Ilam, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Carbon dioxide (CO2) is an influential greenhouse gas that has a significant impact on global
Received 6 May 2016 warming partly. Nowadays, many techniques are available to control and remove CO2 in different
Received in revised form chemical processes. Since the spray dryer has high removal efficiency rate, a laboratory-scale spray
1 October 2016
dryer is used to absorb carbon dioxide from air in aqueous solution of NaOH. In the present study,
Accepted 9 November 2016
the impact of NaOH concentration, operating temperature and nozzle diameter on removal effi-
ciency of CO2 is explored through experimental study. Moreover, the reaction kinetic of NaOH with
Keywords:
CO2 is studied over the temperature range of 50e100
C in a laboratory-scale spray dryer absorber.
CO2
Kinetic
In the present contribution, a simple reaction rate equation is proposed that shows the lowest
Spray dryer deviation from the experimental data with error less than 2%.
NaOH Copyright © 2016, Southwest Petroleum University. Production and hosting by Elsevier B.V. on
behalf of KeAi Communications Co., Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction a well-known process in industry, e.g. for the production of

ceramic precursors, and temperature-sensitive pharmaceuticals.
It is well known that CO2 plays a dominating role in the This device has no wastewater products and can control CO2
greenhouse gases [1e7]. Global climate change leads to the high emission into atmosphere. The performance of spray drying was
interest in the technologies relevant to the CO2 capturing that is improved and high removal efficiency rates were obtained for
one of the potential methods to reduce greenhouse gas emis- this device [10,13e16]. These researches only have used spray
sions [8e12]. Many alternative strategies are proposed to reduce dryer as a simple device and no data regarding its performance
the emission of CO2. Among them, reactive absorption as an on reactive absorption have been reported. Up to now, only a
economically feasible method has been extensively studied for semi-empirical kinetic model has been proposed in Ref. [16] for a
CO2 capturing [8]. spray-dryer setup over the temperature range of 100e200
C. It
Spray dryer is a chamber in which the liquid solution is has been found that when the operating temperature highly
sprayed by atomizer as droplets into hot flow gas, resulting in increases, the removal efficiency of CO2 decreases. Therefore, it
drying the liquid droplets. In spray drying system, the moisture seems that exploring a new reaction rate between CO2 and NaOH
on the droplets is evaporated gradually, while the absorbents in at low temperatures can be helpful for increasing the removal
the droplets react with impurities, simultaneously. Spray dryer is efficiency of CO2. In fact, the description and prediction of the
reaction kinetics in reactive systems, under given process con-
ditions, is still a serious weakness in the modeling of processes
including CO2 capturing. The lack of existing literature in reactive
* Corresponding author. National Iranian Gas Company (NIGC), Tehran, Iran. absorption in spray dryer motivates the authors to study this
E-mail address: [email protected] (Y. Tavan).
process in more details. Accordingly, such study is undertaken
Peer review under responsibility of Southwest Petroleum University.
and a new rate equation is proposed for low temperatures CO2
removal in spray dryer device. Furthermore, effect of absorbent
concentration, operating temperature and nozzle diameter on
Production and Hosting by Elsevier on behalf of KeAi removal efficiency of CO2 is investigated.

http://dx.doi.org/10.1016/j.petlm.2016.11.006
2405-6561/Copyright © 2016, Southwest Petroleum University. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
52 Y. Tavan, S.H. Hosseini / Petroleum 3 (2017) 51e55

2. Experiments
NaOH ðsÞ4NaOH ðaqÞ4Naþ þ OH (4)
Commercial CO2 gas with 99% purity and pellets of sodium ii- Precipitation of sodium carbonate:
hydroxide that were purchased from the Ruham gas Company
(50 kg) and the Kimiaexir Company in Iran, respectively, are CO2 þ
3 þ2Na 4Na2 CO3 ðsÞ (5)
used. The required air for the study is supplied by a laboratory
scale compressor. The NaOH pellets are dissolved in distilled
water and continuously fed into spray dryer by pump. A sche-
matic diagram of the experimental apparatus is shown in Fig. 1. 4 Evaporation of the water in the droplet.
In this setup, flow rate of air is monitored by a velocity meter and
the flow of CO2 is adjusted with a rotameter (to avoid solidifi- Generally, the overall chemical reaction can be written in a
cation, an internal heater is used for CO2 cylinder). The mixture simple form as:
of air and CO2 is preheated by an electronic heater and fed into
the spray dryer from the top. The feed stream (aqueous solution CO2 þ 2NaOH4Na2 CO3 þH2 O (6)
of NaOH) is concurrently fed to the drying chamber. The CO2
concentrations at the inlet and outlet of spray dryer are Each experiment is carried out for 10 min by considering the
measured by an infrared CO2 gas monitor (0e3000 ppm and liquid/gas weight ratio less than 0.2 to prevent weeping and also
0e100% in volume; ±2% uncertainty Edinburgh Instruments Ltd). to reach the complete drying. Hence, no weeping is found during
Typically, the gas mixture (air and CO2) is heated to 50e100
C experiments. It is interesting to note that due to solid formation
and this stream sprayed 3 wt % of aqueous NaOH into the reac- during the reaction, washing the dryer chamber and nozzle is
tion chamber of spray dryer (0.25 m  0.45 m). In this process, crucial. In order to run a new experiment, the dryer chamber is
washed by distilled water for 1 h, while no CO2 and NaOH pre-
heat and mass transfer and the chemical reaction occur in the
reactive spray dryer, simultaneously. Generally the process sent in feed streams. Afterwards, the pump is turn down and
dryer chamber is dried by clean air for 30 min at 150
C. When no
includes:
liquid is seen in the chamber, clean air and CO2 are mixed
together and fed to the dryer. After the temperature in the spray
1 Mass transfer of CO2 from the gas stream to the droplet
surface. dryer reached to 50e100
C range and the inlet concentration of
CO2 became stable, the absorbent is sprayed into the dryer
2 Absorption of CO2 at the droplet surface, dissolution of CO2 in
the droplet and dissociation: chamber. In order to explore the absorption performance,
removal efficiency (h) is used. Removal efficiency defines the
percentage of removed CO2 during absorption operation [17,18].
The removal efficiency for CO2 is simply determined from the
CO2 ðgasÞ/CO2 ðaqÞ (1) difference between the amounts of CO2 entering and leaving the
dryer chamber as follows

CO2 ðaqÞ þ H2 O ðliqÞ4H2 CO3 ðliqÞ (2) Yin  Yout

Eð%Þ ¼ (7)
Yin
H2 CO3 ðliqÞ4HCO þ 2
3 þH 4CO3 þ2H
þ
(3) It is worth mentioning that all experiments were conducted
at summer of 2013 from 7 to 11 a.m., accordingly, a constant
value for relative humidity of clean air is assumed during all
experiments.
3 Chemical reaction between dissolved CO2 and the dissolved
CO2 reagent: 3. Results and discussions

i- Dissolution of sorbent: 3.1. Absorption performance

The removal efficiency of CO2 as a function of operating

temperature is shown in Fig. 2 with the inlet CO2 concentration

Fig. 1. Spray dryer setup. Fig. 2. Effect of operating temperature on absorption performance.
 Y. Tavan, S.H. Hosseini / Petroleum 3 (2017) 51e55 53

of 4%. As observed in the figure, with increasing the operating constant with the values of 3 wt %, 0.063 lit/s and 5 mm,
temperature, the reaction rate increases resulting in enhance- respectively. Based on differential analysis, a rate equation is
ment of the CO2 removal efficiency. Fig. 2 shows that the considered for CO2 capturing in a lab-scale spray dryer and the
maximum removal efficiency of 63% is related to 100
C with kinetics parameters are calculated by fitting experimental data to
3 wt % of aqueous NaOH for the rate of 0.063 lit/s. Moreover, the a kinetic model by using a multivariable nonlinear regression
sharp change in the green line shown in Fig. 2 returns to the method to minimize the sum of the square of residuals. In
accuracy of the CO2 analyzer as well as higher reaction rate. In nonlinear regression method, the dependent variables are
order to evaluate the influence of the absorbent concentration, regressed and modeled as a non-linear function of independent
two different aqueous solution of NaOH with the values of 3 and variables. To achieve this goal, the nonlinear regression toolbox
1 wt % is used and the results are depicted in Fig. 3. As can be of polymath software is used. In authors' previous work, poly-
seen, increasing the absorbent concentration from 1 to 3 wt % math software was also used to predict kinetic constants in
leads to an enhancement in removal efficiency due to providing methanol dehydration process [19].
higher driving force to the reaction. As the concentration of Based on the Lee [20] study, the molar rate of CO2 removal by
absorbent is increased, the rate of reaction will also be favored the NaOH can be described by Eq. (8)
due to providing higher concentration of the reactant.    
Moreover, the effect of nozzle diameter is examined using the 1 dy dy
rCO2 ¼ /  rCO2  MNaOH ¼ RCO2 ¼ (8)
nozzle diameters of 0.5 mm and 1 mm. As shown in Fig. 4, with MNaOH dt dt
an increase in the nozzle diameter, the removal efficiency at
100
C for 3 wt % solution of NaOH reduces due to the smaller
surface area of droplets. Consequently, the smaller nozzle
diameter provides a better performance for spray drying process.

3.2. Kinetic rate equation

To develop a kinetic rate equation over a low range of tem-

perature, the absorption performance is measured for three
different temperatures of 50, 75 and 100
C. The experimental
conditions used in the present study for absorbents concentra-
tion, the absorbent inlet rate and the nozzle diameter are kept

Fig. 5. A comparison between experimental and calculated reaction rates at 50
C.

Fig. 3. Effect of absorbent concentration on absorption performance.

Fig. 6. A comparison between experimental and calculated reaction rates at 75
C.

Fig. 4. Effect of nozzle diameter on absorption performance. Fig. 7. A comparison between experimental and calculated reaction rates at 100
C.
54 Y. Tavan, S.H. Hosseini / Petroleum 3 (2017) 51e55

Fig. 8. The kinetic parameters of (a) K1 and (b) K2.

where rCO2 is the molar rate of CO2 removal per unit mass of inlet rate, relative humidity of air, absorbent inlet rate and
NaOH, and MNaOH is the molecular weight of NaOH. First the mixture of absorbents into the model is suggested for future
change of CO2 mole fraction (dy) versus time (dt) is plotted. After works.
fitting a smooth curve to the available points, slope at each point
is calculated. Each slope equals to the reaction rate multiplied by Nomenclature
the NaOH molecular weight (rCO2  MNaOH ) at that special
point. Figs. 5e7 indicate a well agreement between experimental A1 Parameter of K1 (mol/s)
and calculated reaction rates using Eq. (8) and Eq. (9) at 50
C 75 A1 Parameter of K2 (mol/s)
and 100
C, respectively. The temperature dependencies of the aq Aqueous solution
kinetic parameters are also determined by assuming the Arrhe- E1 and E2 Activation Energy (kJ/mol)
nius equation with R2 of 0.91 as given in Fig. 8. The obtained rate K1 and K2 Kinetic parameters (mol/s)
expression is as follows: liq Liquid
MNaOH Molecular weight of NaOH (g/mol)
expð  K1  K2  tÞ rCO2 Molar reaction rate of carbon dioxide per gram of solid
rCO2  MNaOH ¼ RCO2 ¼ K1  (9)
1 (mol/g/s)
    R Universal gas constant
E 4201 s Solid
K1 ¼ A1 exp  1 ¼ 1  1026 exp (10)
RT RT t Time (s)
T Temperature (K)
   
E 4123 Yin Mole fraction of carbon dioxide entering the dryer
K2 ¼ A2 exp  2 ¼ 6  1024 exp  (11) Yout Mole fraction of carbon dioxide leaving the dryer
RT RT
h Removal Efficiency
In order to find K1 and K2, 17 data points are used, in this
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