1898 Ind. Eng. Chem. Res.

2000, 39, 1898-1902

Reaction Kinetics of Hydrogen Chloride with Calcium Oxide by

Fourier Transform Infrared Spectroscopy
Maosheng Li and Henry Shaw
New Jersey Institute of Technology, University Height, Newark, New Jersey 07012

Chen-Lu Yang*
Beltran Associates, Inc., 1133 East 35th Street, Brooklyn, New York 11210

The chemical kinetics of the HCl reaction with CaO was investigated over the temperature range
of 148-400 °C. A thin film averaging 0.1 ( 0.05 µm CaO was deposited on quartz wool in order
to minimize the effects of pore diffusion for this heterogeneous reaction. The decrease in HCl
and increase in H2O concentration were continuously monitored in a Fourier transform infrared
(FTIR) cell with ZnSe windows. The HCl and H2O spectra were collected automatically at 1.2 s
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intervals using gas chromatography software. The gaseous reactants and products were circulated
continuously between the reactor and FTIR cell using a pump in order to minimize bulk mass-
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transfer effects on the CaO surface. In this way, rapid data collection at constant temperature
could be achieved without sampling problems. The results were in excellent agreement with
first-order reaction kinetics with respect to the HCl concentration. The Arrhenius activation
energy of 31.1 ( 3.0 kJ/mol is slightly larger than that reported in the literature due to
minimization of pore diffusion by study of a very thin layer of CaO and circulation of the reactants
at a high rate to minimize mass-transfer effects.

Introduction

While various types of Ca-based sorbents were studied

for hydrogen chloride (HCl) removal from flue gases,
limited fundamental kinetic information is available to
assist process design and system optimization. Karlsson
et al.1 studied the reaction of HCl with calcium hydrox-
ide [Ca(OH)2] in a temperature range between 150 and
400 °C and determined that the reaction rate is first-
order with respect to HCl. At higher temperatures, the
reaction was found to slow because of the release of H2O
from Ca(OH)2 and the existence of CO2. Weinell et al.2
studied the reaction of 1000 ppm HCl with a Ca(OH)2
fixed bed in a temperature range between 60 and 1000
°C. A maximum 60% utilization of the sorbent was
Figure 1. Schematic diagram of the reaction system.
reported at a temperature of about 600 °C. Reaction
kinetics were controlled by gas diffusion through the
solid product. The utilization was found to be indepen- and temperatures between 150 and 350 °C. First-order
dent of particle size in the range of 2-20 µm. Because reaction rates were observed with an apparent activa-
H2O and CO2 inhibit the chemical reaction of HCl with tion energy of 28.1 kJ/mol. In the temperature range of
Ca-based sorbents, it makes sense to calcine Ca(OH)2 150-350 °C, the reaction is controlled by gaseous
and calcium carbonate (CaCO3) before using them for diffusion through the developing product layer.
HCl removal. Daoudi and Walters3 studied the direct The objective of this research is to determine the gas/
reaction of a calcium oxide (CaO) particle with 0.5-5% solid reaction kinetics of HCl and CaO under a mini-
HCl in the temperature range of 310-670 °C. At the mum influence of bulk mass transfer and pore diffusion.
upper half of the temperature range, the apparent Bulk mass transfer was improved by employing a
activation energy was found to be 22 kJ/mol. The circulation pump in the reaction apparatus. A very thin
reaction rate decreased as the sorbent particle size film of CaO was coated on quartz wool to minimize pore
increased from 10 to 725 µm. Mura and Lallai4 passed diffusion. The gas-phase reactants were automatically
1000 ppm HCl through a fixed bed of CaO particles in and continuously analyzed by Fourier transform infra-
an electric furnace at temperatures of 200-600 °C. An red spectroscopy (FTIR) to avoid sampling errors.
activation energy of 45 kJ/mol was reported with a
particle size between 180 and 920 µm. Gullet et al.5 Apparatus
studied the kinetics of the reaction between HCl and
The preparation of CaO and the reaction of HCl with
CaO at HCl concentrations between 1000 and 7500 ppm
CaO were carried out in a 2.45-cm-i.d. and 26.7-cm-long
quartz tubular reactor as illustrated in Figure 1. A
* Corresponding author. quartz fritted disk was installed to keep the CaO-coated
10.1021/ie990628m CCC: $19.00 © 2000 American Chemical Society
Published on Web 04/20/2000

Figure 2. IR spectrum of 0.5% NO2 in N2.
quartz wool in the middle of the reactor. The reactor
was housed in a one-zone Lindberg tubular furnace. The
desired reaction temperature was measured with a
K-type thermocouple which was inserted into the center
of the quartz wool section in the reactor. A bypass coil
was installed to compensate for the additional volume
of the FTIR cell in the circulation loop. Through the
circulation between the reactor and the FTIR cell,
concentrations of gaseous reactants and products were
continuously and automatically measured by FTIR. The
system was designed to perform the following tasks: (1)
preparation of CaO, (2) quantification of the initial
concentration of HCl, and (3) monitoring of the reaction
progress of HCl and CaO.
IR Identification and Analysis
The FTIR spectrometer was used to conduct the on-
line measurements. A personal computer with a BIO-
3200 data acquisition system allowed measurement of
spectroscopic changes as a function of time. Spectra
were collected through an entire experiment at a rate
that resolved the changes of interest. A GC-32 software
package allowed the FTIR to be used as a detector to
acquire chromatograms for NO2 quantification.
NO2 Identification and Analysis. A half percent
NO2 in nitrogen was passed through the FTIR cell to
obtain the standard IR spectrum as shown in Figure 2.
The spectrum has a split peak at a wavelength of about
1600 nm. The valves were then positioned to allow N2
to purge the FTIR cell. After the purge, the flow rate of
N2 was set at 438 cm3/min and a background chromato-
gram was collected. A volume of 0.5% NO2 was injected
into the flow system to obtain a corresponding chro-
matogram. The experiment was repeated with NO2 of
219, 438, 657, and 876 cm3. A calibration curve was
prepared by plotting the volumes of NO2 injected into
the flow system versus the peak areas.
HCl Identification and Analysis. A cylinder of HCl
in N2 was supplied by Matheson Gas Co. Its concentra-
tion was determined as 4.9% by mass spectroscopy,
when the cylinder was shipped. To check the labeled
concentration, the HCl/N2 gas mixture was passed
through the FTIR cell followed by a sodium hydroxide
aqueous scrubber. The chloride concentration in the
scrubbing solution was then determined by an ion-
selective electrode. While the gas mixture was passed
through the FTIR cell, a standard IR spectrum was
taken for HCl identification. Figure 3 shows the full
spectrum of 4.9% HCl in N2. Only two bands, νp(2) at
2842 nm and νp(3) at 2821 nm, were chosen for kinetic
study.
Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1899
Figure 3. Full IR spectrum of 4.9% HCl in N2.
Figure 4. Time-dependent FTIR spectra of H2O vapor in the
region from 1665 to 1555 cm-1 during the reaction of HCl with
CaO at 400 °C.
Identification of H2O. Water vapor can promote the
backreaction of CaCl2 to HCl and CaO and can interfere
with the measurement of NO2 in the FTIR by aqueous
absorption. Therefore, it is important to identify and
even quantify its presence in the reaction system.
According to eq 1, the amount of H2O increases during
CaO + 2HCl f CaCl2 + H2O (1)
the progress of the reaction. Figure 4 shows how the
intensities of a series of H2O bends in the region 1665-
1555 cm-1 increase with time during the progress of the
reaction at 400 °C. Similar results were obtained for
reactions at other temperatures.
CaO Preparation
Approximately 0.5 g of quartz wool (Alltech Associ-
ates, Inc.) was immersed into a 0.1 M calcium nitrate
[Ca(NO3)2] aqueous solution. The wet quartz wool was
then removed from the solution and spread on a platter.
The quartz wool with the platter was placed in an oven
to dry at about 150 °C. In this way, Ca(NO3)2 was
uniformly deposited on the quartz wool. After drying,
the quartz wool was placed in the reactor, where the
temperature was maintained at 400 °C for 1 h to remove
moisture. The system was set to allow oxygen (O2) to
flow through the bypass coil, reactor, circulation pump,
rotameter, FTIR cell, and scrubber. H2O tends to adsorb
on the surface of quartz and can be removed at tem-
peratures over 300 °C. Therefore, while O2 was passed
through the quartz wool, the reactor temperature was
kept at about 400 °C to make sure that the quartz wool
was dehydrated completely. After the removal of mois-
1900 Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000
Figure 5. Chromatogram of NO2 determination.
ture, the valves to the reactor were closed and the
temperature was increased to 700 °C and kept for about
3 h to quantitatively convert Ca(NO3)2 to CaO. After
the calcination, the reactor was cooled to room temper-
ature to determine the conversion.
Based on eq 2, 2 mol of NO2 is generated for every 1
Ca(NO3)2 f CaO + 2NO2 + 1/2O2 (2)
mol of CaO produced. Therefore, the amount of NO2
given off from the decomposition of Ca(NO3)2 can be
used to determine the quantity of CaO deposited on the
quartz wool.6 During the calcination, O2 was passed
through the FTIR cell directly from the cylinder to purge
the cell and to collect the IR background spectrum. After
the reactor was cooled to room temperature, the valves
were quickly switched to allow O2 to flow through the
reactor and to carry NO2 from the reactor to the FTIR
cell for analysis. The switching valves were operated
just like a gas chromatography (GC) injection. The GC-
32 software allows the FTIR to produce a NO2 peak as
a gas chromatogram for quantification.
Figure 5 is the gas chromatogram of NO2 from the
decomposition of Ca(NO3)2 deposited on 0.5 g of quartz
wool. The IR spectrum was consistent with that of 0.5%
NO2 in N2, shown in Figure 2. The area of the peak was
used to calculate the amount of NO2 from the conversion
of Ca(NO3)2 to CaO. It was found that 56 mg of CaO/g
of quartz wool was deposited. Because the average
quartz fiber diameter was 9 ( 2 µm, the average
uniform CaO layer was estimated to be on the order of
0.1 µm. Thus, the system primarily involves the surface
reaction and minimizes pore diffusion. Bulk mass
transfer through the product layer is minimized by
maintaining a large recirculation rate.
HCl Conversions
After the amount of CaO deposited on the quartz wool
was determined, the whole system was purged with N2
to remove NO2 and possible contaminants. The purge
was continued until the baseline of the chromatogram
became stable. When the system was stabilized, the
valves were positioned to allow the pump to circulate
nitrogen between the reactor and the bypass coil. The
12.5 dm3/min circulation dropped the reactor tempera-
ture quickly to a steady state which can be adjusted to
the desired reaction temperature by manipulating the
initial reactor temperature. While the reactor temper-
ature was equilibrated, 4.9% HCl in N2 was passed
through the rotameter and FTIR cell. After the spec-
Figure 6. Time-dependent FTIR spectra of HCl bends νp(2) at
2842 cm-1 and νp(3) at 2821 cm-1 during the reaction of HCl with
CaO at 400 °C.
Figure 7. Temperature dependency on the reactivity of HCl
toward CaO at temperatures of 148-203 °C.
trum of HCl became stable, the two three-way valves
were positioned to allow the circulation among the
reactor, circulation pump, rotameter, and FTIR cell. The
reaction of HCl and CaO was carried out in the reactor
at a specified temperature. A series of HCl IR spectra
at the desired reaction time interval were obtained after
the GC collection, as shown in Figure 6. The absorbance
at 2842 nm was used to quantify the HCl concentration
and calculate the conversion. The first drop of intensity
at an absorbance of 2842 nm was due to dilution.
Finally, a dilution factor of 0.355 was determined for
the system.
Because the intensity of an IR absorbance band is
proportional to the concentration of the component
absorbing the radiation, the expression is written as
A ) aC (3)
where A is the intensity of the absorbance, C the
concentration of the component of interest, and a the
ratio constant. The fractional conversion is written as
A0 - At
x) (4)
A0
where A0 is the intensity of HCl absorbance at 2843 nm
at time zero and At the intensity of HCl at time t.
Figures 7-9 are plots of HCl conversion with respect
to reaction time in minutes. A parabolic increase of
conversion with reaction time at temperatures between
148 and 400 °C was found. Conversions also increased
with increasing temperature. This suggests that the
 Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000 1901

Figure 8. Temperature dependency on the reactivity of HCl Figure 10. Plot of ln(1 - x) with time from temperatures of 140-
toward CaO at temperatures of 248-300 °C. 275 °C.

Figure 9. Temperature dependency on the reactivity of HCl Figure 11. Plot of ln(1 - x) with time from temperatures of 300-
toward CaO at temperatures of 330-400 °C. 400 °C.

process is controlled by chemical reaction rather than

adsorption.

Reaction Kinetics of HCl and CaO

The overall reaction under study is described in eq 1.
The stoichiometry of the reaction was verified by X-ray
diffraction analysis and by verification that the maxi-
mum weight gain corresponds quantitatively to 100%
conversion of CaO to calcium chloride (CaCl2).7 First-
order kinetics in HCl was found in three previous
studies.2,3,5 Because CaO is in large excess to that
needed for the stoichiometry of the reaction, it does not
enter the rate expression. However, because this is a
heterogeneous reaction the overall rate constant has
units of (g min)-1. The first-order rate equation can be
expressed as
Figure 12. Arrhenius plot for the reaction of HCl with CaO.
CA
ln ) -kt (5) consistent with the first-order reaction with respect to
C0
the HCl concentration at temperatures from 148 to 400
where CA is the concentration of A at time t, C0 the °C.
initial concentration of A, and k the rate constant in The Arrhenius equation was applied to correlate the
1/time, or rate constants derived from these experimental data.
A plot of the results is shown in Figure 12. The
ln(1 - x) ) kt (6) activation energy obtained from the slope of the best-
fit line was found to be 31.1 kJ/mol with a corresponding
where x ) conversion ) (C0 - CA)/C0. preexponential factor of 0.241 (g min)-1, leading to the
Figures 10 and 11 are the plots of logarithms of 1 - following relation expressing the effect of temperature
x versus reaction time. The experimental results were on the rate constant as
1902 Ind. Eng. Chem. Res., Vol. 39, No. 6, 2000
k ) 0.241 exp (-31100
RT )
(7)
where T is the absolute temperature in Kelvin and R )
8.314 J/(mol K). The standard deviation of the activation
energy is 31.1 ( 3.0 kJ/mol.
The activation energy reported here is larger than
that reported by other authors for reaction of Ca-based
sorbents with HCl. Among these authors, Daoudi and
Walters.3 calculated an activation energy of 22.2 kJ/mol
for the system of HCl/CaCO3 under the chemical reac-
tion and mass-transfer control. Weinell et al.2 reported
an activation energy in the range from 10.0 to 15.0 kJ/
mol for the system of HCl/Ca(OH)2 under the control of
pore diffusion and mass transfer. Gullett et al.5 inves-
tigated the reaction of HCl and CaO over the temper-
ature range from 148 to 350 °C under the conditions
that minimized bulk mass transfer and pore diffusion
limitation. The activation energy they reported is 28.1
kJ/mol. The activation energy obtained in this research
indicates that the efforts to minimize the influences of
bulk mass transfer and pore diffusion were effective and
31.1 kJ/mol is probably more representative of a true
surface reaction.
Conclusions
The reaction kinetics of HCl with CaO at tempera-
tures between 148 and 400 °C were studied with the
use of FTIR spectroscopy under conditions minimizing
mass transfer and pore diffusion limitations. The reac-
tion was carried out in a closed system with a pump to
circulate the gas-phase reactant and product between
the reactor and FTIR cell. The initial concentration of
HCl was about 1.74 vol %, and CaO was 28 mg deposited
on 0.5 g of quartz wool. The average calculated thickness
of CaO on the quartz wool is less than 0.1 µm.
The reaction rate of HCl with CaO is first-order with
respect to HCl concentration. The Arrhenius equation
is adequate to express the effect of temperature on the
reaction rate with a preexponential factor of 0.241 (min
mg)-1 and an activation energy of 31.1 kJ/mol. The FTIR
spectrum is suitable for NO2, HCl, and water vapor
identification and analysis. The FTIR with GC-32
software can be effectively applied to real-time monitor-
ing of a gas-solid reaction. The real-time data allow
the determination of kinetics with good precision and
avoid sampling errors.
Literature Cited
(1) Karlsson, H. G.; Klingspor, J.; Bjerle, I. Adsorption of
Hydrochloric Acid on Solid Slaked Lime for Flur Gas Clean Up.
J. Air Pollut. Control Assoc. 1981, 31, 1177.
(2) Weinell, C. E.; Jensen, P. I.; Dam-Johansen, K.; Livbjerg,
H. Hydrogen Chloride Reaction with Lime and Limestone: Kinet-
ics and Sorption Capacity. Ind. Eng. Chem. 1992, 31, 164.
(3) Daoudi, M.; Walters, J. K. The Removal of Hydrogen
Chloride from Hot Gases Using Calcined Limestone. Management
of Hazardous and Toxic Waste in the Process Industries; Elsevier:
London, 1987.
(4) Mura, G.; Lallai, A. The Kinetics of Dry Reaction between
Calcium Oxide and Gas Hydrochloric Acid. Chem. Eng. Sci. 1992,
47, 2407.
(5) Gullett, B. K.; Jozewicz, W.; Stefanski, L. A. Reaction
Kinetics of Ca-Based Sorbent with Gaseous HCl. Ind. Eng. Chem.
Res. 1992, 31, 2437.
(6) Gopalakrishnan, R. A Novel Application of FT-IR Spectros-
copy for the Kinetics of High-Temperature Reaction of SO2 with
CaO. Appl. Spectrosc. 1990, 2, 310.
(7) Daoudi, M.; Walters, J. K. Thermogravimetric Study of the
Reaction of Hydrogen Chloride Gas with Calcined Limestone:
Determination of Kinetic Parameters. Chem. Eng. J. 1991, 47, 1.
Received for review August 19, 1999
Revised manuscript received March 7, 2000
Accepted March 9, 2000
IE990628M