8730 Ind. Eng. Chem. Res.

2005, 44, 8730-8738

APPLIED CHEMISTRY

Study of the Reaction of Lime with HCl under Simulated Flue Gas
Conditions Using X-ray Diffraction Characterization and
Thermodynamic Prediction
Terence Chin, Rong Yan,* and David Tee Liang
Institute of Environmental Science and Engineering, Nanyang Technological University, Innovation Centre,
Block 2, Unit 237, 18 Nanyang Drive, Singapore 637723

Hydrochloric acid (HCl) is commonly removed from flue gases using hydrated lime (Ca(OH)2)
as a sorbent in the dry scrubbing process. Although this method is relatively easy to operate
and the lime sorbent is cheap, this process is highly inefficient, as only ∼25% of the lime used
is converted, due to the short contact time and the lack of understanding of the reaction chemistry
of lime in a complex flue gas system. A comprehensive X-ray diffraction (XRD) characterization
was carried out on the product of a hydrated lime reaction with HCl in a simulated flue gas
system containing SO2, CO2, O2, and moisture. Together with thermodynamic calculations, the
chemical nature of the multiple reactions that happened in this system was investigated. It
was confirmed that the products of hydrated lime with HCl under the simulated flue gas
conditions were chiefly Ca(OH)Cl, CaCl2, CaCO3, CaSO3‚1/2H2O, CaSO4‚2H2O, and anhydrous
CaSO4. Previous results suggested that the presence of CO2 and SO2 in the system formed
products with a high product diffusion resistance, leading to pore blockage and the premature
termination of the reaction. However, in this study, experimental proofs showed that HCl was
able to break down the CaCO3 and CaSO3‚1/2H2O layer, allowing the reaction to continue. In
the presence of excess O2 (and moisture), part of the CaSO3‚1/2H2O was oxidized to CaSO4‚2H2O
and CaSO4. The presence of O2 is, therefore, counterproductive to the full utilization of hydrated
lime, as sulfur in its S(VI) form is more stable and resistant to HCl attack, thereby preventing
blocked pores from being cleared.

Introduction of sorbent relative to the theoretical minimum for acid

Hydrochloric acid (HCl) is formed when halogen-
containing waste components are combusted in munici-
pal and hazardous waste incinerators (MWI and HWI),
when coal with high chlorine content is burned, and also
when various industrial processes are performed. The
pretreatment HCl concentration generated from these
facilities can exceed 1000 ppmv at times and poses
serious environmental problems when released into the
atmosphere. The methods to treat this pollutant include
wet , semidry, and dry scrubbing.1
Although wet scrubbing comes first in terms of
efficiency, it produces wastewater that requires further
treatment and disposal, has corrosion problems, and
tends to generate a visible plume in the flue gas.
Semidry scrubbing systems, where lime slurry is in-
jected into the flue gas, also have a relatively high
efficiency, but they are more complicated to operate and
require additional investment in equipment compared
to dry scrubbing. Dry scrubbing systems are the cheap-
est and easiest to use; they have been widely employed
in industrial processes. To compensate for dry scrub-
bing’s low sorbent utilization efficiency, large quantities
* To whom correspondence should be addressed. Tel.: 65-
67943244. Fax: 65-67921291. E-mail: ryan@ntu.edu.sg.
10.1021/ie058021v CCC: $30.25 © 2005 American Chemical Society
Published on Web 10/14/2005
neutralization are used (usually more than 5 times).
This is mainly due to the short contact time between
the sorbent and the pollutant gas, typically in the range
of a few seconds. This results in a large amount of solid
waste generated.1
The limitations of the dry and semidry scrubbing
systems using various forms of lime as a sorbent led to
much research work done to improve them. Neverthe-
less, the majority of the works focused on the reaction
of lime and HCl itself without considering the effects of
other constituents that are normally present in flue
gas.2-8 So far, there are few published works that
consider the combined effects of HCl and other influenc-
ing species (CO2, SO2, and water)9-13 and fewer still that
consider all the components present in flue gas reacting
with lime simultaneously.14,15 The common issue fea-
tured throughout most previous works is the incomplete
conversion of lime when reacted with HCl, SO2, and CO2
(sometimes as low as a 10% conversion). Some authors
attribute this to the phenomenon of pore-clogging in
lime particles, where the product layer formation on the
surface of the sorbent acts as a barrier for further
reaction.2,13-14,16 Duo et al.15,17 presented a complex
“crystallization and fracture” model, explaining how
crystal formation on the lime surface and its subsequent
fracture affects the lime conversion.

Table 1. Properties of the Hydrated Lime Sample
property value
average particle diameter (µm) 4.50
BET surface area (m2/g) 38.1
micropore area (m2/g) 2.46
external surface area (m2/g) 35.7
pore volume (cm3/g) 0.119
average pore diameter (Å) 125.3
While studying the lime reaction with various acid
gases, most people assumed that standard and conven-
tional reactions are taking place without characterizing
the real products. Those who went on to characterize
the products with XRD were often rewarded with
interesting and unexpected results.2,8,18 This showed
that the reaction of lime with the various reactive
constituents in the flue gas is not as straightforward
as expected. To improve the efficiency of using lime as
a sorbent in the dry scrubbing of HCl, the real reactions
going on in the system have to be known clearly.
Thermodynamic calculations have been widely ap-
plied to predict the predominant reactions and species
in a complicated system containing multicomponents
and multiphases. Yet, their application is still rarely
found in lime/HCl reactions together with other reactive
gases. Verdone and Filipis19 did some theoretical ther-
modynamic calculations for HCl, NOx, and SOx removal
in a typical flue gas dry scrubbing system for incinera-
tors and concluded that sodium based sorbents are more
efficient than calcium based ones over the temperature
range of 100-600 °C.
This paper aims to investigate the actual reactions
taking place when hydrated lime is reacted with the
main flue gas reactive species (HCl, SO2, CO2, and
water) under simulated flue gas conditions. To achieve
this, a thermodynamic calculation was performed to
know the theoretical limits of the system. Extensive
X-ray diffraction (XRD) characterizations (and also
quantification, where possible) of the end products were
carried out. An in-depth discussion of the related
reactions provided a clearer insight into the chemistry
involved in the dry scrubbing system. Also, the results
here lend further support to our previous observations
reported in an earlier publication.20
Experimental Section
Materials and Apparatus. The details of the raw
materials and instruments used were described previ-
ously,2 including the diagram of the whole setup. The
advantage of this setup was that it allowed us to change
the reactive gases or to stop the reaction at any time
and remove the reacted sample from the thermogravi-
metric analyzer (TGA) for XRD identification, facilitat-
ing our study on the reaction of hydrated lime with
various acid gases. The reactive gases used here, CO2
(100%) and HCl (2094 ppmv), were purchased from
Messer Singapore, while the SO2 gas (5000 ppm) was
provided by Linde Gas. The properties of the hydrated
lime sample used here (known as lime 3 in our previous
work2) are shown in Table 1.
Reaction in TGA. A thin layer of hydrated lime
sample (about 10 mg) was spread evenly on the plati-
num pan of the TGA. The pan was then loaded into the
furnace and heated to the desired temperature with a
ramp rate of 10 °C/min in a N2 environment. The
simulated flue gas was then introduced into the furnace
by the switching of a four-way valve. An immediate
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8731
weight increase was seen when the reaction began. To
end the reaction at any time, the four-way valve was
simply switched back to the original position, allowing
N2 to purge the whole system. The rate of weight gain
in the TGA was an indication of the reaction rate of
hydrated lime with the acidic species.
The total flow rate was kept at 150 mL/min. At that
flow rate, the external mass transfer effect was minimal
and was assumed to be negligible2. Also, because the
hydrated lime sample was spread on the TGA sample
pan as a very thin layer, the internal diffusion at the
initial reaction stage was also assumed to be negligible.
In all the results presented here, the O2 concentration
in the simulated flue gas was kept at 9% and the
temperature at 200 °C, similar to real flue gas condi-
tions. Lime-HCl systems refer to hydrated lime react-
ing with HCl as the only reactive species in the gas
mixture, and lime-CO2 refers to the hydrated lime
reaction with CO2 as the only reactive species, and so
forth. Lime-HCl/CO2 or lime-HCl/SO2 refers to the
hydrated lime reaction with a mixture of HCl and CO2
or of HCl and SO2, respectively, as the reactive species
in the flue gas, and so forth.
Besides these straightforward reactions mentioned
above, two sets of sequential reactions were also carried
out. In the sequential lime reaction with CO2 and HCl,
hydrated lime was first reacted with CO2. When the
conversion of hydrated lime reached the limit, CO2 was
replaced with HCl for some time, and then HCl was
replaced by CO2. The CO2 and HCl concentrations used
were 10% and 540 ppm, respectively. Between each
switching, the reaction chamber was purged with N2 to
clear out any residual species. In the same manner, the
sequential hydrated lime reaction with SO2 and HCl
was carried out. The SO2 concentration used was 1000
ppm. The other conditions remained the same.
Thermodynamic Calculations. The thermody-
namic calculations were carried out using the Outo-
kumpu HSC Chemistry version 4.0 software. The ther-
modynamic data for calcium hydroxychloride (Ca(OH)Cl)
was obtained from the work of Allal et al.,21 since it was
not present in the database. The GIBBS equation solver
using the Gibbs energy minimization method was
selected.
XRD Characterization. Owing to the sensitive
nature of the reacted products taken from the TGA
reactor, extra care had to be taken for the storage of
products before the XRD analysis could be carried out.
After each reaction, the product inside the reactor was
cooled with dry N2 to room temperature and placed
immediately inside an airtight bottle. This was done to
minimize its contact with water vapor from the sur-
roundings.
The powder XRD patterns were collected using a
Siemens D5005 diffractometer with Cu KR radiation
and step-scanned over a 2θ range of 5-80° at intervals
of 0.04 s, with a step time of 20 s. Phase identifications
were conducted using the Bruker software Diffrac-plus
EVA supported by the powder diffraction file (PDF-2).
To quantitatively analyze the species in the product, the
Rietveld quantitative phase analysis was carried out
using a fundamental parameter procedure as imple-
mented by TOPAS R (version 2.1). In each case, a
background polynomial, scale factor, cell parameters,
zero point correction, and sample displacement were
refined. Atom positions, site occupancy factors, and
isotropic thermal parameters were fixed. The weight
8732 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Table 2. Summary of the Thermodynamic Results for the Table 3. Summary of the Thermodynamic Results for the
Reaction of Lime with HCl and CO2 Reaction of Lime with SO2 under Various Conditions
reaction temp (°C) ∆G (kJ/mol) log10(K)a temp ∆G°
reaction (°C) (kJ/mol) log10(K)
1 Ca(OH)2 + 2HCl(g) f 100 -118.0 16.5
CaCl2 + 2H2O(g) 200 -120.2 13.2 8 Ca(OH)2 + SO2(g) f 100 -106.5 14.9
300 -122.1 11.1 CaSO3‚1/2H2O + 1/2H2O(g) 200 -94.7 10.5
2 Ca(OH)2 + HCl(g) f 100 -78.6 11.0 300 -82.8 7.5
Ca(OH)Cl + H2O(g) 200 -80.0 8.8 9 Ca(OH)2 + SO2(g) + 1/2O2 f 100 -341.2 47.8
CaSO4 + H2O(g) 200 -326.9 36.1
300 -81.3 7.4
300 -312.4 28.5
3 Ca(OH)2 + CO2(g) f 100 -63.3 8.9
10 Ca(OH)2 + SO2(g) + 1/2O2 + H2O(g) f 100 -338.0 47.3
CaCO3 + H2O(g) 200 -61.5 6.8 CaSO4‚2H2O 200 -295.8 32.7
300 -59.5 5.4 300 -254.5 23.2
4 CaCO3 + HCl(g) f 100 -15.3 2.1 11 CaSO3‚1/2H2O + 1/2O2(g) + 3/2H2O(g) f 100 -231.5 32.4
Ca(OH)Cl + CO2(g) 200 -18.5 2.0 CaSO4‚2H2O 200 -201.1 22.2
300 -21.8 2.0 300 -171.7 15.7
5 CaCO3 + 2HCl(g) f 100 -54.7 7.7 12 CaSO3‚1/2H2O + 1/2O2(g) f 100 -234.7 32.9
CaCl2 + CO2(g) + H2O(g) 200 -58.7 6.5 CaSO4 + 1/2H2O 200 -232.2 25.6
300 -62.5 5.7 300 -229.6 20.9
a 13 CaSO3‚1/2H2O + 2HCl(g) f 100 -11.6 1.6
K: equilibrium constant. CaCl2 + SO2(g) + /2H2O(g)
3 200 -25.5 2.8
percent (wt %) of each Bragg diffracting phase was 300 -39.3 3.6
14 CaSO3‚1/2H2O + HCl(g) f 100 27.8 -3.9
calculated from the refined scale factors. Ca(OH)Cl + SO2(g) + 1/2H2O(g) 200 14.8 -1.6
300 1.4 -0.1
Results and Discussion 15 CaSO4‚2H2O + 2HCl(g) f 100 52.6 -30.8
CaCl2 + SO2(g) + 3H2O + 1/2O2(g) 200 42.0 -19.4
Thermodynamic Considerations. There are quite 300 31.6 -12.1
a number of chemical reactions going on in a real system 16 CaSO4‚2H2O + HCl(g) f 100 62.0 -36.3
Ca(OH)Cl + SO2(g) + 2H2O + 1/2O2(g) 200 51.6 -23.8
when hydrated lime is exposed to various types of 300 41.4 -15.8
reactive contaminants in the flue gas. In this section, 17 CaSO4 + 2HCl(g) f 100 53.3 -31.2
the various possible reactions were first examined CaCl2 + SO2(g) + H2O + 1/2O2(g) 200 49.4 -22.8
individually and then as a whole from a thermodynamic 300 45.5 -17.3
18 CaSO4 + HCl(g) f 100 62.8 -36.8
point of view. While the thermodynamic calculations Ca(OH)Cl + SO2(g) + 1/2O2(g) 200 59.0 -27.3
help in predicting the different types of chemical reac- 300 55.2 -21.1
tions that take place in this complex system, the results
were used with caution, bearing in mind that the kinetic After examining the reaction equations individually,
aspects play a large role in determining whether a the “equilibrium composition” module of the software
predicted reaction actually takes place. The calculations was used to observe the trend with all of the reactants
here merely allowed us to know the theoretical bound- present in the system. The method of calculation by the
aries to work within. software is the same as before, using the Gibbs equa-
Table 2 summarizes the thermodynamic results for tions solver. In Figure 1 is the equilibrium speciation
hydrated lime reactions with HCl and CO2 at varied of a system containing equal starting amounts of HCl,
temperatures (100, 200, and 300 °C). Reactions 1 and 2 SO2, and CO2 (1 kmol) under excess O2 (∼33.3%) and
in Table 2 are reactions of hydrated lime with HCl. moisture (∼16.7%) at 200 °C and 1 atm. The starting
Although both reactions are thermodynamically pos- amount of hydrated lime is limited at 4 kmol. While
sible, as indicated by the decrease of the Gibbs free varying the HCl amount from 1 to 4 kmol, the produc-
energy (∆G° < 0), it has been shown that the reaction tion of CaSO4 and CaCO3 (each at 1 kmol) is thermo-
with HCl to form Ca(OH)Cl has a stronger tendency to dynamically stable. The formation of Ca(OH)Cl takes
occur in both laboratory and real-life (municipal waste priority over CaCl2 when hydrated lime is first reacted
incinerator) conditions.2,8,18 Reactions 3-5 are for sys- with HCl. At larger concentrations of HCl (>2 kmol),
tems containing hydrated lime together with CO2 and when hydrated lime becomes insufficient, the HCl
HCl. Hydrated lime when reacted with CO2 has a continues to react with the Ca(OH)Cl formed to produce
tendency to form CaCO3. However, the CaCO3 that is CaCl2. When subsequent increments of HCl are added
formed can subsequently be attacked by the presence
of HCl (reactions 4 and 5).
The reactions present in Table 3 are for systems
containing hydrated lime together with SO2 and HCl.
Hydrated lime could react with SO2 to form CaSO3‚1/
2H2O. In the presence of excess O2 (and H2O), CaSO4‚
2H2O (gypsum) and CaSO4 can also be formed either
directly or with CaSO3‚1/2H2O as an intermediate (reac-
tions 8-12 in Table 3). The CaSO3‚1/2H2O layer that is
formed can subsequently react with HCl to form CaCl2
(reaction 13) but not Ca(OH)Cl, a reaction with a
positive Gibbs free energy generated (∆G° > 0) at the
temperature range of relevance here (reaction 14). The
oxides of sulfur with +6 valence S(VI) are more stable
than their S(IV) counterparts. It is thermodynamically
impossible for HCl to react with either gypsum or CaSO4
(as given by the positive Gibbs free energy for reactions Figure 1. Predicted equilibrium speciation at varied amounts of
15-18 in Table 3). HCl.
 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8733

input. With the increase of the amount of SO2 from 1

Figure 2. Predicted equilibrium speciation at varied amounts of
SO2.
to the reaction mixture, after all the Ca(OH)Cl has
become converted, the HCl reacts with CaCO3 instead
(according to reactions 4 and 5 in Table 3), causing the
decrease of the amount of CaCO3 for quantities of HCl
larger than 4 kmol. There is a possibility that the
reduction of CaCO3 could also be due to HCl competing
directly with CO2 to react with hydrated lime rather
than HCl reacting with the CaCO3 that was formed, as
the compositions given by the thermodynamic calcula-
tion were at equilibrium states. However, this can only
be determined by the appropriate kinetic data and is
not discussed here. It is noteworthy that in Figure 1 a
slight decrease of CaCO3 from 1 kmol is observed when
HCl varys from 2 to 4 kmol, which corresponds to a
minor increase of Ca(OH)Cl for the same quantity of
HCl. This phenomenon accounts potentially for the
deviation of the manually-inputted database of Ca-
ClOH.21 Yet, the overall tendency of the prediction is
satisfied.
In Figure 2, the amount of SO2 is varied from 1 to 5
kmol instead, under the same conditions discussed
above, while the amount of HCl is fixed at 1 kmol. It
can be seen that equal amounts (1 kmol) of CaSO4,
CaCO3, and Ca(OH)Cl were formed with 1 kmol of SO2
to 5 kmol, the formation of CaSO4 took priority over that
of Ca(OH)Cl, CaCl2, and CaCO3. The decrease of the
amount of CaCO3 and the conversion of Ca(OH)Cl to
CaCl2 at relatively high SO2 input are most likely due
to the limited amount of calcium and an insufficient
oxygen supply in the system. Further calculations with
variation of the temperature from 100 to 600 °C have
been performed, and the results show very little effect
on the overall equilibrium speciation (details not shown
here).
XRD Characterization. The PDF number and the
characteristic peaks of the species identified in the
product samples can be seen in Table 4, for reference.
The strongest peak of each compound is highlighted in
bold. Owing to the existence of two unidentified peaks
(as mentioned in our previous work20), not all the
reacted products could be quantified properly. Further-
more, the product coming from the TGA was not free
from impurities, making the background noisy. Those
that could be quantified are shown in Table 5, with the
error being within the 5-10% range. Any crystalline
phase with less than 5% of weight percentage may be
undetected, as this is the usual lower limit of XRD,
judging from previous experiences. Note that, in the
table, the composition may not always add up to 100%,
as some of the species with smaller quantities (such as
CaSO4) were left out. The results here will be quoted
throughout the discussion in this section. There is also
likely to be a significant amount of amorphous phase
present in the product sample, contributing to the noise
in the background. The “amorphous phase” is composed
of both crystal structures that were too small to be
detected and the truly amorphous portion. Bodénan and
Deniard18 estimated that this amorphous portion ac-
counts for more than 30% of some reacted lime samples
taken from MWIs.
The reaction chemistry derived hereafter is based on
the XRD spectrum and complimented by the thermo-
dynamic predictions from the previous section.
(1) Reaction with HCl. For the sake of completion,
some of the important results regarding the hydrated

Table 4. PDF Numbers and 2-Theta Locations of the Main Peaks Belonging to the Compounds of Interest from the XRD
Analysisa
compound PDF no. 2-theta (θ)
Ca(OH)2, portlandite, syn 72-0156 18.1, 28.7, 34.2, 47.3, 50.9, 54.5, 62.7, 64.5, 72.0
Ca(OH)Cl, calcium hydroxide chloride 73-1885 17.9, 26.6, 28.1, 32.3, 36.3, 38.3, 45.5, 47.0, 50.7, 60.8, 62.1
CaCl2, calcium chloride 24-0223 19.8, 29.3, 31.2, 38.6
Ca(CO3), calcilte, syn 81-2027 23.0, 29.4, 36.0, 40.0, 43.1, 47.5, 48.5
CaSO4‚2H2O, gypsum, syn 33-0311 11.6, 20.7, 29.1, 31.1, 33.3
CaSO3‚1/2H2O, calcium sulfite hydrate 84-0962 15.9, 23.4, 28.2, 34.1
CaSO4, calcium sulfate 45-0157 14.6, 25.5, 32.0
a The strongest peak of each compound (where applicable) is highlighted in bold.

Table 5. Compositions of the Reaction Products Obtained by Quantitative XRD Analysis (wt %)a
portlandite calcite gypsum
reaction Ca(OH)2 CaCO3 Ca(OH)Cl CaSO4‚2H2O CaSO3‚1/2H2O
1. unreacted lime 3b 95 5 - - -
2. lime 3 + HCl (800 mg/m3) + CO2 (2%) 8 49 43 - -
3. lime 3 + HCl (800 mg/m3) + CO2 (10%) 5 14 83 - -
4. lime 3 + CO2 (8%) 58 42 - - -
5. lime 3 + CO2 (10%) 42 58 - - -
6. lime 3 + HCl (800 mg/m3) + SO2 (1000 ppm) 21 16 55 8 -
7. lime 3 + HCl (800 mg/m3) + SO2 (1600 ppm)b - 35 - 59 5
8. lime 3 + SO2 (1000 ppm)b 85 7 - 1 5
a The absence of a species above the 5% range (the usual detection limit of the XRD) is indicated by this symbol, -. b Refers to estimated

values.
8734 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005

Figure 3. XRD spectrum of the products from the reaction of lime 3 with 8 and 10% of CO2, respectively, in the absence of HCl.

Figure 4. XRD spectrum of the products from the reaction of lime 3 with HCl (800 mg/m3) and CO2 at concentrations of 2% (bottom) and
10% (top), respectively. Conditions were as follows: flow rate ) 150 mL/min, temperature ) 200 °C, and [O2] ) 9%.

lime reaction with HCl previously published in our expected to have taken place, judging from the XRD
earlier work2 are summarized here. According to eqs 1 spectrum that was obtained:
and 2, the reaction of hydrated lime with HCl can be
written as follows: Ca(OH)2(s) + CO2(g) f CaCO3(s) + H2O(g) (3)

Ca(OH)2(s) + HCl(g) f Ca(OH)Cl(s) + H2O(g) (1) CaCO3(s) + HCl(g) f Ca(OH)Cl(s) + CO2(g) (4)

Ca(OH)2(s) + 2HCl(g) f CaCl2(s) + 2H2O(g) (2)
It was observed from the XRD spectrum that, for some
hydrated lime samples used (lime 3 in particular), the
Ca(OH)Cl formed was subsequently converted to CaCl2
when the reaction was allowed to continue for a long
time (800 min). This is in agreement with the thermo-
dynamic predictions shown earlier in Table 2 and Figure
1.
(2) Reaction with CO2. In the lime-HCl/CO2 sys-
tem, other than eqs 1 and 2, the following reactions were
The reaction in eq 4 could have taken place when the
highly reactive HCl attacked the CaCO3 layer after it
was formed (in agreement with the thermodynamic
prediction made earlier). Of course, for the lime-CO2
system, only the reaction in eq 3 would have taken
place.
In Figure 3 are the XRD results corresponding to the
hydrated lime reactions with CO2 (at 8% and 10%) in
the absence of HCl (lime-CO2 system). A large amount
of unreacted hydrated lime (∼50%, Table 5, cases 4 and
5) can be observed in the reaction product. Note that

Figure 5. XRD spectra of the products from the reaction of lime 3 with CO2, HCl, and then CO2 again in sequence.
there is even a minor portion of CaCO3 (∼5%) which is
actually from the raw sample (see Table 4, case 1). As
discussed in our previous work,20 this was probably due
to the high resistance from the product layer that tends
to form when hydrated lime is reacted with CO2. This
layer prevented the subsequent CO2 from reaching the
unreacted hydrated lime below the product layer.
In Figure 4 are the spectra of the products from two
selected reactions in the lime-HCl/CO2 system (with 2
and 10% of CO2, respectively). The main products
observed were Ca(OH)Cl and CaCO3. Only a small
amount of unreacted Ca(OH)2 can be seen (Table 5,
cases 2 and 3). When the concentration of CO2 was
increased from 2 to 10%, the amount of CaCO3 in the
product decreased from 49 to 14% with respect to the
increase of Ca(OH)Cl from 43 to 83% instead of the
opposite. This could be due to the HCl reacting with the
CaCO3 that was formed, according to eq 4. It was
previously observed20 in experiments that both CO2 and
SO2 (compared to HCl) demonstrated a very much
higher reaction rate with Ca(OH)2 during the first
minutes. This means eq 1 cannot compete with eq 3 in
terms of reaction kinetics, particularly at increasing CO2
concentrations from 2 to 10%. The generated CO2 from
eq 4 tends to react with the excessive Ca(OH)2 available
there to form more CaCO3 until the “equilibrium” is
reached, i.e., a certain amount of Ca(OH)Cl is formed.
The increased CO2 concentration from 2 to 10% might
initially enhance the formation of CaCO3, but eventu-
ally, it increases the generation of Ca(OH)Cl.
As for the sequential CO2-HCl-CO2 reaction, the
strongest peak (apart from the unidentified peak)
belonged to CaCO3, followed by the peaks for the
unreacted Ca(OH)2 (Figure 5). The unidentified peak
could be due to the presence of a new Ca-based crystal-
line form that is not present in currently available
databases (for details refer to ref 2). The amount of
unreacted hydrated lime in the product after reaction
was not very much, given that the CaCO3 peaks were
higher than the Ca(OH)2 peaks. This was despite the
fact that the hydrated lime was exposed to 10% CO2
for only about 170 min (plus about 10 min of HCl).
Previously in the lime-CO2 system (cases 4 and 5 in
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8735
Table 5 and Figure 3), the hydrated lime was exposed
to the same concentration of CO2 for about 800 min, yet
there was still a substantial amount of unreacted
hydrated lime left in the product. In Figure 3, the Ca-
(OH)2 peaks were almost comparable in height with the
CaCO3 peaks. The introduction of HCl midway through
the reaction, though for a short time, has enabled CO2
to continue reacting with the hydrated lime under the
product layer; that is, the introduction of HCl for a short
period of time enabled more hydrated lime to be utilized
by CO2.
(3) Reaction with SO2. The following reaction was
expected to have taken place in a system with SO2:
Ca(OH)2(s) + SO2(g) f
CaSO3‚1/2H2O(s) + 1/2H2O(g) (5)
In the presence of excess O2, the CaSO3‚1/2H2O formed
can also be converted to either CaSO4‚2H2O (gypsum)
or CaSO4:
CaSO3‚1/2H2O(s) + 1/2O2(g) + 3/2H2O(g) f
CaSO4‚2H2O (6)
CaSO3‚1/2H2O(s) + 1/2O2(g) f
CaSO4 + 1/2H2O(g) (7)
With HCl also present in the system, the reactions in
eqs 1 and 2 would also have taken place. In addition to
that, the HCl gas could have attacked the CaSO3‚1/2H2O
layer in the following manner:
CaSO3‚1/2H2O(s) + 2HCl(g) f
CaCl2(s) + SO2(g) + 3/2H2O(g) (8)
For the lime-SO2 (1000 ppm) system, a large amount
(∼85%) of the hydrated lime remained unreacted, as
expected (case 8 in Table 5 and Figure 6). Similar to
the case of CO2, this was due to the formation of the
product layer that prevented the SO2 from reaching the
unreacted hydrated lime layer below. Also seen in the
8736 Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005
Figure 6. XRD spectrum of the products from the reaction of lime 3 with SO2 at a concentration of 1000 ppm.
Figure 7. XRD spectra of the products from the reaction of lime 3 with HCl (800 mg/m3) and SO2 (1000 and 1600 ppm).
spectrum (Figure 6) were small amounts of CaSO3‚1/
2H2O, CaSO4, CaSO4‚2H2O, and CaCO3. The CaCO3
should be from the raw sample, which contained around
5% of it (Table 5, case 1).
Two concentrations of SO2 (1000 and 1600 ppm) were
chosen for the lime-HCl/SO2 system, and the results
are shown in Figure 7. Some amount of the unreacted
hydrated lime sample (∼21%) can still be seen in the
spectrum containing 1000 ppm of SO2 (case 6, Table 5).
The majority of the product here is Ca(OH)Cl (∼55%),
with a small amount of gypsum (∼8%). When the
amount of SO2 was increased to 1600 ppm (case 7, Table
5), no unreacted hydrated lime was detected and Ca-
(OH)Cl had also disappeared. The majority of the
product formed was gypsum (∼59%) with small amounts
of CaSO3‚1/2H2O (∼5%). However, a surprisingly high
content of CaCO3 was detected in cases 6 and 7, which
might be due to the sample’s exposure to the atmo-
sphere.
At high concentrations of SO2 and with insufficient
hydrated lime reactant, the absence of Ca(OH)Cl agreed
well with the thermodynamic prediction (see Table 3).
Gibbs free energies are all increased for those reactions
relative to reactions generating Ca(OH)Cl. Also from the
thermodynamic predictions, it was known that HCl
could only react with CaSO3‚1/2H2O (reaction 13 in Table
3) but not with the stable gypsum layer (reactions 15-
18 in Table 3). Therefore, the accumulation of gypsum
was seen in the product as the SO2 concentration was
increased from 1000 to 1600 ppm. This was unlike the
case for CO2, where the product with hydrated lime,

Figure 8. XRD spectra of the products from the reaction of lime 3 with SO2, HCl, and then SO2 again in sequence.
CaCO3, was susceptible to reaction with HCl (reactions
4 and 5 in Table 2).
In Chisholm and Rochelle’s work,14 the authors also
reported that the CaSO3‚1/2H2O layer was attacked by
HCl gas to form CaCl2‚2H2O and released SO2 in a
reversible reaction. This is almost similar to the reaction
in eq 8, except that the product was CaCl2 and there
was no evidence of reversibility in the reaction. In their
work, the sulfur becomes stable and resistant to the HCl
reaction when it is oxidized from the S(IV) form to the
S(VI) form in the presence of excess O2, in agreement
with the results here. Anhydrous CaSO4 was detected
by XRD in instances where there were no simultaneous
reactions with HCl (lime-SO2 systems and sequential
SO2 to HCl reactions) (Figures 6 and 8). This could be
due to the fact that there were less water molecules
present in the system, as the lime-HCl reaction that
formed water molecules was absent.
Conclusions
In conclusion, the combined thermodynamic calcula-
tions and the XRD characterization allowed an in-depth
investigation on the actual reaction chemistry behind
the complex system of dry scrubbing of flue gas contain-
ing HCl, SO2, CO2, O2, and moisture using hydrated
lime. When hydrated lime came into contact with HCl,
Ca(OH)Cl had a higher tendency to be formed than
CaCl2. The hydrated lime reaction with CO2 formed
CaCO3. From previous results, it was known that this
species had a high product layer diffusion resistance and
caused the reaction to terminate prematurely by pre-
venting the unreacted hydrated lime below the product
layer from contacting the reactive gas. When HCl was
present, it attacked the CaCO3 layer, forming either Ca-
(OH)Cl or CaCl2, and exposed the unreacted hydrated
lime to further reaction.
The reaction of hydrated lime with SO2 formed the
thermodynamically favorable species, CaSO3‚1/2H2O. In
the presence of excess O2, CaSO4‚2H2O was formed, and
under dryer conditions, the anhydrous CaSO4 was
formed instead. Similar to the case of CO2, the product
Ind. Eng. Chem. Res., Vol. 44, No. 23, 2005 8737
of the reaction of hydrated lime with SO2 also has a high
product layer resistance. When HCl was present, it
attacked the CaSO3‚1/2H2O layer to form CaCl2, as
predicted by the thermodynamic calculation. However,
both CaSO4‚2H2O and CaSO4 were resistant to reaction
by HCl. In this sense, the presence of O2 in the flue gas
was counterproductive for the scrubbing using hydrated
lime, as it caused the sulfur in the S(IV) form to be
oxidized to the more stable S(VI) form, thereby reducing
the efficiency of the hydrated lime. The presence of HCl
helped with the removal of SO2 and CO2 using hydrated
lime. From the point of view of thermodynamics, varying
the temperature from 100 to 600 °C had minimal effect
on the results. Further studies comparing the kinetics
of the reactions of hydrated lime with HCl, SO2, and
CO2 under industrial conditions would be helpful for
gaining a better understanding of the system.
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Received for review February 21, 2005
Revised manuscript received August 31, 2005
Accepted September 2, 2005
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