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Sulfation of gaseous KCl by H2SO4

Chanpirak, Arphaphon; K. K. Jensen, Marcus ; Wu, Hao; Glarborg, Peter

Published in:
Energy & Fuels

Link to article, DOI:

10.1021/acs.energyfuels.2c03705

Publication date:
2023

Document Version
Peer reviewed version

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Citation (APA):
Chanpirak, A., K. K. Jensen, M., Wu, H., & Glarborg, P. (2023). Sulfation of gaseous KCl by H SO . Energy &
2 4
Fuels, 37(3), 2319–2328. https://doi.org/10.1021/acs.energyfuels.2c03705

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and investigate your claim.
 Sulfation of gaseous KCl by H2SO4
Arphaphon Chanpirak, Marcus K. K. Jensen, Hao Wu, and Peter Glarborg*

Department of Chemical and Biochemical Engineering, Technical University of Denmark,

Søltofts Plads 229, 2800 Kgs. Lyngby, Denmark

ABSTRACT: The sulfation of gaseous KCl by H2SO4 in the presence of O2 and H2O was
investigated in a laboratory laminar flow reactor at atmospheric pressure and temperatures ranging
from 873 to 1523 K. The degree of sulfation was characterized by analysis of the elemental
composition (Cl, S, and K) of the sub-micron particles captured on a filter downstream of the
reactor. Furthermore, concentrations of HCl and SO2 in the outlet were measured. The
experimental results were interpreted in terms of a detailed chemical kinetic model for the K/S/Cl
chemistry. The degree of KCl sulfation depends on the reaction temperature and the reactant
concentrations. The results show that H2SO4 is effective in sulfating KCl to K2SO4 at temperatures
in the range 1073-1273 K, in particular at high H2SO4/KCl ratios. At temperatures of 1373 K and
above, the sulfation efficiency decreases rapidly, since alkali sulfate formation is no longer
thermodynamically favored. The kinetic analysis shows that reaction is initiated by decomposition
of sulfuric acid, H2SO4 + H2O ⇄ SO3 + H2O + H2O. Then KCl reacts directly with SO3 to form
the intermediate KSO3Cl, which is further converted via KHSO4 to gaseous K2SO4. As the gas is
cooled downstream of the isothermal zone, potassium sulfate nucleates homogeneously to form an
aerosol, promoting further sulfation in the gas-phase. The simulations are in satisfactory agreement
with the experimental results, predicting correctly the temperature window for the process.
However, the model overpredicts the SO2 yield at high temperature, indicating that the K/S
interactions under these conditions are not fully understood. The results are important, both for
validation of models of K/Cl/S interactions in combustion and for characterization of the sulfation
of KCl by sulfuric acid to evaluate the potential of the sulfur recirculation process and identify the
optimum process conditions.

Keywords: Potassium chloride (KCl); sulfuric acid; gas-phase sulfation; deposition and corrosion.

1
1. INTRODUCTION

The inorganic chemistry has important implications for thermal conversion of biomass and waste.
Alkali metals, chlorides, sulphur and silicon are present in these fuels as the main inorganic
elements. For agricultural residues, the content of K and Cl can reach approximately 1.5% and
1%(wt), respectively,1–7 while woody biomass contains smaller quantities of K and Cl.4,5,8
Municipal solid waste (MSW) has a more complex composition than biomass, as it is typically
composed of a mixture of food waste, paper, plastic, metal, glass, textiles, wood, rubber, leather,
and other materials. The Cl content in waste varies widely, depending on the source.9–13 In addition
to potassium, the waste may contain varying amounts of Na, Zn, Pb, and other elements that may
form chlorides and sulfates.

During pyrolysis and combustion of biomass, the alkali metals (mostly potassium) are partly
released to the gas-phase, typically as alkali chlorides. During wheat straw combustion, potassium
is released primarily as KCl, with lower amounts of KOH and K2SO4.14 Due to the lower chlorine
content, release of KOH is more prominent in woody biomass combustion.15 The presence of
mineral elements such as Si can significantly reduce the alkali release during combustion, because
the alkali can be incorporated into silicate matrices, leading to low-volatile alkali silicates.2,10

The gaseous KCl and KOH may be sulfated by reaction with sulfur oxides to form K2SO4.16–21
During cooling, potassium salts can condense on particulates or heat transfer surfaces. If the
particle loading in the system is low, KCl forms an aerosol by homogeneous nucleation. 22,23 The
condensed potassium compounds may lead to sticky deposits on the heat transfer surfaces,
facilitated by the low melting temperature of KCl and the low viscosity of potassium silicates.24
The ash deposition on the superheater surfaces limits the heat transfer and causes corrosion by
destroying the protective oxide layer,25–28 reducing the electrical efficiency of the plant as well as
the lifetime of the boiler equipment. High concentrations of KCl in the flue gas can enhance deposit
29
formation and a high KCl content in the deposit composition may accelerate corrosion.25,30–36
Other drawbacks are that potassium can deactivate SCR catalysts used for NOx reduction 37–39 and
inhibit CO conversion.40

To minimize these problems, reduction of alkali chlorides has been attempted by capturing the
chloride salt with alumina silicate additives such as kaolin or coal fly ash 41,42 or by sulfating KCl

2
to K2SO4 by co-firing with a sulfur-rich fuel 43 or by using S-based additives. Pettersson et al. 31
reported that K2SO4 is less corrosive towards 304L steel less than KCl and K2CO3. Alkali sulfation
by sulfur oxides can occur homogeneously in the gas phase or heterogeneously in the deposits on
the heat transfer surfaces,22,23,44,45 resulting in a less corrosive alkali sulfate and releasing chlorine
mainly as HCl. Previous studies have investigated addition of elemental sulfur,46 SO2,17,27,47 and
sulfate compounds such as aluminum sulfate,48–50 ammonia sulfate,46,49–52 and ferric sulfate.48,53,54

Recently also sulfuric acid has been proposed as an additive, in a process where sulfur is captured
from the flue gas and recirculated.55,56 This is a novel technique for reducing the high-temperature
corrosion and dioxin formation in waste-fired plants. SO2 is separated from the flue gas in a wet
scrubber downstream of the HCl scrubber. H2O2 dosed into the scrubber reacts with SO2 in the gas
and produces a 15-25 wt% H2SO4 solution, which is then injected into the boiler, thus creating a
sulfur loop. The sulfur recirculation enhances the SO3 levels and decreases the ratio of Cl/S in the
boiler. Andersson et al. 55 pointed out that the sulfur recirculation technique leads to a decrease in
the corrosion rate, the dioxin formation, and the chlorine content in both fly ash and boiler ash,
and an increase in the sulfur content in ash. The emissions of SO2, HCl, NOx, and TOC remained
unchanged, while emissions of NH3 and CO decreased.

There are several studies on the sulfation of gaseous KCl, but details of the process are still in
question. A detailed chemical mechanism was proposed by Glarborg and Marshall,18 involving the
following reactions:

KCl + SO3 (+M) ⇄ KSO3Cl (+M) (R1)

KOH + SO3 (+M) ⇄ KHSO4 (+M) (R2)

KSO3Cl + H2O ⇄ KHSO4 + HCl (R3)

KHSO4 + KCl ⇄ K2SO4 + HCl (R4)

KHSO4 + KOH ⇄ K2SO4 + H2O (R5)

The intermediates KSO3Cl and KHSO4 have not been detected in the gas phase but ab initio
calculations indicate that both of these complexes are sufficiently stable to act as precursors for
alkali sulfate.18 Sulfation is completed by a number of shuffle reactions, which, by analogy to other

3
gas-phase alkali reactions, are all expected to be fast, although they involve stable molecules.
Consequently, Glarborg and Marshall claimed that oxidation of SO2 to SO3 is the rate-limiting
step. The reaction mechanism was shown to be consistent with the entrained flow reactor results
of Iisa et al.,16 and is also supported by the experiment work of Kassman et al.57 Hindiyarti et al. 20
proposed a number of additional sulfation routes to explain observed sulfation rates at lower
21
temperatures where oxidation of SO2 to SO3 is slow. Li et al. added a simplified reaction
description of the homogeneous nucleation of K2SO4. The updated model was validated against
measurements of KCl, HCl, and sub-micron particles in premixed CH4/O2/N2 jet flames fed with
KCl(aq) and SO2. In more recent work,58,59 measurements extended to include both gas-phase KCl
and KOH in the presence of SO2 were compared with modeling predictions. Also, data for the Cl/S
ratio in captured aerosols in the combustion of biomass 17 have been used for model evaluation.15
Despite these efforts, validation of the detailed model for the KCl sulfation is still challenging
because experiments on the sulfation chemistry are difficult to conduct and involve uncertainties
related to alkali release rates, gas-solid interactions, mixing constraints, and temperature gradients.

The purpose of the present work is two-fold. We wish to characterize the sulfation of KCl by
sulfuric acid to evaluate the potential of the sulfur recirculation process and identify the optimum
process conditions. Furthermore, we wish to provide novel experimental data for the sulfation of
KCl for validation of the detailed kinetic model. Thermal dissociation of sulfuric acid,

H2SO4 + H2O ⇄ SO3 + H2O + H2O, (R6)

happens at temperatures as low as 500-600 K and is a clean source of SO3.60 In this way, the
experimental complications associated with other common sulfates such as ammonium sulfate or
ferric sulfate are avoided. Experiments are conducted in a flow reactor with well-controlled
feeding in a wide temperature range (873–1523 K) with reactant levels of 110 or 250 ppm KCl,
230 ppm H2SO4, 5% O2, and 3.4% H2O. The degree of sulfation is estimated from measuring the
content of S, Cl, and K in the fine particles collected downstream in a filter. The results are
interpreted in terms of an updated chemical kinetic model for Cl/S/K interactions to provide a
better understanding of the sulfation process.

4
2. EXPERIMENTAL SETUP

The flow reactor setup was established to supply submicrometer-sized substrates (aerosols) from
an aqueous solution for examining homogenous sulfation. The setup is described in detail
elsewhere.61 and only a brief description of the dosing unit, the experimental process, and the
reactor size is given here. A total gas flow rate of 4 NL/min (298 K, 1 atm) was used in all
experiments. Two atomizers (Model 3076, TSI Inc.) were used to generate aerosol droplets of
dilute aqueous solutions of H2SO4 and KCl, respectively, in the nitrogen carrier gas in the dosing
unit. The generated aerosol droplets and gases were transported into the reactor via a tube, supplied
by a stable and continuous flow.61 The vaporization temperatures of the solution droplets were
assumed to be close to the boiling point of pure water. The uncertainty in these values did not
affect the interpretation of experiments, however; due to the high set point temperature of the
reactor, complete evaporation in the preheating zone would be expected. A downstream line was
controlled at 453 K to prevent product condensation. A schematic view of the experimental setup
used in the current study is shown in Figure. 1.

Mass Flow
Controller

R
e Temperature
a Controller
c
t
O2 N2 N2 o
r

Vent
KCl (aq)

Atomizer Traper
Filter
H2SO4 (aq) Gas Analyzer
FTIR
Atomizer Heating Line

Figure 1. Schematic of the flow reactor setup.

A reactor was quartz tubes with an inner diameter of 10 mm and a height of 900 mm, which was
placed in a heated oven with a three-zone electrically. The reactor temperature was measured by a
type K thermocouple from the top of the oven under a nitrogen flow to obtain the axial temperature
profiles as shown in Figure 2. The results displayed an isothermal region (roughly 8-55 cm) and a
cooling section. The uncertainty in the isothermal temperature, ±10 K, includes the measurement
accuracy (±2 K) and the deviations from the mean value. All profiles are available in the
Supporting Information.

5
 1600
973 K
1173 K
1400 1273 K
1473 K
Temperature (K)

1200

1000

800

600

400

-20 -10 0 10 20 30 40 50 60 70
Distance (cm)

Figure 2. The measured temperature profiles in the laminar flow reactor in an N2 gas atmosphere.

The product gas and particle samples were captured after the gas concentration reached a steady-
state level at each investigated temperature. A series of online gas analyzers including a Fourier
Transform Infrared spectrometer (FTIR) (Multigas 2030 FTIR, MKS instruments) monitored
continuously the concentrations of SO2, H2O, and HCl in the outlet stream. The uncertainty in the
gas analyzer measurements was below 10%. However, both SO2 and HCl easily adsorp on
surfaces, increasing the uncertainty in their quantification. The collected particles were analyzed
for the elemental composition with respect to Cl and S using IC (Ion Chromatography), and to K
using ICP-OES (Inductive Coupled Plasma with Optical Emission Spectroscopy).

3. DETAILED CHEMICAL KINETIC MODEL

The modeling predictions for the sulfation of KCl by H2SO4 in gaseous interactions were
performed with the plug flow reactor configuration in the Chemkin PRO. The reaction mechanism
and thermodynamic data, available as Supplementary Information, were largely drawn from the
recent work of Chanpirak et al.61 It was based on the work of Glarborg and Marshal,18 Hindiyarti
et al.,20 Weng et al.,58 and Berdugo Vilchez et al.,62 consisting of subsets for potassium, 21,58

chlorine,63,64 and sulfur 65,66

chemistry as well as the condensation reaction of K2SO4 (g).21
Modeling predictions compared favorably with experiments in laboratory flow reactors and
entrained-flow reactors,16,19,22 as well as data from other units.49,57,67,68

6
 58
In their re-evaluation of the K species subset, Weng et al. updated selected rate constants for
steps involving KOSO2 and KHSO4. Their mechanism was used subsequently to predict post-
flame sulfation of KCl and KOH during cooling 15 and results from a laminar flame burner.69 Very
recently, Chanpirak and co-workers 40,61 further refined the model to interpret data obtained in a
flow reactor for moist CO oxidation in the presence of K/Cl/S over a wide range of operating
conditions. They updated the thermodynamic properties for KHSO3, KOSO3, and KSO3Cl from
ab initio computations, as well as selected rate constants.

In the present work, the kinetic model of Chanpirak et al.61 was extended with a reaction describing
thermal dissociation of sulfuric acid. It was entered in the reverse direction as SO3+2H2O ⇌
H2SO4+H2O (R6b) with a rate constant of 8.1E4 T exp(6540/T) cm6 mol−2 s−1 according to the low
temperature measurements of Lovejoy et al.70 In the reaction mechanism, the homogeneous
nucleation of gaseous K2SO4 is represented as an irreversible first-order reaction of K2SO4 →
K2SO4 (c) with a rate constant of 1E-61 exp(300000/T) s−1, estimated based on aerosol theory.21
Loss of KOH at the quartz reactor surface is described in terms of a diffusion-limited first-order
reaction,61 but due to the low levels of KOH, the impact is small as shown in the Supporting
Information.

4. RESULTS AND DISCUSSION

Sulfation of KCl by sulfuric acid was studied in the flow reactor for KCl(g)/H2SO4(g) ratios of 0.5
and 1.1. The inlet compositions were: KCl (g) = 110 ppm (set 1) or 250 ppm (set 2); H2SO4 (g) =
230 ppm, O2 = 5%, H2O = 3.4%, and N2 balance. The inlet KCl levels were estimated based on
the measured HCl outlet concentration and the particle composition under conditions with a high
degree of sulfation. Experiments were conducted at atmospheric pressure and a residence time of
135/T(K) s in the isothermal zone (constant mass flow).

The experimental results were interpreted in terms of the detailed chemical kinetic models of
Berdugo Vilchez et al.62 and Chanpirak et al.61 In both mechanisms, the reaction SO3+2H2O ⇌
H2SO4+H2O (R6b) was added to describe decomposition of sulfuric acid. Modeling predictions
were conducted using the temperature profile of the isothermal and cooling zones. In the cooling

7
region, homogeneous nucleation of potassium sulfate is favored, acting as a sink of gas-phase
K2SO4 and driving reaction further towards sulfation.

Predictions with the full temperature profile (see Supplementary Information) indicate that the
final potassium speciation is not very sensitive to transformations in the preheating zone. However,
this region was generally left out the calculations since salt evaporation and gas-solid reactions on
the sub-micron particles are not described in the model.

4.1. Sulfation of KCl by H2SO4. The fine particles were gathered on a filter downstream of the
flow reactor. The collected samples were analyzed using IC and ICP-OES to evaluate their
elemental composition (K, Cl, and S), as shown in the Supporting Information. The degree of
sulfation of KCl was estimated from the Cl/(Cl+S) molar ratio of the fine particles. If the samples
contained only KCl and K2SO4, a Cl/(Cl+S) molar ratio of one would imply no sulfation, while a
ratio of zero would correspond to full sulfation. According to the modeling predictions discussed
below, KHSO4 is converted rapidly to K2SO4 during cooling. In addition to the potassium salts,
sulfuric acid aerosols may also be captured on the filter. Part of the SO3 emitted from the isothermal
region of the reactor would be expected to form H2SO4 by reaction with water vapor at the low
temperatures downstream. Formation of H2SO3 by reaction of SO2 with H2O below the dew point
of water can be disregarded since lines and filter were controlled at 180oC. For this reason, we
assume that the filter samples consist of a mixture of KCl, H2SO4 and K2SO4.

To evaluate to what extent the collected samples were contaminated by sulfuric acid, the
K/(Cl+2S) molar ratio was determined, as shown in Figure 3. For all of the experiments, the
K/(Cl+2S) molar ratio was less than one, implying that the filter sample contained H2SO4, in
addition to KCl and K2SO4. Only at high temperatures, 1473 K and 1523 K, did the K/(Cl+2S)
ratio reach values close to unity (80-90%). Under these conditions, SO3 formed is less thermally
stable and would be partly reduced to SO2. Sulfur dioxide is unlikely to react to form sulfuric acid
during cooling downstream of the reactor. Thus, the sulfur in the sample is the sum of H2SO4 and
K2SO4, the potassium the sum of KCl and K2SO4, while the chlorine results entirely from KCl.
From a mass balance, the content of sulfuric acid can be corrected for and the Cl/(Cl+S) molar
ratio corresponding only to the potassium salts can be calculated.

8
 1.0 Set 1 1.0
Set 2

0.8 0.8
K/(Cl+2S) (-)

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
873 973 1073 1173 1273 1373 1473 1523
Temperature (K)

Figure 3. K/(Cl+2S) molar ratio of the particle samples collected from KCl sulfation with H2SO4.
The inlet composition was 110 ppm KCl (set 1) or 250 ppm KCl (set 2), 230 ppm H2SO4, 5% O2,
3.4% H2O, and N2 as carrier gas. The experiments were conducted at atmospheric pressure and the
residence time in the isothermal zone was 135/T(K) s.

Figure 4 compares the experimental results for the sulfation ratio Cl/(Cl+S) (corrected for sulfuric
acid) with modeling predictions. Data are shown as a function of the temperature and two inlet
concentrations of KCl, corresponding to KCl/H2SO4 ratios of about 0.5 (set 1) and 1.1 (set 2). For
both values of the inlet KCl, the Cl/(Cl+S) ratio is a function of the temperature.

9
 Experiment Experiment
1.0 Model (Berdugo Vilches et al.)
1.0
Model (Berdugo Vilches et al.)
Model (Chanpirak et al.) Model (Chanpirak et al.)

0.8 0.8
Cl/(Cl+S) (-)

Cl/(Cl+S) (-)
0.6 0.6

0.4 0.4

0.2 0.2

Set 1 Set 2
0.0 0.0
873 973 1073 1173 1273 1373 1473 1573 873 973 1073 1173 1273 1373 1473 1573
Temperature (K) Temperature (K)

Figure 4. Comparison of experimental and simulated Cl/(Cl+S) molar ratio of the particle samples
collected from KCl sulfation with H2SO4. The inlet composition was 110 ppm KCl (set 1) or 250
ppm KCl (set 2), 230 ppm H2SO4, 5% O2, 3.4% H2O, and N2 as carrier gas. The experiments were
conducted at atmospheric pressure and the residence time in the isothermal zone was 135/T(K) s.
Symbols denote experimental data, while dashed and solid lines denote modeling simulations with
the mechanisms of Berdugo Vilches et al.62 and Chanpirak et al.,61 respectively.

At temperatures below 1000 K, the data should be interpreted with caution since KCl is only partly
evaporated. According to chemical equilibrium, KCl is largely in condensed form at 873 K, while
at 973 K about 60% of the KCl is in the gas phase. Sulfation of the gaseous KCl would promote
further evaporation since the equilibrium shifts and thereby allow for additional gas-phase
sulfation. The considerable degree of sulfation observed below 1000 K supports this mechanism,
but reaction between the KCl aerosol and gas-phase SO3 may also contribute to sulfation.

The results confirm the capability of H2SO4 to convert gaseous KCl to K2SO4, particularly for
temperatures in the range 1073-1273 K. For 110 ppm KCl, the potassium is fully sulfated in this
temperature range, while for 250 ppm KCl the Cl/(Cl+S) fraction in the aerosols reaches a value
below 0.2 at 1173 K. The impact of the reactant KCl/H2SO4 ratio below 1373 K shows that the
degree of KCl sulfation is partly controlled by the H2SO4 availability, even under conditions where
H2SO4 is in significant excess compared to the stoichiometric ratio.

At temperatures of 1373 K and above, the Cl/(Cl+S) ratio in the fine particles increases sharply,
approaching unity (no or little sulfation) at 1523 K. This observation is in agreement with

10
expectations since potassium sulfate formation is no longer thermodynamically favored at high
temperatures.

The modeling simulations shown in Figure 4 were conducted with the mechanisms of Berdugo
Vilchez et al. 62 and Chanpirak et al.,61 respectively, taking into account the isothermal zone and
the cooling region. Since part of the KCl was in condensed form and thus unavailable for reaction
below 1000 K, modeling predictions are only shown for experiments with set temperatures above
1000 K, and the preheating section was not considered in the calculations.

Both mechanisms capture satisfactorily the KCl sulfation behavior, i.e., the efficient sulfation in
the 1073-1273 K range and the sharp increase in chlorine content in the fine particles at
temperatures of 1373 K and above. However, the degree of sulfation for the higher KCl inlet level
(set 2) is overpredicted. The more recent model by Chanpirak et al.61 offers the best quantitative
agreement with experiment.

4.2. Formation of HCl and SO2. The overall reaction for sulfation of KCl can be written as 2KCl
+ SO3 + H2O → K2SO4 + 2HCl. The sulfation reaction consumes SO3 while it yields gaseous HCl,
along with the potassium sulfate aerosols that are captured downstream in the filter. The HCl
concentration in the product gas is thus a measure of the degree of sulfation. The measured
concentrations of HCl as a function of temperature are illustrated in Figure 5. An additional source
of HCl is from reaction of KCl at the quartz reactor surface, forming potassium silicates (2KCl(g)
+ SiO2(s) + H2O(g) ⇄ K2OꞏSiO2(s) + HCl(g)).61 Results for the conversion of KCl to HCl by the
heterogeneous KCl + SiO2 reaction, shown as Supplemental Information, indicate that formation
of HCl on the surface is limited to at most 15 ppm and has only a small impact under the present
conditions.

11
 600 600
(a) Set 1 Experiment (a) Set 2 Experiment

HCl Concentration (ppm)

HCl Concentration (ppm)
Model (Berdugo Vilches et al.) Model (Berdugo Vilches et al.)
500 Model (Chanpirak et al.) 500 Model (Chanpirak et al.)

400 400

300 300

200 200

100 100

0 0
873 973 1073 1173 1273 1373 1473 1573 873 973 1073 1173 1273 1373 1473 1573
Temperature (K) Temperature (K)

Figure 5. Comparison of measured and predicted HCl in the gas products. The inlet composition
was 110 ppm KCl (set 1) or 250 ppm KCl (set 2), 230 ppm H2SO4, 5% O2, 3.4% H2O, and N2 as
carrier gas. The experiments were conducted at atmospheric pressure and the residence time in the
isothermal zone was 135/T(K) s. Symbols denote experimental data, while dashed and solid lines
denote modeling simulations with the mechanisms of Berdugo Vilches et al.62 and Chanpirak et
al.,61 respectively.

The HCl results are in accordance with the results from IC and ICP-OES analysis. The HCl
formation occurs already at 873 K and peaks in the 1073-1273 K range, as expected. At high
temperature, the HCl formation decreases as the rate of sulfation approaches zero. For set 2 (higher
inlet KCl), the HCl level reaches a higher value. The modeling predictions are in good agreement
with the HCl measurements, even though the calculated HCl is too high for set 2 due to the
overprediction of the degree of sulfation.

Figure 6 compares measured and predicted SO2 concentrations. Sulfur dioxide is detected at
temperatures above 1273 K, where it is formed by decomposition of SO3. The concentration peaks
around 50 ppm, at 1373 K for the lower KCl inlet level (set 1) and at 1473-1523 K for set 2. The
simulations underpredict the temperature for onset of SO2 formation and strongly overestimates
the SO2 level at high temperatures. This issue is discussed further below.

12
 350 350
(a) Set 1 Experiment (b) Set 2 Experiment

SO2 Concentration (ppm)

SO2 Concentration (ppm)
Model (Berdugo Vilches et al.) Model (Berdugo Vilches et al.)
300 Model (Chanpirak et al.)
300 Model (Chanpirak et al.)

250 250

200 200

150 150

100 100

50 50

0 0
873 973 1073 1173 1273 1373 1473 1573 873 973 1073 1173 1273 1373 1473 1573
Temperature (K) Temperature (K)

Figure 6. Comparison of measured and predicted SO2 in the gas products. The inlet composition
was 110 ppm KCl (set 1) or 250 ppm KCl (set 2), 230 ppm H2SO4, 5% O2, 3.4% H2O, and N2 as
carrier gas. The experiments were conducted at atmospheric pressure and the residence time in the
isothermal zone was 135/T(K) s. Symbols denote experimental data, while dashed and solid lines
denote modeling simulations with the mechanisms of Berdugo Vilches et al.62 and Chanpirak et
al.,61 respectively.

To evaluate further the sulfation of KCl with H2SO4, experiments were carried out switching on
and off the KCl feed. At each temperature, H2SO4, O2, and N2 were fed for one hour, followed by
addition of KCl for one hour, and finally purging by N2 for one hour; all with a total flow rate of
4 NL/min. Figure 7 compares results for HCl and SO2 concentrations in the outlet with and without
the KCl feeding. The levels of HCl with KCl in the feed (110 ppm) are similar to those shown in
Figure 5 (set 1). In the range 973-1273 K, almost all chlorine fed with KCl is released as HCl,
while at high temperatures, the HCl concentration decreases rapidly. In addition to the two possible
reactions forming HCl discussed above, i.e., 2KCl + SO3 + H2O → K2SO4 + 2HCl in the gas-phase
or reaction of KCl with SiO2 at the quartz reactor surface, HCl may also be formed from a gas-
solid reaction of KCl(c) + SO3 in the filter. The small amounts of HCl detected in the absence of
KCl feeding (Figure 7) can be explained in terms of this step.

13
 120 H2SO4+O2 120 H2SO4+O2

SO2 Concentration (ppm)

HCl Concentration (ppm)
H2SO4+O2+KCl H2SO4+O2+KCl
100 100

80 80

60 60

40 40

20 20

0 0
873 973 1073 1173 1273 1373 1473 1523 873 973 1073 1173 1273 1373 1473 1523
Temperature (K) Temperature (K)

Figure 7. Comparison of experimental data with feeder switching in the product gas as a function
of temperature. HCl concentration (left) and SO2 concentration (right). The inlet composition was
110 ppm KCl, 230 ppm H2SO4, 5% O2, 3.4% H2O; N2 balance (set 1). The residence time in the
isothermal zone was 135/T(K) s.

The results in Figure 7 show that both in the presence and absence of KCl, the onset of SO2
formation takes place at around 1273 K. With no KCl fed, the SO2 increases monotonically with
temperature. This trend is in agreement with modeling predictions, where SO2 is formed from
decomposition of SO3; a process that is promoted by increasing temperature. However, the amount
of SO2 is overpredicted by the model, indicating that downstream loss of SO2, prior to the analyzer,
may play a role.

In the presence of KCl, there is a peak in SO2 at 1373 K, while the outlet concentration decreases
at higher temperatures. This behavior is not captured by the model, as shown in Figure 6. The
discrepancy indicates that the high temperature interaction between potassium and sulfur is not
fully understood.

4.3 The predicted potassium and sulfur transformations. Figure 8 shows the predicted
concentrations of the major potassium and sulfur species in KCl sulfation with H2SO4 for the
conditions of set 1 and two different peak temperatures (1173 and 1473 K), based on the
mechanism Chanpirak et al.61 In both cases, the first part (0-50 cm) corresponds to the isothermal
zone, while the second part (50-60 cm) represents the cooling zone. At 1173 K, KCl is partly

14
converted to KHSO4 and K2SO4 during the first 5-10 cm, approaching a partial equilibrium
between the potassium species.

250 200 250 200

Set 1_1173 K_K transformation Set 1_1173 K_S transformation
KCl SO2
KHSO4 SO3

Residence time (msec)

Residence time (msec)

200 KSO3Cl 200

Mole fraction (ppm)

Mole fraction (ppm)

H2SO4
150 150
K2SO4 HCl
K2SO4(c)
150 KOH 150

100 100

100 100

50 50
50 50

0 0 0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Distance (cm) Distance (cm)

250 200 250 200

Set 1_1473 K_K transformation Set 1_1473 K_S transformation
KCl SO2
KHSO4
Residence time (msec)

Residence time (msec)

SO3
200 KSO3Cl 200
Mole fraction (ppm)

Mole fraction (ppm)

150 H2SO4 150

K2SO4
HCl
K2SO4(c)
KOH
150 150

100 100

100 100

50 50
50 50

0 0 0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Distance (cm) Distance (cm)

Figure 8. Predicted species profiles for major species involving potassium (left) and sulfur (right)
in a laminar flow reactor at 1173 K and 1473 K. The inlet composition was 110 ppm KCl, 230
ppm H2SO4, 5%O2, 3.4% H2O, 5% O2; N2 balance (set 1). Calculations were conducted with two
zones in the reactor; the isothermal zone (0-50cm), and the cooling zone (50-60 cm). Note that
KCl is primarily converted to (KCl)2 (not shown) during cooling from 1473 K.

It is noteworthy that the thermal dissociation of H2SO4 to form SO3 and H2O is comparatively
slow, despite being strongly favored thermodynamically. The rate constant for the reverse step,
SO3+2H2O ⇌ H2SO4+H2O, has a strong negative temperature dependence.70 However, it was only
measured at low temperature and extrapolation to the present conditions is uncertain. The slow
formation of SO3 affects the partial equilibrium between the K-species, promoting further

15
sulfation. However, most of the SO3 remains unreacted until the cooling starts at around 50 cm.
During cooling, gaseous potassium sulfate nucleates homogeneously to from aerosols. The loss of
K2SO4 in the gas phase shifts the equilibria, promoting further sulfation and depleting most of the
KHSO4. At sufficiently low temperatures, the remaining SO3 reacts with H2O and reform H2SO4.

At 1473 K, the decomposition rate for the sulfuric acid is similar to that at 1173 K, but the
subsequent conversion of SO3 to SO2 proceeds much faster at the higher temperature. The
temperature is too high for KHSO4 and K2SO4 to be thermally stable, and KCl is largely unreacted
in the isothermal zone of the reactor. According to the model, the interaction between potassium
and sulfur species at the high temperature is very limited and there is no indication why the
predictions significantly overestimate the SO2 formation. In the cooling zone, the sulfation
reactions become thermodynamically favored. However, at this stage a large fraction of the SO3
has been converted to SO2 by thermal dissociation. Consequently, only a fraction of the KCl is
converted to gaseous K2SO4. Furthermore, due to the rapid cooling, the partial equilibrium among
the alkali species can no longer be preserved.

Figure 9 shows a reaction pathway diagram for the KCl sulfation by sulfuric acid at 1173 K,
according to the present model. The analysis confirms that SO3 plays a key role in the
transformation of KCl to K2SO4. In the initial step, SO3 is produced from sulfuric acid in a reaction
sequence involving first the sublimation reaction H2SO4 (aq) ⇄ H2SO4 (g), followed by the gas
phase dissociation H2SO4+H2O ⇌ SO3+2H2O (R6b). The presence of SO3 then facilitates the
sulfation through KCl→ KSO3Cl→ KHSO4 → K2SO4. The main pathway involves the following
elementary reactions:

KCl + SO3(+M) ⇄ KSO3Cl(+M) (R1)

KSO3Cl + H2O ⇄ KHSO4 + HCl (R3)

KCl + KHSO4 ⇄ K2SO4 + HCl (R4)

This sequence is initiated by KCl (g) reacting with SO3 to form KSO3Cl; this compound is
converted to KHSO4 by reaction with H2O. According to their thermodynamic properties,18 both
KSO3Cl and KHSO4 are sufficiently stable in the gas phase to act as intermediates in the sulfation.
Gaseous K2SO4 is formed mainly by the reaction of KCl with KHSO4. Potassium sulfate is stable

16
in the gas-phase at elevated temperature, but nucleate homogeneously to form an aerosol during
cooling. This reaction sequence for the sulfation is the same as that reported by Krum et al. 52 for
the addition of ammonium sulfate.

Figure 9. Pathway diagram for K species transformation in KCl sulfation by sulfuric acid under
the investigated condition. The solid lines denote the same pathway of both ratios of KCl/H2SO4,
dash lines denote the only pathway of the lower KCl/H2SO4 ratio and dot lines denote the only
pathway of the higher KCl/H2SO4 ratio.

Of minor importance for the sulfation rate is a number of reactions involving potassium sulfur
oxides, i.e., KOSO, KOSO2, and KOSO3. KOSO3 is generated by reaction of OH with KHSO4 and
K2SO4,

KHSO4 + OH ⇄ KOSO3 + H2O (R7)

K2SO4 + OH ⇄ KOSO3 + KOH, (R8)

or via a sequence involving KOSO2,

KHSO4 (+M) ⇄ KOSO2 + OH (+M) (R9)

K + SO3 (+M) ⇄ KOSO2 (+M) (R10)

KOSO2 + O2 ⇄ KOSO3 + O (R11)

The sulfur oxides KOSO3 and KOSO2 may dissociate to yield SO2,

17
 KOSO3 (+M) ⇄ KO2 + SO2 (+M) (R12)

KOSO2(+M) ⇄ KO + SO2 (+M) (R13)

The potassium sulfur oxide reactions affect the SO2/SO3 ratio in the gas phase. The poor agreement
with experiment for SO2 at high temperature indicates that this part of the reaction mechanism has
short-comings that need to be addressed in future work.

5. CONCLUSIONS

The sulfation of gaseous KCl by H2SO4 was studied by experiments and kinetic modeling in a flow
reactor at atmospheric pressure and temperatures of 873-1523 K. The following main conclusive
were drawn:

 The gas-phase sulfation of KCl by H2SO4 is effective below 1400 K, but the efficiency
declines rapidly above this temperature. The results confirm that a sulfur recirculation
technology applying injection of sulfuric acid may be an effective strategy for control of
KCl levels in boilers.

 The sulfation is initiated by decomposition of sulfuric acid, H2SO4 + H2O ⇄ SO3 + H2O +
H2O, followed by reaction of SO3 with KCl to form the intermediate KSO3Cl. The
subsequent conversion of KSO3Cl via KHSO4 to gaseous K2SO4 involves fast reactions
and is mainly limited by thermodynamics. As the gas is cooled downstream of the
isothermal zone, potassium sulfate nucleates homogeneously to form an aerosol, promoting
further sulfation in the gas-phase.

 Simulations with a detailed reaction mechanism are in satisfactory agreement with the
experimental results, predicting correctly the temperature window for the process.
However, the model overestimates the degree of sulfation at the lower H2SO4/KCl ratio.
Also the high temperature SO2 yield is overpredicted, indicating that the K/S interactions
under these conditions are not fully understood.

18
ASSOCIATED CONTENT

Supporting Information

Measured temperature profiles in the laminar flow reactor and in the preheating zone.
Decomposition of KCl in the flow reactor. Decomposition of sulfuric acid in the flow reactor.

Mechanism (TXT) Thermo all (TXT)

AUTHOR INFORMATION

Corresponding Author

* Peter Glarborg − DTU Chemical Engineering, Technical University of Denmark, 2800 Lyngby,
Denmark; orcid.org/0000-0002-6856-852X; Email: [email protected]

Author Contributions

Arphaphon Chanpirak − DTU Chemical Engineering, Technical University of Denmark, 2800

Lyngby, Denmark; orcid.org/0000-0002-8660-3819

Marcus K. K. Jensen − DTU Chemical Engineering, Technical University of Denmark, 2800

Lyngby, Denmark

Hao Wu − DTU Chemical Engineering, Technical University of Denmark, 2800 Lyngby,

Denmark; orcid.org/0000- 0003-0462-2491

Paul Marshall − Department of Chemistry and Center for Advanced Scientific Computing and
Modeling (CASCaM), University of North Texas, Denton, Texas 76203-5017, United States;
orcid.org/0000-0002-8181-983X

Notes
The authors declare no competing financial interest.

19
ACKNOWLEDGMENT

This work was supported by Ørsted A/S, by the Technical University of Denmark and by the
EUDP project 64020-2091, Sulfur Recirculation for higher green power production and lower
dioxin formation. A.C. is grateful for funding from the Thailand Education and Training Abroad
Center and Naresuan University, Thailand.

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