atmosphere
Review
Moisture Removal Techniques for a Continuous Emission
Monitoring System: A Review
Trieu-Vuong Dinh and Jo-Chun Kim *






Citation: Dinh, T.-V.; Kim, J.-C.
Moisture Removal Techniques for a
Continuous Emission Monitoring
System: A Review. Atmosphere 2021,
12, 61. https://doi.org/10.3390/
atmos12010061
Received: 2 November 2020
Accepted: 29 December 2020
Published: 1 January 2021
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4.0/).
Atmosphere 2021, 12, 61. https://doi.org/10.3390/atmos12010061
Department of Civil and Environmental Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-Gu,
Seoul 05029, Korea; dinhtrieuvuong@gmail.com
* Correspondence: jckim@konkuk.ac.kr; Tel.: +82-2-450-4009; Fax: +82-455-2994
Abstract: A continuous emission monitoring system (CEMS) is a well-known tool used to analyze
the concentrations of air pollutants from stationary sources. In a CEMS, the presence of a high
moisture level in a sample causes a loss of analytes due to artifact formation or absorption. This issue
brings about a bias in the measurement data. Thus, moisture removal is an important pretreatment
step. Condensation and permeation methods have been widely employed to remove moisture from
the CEMS for gaseous compounds. In terms of particulate matter, dilution methods have been
applied to reduce the moisture level in the gas stream. Therefore, condensation, permeation, and
dilution methods are critically reviewed in this work. The removal efficiencies and recovery rates of
analytes are discussed, as well as the advantages and disadvantages of each technique. Furthermore,
the suitable applications of each technique are determined. Condensation methods have not been
well documented so far, while permeation and dilution methods have been continuously studied.
Many types of permeation materials have been developed. The limitations of each method have been
overcome over the years. However, the most reliable technique has not yet been discovered.
Keywords: moisture removal; CEMS; condensation; permeation; dilution; desolvator
1. Introduction
The continuous emission monitoring system (CEMS) has been applied to monitor
the air pollutants emitted from stationary sources. An extractive method, in which air
pollutants are delivered to analyzers located in a shelter, and an in situ method, in which
analyzers are attached directly to an emission stack, are used for the CEMS [1]. The
CEMS is usually applied to detect the emissions of air pollutants such as carbon monox-
ide (CO), carbon dioxide (CO2 ), sulfur oxides (SOx ), nitrogen oxides (NOx ), hydrogen
chloride (HCl), hydrogen fluoride (HF), ammonia (NH3 ), water vapor (H2 O), particu-
late matter, etc. Spectroscopy analyzers have been widely installed in CEMS due to the
advantage of continuous monitoring and good accuracy. As a spectroscopy analyzer,
nondispersive infrared (NDIR) and Fourier transform infrared analyzers have been widely
used because they operate consistently with low energy consumption compared to other
spectroscopy technologies [2]. However, moisture (H2 O) in the gas stream is a signif-
icant interference since it affects the accuracy of the NDIR analyzer [3]. Moisture can
cause a bias of the NDIR analyzer up to 30% for NO2 (i.e., at a wavelength of 6.21 µm),
20% for SO2 (i.e., at a wavelength of 7.45 µm), and 5% for NO (i.e., at a wavelength of
5.25 µm) [4]. For particulate matter, the particle concentration can be monitored by light
scattering analyzers (e.g., optical particle counter or condensation particle counter) [5–9],
light absorption analyzers (e.g., spot meters, aethalometer, photoacoustic soot sensor, or
laser-induced incandescence) [5,6,10], light extinction analyzers (e.g., cavity ring-down
or opacity meter) [5,6,11,12] and microbalance analyzers (e.g., tapered element oscillation
microbalance or quartz crystal microbalance) [5,6,13]. Size distributions of particles can be
continuously determined using a fast-mobility particle sizer and an electric low-pressure
impactor [5,6,14–16]. Among these methods, light-scattering meters, opacity meters, Beta
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Atmosphere 2021, 12, 61 2 of 25

attenuation meters, and electrification devices have been widely applied for CEMS [17,18].
However, H2 O has a significant effect on the light-scattering method used to measure
particulate matter [18–21]. It was found that light-scattering ratios of sodium chloride
particles increased from 1- to 10-fold when the relative humidity increased from 20% to
80%. On the other hand, these values for uranine dye particles were increased 1-2-fold due
to their lower hygroscopicity [18]. Zieger et al. (2013) found that light-scattering ratios were
increased approximately 5-, 7-, 9-, and 16-fold with respect to (NH4 )2 SO4 , NaNO3 , Na2 SO4 ,
and H2 SO4 particles, respectively, at 85% relative humidity and a 589 nm wavelength [19].
It was also found that the number of particles increased by approximately 50%, and the
PM10 concentration increased by as much as 46% when the experiment was conducted
at 75% relative humidity [20]. For electrification devices, wet gas streams had significant
effects on the probe electrification [17]. It is now well known that the moisture content
in the flue gas is high, as shown in Table 1. The United States Environmental Protection
Agency (U.S. EPA) stated that moisture is one of the significant bias sources for extractive
CEMS [22]. Moisture causes effects such as the absorption of water-soluble gases or artifact
formation. For artifact formation in the presence of moisture, HCl may react with NH3 to
produce ammonium chloride salt [23]. In a municipal waste incinerator, NH3 was found to
react with HCl or SO2 to create ammonia salts such as ammonium chloride or ammonium
sulfite [24]. For the absorption, a negative measurement bias for NH3 was found due to
condensation [24]. Thirty percent of 10 ppmv SO2 was found to be lost at 20% absolute
humidity [22]. The condensed water could also corrode the system and cause a leak [22].
In combination with particles in the gas stream, mud could form and plug the system [22].
Hence, moisture removal is an important issue for extractive CEMS.
Reactions and dissociations of several analytes may occur in two ways as follows [25–29]:

Table 1. Humidity in the flue gas of some industrial stacks.

Emission Source Temperature (◦ C) Humidity (vol%)

Blast furnace (coal fuel) [30,31] 72 5.6–10
Heating station [32] 150 0.9
Basic oxygen furnace [31] 54 5.7
Coke oven [31,32] 79–150 0.7–5.1
Electric arc furnace [31] 86.7 4.2
Heavy oil plant [31] 247 7.3
Cement (drying) [31] 103 19.4
Cement (pryo-processing) [31] 142 3.5
Boiler (heavy oil fuel) [33] 310 10
Power plant (coal fuel) [30–32,34,35] 100–177 0.9–8.7
Hazardous waste incinerator [23] – 50
Portland cement kiln [23] – 10–35

In the first case, moisture is condensed as liquid droplets:

CO2 (g) + 2H2 O(aq) ↔ H3 O+ + HCO3 −

HCO3 − + H2 O(aq) ↔ CO3 2− + H3 O+
NH3 (g) + H2 O(aq) ↔ NH4 + + OH−
NH3 (g) + HCO3 − ↔ NH2 COO− + H2 O
SO2 (g) + 2H2 O(aq) ↔ H3 O+ + HSO3 −
2NO2 (g) + H2 O(aq) ↔ NO2 - + 2H+ + NO3 −
2NO2 (g) + HSO3 − + H2 O(aq) ↔ 3H+ + 2NO2 − + SO4 2−
SO2 (g) + H2 O (aq) → H2 SO3
Atmosphere 2021, 12, 61 3 of 25

In the second case, moisture remains in the gas phase:

2NH3 (g)+SO2 (g)+H2 O(g) ↔ (NH4 )2 SO3 (s)

NH3 (g)+SO2 (g)+H2 O(g) ↔ NH4 HSO3 (s)
2NH3 (g)+NO2 (g)+H2 O(g) ↔ (NH4 )2 NO3 (s)
NH3 (g) + NO2 (g) + H2 O(g) ↔ NH4 HNO3 (s)

To reduce the effect of water vapor, three methods have been used to date. In the first
method, both extractive sampling lines and the gas cells of analyzers are heated to prevent
water vapor from forming condensation. The high energy consumption caused by a heater
is a disadvantage of this method. In addition, air pollutants in contact with a high-energy
light source in the analyzer such as UV or IR can cause reactions among the pollutants.
Another disadvantage of the method is the measurement bias because of the sample
temperature [23]. It was found that the HCl measurement results involved a negative bias
when the sample temperature was lower than the stack temperature. In contrast, when the
sample temperature was higher than the stack temperature, particulate ammonium chloride
might volatilize to produce HCl and NH3 , which brought about a positive measurement
bias for HCl and NH3 [23]. The second method involves the dilution of flue gas to reduce
the concentration of water. However, dilution factors are dependent on the detection
limit of the gas analyzer. Therefore, this method requires highly sensitive analyzers that
increase the cost of the CEMS. The third method, which has been popularly employed,
is the cool/dry method. In this approach, moisture in the flue gas is removed using a
moisture removal system. The removal of moisture from the flue gas helps to reduce the
energy consumption of a heater, the interference of target compound detection, and artifact
formation. Due to the high concentration of moisture in the gas stream emitted from a
stack, two types of moisture removal methods are commonly used: condensation and
permeation [1]. Condensation processes are generally classified into homogeneous and
heterogeneous condensation [36]. In homogeneous condensation, a liquid droplet embryo
is formed within the supercooled vapor. On the other hand, in heterogeneous condensation,
liquid droplet nucleation occurs at the interface of another phase (e.g., a cold solid wall or
particle) at a low temperature [36]. For the permeation method, permeation membranes
are divided into dense (i.e., pores of ~0.1 nm) and porous (i.e., pores of ~0.1 µm) types [37].
However, an ideal method has not yet been invented since each of these has limitations [22].
Although moisture removal is an important issue in CEMS, scientific research into
this topic is lacking. Almost all moisture removal technologies are presented as patents
and commercial products. However, many studies have been carried out on moisture
control for other processes such as air conditioning [38–44], chemical analysis [45–52],
clothes drying [53–57], gas turbines [58–60], and laundering [61–63]. Consequently, the
aim of this study is to review the moisture removal methods for extractive CEMS. As for
gaseous compounds, condensation and permeation methods are taken into account here.
For particulate matter, dilution methods are discussed. The advantages and disadvantages
of each gas and particle method will be addressed as well. Furthermore, future research
will be suggested to develop the best moisture removal system for CEMS.

2. Methodology
Moisture removal methods for CEMS are systematically reviewed in this study. Google
Scholar, Google Patent, ScienceDirect, and the library database of Konkuk University were
the databases used to search for references. The scope of the review was condensation
and permeation methods for gaseous compounds and dilution methods for particulate
matter in CEMS. Since the review work was carried out to determine the development
of moisture removal methods for CEMS, publication years of references were not limited.
Published patents, peer-review articles, conference papers, books, and standard methods
were searched out in the English language. All searches were conducted by May 2020. Key-
words including moisture removal, dehumidifier, continuous emission monitoring system,
cooler, moisture permeation, moisture membrane, Nafion® dryer, stack dilution sampling,
Atmosphere 2021, 12, 61 4 of 25

and pretreatment device were used. First, the title and abstract of references were read to
select references relevant to the scope of this study. Then, full-text copies of relevant papers
were downloaded and read. Bibliographies of the selected references were also used to find
more relevant papers. Condensation, permeation, and dilution techniques applied for the
monitoring of gaseous compounds and particulate matter were taken into account. For the
condensation technique, a schematic diagram of a device, condensation type, temperature,
moisture removal efficiency, and loss ratio of an analyte were collected. For the permeation
method, the structure of a device, membrane material, membrane selectivity, membrane
permeability, temperature, purging rate, moisture removal efficiency, and loss ratio of an
analyte were considered. In terms of the dilution method, the flowrate, dilution ratio,
temperature, type of particulate matter, and measurement errors were summarized, and
schematic diagrams of devices were collected. In addition, the advantages and disadvan-
tages of each technique were studied. The bias of each technique was observed in the
study. The advantages and disadvantages were assessed based on the references and the
experience of our authors. Application scopes of each technique were recommended based
on the characteristics of the technique.

3. Results and Discussion

3.1. Condensation Method
On the basis of water physical properties, the temperature of the flue gas in the extrac-
tive line was reduced below the dew point to condense the water vapor. The condensation
system must be suitable for the flow rate and moisture concentration of the sample gas.
Moreover, the structure of the system must avoid contact between the condensed water
and the dried flue gas. To decrease the temperature of the gas stream, two technologies
have generally been employed: refrigeration using a coolant and Peltier.
The typical structure of a refrigerated system is shown in Figure 1. On the basis of this
principle, several apparatuses have been developed. Dowling (1980) invented a moisture
removal system based on the refrigerated method with an improvement to the air-to-air and
air-to-refrigerant heat exchanger [64]. The exchanger consists of a bundle of vertical tubing
in a housing (Figure 2). Parallel sheet metal fins are used to hold the tubing. Moisture is
condensed and deposited on the sheet and then drips down the bottom of the housing due
to gravity. The advantage of this system is the absence of the water separator. Moreover,
the fin sheets help to increase the turbulence of the air and liquid flow, which protects
the surface of the sheet to stave off fouling [64]. Nanaumi and Baba (1980) also improved
the heat exchanger for the refrigerated system [65]. The main novelty of this invention is
the use of an extra heat exchanger to cover the heat exchanger of the refrigerated system
to precool the inlet air [65]. These two inventions improved the cooling efficiency, which
helped to remove more moisture with respect to a high loading capacity. The principle of
both inventions is heterogeneous condensation. The moisture was removed under liquid
phase, and most of the droplets were condensed on the cold surface of a device. Thus, the
loss of highly water-soluble compounds would occur.
A two-stage moisture removal system was developed by Basseen et al. (1988) [66].
First, the inlet air was precooled to −40 ◦ C using a refrigerator to reduce the air temperature
and remove some of the moisture. The flue gas was continued, introducing it to the second
stage, which consists of dual desiccant beds to adsorb the remaining moisture content.
These beds are alternatively working and regenerating. The system can reduce the humidity
from about 15% to 1% [66]. In this invention, the moisture is also condensed by way of
a heterogeneous process. The phase of water is solid, which is suitable for highly water-
soluble compounds. Due to the two stages of moisture removal, the device can operate
at high moisture loading. Moreover, the moisture removal efficiency of the device is also
high. However, a desiccant could adsorb certain compounds, which affected the selectivity
of the device.
Atmosphere 2021, 12, x FOR PEER REVIEW 5 of 26
Atmosphere 2021,
Atmosphere 12, x61FOR PEER REVIEW
2021, 12, 55of
of26
25

Figure 1. Typical structure of a refrigerated moisture removal device [1].

Typicalstructure
Figure1.1.Typical
Figure structure of
of aa refrigerated
refrigerated moisture
moisture removal
removal device
device [1].
[1].

Figure 2. Structure of an air-to-air heat exchanger [64].

Figure 2. Structure of an air-to-air heat exchanger [64].
FigureIn2. particular,
Structure of Tosi
an air-to-air
(2009) heat
usedexchanger
a vortex[64].
tube to cool the flue gas to the dew point
A two-stage[67].
temperature moisture
In the removal
tube, thesystemvorticalwas developed
motion of air atbyhigh Basseen
speedet(i.e.,
al. (1988)
a moving [66].hot
stream with a different direction to that of the cold stream) induced cold air, which[66].
First, A
the two-stage
inlet air wasmoisture
precooled removal
to −40 system
°C using wasa developed
refrigerator by
to Basseen
reduce theet al.
air (1988)
tempera- was
First,
ture andthe
introduced inlet
remove to air
some
the was
heatofprecooled
the moisture.
exchanger toto−40 The
reduce°Cflue
using
thegas a was
refrigerator
temperature continued, to reduce
of the the(Figure
introducing
inlet gas airittempera-
to 3)the[67].
ture
The and
second stage,remove
which some
condensation consists
of waterof the moisture.
ofvapor
dual desiccant Thebeds
is a homogeneous flue togas was continued,
adsorb
process the inremaining introducing
this case. moisture
The itcon-
advantage to theof
second
tent. These
this stage,
system beds iswhich
arelow
its consists
alternatively
energy of dual desiccant
working and
consumption beds to
regenerating.
compared to adsorb
a the remaining
The system
refrigerated moisture
can reduce
technology. con-
the
However,
Atmosphere 2021, 12, x FOR PEER REVIEW 6 of 26
tent.
humidity
due toThese
from beds
about
the direct are15%alternatively
contact towith
1% [66]. working and regenerating.
In this invention,
condensed water in atheheat moisture Theissystem
exchanger, also can reduce
condensed
water-soluble by the
gases
humidity
waycanof be from
a heterogeneous about
absorbed in water, 15% to
process. 1%
which The[66].phase
might In this invention,
of water
affect the
is solid, of
the accuracy moisture
which is also condensed
for highly by
is suitableresults.
the analytical
way of a heterogeneous
water-soluble compounds. process.Due to the The two phase
stagesof of
water is solid,
moisture which the
removal, is suitable
device can for highly
op-
water-soluble
erate at high moisture compounds.
loading.Due to the two
Moreover, the stages
moisture of moisture removal, the
removal efficiency device
of the devicecanisop-
erate
also high.at However,
high moisture loading.could
a desiccant Moreover, adsorbthe moisture
certain removal efficiency
compounds, which affectedof thethe devicese- is
also high. However,
lectivity of the device. a desiccant could adsorb certain compounds, which affected the se-
lectivity of the device.
In particular, Tosi (2009) used a vortex tube to cool the flue gas to the dew point
In particular,
temperature [67]. In theTosi (2009)
tube, the used
vortical a vortex
motion tube to at
of air coolhighthespeed
flue gas
(i.e.,toa the
moving dew hot point
stream with a different direction to that of the cold stream) induced cold air, which washot
temperature [67]. In the tube, the vortical motion of air at high speed (i.e., a moving
stream with
introduced to thea different direction
heat exchanger to that the
to reduce of the cold stream)
temperature of theinduced
inlet gascold air, which
(Figure 3) [67]. was
introduced to the heat exchanger to reduce the temperature
The condensation of water vapor is a homogeneous process in this case. The advantage of of the inlet gas (Figure 3) [67].
The
Figure
this condensation
Figure
system is its lowofenergy
3.3.Fundamental
Fundamental water
flow vapor of
flowdiagram
diagram isofaa avortex
consumption homogeneous
vortex tube
tube[67].
compared process
[67].
to in this case.
a refrigerated The advantage
technology. How- of
thisdue
ever, system
to the is direct
its lowcontact
energywith consumption
condensed compared
water in to a refrigerated
a heat exchanger,technology.
water-soluble How-
ever,TheThe
due advantages
advantages
to the direct ofcontact
of the refrigeration-based
the refrigeration-based
with condensed method
method
water are
in are
a the
heat high
the cooling
high cooling
exchanger, efficiency,
efficiency,
water-soluble high
gases can be absorbed in water, which might affect the accuracy of the analytical results.
working
high
gasesworking capacity (i.e.,
capacity (i.e.,
can be absorbed high air flow
high which
in water, air flow loading),
loading),
might and
affectandtypical
the typical cooling
accuracy coolingtechnology.
of thetechnology. However,
analytical results. How-
a refrigerator
ever, a refrigeratoris a complex systemsystem
is a complex (e.g., evaporator, pump, valves).
(e.g., evaporator, pump, Therefore, it leads to it
valves). Therefore, an
leads to an increase in the dimension of the removal system and the maintenance cost. To
overcome this problem, a Peltier chiller was used instead of a refrigerator. The moisture
removal system based on refrigeration has more volume than the Peltier system. How-
ever, the large volume of the system causes the dilution of the target compounds due to a
Atmosphere 2021, 12, 61 6 of 25

increase in the dimension of the removal system and the maintenance cost. To overcome
this problem, a Peltier chiller was used instead of a refrigerator. The moisture removal
system based on refrigeration has more volume than the Peltier system. However, the
large volume of the system causes the dilution of the target compounds due to a mixing
effect. Consequently, the accuracy of the analytical data will decline [68]. For a moisture
removal system with a small volume, a Peltier is a good choice of cooling device. A Peltier
has been used to cool the flue gas instead of a refrigerator or vortex tube. Chapman et al.
(1980) developed a moisture removal system using a Peltier block for the heat exchanger
(Figure 4) [68]. Water vapor condensed under solid state and then settled to the bottom of
the system by gravity. The diameter of the inlet embodiment was 1.58 to 4.76 mm, and that
of the outlet embodiment was 3.17 to 6.35 mm [68]. The condensation of the moisture in
this device is a heterogeneous process. The advantage of the device is that it is suitable for
highly water-soluble compounds because moisture is removed in the solid phase. However,
since the cooling efficiency of a Peltier is low, the device cannot be applied for high inlet
temperature gas or high moisture loading. Groger (1988) combined a condensate coil
using a Peltier cooling element with a fine membrane filter to remove the moisture from a
sampling gas stream [69]. The flue gas entering the coil was cooled to about 4 ◦ C. In the
coil, the water vapor was condensed, 90% of which was removed by a drain pump. The
distance between the outlet coil and the inlet pump was short. Hence, the condensate was
continuously and immediately extracted to avoid the absorption of target gas in water. The
remaining moisture in the form of aerosol (about 5%) continued to be filtered by the fine
filter [69]. The condensation process of the moisture in this invention was heterogeneous.
The advantage of this invention is the high removal efficiency of moisture. However,
using a filter to get rid of water aerosol will also produce water droplets on the surface
that can absorb target gases. Groger and Groger (1989) proposed an apparatus to remove
moisture with a cooling tube designed as a conical taper [70]. The cone angle was 5◦ . The
inlet gas entered the cooler at the bottom (above the condensate discharge socket) as the
cross-section of the tube produced a countercurrent flow (i.e., the cyclone effect). The outlet
of the gas was at the top of the tube. Due to this design, the retention time of the flue gas
in the cooler was longer with a smaller surface area of the tube. This helped to simplify
the manufacture and reduce the size of the moisture removal device [70]. In this invention,
the phase of H2 O was changed from a gas to a liquid by a heterogeneous condensation
process. This invention only improved the contact surface in a cooling tube, which helped
to improve the moisture removal efficiency. However, the device did not overcome the loss
of target analytes due to an absorption effect. A probe assembly for sampling, coupled
with a Peltier-based cooler, was manufactured by Bacharach, Inc., New Kensington, PA,
USA. The device could work at a flow rate of 1.5 L/min (Figure 5) [71]. An advantage of
this in situ cooler is the reduction in energy consumption for an extractive line because
moisture is removed before entering the extractive line, which helps to reduce the heating
temperature of the line. However, the loss of target compounds due to water droplets is a
drawback of this invention. In general, the advantages of the Peltier-based heat exchanger
are its low cost, simple construction, and reduced energy consumption. However, the
cooling efficiency of the Peltier is lower than that of the refrigerator and of the vortex tube.
Therefore, the Peltier tube could be applied for low-flow-rate sampling.
 compounds due to water droplets is a drawback of this invention. In general, the ad-
compounds
vantages ofdue the to water droplets
Peltier-based heat isexchanger
a drawbackare of
itsthis
lowinvention.
cost, simpleIn construction,
general, the ad-
and
vantages of the Peltier-based heat exchanger are its low cost, simple construction,
reduced energy consumption. However, the cooling efficiency of the Peltier is lower than and
reduced energy
that of the consumption.
refrigerator and of However,
the vortexthe cooling
tube. efficiency
Therefore, of the tube
the Peltier Peltier is lower
could than
be applied
Atmosphere 2021, 12, 61 that of the refrigerator and
for low-flow-rate sampling. of the vortex tube. Therefore, the Peltier tube could be applied
7 of 25
for low-flow-rate sampling.

Figure4.4.The
Figure Theembodiment
embodimentof
ofaaheat
heatexchanger
exchangerusing
usingaaPeltier
Peltier[68].
[68].
Figure 4. The embodiment of a heat exchanger using a Peltier [68].

Figure 5. Schematic diagram of a sampling probe coupled with a Peltier cooler [71].
Figure 5. Schematic diagram of a sampling probe coupled with a Peltier cooler [71].
Figure 5. Schematic diagram of a sampling probe coupled with a Peltier cooler [71].
In our research (see Supplementary Materials), we found that the heat exchanger to
remove In our research
moisture from (see Supplementary
a sampling Materials),
gas under we found
liquid phase that the
reduced inletheat
SO2exchanger to
by approx-
In our
remove researchfrom
moisture (see aSupplementary
sampling Materials),
gas under we found
liquidppmv)
phase that the
reduced heat
inlet SOexchanger
2 by phase
to
approxi-
imately 20% (i.e., the inlet concentration was 1000 and that under solid it
remove
matelymoisture
reduced 20% HClfrom
inlet (i.e., theup
by a to
sampling
inlet (i.e.,gas
theunder
concentration
50% was
inlet liquid
1000 phase reduced
ppmv)was
concentration and50thatinlet SO
under
ppmv). 2 by approxi-
solid phase
Therefore, a cor-it
mately
reduced
rection 20%
factor(i.e.,
inlet HCl
for the
eachbyinlet
up to
targetconcentration
50%should
gas (i.e., the
bewas 1000
inlet
applied ppmv) andanalytical
concentration
to the final that50under
was ppmv).solid phase it a
Therefore,
results. However,
reduced inlet HCl by
the concentration up to 50%gas
of emission (i.e.,
is the inletand
varied, concentration
the removal was 50 ppmv).
efficiency Therefore,
of the a
moisture
removal system is not consistent. Hence, a more optimal measure should be taken. In the
condensation method, water can be removed under solid or liquid phase. The advantage of
the condensation method is its suitability for removing a high concentration of water from a
high loading air volume. However, the condensate might affect the target gases. When the
condensate is collected under the liquid phase, the absorption of soluble gases such as SOx ,
NOx , HCl, and NH3 can occur. It was reported that the loss of ozone was approximately
Atmosphere 2021, 12, 61 8 of 25

10% at 30% relative humidity and 40% at 80% relative humidity when the condensation
method was applied to remove moisture for ozone measurement. Furthermore, SO2 was
found to be lost at rates of 19.3%, 29.3%, and 61.5% at relative humidities of 30%, 50%,
and 80%, respectively, when a cooler was used to remove the moisture [72]. Lee et al.
(2019) investigated the effect of a cooler as a moisture pretreatment device in the analysis of
methyl ethyl ketone (MEK), isobutyl alcohol (i-BuAl), methyl isobutyl ketone (MIBK), butyl
acetate (BuAc), and styrene [73]. These are very highly water-soluble odorous compounds.
It was reported that the losses of i-BuAL, MIBK, BuAc, and styrene were approximately
19%, 4%, 5%, and 10%, respectively, in association with 80% relative humidity. In addi-
tion, the reproducibility of their concentrations was approximately 8–31%. This indicated
that the water liquid in the cooler kept absorbing and desorbing the analytes [73]. The
U.S. EPA stated that HCl and NH3 are lost in the H2 O condensate in a condenser [23,24].
Measurement bias of total hydrocarbon emitted from a hazardous waste incinerator was
found when a refrigerant moisture removal device was used because VOCs and organic
air pollutants might comprise highly, poorly, and non-water-soluble compounds [23]. On
the other hand, if the condensate is removed under the solid phase, the absorption of
soluble gases can be avoided. Several studies addressed a good recovery rate for highly
water-soluble compounds when the moisture was removed under solid phase. It was
found that the loss of SO2 at 150 ppmv was less than 2% when the moisture was removed
at the solid phase (i.e., frost) [72]. Likewise, the losses of MEK, i-BuAl, MIBK, and BuAc at
sub-ppbv level were 0%, 3.4%, 0.5%, and 2.1%, respectively [73]. Son et al. (2013) found
that H2 S (23 ppbv), CH3 SH (16 ppbv), dimethyl sulfide (13 ppbv), and dimethyl disulfide
(8 ppbv) had a recovery rate over 97% when the moisture in the sample was removed
at the solid phase [52]. Nevertheless, these studies were not conducted with respect to
air pollutants in the ambient air with low moisture content rather than emission gases
from a stack. Moreover, HCl or NH3 at the atmospheric conditions could still be absorbed
on the ice surface due to the hydrogen bond [74,75]. Thus, more investigations should
be implemented. In general, the advantages of the condensation method are the low
cost, simple structure, and easy operation and maintenance. However, the loss of target
analytes is a serious issue with the method. Moreover, the treatment of drain water is
another drawback of the condensation method. Consequently, the condensation method is
recommended to be used for the CEMS of poorly water-soluble compounds such as CO,
CO2 , NO, and CH4 when the moisture is removed under a liquid phase. On the other
hand, if moisture is removed under a solid phase, higher water-soluble gases such as SO2
or NO2 could be applied. More comprehensive studies should be carried out to investigate
the influence of the solid phase. A conversion process of highly water-soluble analytes
to poorly water-soluble analytes would be an alternative when the moisture is removed
under liquid phase. For example, the U.S. EPA suggested that a catalytic converter could
be applied to convert the NH3 in the sample gas to NOx [24]. Then the sample gas could
penetrate a condenser to remove moisture before moving into a NOx analyzer [24]. The
summary of condensation methods with respect to different inventions is shown in Table 2.
The condensation process, advantages, disadvantages, and recommendations of applicable
analyte are listed.
Atmosphere 2021, 12, 61 9 of 25

Table 2. Development of condensation devices to remove moisture in the flue gas.

Condensation Recommendation of
No. Method Advantages Disadvantages
Type Applicable Analytes
- Reduced dimension of
Refrigerated the device due to the - Poorly water-soluble
- Complicated
moisture removal absence of a gases such as CO, NO,
structure
device with water separator CO2 , and CH4 due to
1 Heterogeneous - Potential loss of
improvement of - High cooling efficiency water droplets absorbing
highly water-soluble
heat - Less foiling highly water-soluble
compounds
exchanger [64] - Allowable for high compounds
loading of moisture.
- High cooling efficiency - Poorly water-soluble
Refrigerated - Bulky
- Allowable for high gases such as CO, NO,
moisture removal device
temperature of the CO2 , and CH4 due to
2 device with an Heterogeneous - Potential loss of
inlet gas water droplets absorbing
extra heat highly water-soluble
- Allowable for high highly water-soluble
exchanger [65] compounds
loading of moisture. compounds
-High cooling efficiency - Complex and bulky
Two stages: - Allowable for high structure
- Highly water-soluble
refrigeration at loading of moisture - Potential loss of
3 Heterogeneous gases such as SO2 or NO2
−40 ◦ C and - Suitable for highly certain compounds
under a solid phase
desiccant bed [66] water-soluble due to the adsorption
compounds. of desiccants.
- Poorly water-soluble
- Low energy gases such as CO, NO,
- Potential loss of
consumption CO2 , and CH4 due to
4 Vortex tube [67] Homogeneous highly water-soluble
- Less maintenance water droplets absorbing
compounds
required highly water-soluble
compounds.
- Compact size - Not operatable with
- Low energy a high loading amount
Peltier moisture - Highly water-soluble
consumption of moisture
5 removal Heterogeneous gases such as SO2 or NO2
- Suitable for highly - Unsuitable for a high
device [68] under a solid phase.
water-soluble temperature of the
compounds inlet gas
- Potential loss of
certain compounds
- Poorly water-soluble
due to the selectivity
Two stages: gases such as CO, NO,
- Allowable for high of the membrane
6 Peltier and Heterogeneous CO2 , CH4 due to water
loading of moisture. - Potential loss of
membrane [69] droplets absorbing highly
highly water-soluble
water-soluble compounds.
compounds due to
water droplets.
- Compact size Poorly water-soluble gases
- Potential loss of
Conical cooling - Large contact surface such as CO, NO, CO2 , and
highly water-soluble
7 tube using a Heterogeneous - Easy manufacturing CH4 due to water droplets
compounds due to
Peltier [70] due to its simple absorbing highly
water droplets.
structure. water-soluble compounds
- Hard to maintain due
- Easy reduction in the Poorly water-soluble gases
to in situ location
temperature of an such as CO, NO, CO2 , and
- Potential loss of
8 Peltier probe [71] Heterogeneous extractive line CH4 due to water droplets
highly water-soluble
- Saving energy for absorbing highly
compounds due to
a CEMS. water-soluble compounds.
water droplets.
Atmosphere 2021, 12, 61 10 of 25

3.2. Permeation Method

The permeation method is based on the selective permeability of water through a
membrane. The flue gas-contained moisture is fed to the feed side of the membrane while
a dry gas (e.g., nitrogen) flows to the delivery side of the membrane with a counter-current
Atmosphere 2021, 12, x FOR PEER REVIEW 10 of 26
flow direction in order to promote the permeation of water vapor through the membrane
(Figure 6) [76,77]. There are four flow directions of the air in a membrane: perfect mixing,
cross-plug flow, co-current flow, and counter-current flow [37]. It was concluded that the
counter-current flow
counter-current flow systematically
systematically had
had the
the best
best performance,
performance, followed
followed byby cross-plug,
cross-plug, co-
co-
current, and perfect mixing [78]. Therefore, counter-current and cross-plug
current, and perfect mixing [78]. Therefore, counter-current and cross-plug flow have flow been
have
been widely
widely used
used for for permeation
permeation devices
devices [78].optimal
[78]. For For optimal operation,
operation, a membrane
a membrane shouldshould
have
have perfect radial mixing across the substrate porosity, which is calculated by Equation
perfect radial mixing across the substrate porosity, which is calculated by Equation (1) [79]:
(1) [79]:
RM = (ymax − y)/(ymax − ybore ), (1)
RM = (ymax − y)/(ymax − ybore), (1)
where
where yymax isthe
max is theconcentration
concentrationatatthethelow
lowpressure
pressure(computed
(computed byby the
the cross-flow
cross-flow model
model of
of membrane
membrane performance);
performance); y isythe
is the actual
actual concentration
concentration at low-pressure
at the the low-pressure
side side ofsub-
of the the
substrate;
strate; andand
yboreyis is concentration
the
bore the concentration in fiber
in the the fiber
bore.bore.

Figure 6. Schematic of a permeation membrane

Figure 6. membrane tube
tube [76].
[76].

To
To evaluate
evaluate the
the performance
performance of of aa permeation
permeation membrane,
membrane, thethe permeability
permeability and
and selec-
selec-
tivity
tivity are key parameters [37,80]. The permeability of the membrane to water vapor (i.e.,
are key parameters [37,80]. The permeability of the membrane to water vapor (i.e.,
the
the permeation
permeation rate)
rate) should be ≥
should be 100, which
≥100, which can
can be
be calculated
calculated via
via Equation
Equation (2)
(2) [81]:
[81]:

J = JP[(p1 −1 −
= P[(p p2p)/L],
2)/L], (2)
(2)
where JJ isisthe
where thepermeation
permeationraterate(cm
(cm3 /cm
3/cm2·s); p1 and p2 are the pressures of upstream and
2 ·s); p and p are the pressures of upstream and
1 2
downstream of the membrane (cmHg),
downstream of the membrane (cmHg), respectively; respectively; L L is
is the
the membrane
membrane thickness
thickness (mm);
(mm);
and P is the permeability. The common unit for the permeability is Barrer.
and P is the permeability. The common unit for the permeability is Barrer. Alternatively, the Alternatively,
the permeance
permeance is usually
is usually usedused
when when the membrane
the membrane thickness
thickness is unknown
is unknown [82].[82].
The The com-
common
mon unit for the permeance is the gas permeation
unit for the permeance is the gas permeation unit (GPU). unit (GPU).
The selectivity
The selectivity ofof the
the membrane
membrane is is the
the ratio
ratio of of the
the permeability
permeability of of water
water vapor
vapor and
and
the permeability of another compound through the membrane. The selectivity cancal-
the permeability of another compound through the membrane. The selectivity can be be
culated viavia
calculated Equation
Equation(3)(3)
[37,82]:
[37,82]:
αijαij= P=i /P j , j,
Pi/P (3)
(3)
where
wherePPi iisisthe
thepermeability
permeabilityof of
water vapor
water andand
vapor Pj is Pthe permeability of another compound.
j is the permeability of another com-
The
pound. mechanisms for the mass transfer of moisture in a permeation membrane are
pore flow and solution-diffusion. In terms of the pore flow, H2 O is only enough small to
The mechanisms for the mass transfer of moisture in a permeation membrane are
penetrate some of the pores in the membrane to the permeate side. In solution-diffusion,
pore flow and solution‒diffusion. In terms of the pore flow, H2O is only enough small to
penetrate some of the pores in the membrane to the permeate side. In solution‒diffusion,
H2O dissolves in the membrane and then diffuses from the higher H2O concentration side
to the lower concentration side due to the difference in diffusivity [37,80].
Four membrane materials have been used: polymer, zeolite, mixed matrix, and sup-
ported liquid [37,80]. Among these materials, the polymeric membranes are the most
Atmosphere 2021, 12, 61 11 of 25

H2 O dissolves in the membrane and then diffuses from the higher H2 O concentration side
to the lower concentration side due to the difference in diffusivity [37,80].
Four membrane materials have been used: polymer, zeolite, mixed matrix, and sup-
ported liquid [37,80]. Among these materials, the polymeric membranes are the most
widely employed to remove moisture due to their reasonable cost, lack of defects, repro-
ducibility, and strength [37,80]. The polymeric materials consist of cellulose acetate, ethyl
cellulose, natural rubber, PBT/PEO block copolymer, PEBAX® 1074, polyacrylonitrile,
polyamide 6, polycarbonate, polydimethylsiloxane, polyether sulfone, polyethylene, poly-
imide, polyphenylene oxide, polypropylene, polystyrene, polysulfone, polyvinyl alcohol,
sulfonated polyether ether ketone, and sulfonated polyether sulfone [37,80]. PEBAX®
1074 shows the highest moisture permeability. However, the most selective polymer (i.e.,
between H2 O and N2 : H2 O/N2 ) is sulfonated polyether ether ketone [37,80]. The zeolitic
membrane is an inorganic one that is typically produced by the growing of zeolite on
aluminum or stainless steel. The advantages of the zeolitic membranes are their thermal
and chemical stability [37,80]. The combination of polymeric and zeolitic membranes is
known as a mixed matric membrane. High thermal and chemical stability, easy and cheap
fabrication process, high reproducibility, and high transportability are the main advantages
of the mixed-matrix membranes [37]. Supported liquid membranes consist of a single
laminate of a hygroscopic liquid (e.g., triethylene glycol, polyethylene glycol 400, ionic
liquids) and a hydrophobic microporous membrane. The membrane reveals high moisture
selectivity and permeability [37].
Membrane materials have continued to be developed. Hybridizing of polymeric
materials has been widely carried out. Some representative studies are taken into account
in this review. Makino and Nakagawa (1988) used an aromatic imide polymer generated
from a tetracarboxylic acid and diamine component, exhibiting high solubility in an
organic polar solvent [76]. The membrane could remove up to 10% of the water content
from flue gas. The preferred dry gas flow rate was 0.5–8 m/s. The permeation rate was
0.1–10 (cm3 /cm2 ·s) [76]. Keyser et al. (1990) developed a continuous membrane cartridge,
coupled with an intermittent air compressor [83]. Some of the outlet dry air was reused
to maintain the activity of the membrane. The membrane cartridge was also heated up
to improve its efficiency [83]. The heating up of membranes to improve the moisture
removal efficiency and prevent condensation on the surface is the advantage of this device.
Using an air compressor to supply dry air instead of a gas tank is also a good aspect of
this invention. However, a full permeation system would be bulky and consume a lot of
energy. Norlien et al. (1991) developed a permeation moisture removal device using a
perfluorinated polymer [77]. Lovelock (1992) invented a perfluorocarbon polymer with
lithium sulfate group that could work as a membrane at 100 ◦ C [84]. Bartholomew et al.
(2002) compacted a permeation membrane, particle filter, and water droplet collector into
an integral gas dryer and filtration device (Figure 7) [85]. Eckerbom (2009) reported the
Nomoline™ technology to remove moisture in the gas sampling line [86]. Nomoline™
works based on the properties of a polyether block amide cover. Polyamide and polyether
help to sweat water from the gas sample flow to the outer surface of the Nomoline™
cover [86]. Zhao et al. (2015) combined polyacrylonitrile with 1 wt% polydimethylsiloxane.
The polyacrylonitrile has high H2 O/N2 selectivity (i.e., 1,875,000) [87]. However, its
H2 O permeability is only 300 Barrers. In contrast, the polydimethylsiloxane shows high
H2 O permeability and low H2 O/N2 selectivity of 40,000 and 143, respectively [37,80].
Thus, they were combined to complement each other’s disadvantages. The membrane’s
permeance was reported as 12,827 GPU. Its H2 O/N2 selectivity was 220 [87]. Likewise,
the polyacrylonitrile was combined with 0.5 wt% polydimethylsiloxane to produce a
thinner membrane. However, the permeance and selectivity for H2 O were only 3700 GPU
and 13 (H2 O/N2 ) [88]. Baig et al. (2016) fabricated a thin-film nanocomposite using
carboxylated TiO2 and polyamide [89]. The amount of carboxylated TiO2 was 0.2 wt%.
It was reported that the H2 O/N2 selectivity of the membrane was 486. Its H2 O permeance
was 1.340 GPU [89]. Interfacial polymerization using m-phenylene diamine and trimesoyl
Atmosphere 2021, 12, 61 12 of 25

chloride was conducted on the inner surface of the polysulfone hollow fiber membrane
to improve the water permeation. The optimal mass ratios of m-phenylene diamine and
trimesoyl chloride were 2 wt% and 0.25 wt%, respectively. The H2 O permeance of the
membrane was found to be 1500 GPU. In addition, the H2 O/N2 selectivity was 500 [90].
Engelhard titanosilicate-4 was polymerized with polysulfone and polyamide. The amount
of Engelhard titanosilicate-4 was 4 wt%. The membrane was revealed as having 1377
GPU moisture permeance and 346 for the moisture selectivity [91]. Ingole et al. (2017)
combined 0.1 wt% 1,3-benzenedithiol with polyethersulfone to produce a permeation
membrane [92]. It was reported that the H2 O permeance was 2050 GPU and the H2 O/N2
ratio was 119. Moriyama et al. (2019) fabricated a 1,2-bis(triethoxysilyl)ethane (BTESE)
membrane by coating SiO2 –ZrO2 -derived sols onto an α-alumina porous tube [93]. It was
found that the H2 O permeance was 14,925 GPU and that the H2 O/N2 ratio was 160 [93].
Ahhtar et al. (2019) developed two kinds of membranes using a sulfonated penta block
copolymer [94]. For the first membrane, 2 wt% of the sulfonated penta block copolymer
was casted into a tetrahydrofuran solution. Its H2 O/N2 selectivity and H2 O permeability
were found to be approximately 420,000 and 553,000 Barrers, respectively. For the second
membrane, 2 wt% of the sulfonated penta block copolymer was also used to cast into
a solution comprising 85 wt% toluene and 25 wt% isopropanol. It was reported that
the H2 O/N2 selectivity was 24,000 and that H2 O permeability was 850,000 Barrers [94].
Phosphonic acid-based membranes supported by Nafion® 212 were developed by Leoga
et al. (2020) [95]. The substrate was pretreated by 100 W of plasma discharge. It was
reported that the H2 O permeance was approximately 1400 GPU [95]. Zhang et al. (2020)
modified a NaA Zeolite membrane on a hollow fiber using a WS2 nanosheet to improve
the removal of moisture at a low level [96]. It was reported that the membrane could
remove the moisture well at 0.5 wt% [96]. Deimede et al. (2020) casted a membrane
made of a pyridinium-based polymeric ionic liquid film containing a MeSO4 counter
anion [97]. It was reported that the membrane showed very high H2 O permeability and
H2 O/N2 selectivity compared to typical polymeric membranes. The highest permeability
was found to be about 184,000 Barrers. The highest selectivity was 1,840,000 [97]. The
H2 O permeance of the membrane was 5000 GPU. The rest of the development process of
membrane materials can be found elsewhere [37,80].
Nafion® membrane has been widely applied as a permeation method to remove
moisture in CEMS, most recently by [98–100]. Nafion® ionomers were first invented by
Dr. Walther Grot and produced as a commercial product by the DuPont company in the
1960s [101]. Perfluorinated vinyl ether comonomer was copolymerized with tetrafluo-
roethylene to create Nafion® [101]. Jetter et al. (2002) developed a two-stage moisture
removal device using a series of permeable tubes [100]. The difference between the two
stages was the temperature of the tubes. In the first stage, permeable tubes were heated up
to about 70 ◦ C to increase the dew point of the gas stream. In contrast, the second stage was
controlled at 0 ◦ C to enhance the moisture removal efficiency of the device. The moisture
level at the outlet of the device was reported as 700 ppmv with a 12 L/min purging rate.
This low-moisture sample is suitable for the FTIR analyzer [100]. The advantages of this
device are its high moisture removal efficiency and high moisture loading capacity. The
device can be applied to a high-temperature gas stream due to a heater at the first stage.
However, the energy consumption would be relatively high because of the temperature
control process. Wang et al. (2013) wrapped the Nafion® tube in a winding cylinder to
increase the length of the tube with a small-dimension device [99]. Nafion® tubes were
combined with a cold trap to remove the high moisture content from the stack gas. Firstly,
the sample gas was introduced into the Nafion® tubes, which were heated to the desired
sample temperature. Then, the sample gas temperature was reduced to −25 ◦ C in the cold
trap to remove more moisture. The device could remove moisture up to 50% absolute
humidity. The flow rate of sample gas was 50–1000 mL/min. That of dry gas should be
1–3 L/min. The device could operate with an inlet gas temperature of 25–65 ◦ C. It was
found that the outlet relative humidity could reach 15%. In addition, the device helped to
Atmosphere 2021, 12, 61 13 of 25

improve the detection of NO down to 50 ppbv in a high-moisture sample gas using an ion
transfer spectrograph [99]. The advantages of this device were its high moisture removal
efficiency and high moisture loading capacity. Using a Nafion® membrane also resulted in
high selectivity for many gases. The maximum inlet temperature was only 65 ◦ C, which
Atmosphere 2021, 12, x FOR PEER REVIEW 13 of 26
reveals the limitation of this device. Moreover, high energy consumption was another
drawback of the device.

Figure 7. Schematic diagram using a gas dryer coupled with a filtration device [85].
Figure 7. Schematic diagram using a gas dryer coupled with a filtration device [85].
Compared to the condensation method, the permeation method does not require
Nafion® membrane has been widely applied as a permeation method to remove
a condensate trap. In addition, the absorption of the target gas by the condensate is
moisture in CEMS, most recently by [98–100]. Nafion® ionomers were first invented by
avoided. However, condensed droplets could appear due to the different pressures, and
Dr. Walther Grot and produced as a commercial product by the DuPont company in the
the membrane could be plugged by particles. Using a filter to remove the particles before
1960s [101]. Perfluorinated
the membrane vinyl to
could cause water ether comonomer
condense was copolymerized
on the filter surface, which might with tetrafluoro-
also absorb
ethylene to create Nafion ® [101]. Jetter et al. (2002) developed a two-stage moisture re-
target gases [1]. The large dry gas consumption is another disadvantage of the permeation
moval
methoddevice using
[76]. The a series
selective of permeable
property tubes [100].isThe
of the membrane alsodifference
important.between
Son et al.the two
(2013)
stages was the temperature of the tubes. In the first stage, permeable
reported that using the permeation method for sulfur compound analysis resulted in tubes were heated
up to aboutlower
somewhat 70 °Cwater
to increase
removaltheefficiency
dew pointandof the gas loss
higher stream. In contrast,
of target the second
compounds stage
than using
was controlled at 0 °C to enhance the moisture removal efficiency of the
a Peltier-based cooling tube in certain conditions [52]. Lee et al. (2019) found that Nafion®device. The mois-
ture
causedlevel
theatloss
the of
outlet of the
methyl device
ethyl wasand
ketone reported
isobutylas 700 ppmv
alcohol with
(i.e., a 12atL/min
>40% 20–100 purging
ppbv
rate.
of theThis low-moisture
analyte and 50–80% sample is suitable
relative for the
humidity) FTIR
[102]. analyzer
It was [100]. The
also found thatadvantages
artifact (suchof
this device are its high moisture removal efficiency and high
as benzene) formation occurred when the permeation method was applied to remove moisture loading capacity.
The device
moisture in can be applied to process
the measurement a high-temperature
of hazardousgas stream
volatile due to
organic a heater at[103,104].
compounds the first
stage.InHowever, the energy consumption would be relatively high because
general, the permeation method had a higher recovery rate for most of the analytes, of the temper-
ature control
a higher process.
moisture Wangefficiency,
removal et al. (2013)
andwrapped the Nafion
no generation ® tube in a winding cylinder
of by-products compared to the
to increase the length of the tube with a small-dimension device [99]. Nafion® tubes were
combined with a cold trap to remove the high moisture content from the stack gas. Firstly,
the sample gas was introduced into the Nafion® tubes, which were heated to the desired
sample temperature. Then, the sample gas temperature was reduced to −25 °C in the cold
trap to remove more moisture. The device could remove moisture up to 50% absolute
Atmosphere 2021, 12, 61 14 of 25

condensation method. However, there are still certain limitations to the method such
as high cost, loss of certain compounds, and high consumption of dry air. Thus, the
continuous development of a high-selectivity membrane is necessary. Until now, the
Nafion® membrane has been widely applied to CEMS for highly water-soluble gases such
as SO2 , HCl, NH3 , and H2 S. Although the membrane itself sometimes caused the loss of
certain chemical compounds, the amount lost was in the acceptable range. A summary
of permeation devices is given in Table 3. The materials, advantages, disadvantages, and
recommendations of applicable analytes are given. A summary of the development of
membrane materials can be found in other review works [37,80].

Table 3. Development of permeation devices to remove moisture in the flue gas.

Membrane Recommendation of
No. Device Materials Advantages Disadvantages
Type Applicable Analytes
- A dry gas tank is - The device
unnecessary. is bulky
Any Any Target gases depended
Heater - The condensation - It consumes a lot
1 commercial commercial on membrane’s
cartridge [83] does not occur on of energy due to
membrane membrane specification.
the membrane the compressor
surface. and heater.
- The effect of
particles on the
Integral
membrane is
moisture Any Target gases depended
reduced. -Maintaining the
2 membrane and Polymer commercial on membrane’s
- The particle filter filters is costly.
particle product specification.
helps to enhance
filter [85]
the lifetime of the
membrane.
- The device has a
- The device may
high moisture
consume a lot of
removal efficiency.
energy The authors
Two-stage - Condensation
Perfluorinated - Particles may recommend the device
3 permeable Polymer cannot occur on the
polymer plastic damage the be used for an FTIR
tubes [100] membrane surface.
membrane surface analyzer.
- It shows a high
due to the absence
loading amount of
of a filter.
moisture.
- The device has a
high moisture
- The device may
removal efficiency. - Nafion® membrane
consume a lot of
Two-stage - Condensation has been widely
energy
winding cannot occur on the applied for CO, CO2 ,
4 Polymer Nafion® - Nafion®
cylinder membrane surface. NO, NO2 , HCl, NH3 ,
membrane is
device [99] - It has high loading H2 S, and SO2
sensitive to
of moisture. measurements.
particles.
- It shows a high
selectivity.

3.3. Dilution Method

Condensation and permeation methods are suitable for CEMS of gaseous compounds.
For particulate matter, the two methods cannot be employed due to the physical characteris-
tic of the particles. The U.S. EPA classified particulate matter into filterable and condensable
particulate matter [105]. Filterable particulate matter refers to particles emitted directly
by a source such as a solid or liquid at a stack or their release conditions and captured
on the filter of a stack test train [105]. Condensable particulate matter includes materials
that are in the vapor phase at stack conditions but condense and/or react upon cooling
 Atmosphere 2021, 12, 61 15 of 25

and dilution in the ambient air to form solid or liquid particulate matter immediately
after discharge from the stack [105]. In terms of particle size, primary PM2.5 or PM2.5 is
particulate matter with an aerodynamic diameter less than or equal to 2.5 µm [105]. PM2.5
consists of filterable PM2.5 and condensable particulate matter [105]. Primary PM10 or PM10
is particulate matter with an aerodynamic diameter less than or equal to 10 µm [105]. PM10
consists of filterable PM10 and condensable particulate matter [105]. Generally, particulate
matter emitted from a stack is continuously measured by three main techniques, including
direct extraction of high-temperature gasification coupled with laser scattering measure-
ment, high-temperature extractive dilution coupled with laser scattering measurement,
and alternating current coupled with charge induction, opacity meters, Beta attenuation
meters, or electrification devices. The direct extraction and the extractive dilution methods
are the most popular ones [17,106]. Furthermore, the dilution method is a standard method
recommended by the International Organization for Standardization ISO 25597:2013 [107]
as well as U.S. EPA CTM-039 [108] to measure primary PM2.5 and PM10 . Only condensable
particulate matter can be measured by the dry cooling impinger method [105,109] and the
dilution method [109]. Therefore, the dilution method was also reviewed in this study,
although it is not a direct moisture removal method. The simple principle of the dilution
method is presented in Figure 8. The ratio of dilution air to sample air should be at least
20:1 to maintain a relative humidity of the diluted sample of less than 70%. The
Atmosphere 2021, 12, x FOR PEER REVIEW filter
16 of 26
temperature should be maintained at approximately 42 ◦ C by either a high dilution ratio
or a heater [107].

Figure
Figure 8. 8. Schematic
Schematic diagram
diagram ofof a dilution
a dilution module
module [107].
[107].

The development of dilution systems has continued for decades. Hildemann et al.
The development of dilution systems has continued for decades. Hildemann et al.
(1989) invented a U-shaped dilution system for the measurement of organic aerosols emitted
(1989) invented a U-shaped dilution system for the measurement of organic aerosols emit-
from a stack [110]. The fundamental diagram of the invention is presented in Figure 9.
ted from a stack [110]. The fundamental diagram of the invention is presented in Figure
The body of the dilution tunnel and the residence time chamber were made of stainless
9. The body of the dilution tunnel and the residence time chamber were made of stainless
steel. The dilution ratio was 25–100-fold. The sampling flow rate was 30 L/min at 150 ◦ C.
steel. The dilution ratio was 25–100-fold. The sampling flow rate was 30 L/min at 150 °C.
It was reported that the loss of particles 1 µm and 2 µm in diameter was approximately
It was reported that the loss of particles 1 µm and 2 µm in diameter was approximately
7% and 15%, respectively. In the application of a field test at an oil-fired industrial boiler,
7% and 15%, respectively. In the application of a field test at an oil-fired industrial boiler,
using the dilution system was found to collect 10 times more organic carbon than using
using
U.S. the
EPAdilution
Methodsystem
5 [110].was found to
Although collect
this 10 times
dilution more
system organic
helped carbon
improve thethan using
particulate
U.S. EPA Method 5 [110]. Although this dilution system helped improve the particulate
matter measurement, its limitation was bulk (i.e., >17 kg). Therefore, the dilution system
matter measurement,
has kept improving toitsbecome
limitation wascompact.
more bulk (i.e.,
In>17 kg). Therefore,
addition, the dilution
the significant loss of system
particles
has kept improving to become more compact. In addition,
in the range of 1–2 µm was a drawback of this device. the significant loss of particles
in the range of 1‒2 µm was a drawback of this device.
 It was reported that the loss of particles 1 µm and 2 µm in diameter was approximately
7% and 15%, respectively. In the application of a field test at an oil-fired industrial boiler,
using the dilution system was found to collect 10 times more organic carbon than using
U.S. EPA Method 5 [110]. Although this dilution system helped improve the particulate
Atmosphere 2021, 12, 61
matter measurement, its limitation was bulk (i.e., >17 kg). Therefore, the dilution system
16 of 25
has kept improving to become more compact. In addition, the significant loss of particles
in the range of 1‒2 µm was a drawback of this device.

Figure 9. Dilution
Figure 9. Dilution system
system invented
invented by
by Hildemann
Hildemann et
et al.
al. [110].
[110].
Atmosphere 2021, 12, x FOR PEER REVIEW 17 of 26
Lipsky and Robinson (2005) developed a compact dilution system (Figure 10) [111].
Lipsky and Robinson (2005) developed a compact dilution system (Figure 10) [111].
The dilution system was made of stainless steel. The length and diameter of the mixing
The dilution system was made of stainless steel. The length and diameter of the mixing
chamber were 0.9 m and 0.15 m, respectively. The total air flow through the chamber was
chamber were 0.9 m and 0.15 m, respectively. The total air flow through ◦ C. the chamber was
174
174L/min.
L/min.The inlet
The airair
inlet temperature
temperature could
could bebe
varied
variedfrom
from150 150toto300
300°C. The
Thediluted
dilutedoutlet
outlet
air
airwas
wasapproximately ◦
approximately2727°C.C.The Thedilution
dilutionratioratiowaswas20‒350-fold.
20–350-fold.It Itwas wasfound
foundthatthatthe
the
measurement
measurementerrorserrorswere
wereless
lessthan
than10%
10%with withregard
regardtotoa alaboratory
laboratorytest testusing
usinga adiesel
diesel
generator
generatorand
anda awood
woodstove
stove[111].
[111].ForFora afield
fieldtest,
test,measurement
measurementerrors errorsvaried
variedfrom
from5%5%toto
18%.
18%.The
Thechange
changeininparticle
particleshape
shapewith withrespect
respecttotodilution
dilutionratios
ratioswas
wasalso
alsoaddressed.
addressed.The The
densities of PM were 0.5 g/cm 3
and 1.0 g/cm 3
for on dilution ratios
densities of PM2.5 were 0.5 g/cm and 1.0 g/cm for on dilution ratios of 20- and 160-fold,
2.5 3 3 of 20- and 160-fold,
respectively
respectively[111].
[111].The
Theadvantages
advantagesofofthis thisdevice
devicewere wereitsitscompact
compactsize sizeand
andfast
fastretention
retention
time.However,
time. However, the the significant
significant measurement
measurementbias biasand
andthethedependency
dependency of the
of particle shape
the particle
on the
shape ondilution ratio ratio
the dilution werewere
disadvantages
disadvantages of theofdevice.
the device.

10.AA
Figure10.
Figure compact
compact dilution
dilution system
system inventedbybyLipsky
invented Lipskyand
andRobinson
Robinson[111].
[111].

England et al. (2007) improved the compact dilution system and conducted field tests
England et al. (2007) improved the compact dilution system and conducted field tests
on gas-fired and oil-fired boilers [107]. The schematic diagram of this dilution system was
on gas-fired and oil-fired boilers [107]. The schematic diagram of this dilution system was
similar to that in [107]. The system consisted of a multiple parallel jet flow in order to
similar to that in [107]. The system consisted of a multiple parallel jet flow in order to
quickly mix the stack sample with air at a dilution ratio of 20:1, a mixing chamber to well
quickly mix the stack sample with air at a dilution ratio of 20:1, a mixing chamber to well
the sample mix with a retention time of 10 s; and a clean air generator to produce dilution
the sample mix with a retention time of 10 s; and a clean air generator to produce dilution
air (Figure 11). The device was designed for inlet sample temperatures below 175 ◦ C. The
air (Figure
weight of 11). The device
the dilution was was
system designed
aboutfor inlet
9 kg. sample
It was temperatures
reported below 175 detection
that the minimum °C. The
weight of the dilution system was about 93 kg. It was reported that the minimum
limit of the system was 0.13–1.2 mg/m with respect to 1 h sampling at 113 L/min. The detection
limit of the
relative system was error
measurement 0.13–1.2
of mg/m
3 with respect to 1 h sampling at 113 L/min. The
the method was 27–34% [112]. The advantages of this
relative measurement error of the method was 27–34% [112]. The advantages of this in-
vention were its compact size and low minimum detection limit. However, the device still
led to significant measurement bias.
 similar to that in [107]. The system consisted of a multiple parallel jet flow in order to
quickly mix the stack sample with air at a dilution ratio of 20:1, a mixing chamber to well
the sample mix with a retention time of 10 s; and a clean air generator to produce dilution
air (Figure 11). The device was designed for inlet sample temperatures below 175 °C. The
weight of the dilution system was about 9 kg. It was reported that the minimum detection
Atmosphere 2021, 12, 61 17 of 25
limit of the system was 0.13–1.2 mg/m3 with respect to 1 h sampling at 113 L/min. The
relative measurement error of the method was 27–34% [112]. The advantages of this in-
vention were its compact size and low minimum detection limit. However, the device still
invention
led to were
significant its compact bias.
measurement size and low minimum detection limit. However, the device
still led to significant measurement bias.

Atmosphere 2021, 12, x FOR PEER REVIEW 18 of 26

Figure
Figure 11. Schematic
11. Schematic diagram
diagram of a compact
of a compact dilution
dilution system
system invented
invented by England
by England et al.et[112].
al. [112].
(TMF:(TMF:
Teflon
Teflon membrane
membrane filter,
filter, QFF: QFF: quartz
quartz fiberfiber filters,
filters, SMPS:
SMPS: scanning
scanning mobility
mobility particle
particle sizer,
sizer, MFM:MFM: mass
massflow
flowmeter).
meter).
A multipollutant dilution sampling system was developed to measure not only par-
ticulate matter but also gaseous
A multipollutant pollutants
dilution emitted
sampling from
system a stationary
was developedsource such as
to measure carbon
not only partic-
dioxideulate
(COmatter
2), carbon monoxide (CO), nitrogen oxides (NOx), sulfur dioxide (SO2), oxygen
but also gaseous pollutants emitted from a stationary source such as carbon
(O2), and total(CO
dioxide volatile organic compounds (TVOCs) [113–115]. A 90° elbow residence
2 ), carbon monoxide (CO), nitrogen oxides (NOx ), sulfur dioxide (SO2 ), oxygen
chamber(O2 ), and total volatilesteel
made of stainless wascompounds
organic used to increase
(TVOCs)the residence
[113–115].time
A 90up to 28residence
◦ elbow s cham-
(Figureber
12).made
The air
of stainless steel was used to increase the residence time up to 28air
flow rate of the inlet sample was 5 L/min. That of the dilution was 12).
s (Figure
125 L/min.
The airTheflow
inletrate
air of
temperature was 146‒174
the inlet sample °C. TheThat
was 5 L/min. rangeofof
thedilution
dilutionratios was125
air was 20‒L/min.
5-fold.The
It was found
inlet that the relative
air temperature was 146-174 ◦
measurement
C. Theerror
rangewasof less thanratios
dilution 5.1% [113–115].
was 20-5-fold.The It was
invention
foundshowed advantages
that the for multiple functions.
relative measurement error wasFurthermore,
less than 5.1% the[113–115].
device alsoThe had a
invention
reasonable
showed measurement
advantageserror. However,
for multiple maintenance
functions. was anthe
Furthermore, issue duealso
device to its
hadcompli-
a reasonable
cated nature.
measurement error. However, maintenance was an issue due to its complicated nature.

Figure Figure 12. A Schematic

12. A Schematic of the multipollutant
of the multipollutant dilutiondilution
system system [113–115].
[113–115].

For ultra-low particulate matter emitted from a power plant, an electrical low-pres-
sure impactor has been widely applied to investigate the particle size distribution [116].
However, moisture in the flue gas caused a significant bias in the analytical process. An
increase in humidity resulted in an increase in measurement error. It was reported that
 Atmosphere 2021, 12, 61 18 of 25

For ultra-low particulate matter emitted from a power plant, an electrical low-pressure
impactor has been widely applied to investigate the particle size distribution [116]. How-
ever, moisture in the flue gas caused a significant bias in the analytical process. An increase
in humidity resulted in an increase in measurement error. It was reported that the mea-
surement error varied from 1000% to 2500% with respect to different particle sizes and
humidity [116]. Thus, a hybrid dilution system was developed to reduce the moisture
level in the sample gas (Figure 13). The system consisted of a dilution module and a
drying module. The dilution ratio was 8:1. The dilution module had the same structure
as in [107]. The temperature of the inlet gas should not be over 50 ◦ C. The drying module
was a Nafion® tube. It was claimed that the relative measurement errors of PM0.2 , PM1 ,
PM2.5 , and PM10 were within 10% at a relative humidity of 73.7% [116]. The advantage of
Atmosphere 2021, 12, x FOR PEER REVIEW
this invention was its enhanced measurement accuracy for ultra-low particulate19matter. of 26
Atmosphere 2021, 12, x FOR PEER REVIEW ® 19 of 26
However, using the Nafion tube led to an increase in capital cost. Maintenance cost was
also an issue for the system.

Figure 13. Schematic diagram of the hybrid dilution system for measuring low particulate matter
Figurefrom
Figure
emitted Schematic
13.Schematic
13. diagram
a power diagram
plant ofofthe
[116]. thehybrid
hybrid dilution
dilution system
system forfor measuring
measuring low
low particulate
particulate matter
matter
emitted from a power plant [116].
emitted from a power plant [116].
The methods mentioned above were developed to monitor only filterable particulate
Themethods
methodsmentioned
mentionedabove abovewere weredeveloped
developed tomonitor
monitor onlyfilterable
filterableparticulate
particulate
matterThe
or a combination of filterable and condensable to particulate onlymatter. To monitor only
matter
matter or
or aa combination
combination of
of filterable
filterable and
and condensable
condensable particulate
particulate matter.
matter. To
To monitor
monitor only
only
condensable particulate matter, Cano et al. (2017) improved the dilution method CTM-
condensable
condensable particulate
particulate matter, Cano et al. (2017) improved the dilution method CTM-039
039 of U.S. EPA (Figure 14)matter,
[117]. ACano filteret al. (2017)
module wasimproved
employedthe dilution
instead method
of a PM CTM-
2.5 cyclone.
of U.S.
039 of EPA
U.S. EPA (Figure
(Figure14)14)
[117].
[117]. AAfilter
filtermodule
module was
was employed
employed instead
instead of
of a PM
a PM2.5 cyclone.
2.5cyclone.
A quartz fiber filter was used to remove filterable particulate matter. Dilution ratios were
AAquartz
quartzfiber
10‒40-fold,
fiber filter
andfilter waswas
the inlet usedused to remove
to remove
air temperature
filterable
filterable
was in the
particulate matter.
particulate
range ofmatter.
190‒200Dilution
Dilution
°C [117]. ratios ratios
The were
ad-
were 10–40-fold, and theairinlet air temperature was inrange
the range of 190–200 ◦ C [117]. The
10‒40-fold,
vantage and
of this the inlet
method is the temperature
high accuracy was in
forfor the
thethe of
measurement 190‒200
ofof °C
only [117]. The
condensable ad-
advantage of
vantage ofmatter. this method
this method is the
is theit high high accuracy
accuracy measurement
for the measurement only
of onlythe condensable
condensable
particulate matter.However,
particulatematter. However, is is
it difficult
difficult totomaintain
maintainthe thefilter
filterholder
holderatat thesampling
atthe sampling
particulate
probe. The selection However,
ofof
filter size it is
mightdifficult
also to maintain
affect the filter holder sampling
probe. The selection filter size might also affectthe
theaccuracy
accuracyofofthe themeasurement.
measurement.
probe. The selection of filter size might also affect the accuracy of the measurement.

Figure 14. General schematic diagram of a dilution system for measuring condensable particulate
Figure 14. General schematic diagram of a dilution system for measuring condensable particulate
matter14.
Figure [117].
matter [117].General schematic diagram of a dilution system for measuring condensable particulate
matter [117].
In general, the dilution method is useful for the measurement of particulate matter
In general,
because the dilution
it can reduce method
the effect of theishigh
useful for thewithout
moisture measurement
causingofaparticulate matter
loss of particles.
because it can reduce the effect of the high moisture without causing a loss
Another advantage of the dilution method is the minimization of the contamination of theof particles.
Another
system advantage
because of the dilution
the volume of samplemethod is the minimization
gas extracted of the
from the stack contamination
is small of the
[23]. However,
system because the volume of sample gas extracted from the stack is small [23].
this method has some limitations. The dilution might bring about a decrease in the num- However,
Atmosphere 2021, 12, 61 19 of 25

In general, the dilution method is useful for the measurement of particulate matter
because it can reduce the effect of the high moisture without causing a loss of particles.
Another advantage of the dilution method is the minimization of the contamination of the
system because the volume of sample gas extracted from the stack is small [23]. However,
this method has some limitations. The dilution might bring about a decrease in the number
of particles in the flue gas. If this number is lower than the detection limit of the analyzer,
bias will occur. In addition, the method is not suitable for the high vacuum, high pressure,
and high temperature (i.e., >260 ◦ C) of the gas stream [107]. The condensation of certain
organic and acid compounds could occur because of cooling by the dilution air [23].
Moreover, high variations in the concentration, velocity, and temperature of the flue gas
can influence the measurement results [107]. Finally, the stratification of the emission
gas also results in an increase in measurement error when the emission gas is not mixed
well [107]. The dilution method is strongly affected by temperature, pressure, and sample
gas molecular weight [22]. This is a limitation of the dilution method. Correction factors
should be applied to counteract these effects.
Since the dilution method reduced a high-temperature sample gas down to an ambi-
ent level, the condensable particulate matter could be generated [111]. This condensation
process could occur in the dilution system when the phase equilibrium of condensable com-
pounds was less than their residence time in the dilution system [111]. This equilibration
time can be estimated by Equation (4) [111]:

1
τs = R∞ (4)
4πD A 0 n( R P ) R P f (Kn , α)dR P

where DA is the gas diffusivity (~0.06 cm2 /s), n(RP ) is the number of particles at radius RP ,
f (Kn , α) corrects the mass flux for non continuum effects and imperfect accommodation,
and α is the accommodation coefficient. The Fuchs and Sutugin approach could be used to
evaluate f (Kn , α) and α [111].
Based on Equation (4), a dilution chamber could be designed to measure only the
filterable particulate matter or both filterable and condensable particulate matter. To date,
unfortunately, there is no reliable dilution system that can measure filterable and condens-
able particulate matter independently. Using two dilution systems with different volumes
or different sampling ports with respect to retention time could be a potential method to
separate filterable and condensable particulate matter. Various dilution systems are shown
in Table 4. The characteristics, advantages, disadvantages, and application of each device
are given below.

Table 4. Development of dilution systems for particulate matter measurement.

No. Method Characteristics Advantages Disadvantages Application

- Flow rate: 30 L/min
- Bulky system
- Gas temperature: Condensable plus
U-shaped dilution Able to improve the - Significant loss of
1 150 ◦ C filterable
system [110] collection of organic carbon particle in the size
- Dilution ratio: particulate matter
range of 1–2 µm
25–100-fold
- Compact size due to
absence of residence time - Potential change
- Flow rate: 174 L/min
tank of particle shape
- Gas temperature:
Compact dilution - Retention time of sample according to Filterable
2 150–300 ◦ C
system [111] gas < 1 s dilution ratio particulate matter
- Dilution ratio:
- Able to operate at a high - Potential for
20–350-fold
and wide temperature range significant bias
of inlet gas
Atmosphere 2021, 12, 61 20 of 25

Table 4. Cont.

No. Method Characteristics Advantages Disadvantages Application

- Flow rate: 113 L/min
Compact dilution - Gas temperature:
3 - Low minimum detection
system [112] <175 ◦ C
limit of particles compared
- Dilution ratio: 20:1
- Flow rate: 125 L/min
- Gas temperature:
90◦elbow dilution
4 146–174 ◦ C
chamber [113–115]
- Dilution ratio:
20–50-fold
Hybrid dilution
◦C
system coupled - Gas temperature: 50
5 ultra-low particulate matter
with Nafion® - Dilution ratio: 8:1
dryer [116]
Dilution system
- Gas temperature:
with a filter for
190–200 ◦ C
6 filterable
- Dilution ratio:
particulate
10–40-fold
matter [117]
- Small dimensions of the
system - Potential for Condensable plus
significant bias filterable
(27–34%) particulate matter
to a standard method
- Compact size
- Various functions for - Complicated Condensable plus
particulate and gaseous structure filterable
measurements- Low - Hard to maintain particulate matter
measurement bias
- Suitable for a wide range
of particles, especially - Costly due to
Filterable
Nafion® dryer
particulate matter
- Low measurement bias - Hard to maintain
caused by humidity
- Highly accurate for - Hard to maintain
Condensable
condensable particulate - Potential bias due
particulate matter
matter to pore filter size

4. Conclusions
Condensation and permeation are the two general techniques used to remove mois-
ture from flue gas in a CEMS for gaseous compounds. In condensation techniques, the
moisture is removed under liquid or solid phase due to the decrease in flue gas temper-
ature to a dew point. The correction factors or optimal operation conditions should be
determined when employing these technologies. In addition, the condensation methods
should only be applied for very poorly water-soluble compounds to prevent the loss of
analytes. The permeation method seems to be a better technology in terms of moisture
removal efficiency and selectivity. Polymeric membranes were found to be the most widely
used membrane to remove moisture in flue gas besides zeolite, mixed matrix, and sup-
ported liquid membranes [37]. For decades, 19 main kinds of polymeric materials have
been developed in order to remove the moisture. Various fabrication methods have been
conducted with different substrates to improve the moisture removal efficiency and the
membrane selectivity. However, the large amount of dry gas and the lower amount of
sample gas are significant drawbacks of the permeation method. In addition, the loss of
some target compounds, artifact formation, and contamination in the membrane were
found when the permeation method was employed to remove moisture.
In terms of particulate matter, the dilution method has been widely implemented.
The dilution ratio should be carefully considered based on the detection limit of an analyzer
to prevent measurement bias. The effect of dilution ratios on the shape of particulate
matter should also be taken into account. The influence of the pressure, temperature, and
molecular weight of target compounds should be corrected. These are also limitations of
the method. Moreover, the measurement error of the particulate matter using the method
is still significant.
Accordingly, studies to find the best technology for moisture removal should be
carried out. As for the condensation method, the removal of moisture at super-cooling
conditions under a solid phase might be a potential way. The relationship between the
polarities of water and target gases at different phases should be taken into account in
order to predict the extent of their loss. The development of an effective catalytic converter
to convert highly water-soluble analytes to poorly or non-water-soluble ones might be a
Atmosphere 2021, 12, 61 21 of 25

promising solution for the application of the condensation method. In terms of permeation
techniques, the influence of strong oxidative compounds and fine particles on membranes
should be carefully investigated. Their lifetime should be considered as well. On the other
hand, the dilution method is not the best technique for particulate matter measurement.
Other methods that can remove the moisture without damaging particles may be an
alternative. Furthermore, the development of a dilution system that can independently
measure filterable and condensable particulate matter should be considered.

Supplementary Materials: The following are available online at https://www.mdpi.com/2073-443

3/12/1/61/s1: Table S1: Experimental results of water removal under solid phase (−20 ◦ C) for HCl
flue gas sample; Table S2: Experimental results of water removal for SO2 flue gas sample.
Author Contributions: J.-C.K. and T.-V.D. conceptualized the work. T.-V.D. wrote the original draft,
and the review and editing were done by J.-C.K. All authors have read and agreed to the published
version of the manuscript.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Acknowledgments: This paper was supported by Konkuk University Researcher Fund in 2019.
Conflicts of Interest: The authors declare no conflict of interest.

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