energies
Article
Treatment of Flue Gas in a CO2 Capture Pilot Plant for a
Commercial CFB Boiler
Izabela Majchrzak-Kuc˛eba 1, * , Dariusz Wawrzyńczak 1 , Janusz Zdeb 2 , Wojciech Smółka 2 and
Artur Zajchowski 2






Citation: Majchrzak-Kuc˛eba, I.;
Wawrzyńczak, D.; Zdeb, J.; Smółka,
W.; Zajchowski, A. Treatment of Flue
Gas in a CO2 Capture Pilot Plant for a
Commercial CFB Boiler. Energies 2021,
14, 2458. https://doi.org/10.3390/
en14092458
Academic Editor: José Carlos
Magalhães Pires
Received: 16 March 2021
Accepted: 24 April 2021
Published: 26 April 2021
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Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Energies 2021, 14, 2458. https://doi.org/10.3390/en14092458
1 Department of Advanced Energy Technologies, Faculty of Infrastructure and Environment,
Czestochowa University of Technology, Dabrowskiego Street 73, 42-201 Czestochowa, Poland;
dariusz.wawrzynczak@pcz.pl
2 TAURON Wytwarzanie S.A., Promienna Street 51, 43-603 Jaworzno, Poland;
Janusz.Zdeb@tauron-wytwarzanie.pl (J.Z.); Wojciech.Smolka@tauron-wytwarzanie.pl (W.S.);
Artur.Zajchowski@tauron-wytwarzanie.pl (A.Z.)
* Correspondence: izabela.majchrzak-kuceba@pcz.pl; Tel.: +48-343250463
Abstract: The problem of reducing carbon dioxide emissions from flue gas, particularly from flue gas
originating from coal-firing CFB systems, is currently an important challenge. Many centers around
the world have tested post-combustion CO2 capture systems. One of these systems, operated using
DR-VPSA adsorption technology (dual-reflux vacuum pressure swing adsorption), was tested under
the Strategic Project in Poland. The flue gas in this study originated from a supercritical CFB boiler
(460 MWe). An important problem involved in capturing CO2 from flue gas is the occurrence of
SO2 and NOx . These substances have a negative effect on the CO2 adsorption process. In this study,
commercial impregnated activated carbon was used to remove SO2 and NOx from CFB flue gas in
the pre-treatment section during the tests of a pilot CO2 capture unit in a large-scale CFB boiler at
the Lagisza Power Plant (Poland). The spent activated carbon was analyzed using several different
methods (N2 adsorption–desorption isotherms, SEM-EDX, XRD, FTIR, and TG) to evaluate the
efficiency of the operation and life span of the adsorbent used in the SO2 and NOx removal unit. The
results demonstrate that using commercial impregnated activated carbon in the pre-treatment section
ensures sufficient flue gas purification and the removal of sulfur oxides but remains insufficient for
nitrogen oxides.
Keywords: flue gas; CO2 capture; DR-VPSA; CFB boiler; SO2 /NOx removal
1. Introduction
Reducing the emissions of CO2 and other greenhouse gases contributing to global
warming is a global challenge. Among the many proposed CO2 emission reduction
solutions is CCSU (carbon capture and storage/utilization), which enables CO2 to be
captured and then stored or utilized by processing it into a usable product such as methanol
using renewable energy sources [1,2]. The most developed and advanced CO2 capture
technologies are amine-based absorption systems such as the large-scale absorption units
operating at the coal-fired Boundary Dam power plant in Canada and at the coal-fired Petra
Nova power plant in Texas in the United States [2]. Another dynamically developing CO2
capture technology is the solid adsorbent-based adsorption technique involving vacuum
pressure swing adsorption (VPSA) technology [3–9]. To date, at a pilot scale and under
real power plant conditions, adsorption units for CO2 capture on fixed beds have been
tested in Japan [4,5], China [6], Australia [7], and Poland [8,9]. According to the tests
carried out on all pilot adsorption CO2 capture units treating real flue gas [4–9], one of
the most important factors influencing the effectiveness of CO2 adsorption is the content
of H2 O and other impurities such as SO2 , NOx , dust, alkalis, and volatile metals in the
flue gas [10–16]. These components have negative effects on the physical adsorbents
https://www.mdpi.com/journal/energies
 Energies
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the adsorption used in the (activated

method adsorptioncarbon method (activated zeolites
[4–9,17–19], carbon [4–9,17–19], zeolites [4–9],
[4–9], metal–organic frame-metal–organic
works [20,21], frameworks
and mesoporous[20,21],silicaand [22]),
mesoporous
thereby silica
reducing[22]), thereby
their reducingcapacity,
CO2 sorption their CO2 sorption
which affectscapacity,
CO2 purity which
andaffects CO2Meanwhile,
recovery. purity and recovery.
many growing Meanwhile, many recycling
present-day growing present-day
methods for recycling
CO2 captured methods
from for CO2plants
power captured from branches
and other power plants and other
of industry branches
require clean of industry
CO2 streams.require cleanthe
Moreover, CO2presence
streams.of Moreover, the presence
the above-listed of the above-listed
impurities impurities accelerates
accelerates deactiva-
tion of the CO deactivation
2 adsorbent,of the COmore
making 2 adsorbent,
frequentmaking more frequent
replacement replacement
of the adsorbent of the adsorbent
necessary
necessary and thus increasing total costs
and thus increasing total costs of capturing CO2 from flue gas. Therefore, of capturing CO 2 it is importantTherefore, it
from flue gas.
is important to ensure the effective
to ensure the effective removal of SO2 and NOx from flue gas before removal of SO 2 and NO
the COx from flue gas before the
2 adsorption

process becauseCO2bothadsorption
SO2 andprocess
NOx canbecause
adsorb both
and/or SOreact
2 and NOCO
with x can adsorb and/or
2 adsorption materials react with CO2
adsorption
[10–19]. Similar materialsabsorption
to amine-based [10–19]. Similar
systems to amine-based
[23], the SO2 absorption
and NOx contentsystems in[23],
flue the SO2 and
NO 3 before the flue gas is sent to the CO
gas should be x content
ca. 10 mg/Nm in flue gas the
3 before should
flue be
gasca.
is 10
sentmg/Nm
to the CO 2 adsorption unit, while 2
adsorption unit, while the limits of SO 2 and NO x
the limits of SO2 and NOx emissions from flue gas needed for coal power plants in the EUemissions from flue gas needed for coal
3 [24]. As a result, all pilot CO separation
are now 200 power
mg/Nm plants
3 [24]. in
Asthe EU are
a result, allnow
pilot200
COmg/Nm
2 separation units described in the liter-2

ature comprise units described in sections

pre-treatment the literature comprise
designed to dry pre-treatment
and purify flue sections designed
gas, which to dry and purify
primar-
flue gas, which primarily involves the
ily involves the removal of SO2 and NOx before it is sent to the CO removal of SO and NO
2 2 capture before it
x section. Thisis sent to the CO2
assignment is impacted by using various methods and adsorbents (Figure 1). Regrettably, adsorbents
capture section. This assignment is impacted by using various methods and
(Figure 1). Regrettably, there is little information concerning the functioning of these units,
there is little information concerning the functioning of these units, their efficiency, and
their efficiency, and the effectiveness of adsorbents used to remove SO and NO [4,7]. For
the effectiveness of adsorbents used to remove SO2 and NOx [4,7]. For flue gas2 drying x
flue gas drying alongside the removal of SO2 and NOx in a pilot VPSA CO2 capture unit,
alongside the removal of SO2 and NOx in a pilot VPSA CO 2 capture unit, Wang et al. [6]
Wang et al. [6] proposed a pre-treatment unit consisting of a two-column TSA (temperature
proposed a pre-treatment unit consisting of a two-column TSA (temperature swing ad-
swing adsorption) module in which 156 kg of alumina was used as the adsorbent [6]. This
sorption) module in which 156 kg of alumina was used as the adsorbent [6]. This adsor-
adsorbent was also used by Ishibasi et al. as a packing material in a PSA (pressure swing
bent was also used by Ishibasi et al. as a packing material in a PSA (pressure swing ad-
adsorption) unit employed as the pre-treatment section for flue gas drying and additional
sorption) unit employed as the pre-treatment section for flue gas drying and additional
SO2 removal in an adsorption CO2 capture unit [4,5]. Studies demonstrated that in addition
SO2 removal in an adsorption CO2 capture unit [4,5]. Studies demonstrated that in addi-
to adsorbing moisture, the applied alumina also co-adsorbed CO2 . As a result of these
tion to adsorbing moisture, the applied alumina also co-adsorbed CO2. As a result of these
tests, it was observed that in the primary stage, alumina acted as a moisture absorbent and
tests, it was observed that in the primary stage, alumina acted as a moisture absorbent
also captured SO2 in the form of sulfuric acid and aluminum sulfate, which was found in
and also captured SO2 in the
an adsorbent form
taken of sulfuric
from acid and
the bottom part aluminum sulfate, column.
of the adsorption which was found
It was demonstrated
in an adsorbent taken from the bottom part of the adsorption column. It was
that this result did not affect dryer efficiency. The SO2 removal was so effective that no demonstrated
that this result
SO2did not affect dryer
accumulation efficiency.inThe
was observed theSO CO2 removal was so effective that no
2 adsorbent removed after 2000 h of use in a
SO2 accumulation was observed in the CO 2 adsorbent removed after 2000 h of use in a
PTSA/PSA adsorption unit installed to capture CO2 . These studies confirmed that the
PTSA/PSA adsorption
applied aluminaunit installed
workedtoascaptureboth a CO 2. These studies confirmed that the ap-
moisture adsorbent and as a filter protecting against
plied alumina worked
SO2 . as both a moisture adsorbent and as a filter protecting against SO2.

Figure 1. sections
Figure 1. Pre-treatment Pre-treatment sections
in global in global pilot
pilot adsorption CO2adsorption CO(PTSA:
capture units 2 capture units (PTSA:
pressure pressure
temperature tem-
swing adsorption;
perature swing adsorption; PSA: pressure swing adsorption; VSA: vacuum swing adsorption;
PSA: pressure swing adsorption; VSA: vacuum swing adsorption; VPSA: vacuum pressure swing adsorption; DR-VPSA:
VPSA:pressure
dual-reflux vacuum vacuum swing
pressure swing adsorption; DR-VPSA: dual-reflux vacuum pressure swing adsorp-
adsorption).
tion).
Energies 2021, 14, 2458 3 of 15

On the other hand, in the solution proposed by Qader et al. [7], no separate unit for
the drying and removal of SO2 and NOx from flue gas was used, but the pre-treatment
unit’s function was affected by an adsorber column with multiple layers, removing
H2 O/SO2 /NOx in the first layer of the adsorbent and CO2 in the second layer [7]. Multi-
layer adsorbents were applied in this solution: The first layer consisted of adsorbents used
to remove water and SO2 /NOx from flue gas, and the second consisted of adsorbents
selective to CO2 . This system’s functionality demonstrated that SO2 and NOx not captured
from flue gas may cause blower corrosion induced by generated sulfuric acid. Thus, the
elimination of SO2 , NOx , and water from flue gas is required in the commercial use of
adsorption installations for capturing CO2 because these impurities may negatively affect
the functionality of the installation elements. A different solution was employed in a Polish
installation [8] where the pre-treatment section consisted of three different subsections:
a cooling and heat recovery section, desulfurization and NOx removal adsorbers, and a
drying section. To date, only in this solution were far flue gas drying and the removal of
SO2 and NOx carried out in separate sections. Another innovation was to use activated
carbon impregnated with potassium hydroxide and potassium iodide for the simultaneous
removal of SO2 and NOx [8]. This adsorbent was chosen because impregnated activated
carbon was proposed, primarily for the simultaneous removal of SO2 and NOx . While
the adsorption of gases on activated carbon is predominantly driven by physisorption,
that of the modified carbon surface is driven by both physisorption and chemisorption.
Modification of the AC surface is necessary to improve attraction between the adsorbent
and target gases, resulting in a higher adsorption capacity of gases, especially at low gas
concentrations in the flue gas. As an impregnating substance, KOH is known to have an
excellent selective adsorption capacity for acid gases. An AC upgraded by impregnating it
with KOH and KI promoted chemisorption with SO2 and NOx [25–30].
Moreover, no data are available on the use of activated carbon impregnated with
KOH/KJ for the simultaneous removal of SO2 and NOx in pilot adsorption CO2 capture
installations under the operational conditions of large-scale CFB facilities. Valuable pilot
plant data from commercial CFB units are presented in this work. Only a few studies have
been devoted to the impacts of impurities such as SO2 and NOx on CO2 adsorption by
VSA (vacuum swing adsorption) [13] in the extant literature. Considering this factor, the
present article focuses on assessing the efficiency of applied adsorbents in the removal
of SO2 and NOx from flue gas prior to the CO2 removal process at the Lagisza Power
Plant. To assess the efficiency of using impregnated activated carbon in pre-treatment units
to remove SO2 and NOx from CFB (circulating fluidized bed) flue gas, a comprehensive
analysis of the adsorbents was carried out before and after their use in the desulfurization
and NOx removal section in a pilot adsorption (DR-VPSA) CO2 capture unit under typical
flue gas conditions. Studies of this type have not been reported in the CFB literature. Many
articles discuss and focus on H2 O impacts on CO2 sorption in adsorption installations, but
there are no detailed analyses regarding effective SOx and NOx removal from flue gas. The
available literature rarely reports real CFB flue gas treatments. Studies of this type would
not only help us understand the principles of impurity adsorption and the efficiency of
applied adsorbents but would also provide valuable data for the design of adsorption-
based demonstration CO2 capture installations. The purpose of the current research was to
understand simultaneous SO2 and NOx adsorption on impregnated activated carbon at
the stage of CFB flue gas pre-treatment in post-combustion CO2 capture. Evaluation of the
desulfurization/denitrification mechanism was performed through spent activated carbon
post-analysis.

2. Experimental Section
2.1. Pre-Treatment Section in a Pilot-Scale DR-VPSA Carbon Capture Unit
In 2015–2016, under the Strategic Project financed by NCBiR (the National Centre for
Research and Development) in Poland, research was carried out on post-combustion CO2
capture in a pilot DR-VPSA mobile unit located at Tauron Wytwarzanie S.A.—The Lagisza
 Energies 2021, 14, x FOR PEER REVIEW 4 of 16
Energies 2021, 14, 2458 4 of 15

capture in a pilot DR-VPSA mobile unit located at Tauron Wytwarzanie S.A.—The

Power
Lagisza Plant
Powerin Poland. The flueThe
Plant in Poland. gasflue
originated from the
gas originated world’s
from first supercritical
the world’s CFB
first supercritical
boiler (460 MW
CFB boiler e ).MW
(460 Thee).mobile CO2 capture
The mobile unit consisted
CO2 capture of a flueofgas
unit consisted pre-treatment
a flue section
gas pre-treatment
and a carbon
section and adioxide
carbonseparation section (four-bed
dioxide separation section DR-VPSA) (Figure 2). (Figure
(four-bed DR-VPSA) In the proposed
2). In the
solution, a complex pre-treatment section was used for the first time
proposed solution, a complex pre-treatment section was used for the first time and and compared to other
com-
pilot CO adsorption units [4–7]. The pre-treatment unit consisted of heat
pared to2 other pilot CO2 adsorption units [4–7]. The pre-treatment unit consisted of heat exchangers, an
isothermal
exchangers, absorber, a deSOxabsorber,
an isothermal and deNO x adsorber,
a deSO and a xglycolic
x and deNO adsorber, gasanddehydration
a glycolicsystem.
gas de-
The CO2 separation
hydration system. Theunit CO
consisted of fourunit
2 separation two-section
consisted adsorbers [8]. Detailedadsorbers
of four two-section information[8].
about the mobile pilot DR-VPSA unit and the performed tests
Detailed information about the mobile pilot DR-VPSA unit and the performed tests isis available in previous
studies
available[8,9]. The present
in previous article
studies focuses
[8,9]. only onarticle
The present the functionality
focuses onlyofon desulfurization
the functionalityandof
the NO removal adsorber, which is an element of the flue gas pre-treatment
desulfurization and the NOx removal adsorber, which is an element of the flue gas pre-
x section. More
specifically, this study
treatment section. focuses
More on evaluating
specifically, this the desulfurization/denitrification
study focuses on evaluating the mechanism desulfuriza-
through spent activated carbon post-analysis.
tion/denitrification mechanism through spent activated carbon post-analysis.

Figure2.2.The
Figure Thescheme
schemeofofthe
thepilot
pilotDR-VPSA
DR-VPSAunit
unitincluding
includingthe
thelocations
locationsof
ofthe
theAC
ACsample
sampleretrieval
retrieval
for analysis purposes (1, 2: flue gas drawing locations).
for analysis purposes (1, 2: flue gas drawing locations).

Beforethe
Before theflue
fluegas gasgenerated
generatedininLagiszaLagiszaPower PowerPlant Plantwas wassent
senttotothe thepilot
pilotfour-bed
four-bed
DR-VPSA unit, the following impurities were removed
DR-VPSA unit, the following impurities were removed from the gas at the plant: from the gas at the plant: SOSO 2, us-
2,
ing a dry desulfurization method, and NO , using selective,
using a dry desulfurization method, and NOx , using selective, non-catalytic reduction. The
x non-catalytic reduction. The
resultingaverage
resulting averageSO SO andNO
2 2and NOxxcontent
contentin inthe
theflue
fluegasgasfrom
fromthe theCFB
CFBboiler
boilerwas wasas asfollows:
follows:
SO2 2of
SO of 154.6 mg/Nm33and
154.6 mg/Nm andNO NO x of 179.8
x of mg/Nm
179.8 mg/Nm 3 [8].
3 [8]. These content
These levelslevels
content satisfy the appli-
satisfy the
cable emission
applicable emissionstandards
standards for these gases
for these but remain
gases but remain too high
too highfor COfor2COcapture
2 units.
capture As
units. a
result,
As the the
a result, CO2CO capture
2 captureinstallations
installations need a
need pre-treatment
a pre-treatment section to
section reduce
to reducethe SO
the SO
2 and
2
NONO
and x from the flue gas to ca.to10ca.mg/Nm 3 . Effective
3. Effective SO2 andSO NO x removal in this section
in thisis
x from the flue gas 10 mg/Nm 2 and NOx removal
essential
section because this
is essential removal
because this affects
removal the puritythe
affects of purity
the COof 2 captured in the COin
the CO2 captured 2 separation
the CO2
unit [9], which
separation is important
unit [9], for recycling
which is important the obtained
for recycling CO2 stream.
the obtained CO2Manystream. of the
Many proposed
of the
proposed
recyclingrecycling
methodsmethods require arequire a high-purity
high-purity CO2 stream. CO2 For
stream. For example,
example, NOx canNO be xacan be a
problem
problem
in the CO in2 the CO2ifstream
stream the stream if theisstream
intended is intended
to be used to in
bethe
usedfoodin the
andfood
beverageand beverage
industry.
industry.
2.2. Characterization of the Adsorbent Used in the deSOx and deNOx Adsorber
2.2. Characterization of the Adsorbent Used in the deSOx and deNOx Adsorber
Activated carbon (AC-P) Airpel 10 impregnated with potassium iodide KI (ca. 2
Activated
wt.%) and KOH carbon(ca. 3(AC-P)
wt.%) Airpel 10 impregnated
manufactured by DESOTEC with potassium
ActivatediodideCarbon KI was
(ca. 2used
wt.%) for
and
the simultaneous removal of SO2 and NOx in the flue gas pre-treatment section pilot the
KOH (ca. 3 wt.%) manufactured by DESOTEC Activated Carbon was used for DR-
simultaneous
VPSA CO2 capture removalunit. of SOThis2 andcarbon
NOx in(130the flue
kg) gaswaspre-treatment
used as packing section in pilot DR-VPSA
the deSOx and
CO 2
deNOx capture unit. This carbon (130 kg) was used as packing
adsorber (Figure 3). The activated carbon (AC-P) in this study was granulated in the deSOx and deNOx
adsorber
activated(Figure
carbon3). The activated
produced carbon (AC-P)
from anthracite with ainpellet
this study
radiuswas granulated
of >2.36 activated
(99% mass), den-
carbon produced
sity of 520 from anthracite with a pellet radius of >2.36
kg/m , water vapor capacity of 40.1%, and a highly developed surface of2 959
3 (99% mass), density of
3
5202 kg/m , water vapor capacity of 40.1%, and a highly developed surface of 959 m /g.
m /g. While the adsorption of gases on porous activated carbon is driven primarily by
While the adsorption of gases on porous activated carbon is driven primarily by physical
physical adsorption, in the case of a modified carbon surface (KOH), the adsorption of
adsorption, in the case of a modified carbon surface (KOH), the adsorption of gases is
gases is driven by both physical adsorption and chemisorption with a chemical reaction
driven by both physical adsorption and chemisorption with a chemical reaction between
the surface function groups and adsorbed gases. AC surface modification is necessary to
 Energies 2021, 14, x FOR PEER REVIEW 5 of 16
Energies 2021, 14, 2458 5 of 15

between the surface function groups and adsorbed gases. AC surface modification is nec-
improve
essary tothe pull between
improve the pullthe adsorbent
between theand gases, especially
adsorbent and gases,when the gaswhen
especially concentration
the gas con-in
flue gases isinlow.
centration flueThis
gasestype
is of modification
low. This type of is required to increase
modification the alkalinity
is required to increaseandthegeneral
alka-
chemistry of the carbon
linity and general surface
chemistry under
of the the surface
carbon pull of under
strongly thepolarized SO2 gas.
pull of strongly Potassium
polarized SO2
iodide performs the role of an “oxygen carrier”.
gas. Potassium iodide performs the role of an “oxygen carrier”. The deSO x and deNO
The deSO adsorber
x x and deNOx was
designed to reduce SO2totoreduce
ca. 10SOmg/Nm 3 3 . The 3deSO and
adsorber was designed 2 to ca. 10and
mg/Nm NOx3 andto 40NO mg/Nm
x to 40 mg/Nm . The xdeSOx
deNO x adsorber
and deNO functioned
x adsorber continuously
functioned continuously for 808
for h
808in hthe
in pilot CO2CO
the pilot capture installation
2 capture installa-
(DR-VPSA)
tion (DR-VPSA) underunder
the operational conditions
the operational of a large-scale
conditions of a large-scaleCFB facility. The activated
CFB facility. The acti-
carbon (AC-P)(AC-P)
vated carbon samples were were
samples takentaken
for analysis afterwards.
for analysis afterwards. Replacement
Replacement of of
thethe
AC-P
AC-
sorbent that filled the deSO /deNO adsorber was not necessary after
P sorbent that filled the deSOx/deNOx adsorber was not necessary after 808 h of DR-VPSA
x x 808 h of DR-VPSA
operation
operation because
because no no increase
increase waswasobserved
observedininthe theSO SO 2 concentration
2 concentration at at
thethe outlet
outlet of
of the
the column. If necessary, regeneration of the spent adsorbent was
column. If necessary, regeneration of the spent adsorbent was carried out using the acti-carried out using the
activated carbon
vated carbon producer
producer (DESOTEC
(DESOTEC Activated
Activated Carbon).
Carbon). Figure Figure
3 shows3 shows the locations
the locations where
where activated carbon samples were retrieved for the tests (bottom,
activated carbon samples were retrieved for the tests (bottom, middle, and top of the ad- middle, and top of
the adsorption
sorption column). column).

Figure3.3. Retrieval
Figure Retrievallocations
locationsfor
forthe
theactivated
activatedcarbon
carbon AC-P
AC-P used
used as as packing
packing forfor
thethe deSOx
deSOx andand
deNOx
deNOx adsorber in the pilot DR-VPSA CO2 capture unit.
adsorber in the pilot DR-VPSA CO2 capture unit.

Thespent
The spent activated
activated carbon
carbon was analyzed
was analyzed using different
using different methodsmethods (N2 adsorption–
(N2 adsorption–desorption
desorption isotherms, SEM-EDX, XRD, FTIR, and TG) to evaluate the
isotherms, SEM-EDX, XRD, FTIR, and TG) to evaluate the desulfurization/denitrification desulfurization/de-
nitrification efficiency
mechanism, mechanism, efficiency and
of operation, of operation,
durabilityand durability
of the adsorbent ofused
the adsorbent
in the deSO used
x and
in
the deSO
deNO x x and deNO
adsorber. The adsorber.
x impregnated The impregnated
activated carbonactivated
AC-P carbon
was also AC-P was also
characterized charac-
before
terizedused
being before being
in the deSOused in the
x and deNOdeSO x and deNO
x adsorber. adsorber.
AxLeco A Leco
Elemental Elemental
Analyser CHNSAnalyser
was
CHNS was used to assess the AC-P chemical composition. The porous
used to assess the AC-P chemical composition. The porous properties of AC-P activated properties of AC-
P activated carbon after 808 h of use in deSOx and deNO adsorber
carbon after 808 h of use in deSOx and deNOx adsorber were assessed based on the N2
x were assessed based
on the N2 adsorption–desorption
adsorption–desorption −196 ◦ C using
isotherm atisotherm at −196a Micromeritics
°C using a Micromeritics
model ASAP model
2010. ASAP
Prior
2010.
to the Prior to the measurements,
measurements, the sample was the sample
outgassedwasatoutgassed
473 K under at 473
an NK2under an at
flow for N2least
flow3forh.
at least
The BET3method
h. The BET method
was then usedwas then used the
to determine to determine the specific
specific surface area ofsurface
the AC-P,area
andof the
the
AC-P,
BJH and the
method BJH
was method
used was the
to assess used to assessdistribution.
pore-size the pore-sizeBefore
distribution.
and after Before and after
adsorption, a
adsorption,
surface a surface
chemical chemical
analysis of theanalysis
sampleof theperformed
was sample was performed
using using SEM
SEM (EVO-40 (EVO-40
Series, Carl
Zeiss SMT electron microscope equipped with an energy dispersive X-ray spectroscope),
Energies 2021, 14, 2458 6 of 15

FTIR (Nicolet 6700 spectrometer), and XRD (X-ray diffractometer Panalytical X’PERT PRO).
TG was performed using a Mettler TGA/DSC1 thermal analyzer. About 10 mg of the
activated carbon was heated at 20 ◦ C min−1 to 1000 ◦ C with a flow ratio of nitrogen equal
to 50 cm3 min−1 . The online analysis of SO2 and NOx concentrations in the flue gas was
carried out during the measuring tests of the pilot DR-VPSA unit installation with real CFB
flue gas at the Lagisza Power Plant to complete the information obtained from analyzing
the physicochemical properties of the impregnated activated carbon (AC-P) before and
after its use in the deSOx and deNOx adsorber. The concentration of SO2 and NOx gases
was registered before (point 1) and after the deSOx and deNOx adsorber (point 2) to
continuously monitor the effectiveness of the process involving SO2 and NOx removal
from the flue gas (Figure 2). During testing, gas samples were taken continuously using a
multiplexer and directed to an analyzer equipped with an FTIR sensor to measure the SO2
and NOx concentrations. This analysis was also carried out in the CO2 separation section
to assess the effect of these impurities on the working efficiency of the CO2 adsorbent
and on the captured CO2 purity. Detailed information on the results obtained in the CO2
separation section is available in [9]. The present article focuses only on analyzing the SO2
and NOx content in flue gas at the inlet to the deSOx and deNOx adsorber and at the exit
from the deSOx and deNOx adsorber.

3. Results and Discussion

3.1. Chemical Composition of the Spent Activated Carbon
The elemental chemical compositions of the fresh and used impregnated activated
carbon AC-P in desulfurization and the NOx removal adsorber are shown in Table 1. The
primary differences in constitution between the fresh AC-P and the three used AC-Ps
(retrieved from the bottom, middle, and top of the desulfurization unit) were their sulfur
contents. Samples of used AC-P taken from the desulfurization unit had a notably higher S
content (from 0.98 to 4.14 wt.%) compared to the fresh AC-P (0.29 wt.% S), which led to
effective SO2 adsorption from the flue gas under treatment, primarily in the lower part of
the deSOx and deNOx adsorber (used AC-P (1)). Analysis of chemical composition also
demonstrated that AC-P impregnated with KOH/KJ, which was used in the deSOx and
deNOx adsorber, did not adsorb nitric oxides from treated gas and was not effective in this
regard. In the samples of used AC-P retrieved from the deSOx and deNOx adsorber, no N
content was observed to be higher than that in fresh AC-P.

Table 1. The elemental composition of the fresh and used activated carbon AC-P.

Elemental Composition
Adsorbent
C, wt.% H, wt.% N, wt.% S, wt.% Other, O wt.%
fresh AC-P 72.34 1.80 0.86 0.29 24.71
used AC-P (1)—bottom 63.16 2.66 0.67 4.14 29.37
used AC-P (2)—middle 66.81 2.56 0.53 2.75 27.35
used AC-P (3)—top 69.86 2.44 0.73 0.98 25.99

3.2. Porous Structure of the Spent Activated Carbon

By analyzing data on the porous structure (Table 2) of the activated carbon before and
after 808 h of use in the deSOx and deNOx adsorber, it was possible to observe changes in
the specific surface area and volume and surface area of the pores. The specific surface area
of AC-P after 808 h of use in the adsorber decreased for the used AC-P by 23.21%–42.11%
(depending on the location of AC-P retrieval in the deSOx and deNOx adsorber) compared
to fresh AC-P (whose specific surface was 959 m2 g−1 ). The volume of pores also decreased
by 19.52% to 43.91% depending on the location of AC-P retrieval in the deSOx and deNOx
adsorber). Moreover, the total area of pores in all spent AC-Ps decreased by 22.54–37.92%
(Table 2). The spent samples had smaller specific surface areas and volumes of micropores,
likely due to the presence of SO2 adsorbed from the polluted flue gas and perhaps from
 22.54–37.92% (Table 2). The spent samples had smaller specific surface areas and volumes
of micropores, likely due to the presence of SO2 adsorbed from the polluted flue gas and
perhaps from other impurities such as dust. The SO2 adsorption process resulted in a de-
crease in the BET surface areas and pore volume of the activated carbon materials, indi-
cating a blocking of pores due to clusters of new stable ionic crystals of K2SO3 and K2SO4.
Energies 2021, 14, 2458 7 of 15
The degree of reduction in terms of both the area and the pore volume was the greatest
for the used AC-P (1) taken from the lower part of the desulfurization unit. This used AC-
P adsorbed the largest amount of SO2 from the flue gas.
other impurities such as dust. The SO2 adsorption process resulted in a decrease in the
Table 2. Porous
BET surface properties
areas of the
and pore fresh and
volume used
of the impregnated
activated activated
carbon carbon
materials, AC-P. a blocking
indicating
of pores due to clusters of new stable ionic crystals of K2Properties
Textural SO3 and K2 SO4 . The degree of
reduction in terms of both the area and the pore volume was the greatest for the used AC-P
Sample BET Surface Area, Total Pore Volume, Total Pore Area,
(1) taken from the lower part of the 2desulfurization unit. 3This used AC-P adsorbed the
m g−1 cm g−1 m2 g−1
largest amount of SO2 from the flue gas.
fresh AC-P 959.00 0.41 739.30
Table 2. Porous properties of the fresh and used impregnated activated carbon AC-P. 459.03
used AC-P (1)—bottom 555.20 0.23
used AC-P (2)—middle 692.13 0.31 572.67
used AC-P (3)—top 736.46 Textural Properties
0.33 515.95
Sample BET Surface Area, Total Pore Volume, Total Pore Area,
2m g−1 by analyzingcm 3 2
Sulfur presence was also confirmed theg− 1
chemical m g−1 of the
composition
samples (Table 1). Figure 4 presents959.00
fresh AC-P the nitrogen adsorption–desorption
0.41 isotherms
739.30(Figure
4a) and pore-size distributions (Figure 4b) for the activated carbon AC-P samples
used AC-P (1)—bottom 555.20 0.23 459.03 before
used AC-P (2)—middle 692.13 0.31
and after use in the deSOx and deNOx adsorber. The adsorption/desorption isotherm of 572.67
fresh used
AC-PAC-P was(3)—top
a type I isotherm, which736.46 confirmed the adsorbent’s
0.33 515.95 with a
microporosity
large number of mesopores, as demonstrated by the hysteresis loop starting at relative
pressure
Sulfur (p/p 0) over was
presence 0.35.also
Theconfirmed
adsorption/desorption
by analyzing the isotherms
chemicalof the used AC-P
composition of the pre-
sam-
sented the same
ples (Table shapes,
1). Figure and differences
4 presents the nitrogenin relation to fresh AC-P mainly
adsorption–desorption applied
isotherms to the
(Figure 4a)
and pore-size
volume distributions
of adsorbed nitrogen(Figure
(Figure 4b)4a)for the activated carbon AC-P samples before and
afterThis
use in thedemonstrated
was deSOx and deNO x adsorber.
by the behaviorThe adsorption/desorption
of the porous structures ofisotherm
the usedofAC-P
fresh
AC-P was
samples a type
after 808I hisotherm,
of use in which confirmed the adsorbent’s
the desulfurization unit. As shownmicroporosity
in Figurewith4b, aminor
large
number can
changes of mesopores, as demonstrated
also be observed by thedistributions
in the pore-size hysteresis loopfor starting at relative
the activated pressure
carbon AC-P
(p/p
samples,
0 ) over 0.35. The adsorption/desorption isotherms of the used AC-P
both fresh and used. This confirms the presence of minor changes in the porous presented the
same shapes, and differences in relation to fresh AC-P mainly applied
structures of the AC samples after 808 h of using them to remove sulfur and nitrogen from to the volume of
adsorbed
flue nitrogen
gas before (Figurethe
delivering 4a).gas to the adsorption installation for CO2 separation.

Figure 4. Cont.
Energies 2021, 14, x FOR PEER REVIEW 8 of 16
Energies 2021, 14, 2458 8 of 15

Figure 4. Nitrogen adsorption–desorption isotherms (a) and pore-size distributions (b) for activated
Figure
carbon4.samples:
Nitrogenfresh
adsorption–desorption isotherms
AC-P, used AC-P (1), (a) and
used AC-P pore-size
(2), and distributions
used AC-P (3). (b) for acti-
vated carbon samples: fresh AC-P, used AC-P (1), used AC-P (2), and used AC-P (3).
This was demonstrated by the behavior of the porous structures of the used AC-P
3.3. Microstructure
samples after 808ofhthe
ofSpent Activated
use in Carbon
the desulfurization unit. As shown in Figure 4b, minor
changes can also be observed in the pore-size distributions
The presence of sulfur in the spent activated carbon AC-P for the
wasactivated
confirmedcarbon AC-P
by SEM-
samples, both fresh and used. This confirms the presence of minor changes
EDX analysis, according to which the sulfur content was a maximum of 14.0 wt.% for usedin the porous
structures
AC-P of the AC
(3) retrieved samples
from after 808
the adsorber h of
top, using
14.92 them
wt.% fortoused
remove
AC-P sulfur and nitrogen
(2) retrieved fromfrom
the
flue gas middle,
adsorber before delivering
and 20.29the
wt.gas to the
% for usedadsorption installation
AC-P (1) from for CObottom.
the adsorber 2 separation.
Figure 5 shows SEM photographs and the results of the SEM-EDX chemical constitu-
3.3. Microstructure of the Spent Activated Carbon
tion analysis on the surface of the impregnated activated carbon (both fresh and used) in
Thex presence
the deSO and deNO ofxsulfur in the
adsorber. spent
The activated of
observation carbon AC-P was confirmed
the microstructure by SEM-EDX
in the tested AC-P
analysis, according to which the sulfur content was a maximum of 14.0
samples confirmed the occurrence of new structures as a result of the use of the samples wt.% for used
inAC-P (3) retrieved
the adsorber. from the adsorber
Photographs top,AC-P
of the spent 14.92showed
wt.% forcrystals
used AC-P (2) retrieved
of sulfate from the
and potassium
adsorber
sulfite middle,
formed as a and 20.29
result wt.2 %
of SO for usedMost
sorption. AC-Pof(1)
thefrom
K2SOthe adsorber bottom.
4 crystals were formed in the
Figure 5 shows SEM photographs and the results
bottom of the desulfurization unit (used AC-P (1)), as demonstratedof the SEM-EDX chemical
by the consti-
SEM photo-
tution analysis on the surface of the impregnated activated carbon (both
graphs (Figure 5b) showing the greatest amount of potassium sulfate crystals. This result fresh and used)
in the deSO x and deNO x adsorber. The observation of the microstructure
was also confirmed by analyzing the chemical composition on the surfaces of the activated in the tested
AC-P samples
carbons, confirmed
which showed thesulfur
higher occurrence of new structures
and potassium (K2SO3 and asKa2SO
result of the use of the
4) content compared
samples in the adsorber. Photographs of the spent AC-P showed crystals of sulfate and
to fresh AC-P in the AC-P samples retrieved after 808 h of use in the adsorber.
potassium sulfite formed as a result of SO2 sorption. Most of the K2 SO4 crystals were
formed in the bottom of the desulfurization unit (used AC-P (1)), as demonstrated by the
SEM photographs (Figure 5b) showing the greatest amount of potassium sulfate crystals.
This result was also confirmed by analyzing the chemical composition on the surfaces of
the activated carbons, which showed higher sulfur and potassium (K2 SO3 and K2 SO4 )
content compared to fresh AC-P in the AC-P samples retrieved after 808 h of use in the
adsorber.

3.4. Surface Chemistry of the Spent Activated Carbon

Characterization of the FTIR spectra for sample surface chemistry was carried out to
obtain information on changes in the functional groups on the AC-P surface before and
after desulfurization and denitrification. Analysis of the FTIR spectra for fresh AC-P and
AC-P after use in the adsorber, as presented in Figure 6, confirmed surface changes in the
used AC-P due to SO2 adsorption.
Energies 2021, 14, 2458 9 of 15
Energies 2021, 14, x FOR PEER REVIEW 9 of 16

Figure 5. SEM-EDX analysis of activated carbon (fresh and used) in the deSOx and deNOx adsorber: (a) AC-P; (b) used
AC-P (1); (c) used AC-P (2) and (d) used AC-P (3).

3.4. Surface Chemistry of the Spent Activated Carbon

Characterization of the FTIR spectra for sample surface chemistry was carried out to
obtain information on changes in the functional groups on the AC-P surface before and
after desulfurization and denitrification. Analysis of the FTIR spectra for fresh AC-P and
Figure
Figure 5.
5. SEM-EDX
SEM-EDX analysis
analysis of
of activated
AC-P activated
after usecarbon
in the(fresh
carbon (fresh and
and used)
adsorber, used) in the deSO
in the
as presenteddeSO and
and deNO
deNO
in xxFigure x adsorber: (a)
(a) AC-P;
x adsorber:surface
6, confirmed AC-P; (b)
(b) used
changes used
in the
AC-P (1); (c) used AC-P (2) and
AC-P (1); (c) used AC-P (2)used (d)
and (d) used AC-P
useddue
AC-P (3).
AC-P to(3).
SO2 adsorption.
3.4. Surface Chemistry of the Spent Activated Carbon
Characterization of the FTIR spectra for sample surface chemistry was carried out to
obtain information on changes in the functional groups on the AC-P surface before and
after desulfurization and denitrification. Analysis of the FTIR spectra for fresh AC-P and
AC-P after use in the adsorber, as presented in Figure 6, confirmed surface changes in the
used AC-P due to SO2 adsorption.

FTIRprofiles
Figure6.6.FTIR
Figure profilesof
of impregnated
impregnated activated carbon:
carbon: fresh
fresh and
andafter
afteruse
usein
inthe
thedeSO
deSOx xand
anddeNOx
deNOx adsorber:
adsorber: freshused
fresh AC-P, AC-P, used(1),
AC-P AC-P (1),
used used(2),
AC-P AC-Pand(2),
usedand used(3).
AC-P AC-P (3).

Noobserved
No observedchanges
changesindicated
indicatedNO NOxxadsorption.
adsorption.TheThefresh
freshand
andused
usedAC-P
AC-P spectra
spectra
showed characteristic peaks related to -OH vibrations at 1650 cm −1 and 3500 cm−1 due
showed characteristic peaks related to -OH vibrations at 1650 cm and 3500 cm due to
−1 −1
to the presence of the basic group -OH (originating from KOH and moisture). Moreover,
at the 1800–1690 cm−1 wavelength, we observed a peak generated by the ketone group
C=O and
Figure at 1630
6. FTIR cmof−impregnated
profiles
1 from the aromatic group C=C. Below 1600 cm−1 , we observed
activated carbon: fresh and after use in the deSOx and
low-intensity
deNOx adsorber:peaks from the
fresh AC-P, usedC=O,
AC-PC-O, andAC-P
(1), used -OH(2),
groups.
and usedExtra
AC-P peaks
(3). appeared in the
spectra of all used AC-P samples retrieved from the deSOx and deNOx adsorber, which
confirmed changeschanges
No observed on the surfaces
indicatedof the
NOspent activatedThe
x adsorption. carbons.
fresh The
and signals at 1150
used AC-P cm−1
spectra
could becharacteristic
showed linked to sulfates
peaksgenerated after
related to -OH SOvibrations
2 adsorptionat(the
1650strong band/spectrum
cm−1 and 3500 cm−1 dueof the
to
Energies 2021, 14, 2458 10 of 15

-OH group belonging to the -SO-OH group was generated during SO2 adsorption on the
AC-P at 3435 cm−1 , the band at 1159 cm−1 originated from the –SO3 - group, and the strong
band at 1113 cm−1 originated from the -O-SO3 - group) [28]. During the analysis of SO2
adsorption on activated carbon with potassium hydroxide activation, many of the same
groups were observed by Lee et al. [28]. No groups indicating the formation of nitrates
were found on the surface of the used AC-P. Moreover, a weak band of the -SO2 - group
appeared at 984 cm−1 . However, as emphasized by other authors [28], low-intensity peaks
that induce microscopic changes via functional groups generated through SO2 adsorption
might become hidden or overlap and thus would not be observed. To sum up, during
SO2 adsorption, activated carbon impregnated with KOH works as a selective site of
adsorption, with the OH- groups guaranteeing basic atmosphere and K+ ions facilitating
stable SO2 adsorption on carbon. Due to potassium, the chemicals created on the surface
during adsorption include stable ionic crystals such as K2 SO3 and K2 SO4 . This is because
potassium is highly reactive and cannot exist as a single element; instead, potassium exists
in chemical compounds [28]. Previous studies on the properties of carbon surfaces after
SO2 adsorption indicate that strong chemical interactions between KOH and SO2 largely
depend on the impregnated carbon’s surface chemistry.

3.5. Stability of the Spent Activated Carbon

Based on the information for the surface functional groups obtained from the FTIR
analysis, the presence of adsorbed substances on the used AC-P was also examined using
XRD analysis. The XRD analysis allowed us to identify the substances formed on the
surface of the activated carbon after SO2 adsorption. Figure 7 shows the XRD spectra
for fresh and used AC-P. For fresh AC-P, a high-intensity peak (2θ = 26.5) was observed.
This peak was not seen on any of the used AC-Ps. This peak may indicate the presence
of potassium and basic OH ions (AC impregnated with KOH) on the external surface of
fresh AC-P that disappeared after SO2 adsorption. The XRD spectra of all the used AC-Ps
indicated the presence of K2 SO4 generated as a result of a reaction between sulfur oxides
and potassium hydroxide (high-intensity peak at 2θ = 30.7), whereas high-intensity peaks
Energies 2021, 14, x FOR PEER REVIEW 11 of 16
at 2θ = 21.24, 29.7, 30.74, and 43.36 as well as small intensity peaks at 35.8 and 37.04 were
observed in all the samples after SO2 adsorption.

Figure 7. The XRD

XRD spectra
spectraofofactivated
activatedcarbon
carbon(fresh
(freshand
andafter use
after in in
use thethe
deSO x and
deSO deNO
x and x adsorber):
deNO x ad-

sorber):
fresh fresh
AC-P, AC-P,
used used
AC-P (1),AC-P
used (1),
AC-Pused
(2) AC-P (2) and
and used used
AC-P (3).AC-P (3).

Figure 8a,b shows the TG and DTG curves of activated carbon (fresh AC-P and AC-
P after use in the deSOx and deNOx adsorber) under an inert atmosphere (N2). As shown
in Figure 8a, each sample was characterized by varying the mass loss during the experi-
ment. The greatest mass loss was observed for activated carbon with AC-P (1) after use in
the deSOx and deNOx adsorber. The loss amounted to 35%, whereas fresh AC-P’s mass
 Energies 2021, 14, 2458 11 of 15

Figure 7. The XRD spectra of activated carbon (fresh and after use in the deSOx and deNOx ad-
sorber): fresh AC-P, used AC-P (1), used AC-P (2) and used AC-P (3).
Figure 8a,b shows the TG and DTG curves of activated carbon (fresh AC-P and AC-P
after use in8a,b
Figure theshows
deSOx theandTGdeNO adsorber)
andx DTG under
curves an inert carbon
of activated atmosphere
(fresh(N 2 ). Asand
AC-P shown
AC-in
Figure
P after 8a,ineach
use the sample
deSOx and wasdeNO
characterized by under
x adsorber) varying anthe mass
inert loss during
atmosphere (Nthe experiment.
2). As shown
inThe greatest
Figure mass
8a, each loss was
sample wasobserved for activated
characterized by varying carbon with AC-P
the mass (1) after
loss during theuse in the
experi-
deSO
ment. The and deNO
x greatest massx adsorber.
loss was observed for activated carbon with AC-P (1) after use loss
The loss amounted to 35%, whereas fresh AC-P’s mass in
was
the 20%.
deSO As indicated
x and by the TG/DTG
deNOx adsorber. The loss curves
amounted(Figure 8a,b),
to 35%, two types
whereas of mass
fresh AC-P’s loss were
mass
observed
loss was 20%. in the fresh AC-Pbysample.
As indicated The first
the TG/DTG type (Figure
curves of mass 8a,b),
loss wastwodue
typesto the desorption
of mass loss
of physically adsorbed water. ◦
were observed in the fresh AC-PThe second
sample. Thetype oftype
first massofloss
mass(200–1000
loss was C) due resulted from
to the de-
the slow thermal decomposition of the surface functional groups
sorption of physically adsorbed water. The second type of mass loss (200–1000 °C)with low stability and the
least thermally stable carbon structure.
re-sulted from the slow thermal decomposition o

Energies 2021, 14, x FOR PEER REVIEW 12 of 16

Figure
Figure 8. 8.
TG TG(a)(a) andDTG
and DTG(b)
(b)curves
curvesofofactivated
activatedcarbon
carbon(fresh
(fresh and
and after
after use
use in
in the
the deSO
deSOxx and
and deNOx
adsorber): fresh AC-P, used AC-P (1), used AC-P (2), and used AC-P
deNOx adsorber): fresh AC-P, used AC-P (1), used AC-P (2), and used AC-P (3). (3).

Differentsituations
Different situationswere
wereobserved
observedfor
forallallspent
spentAC-P-activated
AC-P-activatedcarbon.
carbon.AsAsindicated
indicated
by the TG/DTG curves (Figure 8a,b), four types of mass loss were observed in
by the TG/DTG curves (Figure 8a,b), four types of mass loss were observed in the spentthe spent AC-
AC-P samples. The first type of mass loss (30–200 °C) was due to the desorption of surface
water. The second type of mass loss (200–400 °C) resulted from the removal of water from
the pores of the adsorbent. The third type of mass loss (440–650 °C) was due to the de-
sorption of sulfur. The fourth type of mass loss (>650 °C) resulted from the decomposition
Energies 2021, 14, 2458 12 of 15

P samples. The first type of mass loss (30–200 ◦ C) was due to the desorption of surface water.
The second type of mass loss (200–400 ◦ C) resulted from the removal of water from the
pores of the adsorbent. The third type of mass loss (440–650 ◦ C) was due to the desorption
of sulfur. The fourth type of mass loss (>650 ◦ C) resulted from the decomposition of
potassium sulfate. All completed analyses demonstrated that the mechanism of deep flue
gas purification on the activated carbon using AC-P involved the reaction of SO2 to K2 SO3
and, through oxidation of SO2 to SO3 and adsorption, a reaction to K2 SO4 . The presence
of these compounds was confirmed by XRD, SEM-EDX, and TG analyses. However, the
presence of nitrogen oxide removal products was not observed, indicating that nitrogen
oxides, especially NO, were not oxidized in the desulfurization unit to N2 O5 and N2 O4
and thus did not react with KOH to produce potassium nitrites and nitrates (KNO2, KNO3 ).
The FTIR, XRD, SEM-EDX, and TG analyses also did not confirm the existence of these
compounds. A previous study carried out by the present authors also confirmed that NOx
was not removed from flue gas before CO2 adsorption in a special section [9]. According to
these studies, a large part of the NOx was adsorbed—not in the desulfurization and NOx
removal section, but in the CO2 separation section, thus contaminating the activated carbon.
The used activated carbon materials (in the four adsorption columns—CO2 separation
section) featured increased nitrogen content, which suggested the slight adsorption of
NOx captured from the flue gas. Details of this analysis can be found in [9]. Many of the
same results were obtained by Lee et al. [29] during a study on the surface of impregnated
activated carbon after NOx and SO2 adsorption. The authors observed that in most cases,
adsorption proceeded during chemical reactions. Due to the presence of OH groups on the
surface, the KOH-impregnated activated carbon oxidized due to NOx and SO2 adsorption.
In particular, SO2 presented strong interactions with KOH-impregnated activated carbon,
forming K2 SO4 on the external surface of activated carbon. Lee et al. [29] also observed that
more SO2 adsorbed on the surface of KOH-impregnated activated carbon corresponded to
less NOx being adsorbed. The authors in [29] showed that the individual adsorption of
NOx and SO2 proceeded differently than the simultaneous adsorption of both impurities.
Many of the same conclusions were presented by Abdulrasheed et al. [27], who observed
that the simultaneous removal of NOx and SO2 using KOH-impregnated activated carbon
in an environment rich in O2 showed SO2 to have higher affinity to the adsorbent than
NOx . This was likely also the case in our research. On the other hand, when these gases
were removed separately, NOx showed higher affinity than SO2 . The stronger affinity
of SO2 ensured a higher rate of chemisorption on the surface of impregnated activated
carbon and the bonding of oxygen groups (needed for NO oxidation and further NO2
adsorption on activated carbon), especially in the presence of moisture and sulfuric acid
formation. The conducted research shows that the practical use of technology involving
the simultaneous removal of both SO2 and NOx still makes flue gas desulfurization and
denitrification challenging and requires significant research in this area. This result was
also confirmed by the study of Neathery et al. [30] on selective NOx capture from flue
gas containing SO2 , CO2 , H2 O, O2 , and N2 . Neathery et al. observed that NOx can be
selectively adsorbed from flue gas mixtures, but only under the proper conditions—i.e., a
sufficiently high oxygen concentration, low SO2 concentration, and a proper temperature
range of 35–120 ◦ C. This suggests that under our real research conditions on simultaneous
SO2 and NOx adsorption from flue gas, the above conditions were not met, leading NOx
adsorption to be minimal. The conclusions of the study highlight that the simultaneous
removal of both SO2 and NOx from real CFB flue gas on impregnated activated carbon is
still challenging and dependent on the particular conditions of the flue gas.

3.6. Analysis of Flue Gas Constitution before and after Leaving the Adsorber
Information obtained based on analysis of the physicochemical properties of AC-P
before and after use in the deSOx and deNOx adsorber was also confirmed by analyzing
the flue gas constitution before and after leaving the adsorber (marked as points 1 and 2 in
Figure 2). Figure 9a shows that before entering the adsorber, almost all the SO2 contained
 that the simultaneous removal of both SO2 and NOx from real CFB flue gas on impreg-
nated activated carbon is still challenging and dependent on the particular conditions of
the flue gas.

3.6. Analysis of Flue Gas Constitution before and after Leaving the Adsorber
Energies 2021, 14, 2458 13 of 15
Information obtained based on analysis of the physicochemical properties of AC-P
before and after use in the deSOx and deNOx adsorber was also confirmed by analyzing
the flue gas constitution before and after leaving the adsorber (marked as points 1 and 2
in Figure 2). Figure 9a shows that before entering the adsorber, almost all the SO2 con-
in the flue gas was captured via impregnated AC-P, and the volume of SO2 in flue gas
tained in the flue gas was captured via impregnated AC-P,3 (SOand the volume of SO2 in flue
leaving the adsorber did
gas leaving the adsorber
didnot
notexceed
exceed5
5 mg/Nm
mg/Nm 2 content
3 (SO2 content at the adsorber inlet was
at the adsorber inlet was
1–111 mg/Nm 3 ).
1–111 mg/Nm3).

Energies 2021, 14, x FOR PEER REVIEW 14 of 16

Figure 9. Online analysis of SO2 concentration (a) and NOx concentration (b) in the flue gas before
and after leaving the deSOx and deNOx adsorber (the temperature of the CFB flue gas was 25 ◦ C,
Figure 9. Online analysis of SO2 concentration (a) and NOx concentration (b) in the flue gas before
the maximum capacity of the DR-VPSA installation was 100 Nm3 /h, the measuring campaign was
and after leaving the deSOx and deNOx adsorber (the temperature of the CFB flue gas was 25 °C,
the808 h).
maximum capacity of the DR-VPSA installation was 100 Nm3/h, the measuring campaign was
808 h).
This result confirmed the efficacy of desulfurization in the deSOx and deNOx adsorber.
The total
This SOxconfirmed
result removal efficiency
the efficacyamounted to 95.5–100%.
of desulfurization Similarand
in the deSOx results
deNOxweread-reported by
sorber. The total
Ishibashi SOx
et al. removal
[4,5]. efficiency
In [4,5], amounted
SO2 removal to 95.5–100%.
was so effectiveSimilar
that noresults
SO2 were re-
accumulation was
ported by Ishibashi
observed in theetCO al.2[4,5]. In [4,5], removed
adsorbent SO2 removal was2000
after so effective
h of use that
in no SO2 accumu-adsorption
a PTSA/PSA
lation was observed
installation for CO in the CO2 adsorbent removed after 2000 h of use in a PTSA/PSA
2 capture. The authors also stated that for CO2 capture VPSA processes,
adsorption installation for CO2
installing a SOx desulfurization capture.
and NOxThe authors
removalalso stated
section wasthat
lessforexpensive
CO2 capturethan accepting
VPSA processes, installing a SOx desulfurization and NOx removal section was less ex-
the adsorbent degradation when the flue gas contained more than 10 mg/Nm3 SO2 and
pensive than accepting the adsorbent degradation when the flue gas contained more than
10 mg/Nm3 NOx [4,5]. Our analysis of the adsorbent also confirmed the effective removal
10 mg/Nm3 SO2 and 10 mg/Nm3 NOx [4,5]. Our analysis of the adsorbent also confirmed
theofeffective
SO2 in removal
the pre-treatment
of SO2 in the section. Replacement
pre-treatment section.of the AC-P sorbent
Replacement of the AC-Pthat filled the
sorbent that filled the deSOx/deNOx adsorber was not necessary after 808 h of DR-VPSA because
deSOx/deNOx adsorber was not necessary after 808 h of DR-VPSA operation
no increase
operation in no
because theincrease
SO2 concentration at the outlet
in the SO2 concentration of outlet
at the the column was observed.
of the column was This
result confirmed
observed. the effectiveness
This result confirmed and lifespan
the effectiveness of theofadsorbent
and lifespan the adsorbentused to remove
used to SO2 .
However,
remove the situation
SO2. However, was different
the situation for nitrogen
was different oxides,oxides,
for nitrogen whichwhich
were not
werecaptured
not in the
captured in the
adsorber, asadsorber,
shown in asFigure
shown in 9b.Figure 9b. The content
The content of nitrogen
of nitrogen oxidesoxides in flue
in the the flue
gas (reaching
gas (reaching 55–120 mg/Nm3 before entering the adsorber) dropped by only a few
mg/Nm3 after leaving the adsorber. However, it never exceeded 120 mg/Nm3. In a previ-
ous study completed by the same authors of the present work [9], uncaptured NOx pro-
gressed to the CO2 separation section (DR-VPSA), where it was adsorbed on the CO2 ad-
sorbent and as a result of cyclic sorption/desorption processes, mixed with recirculating
Energies 2021, 14, 2458 14 of 15

55–120 mg/Nm3 before entering the adsorber) dropped by only a few mg/Nm3 after
leaving the adsorber. However, it never exceeded 120 mg/Nm3 . In a previous study
completed by the same authors of the present work [9], uncaptured NOx progressed to the
CO2 separation section (DR-VPSA), where it was adsorbed on the CO2 adsorbent and as a
result of cyclic sorption/desorption processes, mixed with recirculating gas and ultimately
appeared as impurities in the final CO2 product [8]. This result confirmed that the process
of removing NOx in desulfurization and the NOx removal section was ineffective.

4. Conclusions
The present results based on real CFB flue gas at the Lagisza Power Plant demonstrated
that using AC impregnated with KOH and KJ in the adsorber to remove sulfur and nitrogen
oxides in the pre-treatment module of the adsorption CO2 capture unit (DR-VPSA) was
a solution that ensured sufficient flue gas purification and the removal of sulfur oxides.
However, this method is insufficient for nitrogen oxides. The impregnated activated
carbon showed adequate sorptive properties and proper thermal stability. It also did not
change its properties during prolonged use in the adsorber. The tested activated carbon
allowed for the effective removal of sulfur oxides under the continuous operation of the
DR-VPSA installation for variable SO2 and NOx loading in real flue gas conditions. This
was confirmed by completed analyses of the spent activated carbon, which allowed finding
the presence of SO2 adsorption products with chemical reaction, as potassium sulfate, on
the surface of the spent activated carbon. From among the various alternatives, the removal
of impurities from the flue gas through adsorption on surface-modified KOH/KJ activated
carbon proved to be an efficient and reliable technology for sulfur oxides. However, the
removal of nitrogen oxides under real conditions was not assessed.

Author Contributions: Conceptualization, I.M.-K.; investigation, I.M.-K., D.W., A.Z., J.Z., and W.S.;
methodology, I.M.-K.; writing—original draft preparation, I.M.-K.; writing—review and editing,
I.M.-K. and D.W. All authors have read and agreed to the published version of the manuscript.
Funding: The funds for covering the costs to publish with open access were provided by the statute
subvention of Czestochowa University of Technology, Faculty of Infrastructure and Environment.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors are thankful to the stuff from Lagisza Power Plant for valuable
support during the long-term field tests. The results presented in this paper were obtained from
research work co-financed by the National Centre of Research and Development in the framework of
Contract SP/E/1/67484/10—Strategic Research Program—Advanced technologies for obtaining
energy: Development of a technology for highly efficient zero-emission coal-fired power units
integrated with CO2 capture. This article has been supported by the Polish National Agency for
Academic Exchange under Grant No PPI/APM/2019/1/00042.
Conflicts of Interest: The authors declare no conflict of interest.

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