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Chemosphere 133 (2015) 90–96

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Chemosphere
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Simultaneous removal of PCDD/Fs and NOx from the flue gas


of a municipal solid waste incinerator with a pilot plant
Xiaolong Liu a, Jian Wang a,b, Xue Wang a, Tingyu Zhu a,⇑
a
Beijing Engineering Research Center of Process Pollution Control, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology,
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, China

h i g h l i g h t s

 The influence of temperature on the catalytic decomposition of PCDD/Fs and the SCR of NOx was studied.
 The removal efficiencies for PCDD/Fs in the gas-phase and particle-phase were compared.
 The effect of the SCR process on the removal of PCDD/Fs was also studied at 220 °C.
 The NOx emissions and the NH3-SCR were presented.

a r t i c l e i n f o a b s t r a c t

Article history: The pilot-scale plant on the simultaneous removal of PCDD/Fs and NOx from the flue gas of a municipal
Received 2 November 2014 solid waste incinerator is presented. In order to research the influence of temperature on the catalytic
Received in revised form 26 February 2015 decomposition of PCDD/Fs and the selective catalytic reduction of NOx, the experiments were performed
Accepted 5 April 2015
at 220 °C, 260 °C, and 300 °C, and the congener profiles of PCDD/Fs for the samples collected at the inlet
and outlet were illustrated. Noteworthy, the detailed congener distributions of PCDD/Fs in the gas-phase
Handling Editor: H. Fiedler and particle-phase of the inlet and 300-outlet (decomposition temperature = 300 °C) samples are pre-
sented, and the removal efficiencies gg-I-TEQ and gp-I-TEQ reached to 94.94% and 99.67%, respectively.
Keywords: The effect of the SCR process on the removal of PCDD/Fs was also studied at a relatively low temperature
PCDD/Fs of 220 °C. Additionally, the NOx emissions and the SCR efficiencies were investigated.
NOx Ó 2015 Elsevier Ltd. All rights reserved.
V2O5–WO3/TiO2
Catalytic oxidation
Selective catalytic reduction

1. Introduction 2012; Lu et al., 2012). In the past few years, PCDD/Fs in the air were
subject to intensive monitoring. The emission standards become
Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/ increasingly stringent globally, and much attention has been
Fs) are commonly known as harmful pollutants that are formed devoted to the development of effective end-of-pipe treatment
unintentionally during various industrial thermal processes, technologies (Hung et al., 2014; Korell et al., 2009; Lin et al.,
including municipal solid waste incinerations (MSWIs) (Chang 2008). Among the air pollutant control devices (APCDs) applied
et al., 2011; Choi and Lee, 2007; Liu et al., 2013), power generations (Choi and Lee, 2007; Inoue and Kawamoto, 2008; Ji et al., 2014),
(Zhang et al., 2013), metallurgical facilities (Kuo et al., 2012; Lee spraying of powdered activated carbon (PAC) into flue gas or
et al., 2009; Lenoir et al., 2012), and some chemical processes (Li installing a fixed-bed adsorption system to remove PCDD/Fs has
et al., 2014). They are classified as persistent organic pollutants been considered as the most convenient strategy (Chang et al.,
(POPs) targeted for international source reduction by Stockholm 2009; Hung et al., 2011; Lu et al., 2013). Due to its simplicity in
Convention. PCDD/Fs have attracted great social, technical, and sci- engineering and high efficiency, activated carbon injection (ACI)
entific interests for their severe toxicities, persistence, and poten- has become the popular technology for reducing PCDD/Fs emis-
tial to accumulate in the tissues of organisms (Kaivosoja et al., sions at most MSWIs (Chi and Chang, 2005; Lin and Chang, 2008;
Wang et al., 2009). However, some issues still exist in removing
PCDD/Fs from MSWIs with ACI. It has been reported that even
⇑ Corresponding author. Tel./fax: +86 10 82544821.
though ACI technology can efficiently remove PCDD/Fs in flue
E-mail address: tyzhu@ipe.ac.cn (T. Zhu).

http://dx.doi.org/10.1016/j.chemosphere.2015.04.009
0045-6535/Ó 2015 Elsevier Ltd. All rights reserved.
X. Liu et al. / Chemosphere 133 (2015) 90–96 91

gases, the total PCDD/Fs discharge (including those contained in fly removing PCDD/Fs and NOx from the flue gas simultaneously have
ash and flue gas) actually increases due to the memory effect never been reported in china. Recently, we have studied the simul-
(Chang and Lin, 2001; Li et al., 2011). taneous control of chlorobenzene and NO over V2O5/TiO2 catalyst
Nitrogen oxides (NOx) exist in the flue gas of many industrial in NH3-SCR reaction, where chlorobenzene was employed as the
processes, such as MSWIs and iron ore sintering. Accordingly, con- model compound of PCDD/Fs (Wang et al., 2013). However, signif-
trolling the PCDD/Fs and NOx emissions in one chemical engineer- icant difference exists between the lab-scale and field-scale tests.
ing unit has become a big challenge. Selective catalytic oxidation Herein, we built a pilot-scale plant in a waste incineration plant
(SCR) has been considered the most efficient method to remove located in eastern China. The plant was equipped behind the bag
the NOx emissions with NH3 as the reducing agent which turns filter with as-designed amount of flue gas introduced, and simulta-
NOx into N2 (Topsoe et al., 1995). Previous studies revealed that neous removal of PCDD/Fs and NOx using commercial V2O5–WO3/
NH3-SCR catalysts (V2O5–WO3/TiO2) could effectively promote TiO2 catalyst was systematically studied.
the decomposition of PCDD/Fs through catalytic oxidation reac-
tions (Boos et al., 1992; Dvorák et al., 2010; Jones and Ross,
1997). In Europe and Japan, commercial V2O5–WO3/TiO2 catalysts 2. Materials and methods
have been applied in MSWIs to remove PCDD/Fs and NOx simulta-
2.1. Characterization of V2O5–WO3/TiO2 catalyst
neously (Bonte et al., 2002; Ide et al., 1996). In comparison to the
NH3-SCR catalysts only designed for NOx removal, higher vana-
Commercial V2O5–WO3/TiO2 catalyst with a honeycomb struc-
dium contents are commonly needed to increase the oxidation
potential of the catalysts (Debecker et al., 2011; Weber et al., ture was purchased from a local company. The catalyst was
employed for the simultaneous removal of PCDD/Fs and NOx. The
1999; Yang et al., 2008). For lab-scale or pilot plant tests, the tem-
perature below 210 °C might be sufficient for the decomposition of vanadium oxide (V2O5) and tungsten oxide (WO3) loadings were
2.1 wt% and 4.8 wt%, respectively. The BET special surface area
PCDD/Fs (Liljelind et al., 2001; Weber et al., 2001). However, con-
sidering the simultaneous removal of NOx, higher temperatures are was measured to be 50.8 m2 g1. The X-ray diffraction (XRD) anal-
ysis showed TiO2 being anatase type, and the diffraction peaks due
generally needed in MSWIs (Liljelind et al., 2001; Yang et al., 2008).
In MSWIs, much attention has been paid to the voluminous to V2O5 and WO3 were not observed, indicating V2O5 and WO3 are
either in an amorphous or microcrystalline form.
emission monitoring. However, systematic research on simultane-
ous removal of PCDD/Fs and NOx with V2O5–WO3/TiO2 catalysts in
a practical MSWIs flue gas has been rarely reported (Goemans 2.2. Description of the pilot plant
et al., 2003; Ide et al., 1996). In standard isokinetic sampling proce-
dure, the gas-phase and particle-phase PCDD/Fs are collected The pilot installation was equipped between the stack and
simultaneously. Detailed analysis of the gas and particle partition- induced draft fan, which was behind the bag filter in the MSWI
ing of PCDD/Fs congeners for flue gas samples collected from located in eastern China. As shown in Fig. 1, as-designed amount
MSWIs at the inlet and outlet of the NH3-SCR reactor would be of flue gas was introduced to the pilot system with a globe valve
greatly useful for the practical applications of this catalytic decom- controlling the amount of gas flow. Since the temperature of the
position method. original flue gas is 125 ± 5 °C, the reheating is needed to corre-
China, as the largest developing country in the world, generates spond to the temperature range of 220–300 °C for removal of
huge amounts of municipal solid waste every year. Lack of landfill PCDD/Fs and NOx. The flue gas induced was heated to the temper-
has led to the incineration being an efficient alternative way to dis- ature needed in the gas–gas heat exchanger by the gas flow with a
pose the waste (Du et al., 2011; Wang et al., 2014). To the best higher temperature resulted from the combustion chamber. The
knowledge of us, applications of V2O5–WO3/TiO2 catalysts in ammonia injection system consists of an air compressor, a

Gas-Gas heat
exchanger
Flowmeter
Flue gas

ID-Fan
Air compressor

Peristaltic Aqueuous
pump ammonia
Combustion Catalytic
chamber reactor

Liquefied
petroleum gas
Air

ID-Fan

Gas-Gas heat
exchanger

Fig. 1. The pilot plant for the simultaneous removal of PCDD/Fs and NOx.
92 X. Liu et al. / Chemosphere 133 (2015) 90–96

Table 1 hourly space velocity was kept as 3700 h1. The other process data
The measured concentrations of Cg, Cg-PCDFs, Cg-PCDDs, Cg-I-TEQ, Cp, Cp-PCDFs, Cp-PCDDs, Cp-I- of the induced flue gas and pilot plant are listed in Table S1.
TEQ, Ct, Ct-PCDFs, Ct-PCDDs and Ct-I-TEQ, for samples of inlet and 300-outlet and their
corresponding removal efficiencies.

Inlet (ng Nm3) 300-Outlet (ng Nm3) Removal efficiency (%) 2.3. Gas sampling
Cg 13.04 0.87 93.35
Cg-PCDFs 12.29 0.73 94.02 The NOx concentrations were measured using two flue gas ana-
Cg-PCDDs 0.76 0.13 82.50 lyzers (MRU VARIO PLUS) during the experiments of simultaneous
Cg-I-TEQ 2.45 0.12 94.94
removal of PCDD/Fs and NOx. The instruments were calibrated
Cp 12.72 0.14 98.87
Cp-PCDFs 11.87 0.08 99.32
before the tests. Meanwhile, the PCDD/Fs samples were collected.
Cp-PCDDs 0.85 0.06 92.71 The sampling sites for PCDD/Fs and NOx were both located at the
Cp-I-TEQ 2.31 0.008 99.67 inlet and outlet of the catalytic reactor.
Ct 25.76 1.01 96.08 The PCDD/Fs samples were collected by an automatic isokinetic
Ct-PCDFs 24.15 0.82 96.62
sampling system, Isostack Basic (Tecora Corp., Milan, Italy) accord-
Ct-PCDDs 1.61 0.19 87.91
Ct-I-TEQ 4.76 0.13 97.24 ing to the EU standard method EN-1948. The sampling system was
mainly composed of a heated probe, a filter box with a quartz fiber
filter, and a water-cooled XAD-2 adsorbent trap. The quartz fiber
filter was used to collect particle-bound pollutants, and XAD-2
peristaltic pump, aqueous ammonia, and a twin fluid nozzle. The adsorbent resin was applied for trapping the vapor-phase contam-
simultaneous decomposition of PCDD/Fs and NOx proceeds in the inants. Five surrogate target compounds (Wellington Laboratories,
catalytic reactor, and the purified gas flow was discharged by an Guelph, Canada) were added into the XAD-2 resin in the adsorbent
internal draught fan (ID-fan). During all the experiments, the gas sampling cartridge before sampling. All samples were tightly

5 0.4
(a) (a) 3
ng/Nm
3 ng/Nm
4 Inlet-gas 300-gas 3
ng I-TEQ/Nm
3
0.3 ng I-TEQ/Nm

3
3
ng/Nm

3
ng/Nm

0.2
2

0.1
1

0 0
OCDD
2,3,7,8-TeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD

OCDD
2,3,7,8-TeCDF

OCDF

1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
2,3,7,8-TeCDD

1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF

1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF

2,3,7,8-TeCDF

OCDF
1,2,3,4,7,8-HxCDF

2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF

1,2,3,6,7,8-HxCDF

1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF

3 0.05
(b) 3
(b) 3
ng/Nm ng/Nm
Inlet-particle 0.04 300-particle 3
3 ng I-TEQ/Nm
ng I-TEQ/Nm
2
0.03
3
3

ng/Nm
ng/Nm

0.02
1

0.01

0 0
2,3,7,8-TeCDD

OCDD
2,3,7,8-TeCDD
1,2,3,7,8-PeCDD

1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD

1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDF
2,3,7,8-TeCDF

1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
2,3,7,8-TeCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF

OCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF

1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF

Fig. 2. The congener profiles of PCDD/Fs for gas-phase and particle-phase of Inlet Fig. 3. The congener profiles of PCDD/Fs for gas-phase and particle phase of 300-
samples. outlet samples.
X. Liu et al. / Chemosphere 133 (2015) 90–96 93

wrapped in aluminum foil to avoid contamination and loss. When 3. Results and discussion
the sampling was finished, the samples were immediately trans-
ferred to a refrigerator where they were stored until analysis. 3.1. Chemical reactions

2.4. PCDD/Fs analysis In the incinerators, most of the PCDD/Fs decompose at a high
temperature (Lundin and Marklund, 2007), whereas they could
Seventeen homologues of 2,3,7,8-substituted PCDD/Fs were be resynthesized in presence of the transition metal elements
analyzed using method EU 1948. The samples were spiked with (Cu, Fe) contained in fly ash, the organic substances, the chlorine
certain amounts of 13C12-PCDD/Fs internal standards and then sources (HCl, Cl2), and O2. The formation mechanisms and kinetical
extracted with 250 mL of toluene for approximately 24 h in a aspects have been thoroughly studied in previous reports (Conesa
Soxhlet apparatus. The extracts were concentrated and then sub- et al., 2002; Lomnicki and Dellinger, 2003; Mätzing, 2001; Ryu
jected to a series of adsorption chromatography cleanup proce- et al., 2004; Stanmore, 2002). In the flue gas of MSWIs, NOx primar-
dures, including an acidic silica gel column, a multilayer silica gel ily exist in the form of NO with only a small amount of NO2.
column, and a basic alumina column. The final extracts were then At the appropriate temperatures, PCDD/Fs proceed a catalytic
concentrated to 20 lL and spiked with 1.0 ng of 13C12-PCDD/Fs oxidation process over a V2O5–WO3/TiO2 catalyst, resulting in inor-
internal standards for the recoveries of the internal standards to ganic substances, such as H2O, CO2 and HCl. The NOx are reduced
be estimated before the instrumental analysis. into N2 over the V2O5–WO3/TiO2 catalyst using NH3 as reducing
The PCDD/Fs analyses were performed by an Agilent 6890 gas agent, simultaneously. The NH3-SCR reactions are described as
chromatograph (Agilent Technologies, Santa Clara, CA, USA) below:
coupled with an Autospec Ultima high-resolution mass spectrom- V2 O5 —WO3 =TiO2
eter (Waters, Milford, MA, USA). The gas chromatograph was 4NO þ 4NH3 þ O2 ƒƒƒƒƒƒƒƒ! 4N2 þ 6H2 O
equipped with a DB-5 ms fused-silica column (60 m  0.25 mm
V2 O5 —WO3 =TiO2
i.d.  0.25 lm) to achieve the chromatographic separation of the 4NO þ 8NH3 þ 2O2 ƒƒƒƒƒƒƒƒ! 6N2 þ 12H2 O
congeners. The mass spectrometer was tuned and operated at
P10 000 resolution with 38 eV EI energy. Selected ion monitoring
(SIM) mode was used for data acquisition. 3.2. Catalytic decomposition of PCDD/Fs
The removal efficiency for PCDD/Fs or NOx is defined as follows:
In this study, the gas-phase PCDD/Fs and particle-phase PCDD/Fs
½CðinletÞ  CðoutletÞ of the inlet samples and 300-outlet (decomposition temperature =
gð%Þ ¼  100%
CðinletÞ 300 °C) samples were analyzed separately. The I-TEQ concentrations
were estimated using the international toxic equivalence factors.

(a) 6
300-total
5
260-total
4
220-total
ng/Nm3

3
Inlet-total
2
1
0

(b) 3 300-total
ng I-TEQ/Nm3

260-total
2 220-total
Inlet-total
1

Fig. 4. The congener profiles of PCDD/Fs for the inlet and outlet samples.
94 X. Liu et al. / Chemosphere 133 (2015) 90–96

Table 1 shows the concentrations of Cg, Cg-PCDFs, Cg-PCDDs, and Cg-I-TEQ, the operating temperatures for simultaneous removal of PCDD/Fs
and the corresponding values of particle-phase and the total and NOx. The congener profiles of PCDD/Fs for the outlet samples
concentrations. named as 220-, 260-, 300-total were summarized in Fig. 4 for com-
For inlet samples, Cg was comparable to Cp, while the Cg/Cp and parison with the original flue gas, and the detailed concentration
Cg-I-TEQ/Cp-I-TEQ ratios were 1.03 and 1.06, respectively. The concen- values of all the samples were shown in Table S2. It could be seen
tration of PCDFs was much higher than that of PCDDs in gas-phase that all the congeners showed apparent decrease after the treat-
and particle phase, giving the CPCDFs/CPCDDs ratios of 16.17, 13.96, ment over a V2O5–WO3/TiO2 catalyst. The total I-TEQ concentra-
and 15.00 for gas-phase, particle-phase, and total samples, respec- tions of 220-, 260-, 300-total samples were 0.353, 0.195, and
tively. For the samples collected at outlet at 300 °C, Cg was much 0.131 ng I-TEQ Nm3, and their corresponding removal efficiencies
higher than Cp, and the Cg/Cp and Cg-I-TEQ/Cp-I-TEQ ratios were 6.05 were 92.58%, 95.90%, and 97.24% (Fig. 5a), respectively. The results
and 16.28, respectively, illustrating that PCDD/Fs in particle-phase revealed that higher temperature facilitates the decomposition of
showed higher removal efficiencies than those in gas-phase, which PCDD/Fs within the temperature range of 220–300 °C.
is consistent with previous reports (Kuo et al., 2012). It was pro- During the catalytic oxidation of PCDD/Fs, NH3 could be also
posed this phenomenon was mainly resulted by two reasons. The adsorbed on the surface of the catalysts, which might lead to a
reheating of the flue gas from 120 °C to 300 °C facilitates the competitive adsorption. Hence, the single removal of PCDD/Fs
release of particle-phase PCDD/Fs into the flue gas, becoming the without ammonia injection was tested at 220 °C in order to
gas-phase PCDD/Fs, and the particle-phase could be more easily research the effect of NH3-SCR on the catalytic decomposition of
adsorbed on the surface of the V2O5–WO3/TiO2 catalyst, leading PCDD/Fs, and the results were compared with those of simultane-
to the lower removal efficiency for gas-phase PCDD/Fs than the ous removal experiment at the same temperature. As shown in
particle-phase PCDD/Fs. The CPCDFs/CPCDDs ratios were 5.56, 1.31, Fig. 5b, most congeners showed comparable removal efficiencies
and 4.20, respectively, for gas-phase, particle-phase, and total con- for both experiment conditions. However, apparently higher
centrations, showing apparent difference from those of the original removal efficiencies were observed for 2,3,7,8-TeCDF, OCDF, and
flue gas. The Ct and Ct-I-TEQ of 300-outlet samples were 2,3,7,8-TeCDD for the sample of 220-without SCR. Accordingly,
1.01 ng Nm3 and 0.13 ng I-TEQ Nm3 with their corresponding the total removal efficiencies calculated from the total I-TEQ
removal efficiencies of 96.08% and 97.24%, respectively.
Fig. 2 shows the detailed gas-phase and particle-phase congener 100
profiles of the seventeen 2,3,7,8-substituted PCDD/Fs obtained (a)
PCDD/Fs removal efficiency %

from the flue gas collected at the inlet of the reactor. In the gas-
phase sample, the top three abundant congeners were 2,3,7,8- 95
TeCDF, 1,2,3,7,8-PeCDF, and 2,3,4,7,8-PeCDF with the concentra-
tions of 4.71, 3.17, and 2.65 ng Nm3, respectively. In sequence,
the top three I-TEQ abundant congeners were 2,3,4,7,8-PeCDF, 90
2,3,7,8-TeCDF, and 2,3,7,8-TeCDD with the I-TEQ concentrations
of 1.32, 0.47, and 0.25 ng I-TEQ Nm3. For the particle-phase sam-
ple, 2,3,4,7,8-PeCDF contributes the highest concentration and I- 85
TEQ concentration of 2.74 ng Nm3 and 1.37 ng I-TEQ Nm3,
respectively. The concentrations of PCDDs were much lower than
those of PCDFs, and the top two I-TEQ abundant PCDDs were 80
1,2,3,7,8-PeCDD and 2,3,7,8-TeCDD with the I-TEQ concentrations al al al s
SC
R
tot tot tot ga cle
of 0.124 and 0.073 ng I-TEQ Nm3. 0- 0- 0- 0- rti
out 22 26 30 30 -pa
300 °C was generally considered as an appropriate temperature th 0
wi 30
0-
to promote the simultaneous abatements of PCDD/Fs and NOx over 22
V2O5–WO3/TiO2 catalysts. However, 300 °C was also considered as
a suitable temperature in favor of the de novo synthesis process
(Vermeulen et al., 2014), which might reflect a significant influence 220-total
(b) 220-without SCR
on the congener distribution in the gas-phase and particle-phase 100
PCDD/Fs removal efficiency %

after heating treatment. In order to research the detailed decompo-


sition performance at this temperature, the congener profiles of 80
PCDD/Fs for gas-phase and particle-phase of the 300-Outlet sample
were obtained. As illustrated in Fig. 3, each congener in the gas- 60
phase was reduced to below 0.4 ng Nm3. In sequence, the top
three I-TEQ abundant congeners were 2,3,4,7,8-PeCDF, 2,3,7,8- 40
TeCDF, and 2,3,7,8-TeCDD, with the I-TEQ concentrations of
0.0538, 0.0349, 0.0143 ng I-TEQ Nm3, respectively. For the parti-
20
cle-phase of 300-outlet sample, the concentration of each congener
was below 0.04 ng Nm3 with the I-TEQ concentration below
0.005 ng I-TEQ Nm3. Almost all the congeners showed great 0
OCDD
2,3,7,8-TeCDD
1,2,3,7,8-PeCDD
OCDF

1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
2,3,7,8-TeCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF

removal efficiencies above 80% for both gas-phase and particle-


phase. However, moderate removal efficiencies were observed for
octa-chlorinated OCDF and OCDD, whereas the concentration of
OCDD showed an apparent rise from 0.025 ng Nm3 to
0.039 ng Nm3 in the particle-phase, possibly due to the measure-
ment error or the practical rise of its concentration during the sam-
pling process. Fig. 5. (a) The total removal efficiencies for all the samples. (b) The removal
In order to investigate the effect of temperature on the catalytic efficiencies of all the congener profiles of PCDD/Fs for the samples of 220-total and
decomposition of PCDD/Fs, 220 °C and 260 °C were then tested as 220-without SCR.
X. Liu et al. / Chemosphere 133 (2015) 90–96 95

250 250
Inlet
(a) Inlet (b) Outlet
NO x concentration (mg/Nm ) Outlet
200 200

NOx concentration (mg/Nm )


3

3
150 150

100 100

50 50

0 0
0 10 20 30 40 50 0 10 20 30 40 50
Time (min) Time (min)

250
100
(c) Inlet (d)
Outlet
200
NOx concentration (mg/Nm )
3

80

NOx conversion %
150
60

100 40

50 20

0 0
0 10 20 30 40 50 220 240 260 280 300
o
Time (min) Temperature ( C)

Fig. 6. The removal efficiencies for NOx at 220–300 °C.

concentrations for the two samples were 92.58% and 95.93%. It was incinerators, even when the moisture content of the flue gas
tentatively proposed that weak competition adsorption exists reached to 38%. Within the temperature range of 220–300 °C, the
between PCDD/Fs and NH3 during the catalytic process. removal efficiencies of PCDD/Fs and NOx both increased along with
Accordingly, when NH3-SCR reaction was introduced to the cat- the rise of the temperature, revealing that higher temperature
alytic system, the decomposition of PCDD/Fs was slightly inhibited. facilitates the catalytic oxidation of PCDD/Fs and the selective cat-
alytic reduction of NOx. The test at 300 °C gave the highest removal
3.3. Selective catalytic reduction of NOx efficiencies of PCDD/Fs and NOx being 97.24% and 90.3%, respec-
tively. Detailed congener distributions of PCDD/Fs in the gas-phase
The NOx-emissions at the inlet and outlet of the reactor were and particle-phase of the inlet and 300-outlet samples were given,
measured using two flue gas analyzers (MRU VARIO PLUS), which and apparently higher removal efficiency was observed for the
were calibrated before the tests. For the inlet, the NOx concentra- PCDD/Fs in the particle-phase. Additionally, the SCR process
tion varied over time with an average value of 120 mg Nm3. showed slight inhibition to the decomposition of PCDD/Fs at
NOx primarily exists in the form of NO with only a small amount 220 °C.
of NO2. Basically, the NO2 concentration was within the range of
3–5 mg Nm3. During the experiments, the ammonia was injected Acknowledgement
with a stoichiometric NH3/NOx-average ratio of 1.0. The NOx concen-
trations were recorded 50 min for each temperature. As shown in This work was supported by the State 863 Project (No.
Fig. 6, when the reaction temperatures were 220, 260, and 2012AA062803).
300 °C, the NOx-emission could be reduced to approximately 57,
32, and 12 mg Nm3, and the removal efficiencies of NOx were Appendix A. Supplementary material
52.3%, 71.9%, and 90.3%, respectively. The results indicated that
higher temperature was conductive to the SCR process in the range Supplementary data associated with this article can be found, in
of 220–300 °C. the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2015.04.009.
4. Conclusions
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