Chemosphere 73 (2008) 890895

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5WO3/TiO2-based catalysts
Chia Cheng Yang a, Shu Hao Chang a, Bao Zhen Hong a, Kai Hsien Chi a,b, Moo Been Chang a,*
a b

Graduate Institute of Environmental Engineering, National Central University, Chungli 320, Taiwan Research Center for Environmental Changes, Academia Sinica, Taipei 115, Taiwan

a r t i c l e

i n f o

a b s t r a c t
Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efciency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100 ng TEQ N m3 while reproducibility test indicates that the PCDD/F recovery efciencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is rst applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V2O5WO3/TiO2-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efciencies are achieved with catalysts A and B, respectively, at 280 C with the space velocity of 5000 h1. The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and MarsVan Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8 kJ mol1 and 25.2 kJ mol1, respectively. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 29 February 2008 Received in revised form 11 July 2008 Accepted 14 July 2008 Available online 26 August 2008 Keywords: V2O5WO3TiO2 supported catalyst PCDD/Fs SCR Destruction PCDD/F generating system

1. Introduction How to effectively control pollutant emissions while pursuing a high economic growth rate has become a big challenge. PCDDs (Polychlorinated Dibenzo-p-dioxins) and PCDFs (Polychlorinated Dibenzofurans) are commonly known as dioxin which has been listed as one of the persistent organic pollutants (POPs). PCDD/Fs have attracted extensive social, technical, and scientic interests for their acute and chronic toxicity and carcinogenic, teratogenic, and mutagenic effects. As the PCDD/F emission standards become more stringent globally, effective end-of-pipe treatment technologies with higher efciency need to be developed. PCDD/F emission sources are equipped with various types of air pollutant control devices (APCDs), leading to different levels of PCDD/F control. Among the methods applied, spraying of powdered activated carbon (PAC) into gas streams or installing a xed-bed adsorption system to remove PCDD/Fs from ue gas has been considered as the simplest one. Nevertheless, some problems exist in controlling PCDD/F emissions from municipal waste incinerators with activated carbon injection (ACI). Previous study (Chang and Lin, 2001) indicates that ACI technology can effectively reduce PCDD/F concentrations
* Corresponding author. Tel./fax: +886 3 422 6774. E-mail address: mbchang@ncuen.ncu.edu.tw (M.B. Chang). 0045-6535/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2008.07.027

in ue gases, but actually increases the total PCDD/F discharge (including those existing in y ash and ue gas) from waste incinerators. Relevant studies (Weber et al., 1999; Liljelind et al., 2001) indicate that selective catalytic reduction (SCR) catalysts (TiO2-based V2O5WO3) commonly applied to control NOx via selective catalytic reduction (SCR) of NO with NH3 are also effective in the decomposition of PCDD/Fs. Commercial SCR catalysts have been applied for the simultaneous removals of NOx and PCDD/Fs. This is mainly achieved by increasing the oxidation potential of the catalysts by increasing vanadium content (Weber et al., 1999; Liljelind et al., 2001). For the effective catalytic destruction of PCDD/Fs, the temperature lower than 210 C might be sufcient in pilot plants, however, higher temperatures of 240260 C are generally needed in the eld tests (Ide et al., 1996; Weber et al., 1999; Liljelind et al., 2001). Another study (Weber et al., 2001) also indicates that catalytic decomposition and removal efciencies of semi-volatile compounds (such as PCDD/Fs and PCBs) strongly depend on volatility and oxidative behavior of the compounds. Both properties are closely related to the chlorination level of the compound. The volatility of PCDD/Fs decreases with increasing chlorination level as can be derived from the vapor pressure of the PCDD/F. Highly chlorinated PCDD/Fs are retained on the catalyst surface longer, therefore, increasing the

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chance of oxidation. Up to now, a variety of catalysts have been developed for PCDD/F removal. Generally, these catalysts can be classied into noble and transition metals based on the active metals applied. Among the noble metals, Pt, Pd, and Rh are commonly used. Those catalysts can achieve as high as 90% removal efciency at 300 C; however, relatively high cost has limited its application (Becker and Forster, 1997; Van den Brink et al., 2000; Taralunga et al., 2004). Major transition metals being used as catalysts include VOx, CrOx, MnOx, and FeOx (Krishnamoorthy et al., 1998; Liu et al., 2001; Cho and Ihm, 2002; Yim et al., 2002). V2O5 is of the highest while FeOx is of the lowest activity toward PCDD/F decomposition. Relevant studies indicate the activities of V2O5 catalysts on different supports from high to low are in the order of TiO2 > CeO2 > ZrO2 > Al2O3 > SiO2 (Wachs and Weckhuysen, 1997; Krishnamoorthy and Amiridis, 1999; Guliants, 1999). The support and active metals are of the same importance for catalytic performance. Most tests were conducted with powder catalyst on the laboratory-scale reactor. However, signicant difference exists between the lab-scale and eld-scale conditions. In lab-scale experiment, a gas stream containing stable PCDD/F concentration is needed to evaluate the PCDD/F removal efciency achieved with specic control technology. However, PCDD/F-containing gas stored in steel cylinders is not available so far. In this study, an innovative PCDD/F gas stream generating system is developed for this purpose. Additionally, the inuences of temperature, space velocity, and water vapor content on PCDD/ F conversions achieved with commercial honeycomb catalyst (V2O5WO3/TiO2) in a lab-scale reactor are also evaluated. Moreover, combined integral reaction and MarsVan Krevelen model are applied to calculate the activation energies of OCDD and OCDF conversion. 2. Materials and methods 2.1. Characteristics of V2O5WO3 catalysts supported on TiO2 The catalyst used in this study consists of ceramic elements with a honeycomb structure. Two commercial catalysts (V2O5 WO3/TiO2) especially developed for the simultaneous destruction of NOx and PCDD/Fs were used in this study. The major differences of two catalysts are in terms of vanadium and tungsten loadings (approximately 1 wt% V2O5 and 2 wt% WO3 for catalyst A, and 3 wt% V2O5 and 2 wt% WO3 for catalyst B) and BET surface areas (approximately 66 m2 g1 for catalyst A and 55 m2 g1 for catalyst B). The X-ray diffraction (XRD) analysis of these catalysts indicates

that the structure of the TiO2 phase is of anatase type, suggesting that V2O5 and WO3 are either in an amorphous or microcrystalline form. 2.2. Dioxin-containing gas stream generating system The experimental tests were carried out in a continuous gas ow system. The dioxin-containing gas stream generating system developed consists of the PCDD/F stock solution injector, temperature-controller, evaporator, and gas ow rate controllers. The experimental setup is schematically shown in Fig. 1. With different types of PCDD/F stock solutions being injected into the system, the distributions of PCDD/F congeners in the gas stream can be varied. The PCDD/F stock solution used in this study was prepared by the extraction of y ash sampled from a large-scale municipal waste incinerator. In this study, the effects of operating parameters including shapes of catalyst bed, operating temperature, space velocity, and water vapor content on the destruction efciencies of PCDD/Fs are investigated. The catalyst was supported in a horizontal stainless steel reactor (30 cm long, 3 cm wide). The reactor was then installed in an electric furnace and the temperature was controlled by a regulator. The temperature of the catalyst bed was monitored with a K-type thermocouple located in the middle of the reactor. 2.3. Activity measurement and kinetic study Catalytic activity measurements were carried out in a xed bed reactor with a commercial honeycomb catalyst (V2O5WO3/TiO2) at atmospheric pressure in the temperature range of 220280 C. The gas ow rates through the reactor were set as 4.15, 8.3, and 11.6 standard liters per minute (slpm) for the gas hourly space velocity (GHSV) of 5000, 10 000, and 14 000 h1, respectively. The water vapor was introduced into the system using a syringe pump to investigate its effect on dioxin removal. PCDD/F sample was collected by XAD-2. Thereafter, the XAD-2 samples were Soxhlet extracted with toluene for twenty four hours. The toluene extract was then concentrated to about 1 ml by rotary evaporation and was replaced by 5 ml hexane for pretreatment process. Having been treated with concentrated sulfuric acid, the sample was then subjected to a series of clean-up columns including sulfuric acid silica gel column, acidic aluminum oxide column, and Celite/carbon column. Finally, the cleaned up solution was spiked with known amounts of Method 23 recovery standard solution. In this study, only seventeen 2,3,7,8substituted PCDD/F congeners were analyzed. For kinetic experi-

Fig. 1. Schematic diagram of the experimental apparatus.

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ments, different levels of PCDD/F-containing gas streams were passed through the honeycomb catalyst (catalyst A) bed. Conversions of PCDD/Fs were determined by analyzing inuent and efuent gas streams with high resolution gas chromatography (HRGC) (Hewlett Packard 6890 plus)/high resolution mass spectrometer (HRMS) (JEOL JMS-700) equipped with a fused silica capillary column DB-5 MS (60 m 0.25 mm 0.25 lm, J&W). The mass spectrometer was operated with a resolution greater than 10 000 under positive EI conditions, and data were obtained in the selected ion monitoring (SIM) mode. 3. Results and discussion 3.1. Effect of catalytic shapes In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efciency and effectiveness of innovative PCDD/F control technologies. The generating system developed consists of a PCDD/F stock solution injector, temperature-controller, evaporator, and gas ow rate controller. The reactant mixture consists of a pre-mixed gas (20% O2 and 80% N2) with a PCDD/F concentration of 4.17 ng TEQ N m3. The results presented in Fig. 2 indicate that the inlet PCDD/F concentrations range from 3.94 to 4.14 ng TEQ N m3 during the sampling time of 30 to 90 min as the temperature of injection port was controlled at 525 C. Overall, the PCDD/F recovery efciencies range from 93% to 112%. Therefore, the generating system developed in this study can stably generate the gas streams containing specic concentrations of PCDD/Fs. Investigations on PCDD/F decomposition via catalysts are generally carried out either with the labscale reactor or eld experimentation (Finocchio et al., 2006). In the lab-scale testing, the reactor was lled with the powder catalyst while honeycomb catalyst was more often used in the eld application. The results obtained in lab-scale experimentation (Becker and Forster, 1997; Van den Brink et al., 2000; Taralunga et al., 2004) usually are of high PCDD/F conversions with powder catalyst, but the efciency in the eld sometimes does not meet the expectation. Some researchers attributed the lower efciency achieved in eld operation to the complex and unstable ue gas composition. To evaluate the effect of PCDD/F decomposition via different shapes of catalyst bed, the tests were conducted in the lab-scale reactor to avoid the inuence of complicated ue gas composition. In this experiment, the powder packed and honeycomb shapes of catalyst A are used, respectively. The powder catalysts are obtained by crushing the same honeycomb catalyst. The

inlet PCDD/F concentrations of the experiments are both controlled at the same level (4.17 ng TEQ N m3). PCDD/F conversion describing the ability of the catalyst to remove PCDD/Fs is dened as follows:

PCDD=F conversion % PCDD=F inflow ng TEQ PCDD=F outflow ng TEQ PCDD=F inflow ng TEQ 100
The lab-scale test (operating temperature: 200 C, GHSV: 14 000 h1, gas composition: 20% O2 in nitrogen and H2O(g) is absent) results indicate that the PCDD/F conversions achieved with two catalyst beds are quite different. The PCDD/F conversion achieved with powder packed bed is greater than 85%, while that achieved with honeycomb catalyst bed is only 36%. This phenomenon is in common with the eld-scale tests, which reveals that the lower conversions are not simply caused by complicated ue gas composition. Perhaps, other reasons cause the low PCDD/F conversions. Observing the gas ow passing through the catalyst may give us some clues, and collision frequency may be one of them. Due to the lower porosity in the powder catalyst, the PCDD/F containing gas stream can make good contact with the catalyst. On the other hand, honeycomb catalyst with larger channel section results in a reduced contact and lower collision frequency between active sites and PCDD/Fs. 3.2. Effect of operating temperature and space velocity In general, the operating temperature of catalyst bed is one of the most important factors affecting the conversion efciency. A series of experimental tests were carried out at different temperatures and space velocities, with the same inlet PCDD/F concentration of 4.17 ng TEQ N m3. Fig. 3 shows the PCDD/F conversion achieved with two kinds of honeycomb V2O5WO3/TiO2 catalysts (catalyst A and catalyst B) at different operating temperatures (220, 250, and 280 C) and space velocities (5000, 10 000, and 14 000 h1). The experimental results indicate that the conversions of PCDD/Fs over both catalysts strongly depend on the operating temperature. As the temperature is increased from 220 C to 280 C, the PCDD/F conversion achieved with catalyst A increases from 68% to 84% at the space velocity of 5000 h1. As the space velocity is increased to 14 000 h1, the PCDD/F conversion ranges from 38% (220 C) to 55% (280 C). In addition, higher PCDD/F conversion is observed in the case of catalyst B compared with catalyst A. As the temperature is increased from 220 C to 280 C, the catalytic conversions of PCDD/Fs achieved with catalyst B increase from 89% to 91% at the space velocity of 5000 h1. As the space velocity is controlled at 14 000 h1, the PCDD/F conversion increases from 57% to 70% as the temperature is increased from 220 C to 280 C. The PCDD/F conversion achieved with catalyst B is less signicantly affected by the variation of operating temperature compared to catalyst A. It is attributed to the fact that the vanadium loadings of catalyst B is 3% while that of catalyst A is around 1%. This interpretation indicates that the activity of catalyst is signicantly affected by the active metal content in catalyst. In addition, at xed temperature and inlet PCDD/F concentration, catalytic decomposition of PCDD/Fs increases with decreasing space velocity due to longer retention time. Fig. 4 shows the conversion efciencies of seventeen 2,3,7,8-substituted PCDD/F congeners. In general, the conversions of PCDD/F congeners decrease with increasing chlorination level. It is attributed to the fact that the highly chlorinated PCDD/F congeners are of more stable structures compared with the lowly chlorinated congeners, resulting in lower oxidation rates.

Inlet PCDD/F concentration (ng TEQ Nm-3)

5.0

4.0

3.0
30 min

2.0

60 min 90 min

1.0 500 525 550

Temperature at injection port ( c )

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100
GHSV: 5,000 GHSV: 10,000 GHSV: 14,000

100

80

Catalyst A

PCDD/F conversion(%)

80 60 40 20 0 100 Catalyst A

PCDD/F conversion (%)

60

GHSV: 5,000 GHSV: 10,000 GHSV: 14,000

40

20

0 100

PCDD/F conversion(%)

80 60
GHSV: 5,000

GHSV: 5,000

GHSV: 10,000

GHSV: 14,000

40 Catalyst B 20 0

GHSV: 10,000 GHSV: 14,000

Catalyst B

PCDD/F conversion (%)

80

60

40

20

Fig. 4. The conversions of seventeen 2,3,7,8-substituted PCDD/F congeners achieved with honeycomb catalysts A and B, respectively, at different space velocities (temperature: 280 C, O2: 20%, N2: 80%, H2O(g): 0%).

0 220 250 280

Operating temperature (C) PCDD/F conversion (%)

3.3. Effect of water vapor content Activity measurements were also conducted in the absence and presence of water vapor (015% by volume), since water vapor is present in signicant quantities in the typical ue gases of different combustion processes (Amiridis et al., 1996). Water vapor plays two important roles in the catalytic reaction (Krishnamoorthy et al., 2000; Poplawski et al., 2000; Lomnicki et al., 2003). Firstly, via competitive adsorption mechanism water vapor may reduce the contact between PCDD/F molecules and active sites of catalyst, and hence inhibits the rate of the reaction. On the other hand, water vapor can also facilitate the removal of Cl present on the catalyst surface via the following reaction (Krishnamoorthy et al., 2000):

Fig. 5. PCDD/F conversions achieved with honeycomb catalysts A and B, respectively, at different water vapor contents (temperature: 250 C, GHSV: 5000 h1, O2: 20%, N2: 80%).

Cl H2 Og ! HCl OH

Fig. 5 shows the PCDD/F conversions achieved with both honeycomb catalysts (catalyst A and catalyst B) with the water vapor contents varying from 0% and 15% by volume. The results indicate that the presence of water vapor inhibits the conversion of PCDD/Fs due to its competition with PCDD/F molecules for adsorption on the active vanadium sites for both catalysts. Due to the dechlorination mechanism, some highly chlorinated PCDD/F congeners reacted

with OH radical and were converted to lowly chlorinated PCDD/Fs (Jina et al., 2004). Therefore, conversion of seventeen 2,3,7,8-substituted PCDD/F congeners is affected by the water vapor content. In the absence of water vapor, conversions of PCDD/F congeners decrease with increasing chlorination level (Fig. 6) and the trend changes signicantly in the presence of water vapor. In this study, only seventeen 2,3,7,8-substituted PCDD/F congeners were analyzed, hence, the degradation products of PCDD/F destruction cannot be fully investigated. However, our results indicate that the PCDD/F congeners were mainly converted to chlorinated products

2, 1, 3,7, 2, 81, 3,7 TC 2, 3 ,8- D 1, ,4,7 PeC D 2, 3, ,8- DD 1, 6,7 Hx 2, C , 1, 3,7 8-H DD 2, ,8 x 3, ,9 C 4, -H DD 6, x 7, C 8- D H D pC O DD C D 2, D 3, 1, 7,8 2, -T 3, C 2, 7,8 DF 3, -P 4, eC ` 1, 2 7, D 1, ,3,4 8-P F 2, 1 ,7 eC 3, ,8 D 1, 6,7 ,-H F 2, ,8 x 2, 3,7, -Hx CD 1, 3,4, 8,9- CD F 2, 6, H F 3 7 1, ,4,6 ,8-H xCD 2, ,7 3, ,8 xC F 4, -H D 7, 8, pC F 9- D H F pC D O F C D F

100
Catalyst A Catalyst B

80

60

40

20

0%

5%

10%

15%

Water vapor content(%)

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2.5
y = -2.8648x + 7.1419 OCDF OCDD
2

PCDD/F conversion (%)

80 60

2.0

R = 0.8343

1.5
0% 5%

ln k
1.0 0.5
y = -2.2185x + 4.7123 R = 0.8175
2

40 20 0 100 Catalyst A

10% 15%

PCDD/F conversion (%)

80 60 40
0% 5%

0.0 1.70

1.80

1.90

2.00

2.10

1 1000 (K-1) T
Fig. 7. Arrhenius plots for the rate constants of OCDD and OCDF conversions, respectively, by honeycomb catalyst A.

20 Catalyst B 0

10% 15%

Fig. 6. The conversions of seventeen 2,3,7,8-substituted PCDD/Fs achieved with honeycomb catalysts A and B, respectively, in the presence of different water vapor contents (temperature: 250 C, GHSV: 5000 h1, O2: 20%, N2: 80%).

2 1, ,3,7 2, ,8 1, 3, -T 2, 7, C 3 8 D 1, ,4,7 -Pe D 2, ,8 C 3, -H D 1, 6,7 x D 1, 2,3, ,8- CD 2, 7, H D 3, 8, xC 4, 9- D 6, H D 7, x 8- C H DD pC O DD C 2, D 3 D 1, ,7,8 2, -T 3, 2 71 C 1, ,3,4 ,8-P DF 2, ,7 eC 3, ,8 1, 4,7, -Pe DF 2, 8, C 3 - D 1, ,6,7 Hx F 2, ,8 C 3, -H DF 2, 7,8 x 3 , C 1, ,4,6 9-H DF 2, ,7 x 3 ,8 C 1, ,4,6 -H DF 2, 3, ,7,8 xCD 4, 7, -Hp F 8, 9- CD H pC F D O F C D F

XA = fraction of PCDD/F removed (%), CA0 = inlet PCDD/F concentration (mol cm3), VR = catalyst volume (cm3), A = pre-exponential factor, Ea = activation energy (J mol1), R = gas constant 8.31447 (J (K mol)1), T = gas temperature (K). The reaction rate constants are calculated from the experimental decomposition yields by Eq. (1) and plotted against 1/T. Fig. 7 shows that the linear relationships are obtained, conrming the Arrhenius dependency. Within the operating temperature ranges of 220280 C, the activation energies of OCDD and OCDF via catalysis are 24.8 and 25.2 kJ mol1, respectively. Previous study (Tagashira et al., 1999) indicated that the activation energies of OCDD and OCDF for the thermal (homogeneous) oxidation were 400 and 330 kJ mol1, respectively. Apparently, application of the catalyst signicantly decreases the activation energy compared with the homogeneous oxidation reaction.

such as trichloro-, dichloro-, and monochlorodibenzo-p-dioxin/furans via dechlorination mechanism. Therefore, the dechlorination proceeds stepwise to give the chlorine-free product. Previous study (Bonte et al., 2002) also indicated that the PCDD/F congeners treated with catalyst possibly react to form trace amounts of CO2, H2O(g), and HCl. 3.4. Activation energies of OCDD and OCDF This study also investigates the activation energies of OCDD and OCDF decompositions by honeycomb catalyst A. Those two congeners are of the highest boiling points and longest half-life times among seventeen 2,3,7,8-substituted PCDD/Fs and usually predominate other congeners in the stack gas of different PCDD/F emission sources. To simplify the calculation, the pore diffusion resistance and membrane resistance are assumed negligible. The reaction rate constant was calculated by combining integral plug ow reactor and MarsVan Krevelen model (Chang and Weng, 1993). The source of the activation energy which enables a reaction to occur is often heat. At a higher temperature, more collisions occur and a higher fraction of the collisions will possess the activation energy needed for reaction. This temperature dependence of the reaction rate constant is expressed by the Arrhenius equation (Hung and Pfefferle, 1989):

4. Conclusions In this study, a PCDD/F-containing gas stream generating system which can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100 ng TEQ N m3 was developed. This new PCDD/F-containing gas stream generating device is applied in the investigation of the PCDD/F decomposition with two types of commercial V2O5WO3/TiO2-based catalysts (honeycomb) at controlled temperature, water vapor content, and space velocity. With the space velocity of 5000 h1 and inlet PCDD/F concentration of 4.17 ng TEQ N m3, the PCDD/F decomposition achieved with catalyst A increases from 68% to 84%, as the temperature is increased from 220 C to 280 C. Due to the higher vanadium loadings of catalyst B, the higher PCDD/F decompositions (89% to 91%) are observed compared to catalyst A at the same operating temperature and space velocity. In addition, experimental results also demonstrate that the presence of water vapor inhibits the PCDD/F decomposition via catalyst. That is attributed to the fact that water vapor may reduce the contact between PCDD/F molecules and active sites of catalyst, and hence, inhibits the rate of the reaction. However, highly chlorinated PCDD/F congeners tend to react with OH radical and are converted to lowly chlorinated PCDD/Fs via dechlorination mechanism in the presence of water vapor. Therefore, the slight in-

  F A0 1 ln 1 XA C A0 V R   Ea k A exp RT
k = rate constant for PCDD/F oxidation (s1), FA0 = molar ow rate of PCDD/Fs (mol s1),

1 2

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creases of OCDD and HpCDD decompositions are observed in the presence of water vapor content. Acknowledgments The authors gratefully acknowledge the nancial supports provided by NSC (NSC94-EPA-Z-008-002) and NCU-ITRI (04-03-02). Assistance provided by Prof. W.H. Ding of Department of Chemistry, National Central University, in analyzing the samples is also acknowledged. References
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