Chemical Engineering Journal 222 (2013) 274281

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Chemical Engineering Journal

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Inuence of geometrical parameters of honeycomb commercial SCR-DeNOx-catalysts on DeNOx-activity, mercury oxidation and SO2/SO3-conversion
T. Schwmmle a,, F. Bertsche a, A. Hartung b, J. Brandenstein c, B. Heidel a, G. Scheffknecht a
a b c

University of Stuttgart, Institute of Combustion and Power Plant Technology IFK, Department Fuels and Flue Gas Cleaning, Pfaffenwaldring 23, 70569 Stuttgart, Germany IBIDEN Porzellanfabrik Frauenthal GmbH, Gamserstr. 38, 8523 Frauental, Austria E.ON New Build & Technology GmbH, Alexander-von-Humboldt-Strae 1, 45896 Gelsenkirchen, Germany

h i g h l i g h t s
" Catalysts with different geometrical parameters have been tested. " Tests have been performed and compared in a micro reactor and bench reactor. " We investigated DeNOx-activity, SO2/SO3-conversion and mercury oxidation. " Small pitch favours DeNOx-activity due to enhanced external mass transfer. " Tests showed higher mercury oxidation at catalysts with increased wall thickness.

a r t i c l e

i n f o

a b s t r a c t
A systematic study on the inuence of geometrical parameters (pitch and wall thickness) of commercial high-dust honeycomb SCR-DeNOx catalysts on DeNOx-activity, mercury oxidation and SO2/SO3-conversion is described. All catalysts had an identical chemical composition of 0.6 wt.% V2O5. The study was conducted in a laboratory micro reactor and a technical scale bench reactor and focuses on the effect of different honeycomb geometrical parameters on the reactions at the catalysts. The combined variation of pitch and wall thickness showed lower DeNOx-activity at catalysts with larger channel openings. This indicates mass transfer limitations when the ow regimes are developed in the catalysts channels due to the relatively fast reaction kinetics of the DeNOx-reaction. Results showed that the SO2/SO3-conversion is linearly dependent on catalysts wall thickness. Mercury oxidation increased slightly linear with increasing wall thickness of the catalyst, indicating that the reaction takes also place in the catalysts bulk because of its slow chemical reaction kinetics in contrast to DeNOx-reaction being controlled by diffusion. The importance of ue gas HCl-concentration on mercury oxidation was pointed out. Additionally, research on the co-inuence of DeNOx-reaction and SO2/SO3-conversion was performed. A strong inhibition of SO2/SO3-conversion by ue gas ammonia was shown. However, DeNOx-activity is enhanced by conditioning with SO2 due to superior acidity of active sites. Summarising the results, due to the drawback of elevated SO2/SO3-conversion, higher risk of channel blocking and material costs, increasing wall thickness cannot be considered a reasonable strategy to enhance mercury oxidation by SCR catalysts. 2013 Elsevier B.V. All rights reserved.

Article history: Received 27 November 2012 Received in revised form 11 February 2013 Accepted 15 February 2013 Available online 26 February 2013 Keywords: SCR-DeNOx-catalysts DeNOx-activity Mercury oxidation SO2/SO3-conversion

1. Introduction Over 40% of the global electricity is produced in coal red power stations, either by ring hard coal or lignite [1]. The total amount of coal consumed globally will increase over the next years. Coal derived ue gas consists of several pollutants, such as nitrogen oxides (NOx), sulphur oxides (SO2, SO3), particulate matter (PM) and trace elements e.g. mercury (Hg). Particulate matter is
Corresponding author. Tel.: +49 711 685 67760; fax: +49 711 685 63491.
E-mail address: tobias.schwaemmle@ifk.uni-stuttgart.de (T. Schwmmle). 1385-8947/$ - see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cej.2013.02.057

controlled by electrostatic precipitators or baghouse lters. SO2 is removed by dry or wet ue gas desulphurisation (FGD). During technical combustion, nitrogen oxides are mainly formed by two different mechanisms, namely by oxidation of the nitrogen content of the fuel and depending on combustion temperature via oxidation of air-nitrogen [2]. For the reduction of NOx (DeNOx), the selective catalytic reduction process (SCR) is the most common applied technology since it was commercially vended in the 1980s [3,4]. The overall reaction can be expressed as:

4NO 4NH3 O2 ! 4N2 6H2 O

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Ammonia (NH3) is therefore injected upstream of the catalyst unit and reacts with NOx at the catalyst to nitrogen (N2) and water (H2O). SCR-catalysts are designed either as homogeneous extruded ceramic honeycombs, plate catalysts or corrugated catalysts. Various catalyst materials have been investigated in the last decades [5]. Today, the most common carrier material for power plant application is TiO2 in its anatase modication and vanadia (V2O5) as active phase [6]. Certain promoters, such as WO3 or MoO3, are added in order to increase the thermal stability of the TiO2 phase [7]. As an undesired side reaction, sulphur dioxide is heterogeneously oxidized to sulphur trioxide at the SCR catalysts, which is called SO2/SO3-conversion:

1 SO2 O2 ! SO3 2

The rate of this reaction is linked to the vanadia content of the catalyst [5]. There are various reactions of SO3 with other ue gas components, causing corrosion or deposits downstream of the SCR-unit. In SCR-DeNOx-catalysts, WO3 is introduced to suppress the SO2/SO3 conversion [4]. Depending on their origin, coals contain 0.02 up to 10 mg/kg mercury [8]. At high temperatures in the combustion chamber, mercury is released in its elemental form Hg0 [9]. When ue gas cools down, gas-phase transformations occur and elemental mercury is homogeneously or heterogeneously oxidized to Hg2+. Due to adsorption processes, mercury is partially bound on y ash particles (HgP). Elemental mercury is considered as inert and is almost insoluble in water. In ue gases of combustion processes, the dominant oxidized mercury compound is HgCl2, as it was shown by theoretical calculations performed by Martel [10]. The overall oxidation reaction of elemental mercury in ue gas can be described as:

Since combustion of coal accounts for almost 50% of the global mercury emissions [18] and due to its high toxicity, mercury was identied as a chemical of global concern. There are global efforts to reduce mercury emissions from coal red power plants [18]. Driven by the reduction of the overall CO2-emissions in coal red power plants, co-ring of biomass and refuse derived fuels is an alternative way to CCS-technology to reduce CO2-emissions [19]. However, standard commercial high-dust SCR-DeNOx-catalysts have not initially been designed for increased mercury oxidation over a long time at various fuels. Additionally, high-dust SCRcatalysts are facing further challenges, such as erosion and blocking by y ash [20], leading to lower efciency and lifetime of the catalyst. Standard commercial honeycomb catalysts are produced with a 7 mm pitch. Increasing the catalyst pitch at honeycomb catalysts would reduce the risk of blocking of the channels. Thicker walls of the catalysts honeycomb structure would lead to an increased lifetime of the catalyst monolith in the ue gas. It is assumed, that the modication of the catalysts geometrical parameters will also have an effect on the reactions catalysed. In order to quantify the extent of this effect, a systematic study at different test conditions is performed, giving an overall insight in the most important reactions for emission reduction on commercial SCR-DeNOx-catalysts. Finally, the economic aspects of different catalyst geometries of honeycomb catalysts are addressed. 2. Experimental method 2.1. Catalysts In this study, the behaviour of standard commercial honeycomb catalysts is addressed, which are one of the major catalyst types for power plant application. The catalysts were of V2O5WO3/TiO2type with a V2O5-content of 0.6 wt.%. This is a typical value for high-dust catalysts in coal-red power plants located downstream of the boiler [5,20,21]. Honeycomb catalysts have been produced by kneading and extrusion followed by calcination in full scale monolith size (150 mm 150 mm) by IBIDEN Porzellanfabrik Frauenthal GmbH, Austria. All catalysts had the same chemical composition, which was veried by surface and bulk XRF-analysis. Geometrical properties of honeycomb catalysts can be characterized by pitch, wall thickness and length. Fig. 1 shows a honeycomb catalyst sample, with the homogeneous catalyst wall (w) and the clear width (d) of the ow channel. The catalyst pitch is equal to one clear width and one wall thickness. A combined variation of pitch and wall thickness has been performed, in order to get an overview on both: channel opening and wall thickness of the catalyst. In Table 1, the dimensions of the tested catalysts are listed: The catalysts are named according to their pitch. Reference is a 7 mm pitch catalyst with 21 21 channels of the full size monolith, which is the typical high-dust catalyst pitch. Variation of pitch was performed in the range of 6 mm up to 9.7 mm and accordingly

2Hg0 4HCl O2 $ 2HgCl2 2H2 O

The impact of SCR-DeNOx-catalysts on the oxidation of mercury was investigated by several authors in lab- and full scale measurements [9,11,12]. They demonstrate consistently that the oxidation of mercury is enhanced in the presence of SCR-catalysts. The results were highly dependent on coal composition, especially on halogen content (Cl, Br), but also on sulphur content. Catalyst deactivation state plays a key role in mercury oxidation. There are various reaction-pathways discussed for mercury oxidation at SCR-catalysts. Niksa and Fujiwara [13] and Hong et al. [14] proposed EleyRideal reaction mechanisms, in which HCl adsorbs on the active sites of the catalyst surface, competing with ammonia. Either in the gas phase or as weekly adsorbed species, mercury reacts with the adsorbed HCl. Another possible mechanism is the Deacon process, proposed by [11] and described as:

4HCl O2 $ 2Cl2 2H2 O Hg0 Cl2 $ HgCl2

4 5

In this possible reaction pathway for mercury oxidation at SCR-catalysts, Cl2 is produced by the reaction of HCl with catalyst active sites (Eq. (4)). Highly reactive Cl2 subsequently oxidises Hg0 in the gas phase (Eq. (5)). It was shown by [15] that the direct oxidation of elemental mercury with Cl2 and Br2 in the gaseous phase is faster than the indirect reaction of Eq. (3). Due to its physical and chemical properties [16], HgCl2 adsorbs on y ash and can be absorbed in wet ue gas desulphurisation units [9,17], leading to lower overall mercury concentrations in the gas phase. Therefore, the combination of SCR-DeNOx-catalyst, ESP and wet-FGD, which is a common set-up for installed air pollution control devices in Western Europe, forms an ideal arrangement with the co-benet of mercury removal.

Fig. 1. Geometrical properties of honeycomb catalysts.

276 Table 1 Dimensions of the tested catalysts. Pitch (mm) P6 P6.7 RC P8.2 P9.2 P10 6.0 6.7 7.0 8.2 9.2 9.7

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area of the catalyst, are of great importance. These values are calculated at standard temperature and pressure (STP).
Wall (mm) 0.8 0.9 0.9 1.0 1.2 1.4

2.2.1. Micro reactor In micro reactors, samples of 3 3 channels of the full scale monoliths are tested in laboratory in synthetic ue gas. The reactor is constructed of glass. Flue gas ow rate is adjusted to a LV of 1 m/ s and an AV of 27.5 m/h. Due to different geometries of the catalysts, the length of the catalysts has been adjusted to meet the test conditions, resulting in catalyst samples with differing length. 2.2.2. Bench reactor This technical scale reactor is constructed of stainless steel and ue gas is generated by a propane burner. In a bench reactor, full scale catalyst monoliths of 150 mm 150 mm are tested in their original manufactured dimensions. Flue gas ow rate is set to 150 m3/h. Results of the bench reactor test can directly be transferred to full scale catalyst reactors and bench reactor measurements are a reference for guarantee values of manufacturers [20]. Due to safety reasons, no mercury oxidation measurements were performed at this reactor. 3. Determined parameters In order to fully cover all relevant reactions at the SCR-DeNOxcatalysts, DeNOx-activity, SO2/SO3-conversion and mercury oxidation have been researched in this study. 3.1. DeNOx-activity DeNOx activity describes the performance of the catalyst related to NOx-reduction with ammonia, considering the AV. It is determined at dened and xed NH3/NO-ratios of a = 1.0 in bench reactor and a = 1.2 in micro reactor. There is a higher NH3/NO ratio applied at the micro reactor in order to minimise the effect of possibly unequal distribution of ammonia in the small sample size. At this test condition, there is always excess ammonia in the ue gas, showing the maximum value of NOx-reduction. DeNOx-activity is calculated according to the rst order reaction equation in the following formula [22] with the AV and NOx-reduction g(a):

wall thickness was varied between 0.8 mm and 1.4 mm, covering the whole reasonable range for high-dust application. 2.2. Test setup Investigations on the reactions at the catalyst have been performed at two different test rigs: The micro reactor and the bench reactor, both constructed and operated according to the guideline for testing of DeNOx catalysts [22]. Fig. 2 describes the general setup of the reactors. In both test rigs, ue gas is doped with the relevant components, which are added from gas bottles or by evaporation of liquid solutions of these compounds. Table 2 summarizes the test conditions. Water content is adjusted either by evaporation or by condensation. The gas mixture is heated up in the reactor. Thermocouples up- and downstream of the catalyst ensure a constant temperature of 380 C. Samples are taken at ports up- and downstream of the catalyst and analysed as described below. For the operation of the test reactors and testing of the catalysts, the linear velocity (LV), describing the ue gas ow rate divided by the catalyst surface area exposed to ow, and area velocity (AV), which is the quotient of ue gas ow rate and geometric surface

K NOx a

hmi h

AV ln1 ga

Nitrogen oxide concentration up- and downstream of the catalyst is measured by continuous monitors, working on the principle of chemiluminescence [22].
Fig. 2. Test reactor design.

3.2. SO2/SO3-conversion SO2/SO3-conversion is an indicator for the amount of SO3 produced over the catalyst. SO3-concentration is measured up- and downstream of the catalysts in the ue gas according to the VDI method 2462 [23] by controlled condensation of sulphuric acid aerosols in a glass condenser at a temperature of 85 C. The temperature is high enough to avoid condensation of water in ue gas, but low enough to condense SO3 as sulphuric acid aerosols. The conversion is calculated considering the ue gas SO2-concentration, which was measured by continuous monitors working on the principle of UV absorption, and the SO3-inlet- and outlet concentration according to [22]:

Table 2 Test conditions. Micro reactor LV (m/s @ STP,wet) AV (m/h @ STP,wet) Channels Flue gas ow rate (m3/h @ STP) Temperature (C) O2 (vol.%) CO2 (vol.%) N2 H2O (vol.%) NO (ppmv; STP dry) NH3 (ppmv; STP dry) SO2 (ppmv; STP dry) Hg (lg/m3; STP dry) HCl (mg/m3; STP dry) 1 27.5 Up to 9 1.2 380 4 15 Balance 7 300 360 500 50 10100 Bench reactor 2.5 1018 Up to 625 150 380 5 14 Balance 6 300 300 500

SO2 =SO3 conversionj23 %

cSO3 out cSO3 in 80 cSO2 in

The different molar ratios of SO2 and SO3 account for the factor of 80 [%]. SO2/SO3-conversion coefcient is calculated similar to the DeNOx-activity.

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3.3. Mercury oxidation The concentration of elemental mercury is measured by a continuous mercury analyser (Hg2010, Semtech Metallurgy AB) working with cold vapour atomic adsorption and a Zeeman background correction. Oxidised mercury is determined as the difference between total mercury, which is measured by wet chemical reduction with tin(II)chloride solution upstream of the analyser, and the concentration of elemental mercury. Mercury oxidation is therefore calculated according to:

jHg0 =Hg2 %

cHg2 out cHg2 in cHg0 in

100

It has to be stressed, that the in- and outlet total mercury concentration has to be identical, in order to ensure steady state operation of the catalyst. These conditions are not reached before sufcient preconditioning time.

4. Results 4.1. DeNOx-activity The most important reaction, which SCR-DeNOx-catalysts are originally designed for, is the NOx-reduction. First of all, the effect of the different pitch size on NOx-reduction was studied in micro reactor at selected fresh catalyst samples. Measurements were performed with the fresh catalyst sample in absence of sulphur dioxide in the ue gas. Following, the catalyst was exposed to SO2 for some days and the measurements were repeated. Fig. 3 shows the results of these measurements. The results of the experiments in the presence and in the absence of sulphur dioxide differ signicantly. Fresh catalyst samples show a limited sulphating of active sites. When exposed to ue gas containing SO2, the Lewis and Brnsted acidity of the active sites is increased due to the adsorption of SO2 [24]. Being a Brnsted base, NH3 is adsorbed at the acidic active sites, leading to an increased DeNOx-activity. At TiO2-based industrial SCR-catalysts, sulphating is only partially and reversibly and does not cause any deactivation, rather leading to enhanced DeNOx-activity [25]. In contrast to Svachula et al. [26], it can be stated here, that for measuring the DeNOx-activity of commercial SCR-DeNOx-catalysts, preconditioning is essential because there is a difference in activity comparing fresh and preconditioned results. For commercial application, sulphating is performed during the rst start-up of the plant with installed new catalysts, so the test with ue gas SO2 shows the more realistic test conditions. Nevertheless, measurements at

3000 mg/m3 SO2 (not shown here) showed no further increase in DeNOx-activity. The comparison of catalysts with different pitch at constant area velocity leads to the conclusion, that there is no inuence of the catalysts geometry on DeNOx-activity evident, regardless of the sulphating of the active sites. An inuence of the thickness of the wall cannot be seen from these measurements, which can be referred to the fast reaction kinetics of the NOx-reduction. According to [27], the reaction takes place only in the rst 50 lm of the catalyst walls. Fig. 4 shows the DeNOx-activity measurement of all tested catalyst determined at the bench reactor. When comparing the results at the micro reactor and bench reactor of the measurements of the reference catalyst RC, it is obvious that the DeNOx-activities are approximately the same. Deviations can be explained by the higher NH3/NO-ratio in micro reactor measurement, leading to an excess of ammonia and slightly higher DeNOx-activity. Catalyst reactors of full scale power plants are designed with DeNOx-activity values of fresh honeycomb catalysts of around 40 m/h [20], thus the determined values are quite representative for standard commercial honeycomb catalysts. These measurements also conrm the fast reaction kinetics of NOx-reduction, since there is no dependence on wall-thickness. In contrast to the results of the micro reactor, a decrease of DeNOx-activity was measured with increasing pitch. This can be explained by differing ow conditions. The reaction process in the catalyst is the result of external mass transfer (from bulk gas phase to the surface of the catalyst), internal mass transfer (diffusion of reactants through internal pores to and from active sites) and chemical reaction kinetics. Fig. 5 gives an insight in ue gas ow regimes through catalyst channels. In the inlet-zone, ue gas enters the channel, while the ow prole is not yet fully developed. There is mass exchange from the bulk phase to the surface due to convection and diffusion. Downstream the inlet zone, the laminar ow prole has been fully developed. In this prole, mass exchange is only due to diffusion, being limited when compared to convection. In literature [20], the inlet-zone of a catalyst channel is often called turbulent inlet zone. Therefore, the rate of NOx-reduction is much greater in the inlet zone of the catalyst. The dimensions of the test samples for micro reactor and bench reactor result in different ratios of free width (d) to length (l). For micro reactor catalysts, the d/l ratio equals to 0.03. In contrast to that, the d/l ratio of full scale monoliths, investigated with the bench reactor, varied between 0.005 and 0.008. Due to the short length of the micro reactor samples and the relatively high area velocity, the fraction of the turbulent

Fig. 3. DeNOx-activity of catalysts with different pitch at NH3/NO = 1.2 in micro reactor.

Fig. 4. DeNOx-activity of all 6 tested catalysts measured in bench reactor at NH3/ NO = 1.

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Fig. 5. Flow conditions in a catalyst channel.

zone is dominating, thus no dependence on pitch of DeNOxactivity can be observed. In bench reactor (long samples), where mass exchange is mainly controlled by diffusion, the impact of ow regime on DeNOx-activity is obvious, resulting in reduced activity at larger channel openings. This effect of external mass-transfer on NOx-reduction at honeycomb catalysts was also observed and described by [26,28,2931]. They considered not only the interphase mass transfer, but also the intra-phase mass transfer in the catalyst porous system. Inter-phase mass transfer can be described by correlations of the Sherwood number and is described in detail in the given references. 4.2. SO2/SO3-conversion SO2/SO3-conversion was determined by micro reactor and bench reactor measurements in the absence of ammonia in ue gas after at least 48 h of preconditioning. Hence, the values presented in Fig. 6 show the maximum values at the measured SO2-concentration. For decreasing ue gas SO2-concentrations, the relative SO2/SO3-conversion will increase, however the absolute SO3concentration downstream of the SCR is decreasing. This is in good agreement with previous ndings in [32,33]. Differences between the micro reactor and bench reactor values can be referred to temperature deviations. The effect of temperature on SO2/SO3conversion was discussed in a previous work [33], pointing out the exponential dependence. After nishing the test series in the micro reactor, a deviation in temperature of 14 C above 380 C during the SO3-measurementes was determined. This explains the deviations between the measurements in micro- and bench reactor.

It can be seen, that there is an increase in the SO2/SO3-conversion for higher pitch in micro reactor measurements. Unfortunately, the results gained in bench reactor measurements, as presented in Fig. 6 show a less distinctive interrelation. Further correlations have been performed and are shown in Figs. 7 and 8. Unlike the characteristics of the DeNOx-reaction, a dependency of the SO2/SO3-conversion on pitch cannot be traced back to the clear width of the catalysts channels. Taking into account that NOx-reduction is limited by external mass transfer and diffusion, mass transfer controlled SO2-conversion would lead to lower SO2/SO3-conversion values. As shown in Fig. 7, there is a linear dependency of the SO2/SO3-conversion on the catalysts wall thickness. This effect can be explained by the relatively low kinetics of this chemical reaction [32]. In contrast to NOx-reduction, which proceeds rapidly when the reactants occupy the active sites, the reaction of SO2 is comparatively slow. Thus, SO2 diffuses in the catalysts bulk and penetrates into the macroporous system of the catalyst wall. Thus, the reaction takes place within the whole catalyst material. According to Dunn et al. [34], SO2 oxidation has

Fig. 7. Correlations of SO2/SO3-conversion measured in micro reactor.

Fig. 6. SO2/SO3-conversion coefcient determined in micro- and bench reactor without NH3, NO.

Fig. 8. Correlation of SO2/SO3-conversion measured in bench reactor.

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a very low turnover frequency, caused by the inefcient adsorption of SO2 on the acidic surface vanadia species under reaction conditions. Correlations with limited amount of variations have also been performed by Svachula et al. [32], who concluded, that there is a linear dependency of SO2 oxidation on catalyst wall thickness. Since the catalysts wall and therefore the whole volume of the catalyst is responsible for the increase in SO2/SO3-conversion, a correlation of the SO2/SO3-conversion over the weight per channel has been performed in Fig. 7. The weight per channel ratio was calculated by dividing the total mass of the sample by its amount of channels and provides plausible results, tracing back SO2/SO3-conversion directly to the catalysts mass. For bench-reactor SO2/SO3conversion measurements, a similar correlation with catalysts mass was performed (Fig. 8). For a comparative presentation, the SO2/SO3-conversion was divided by the catalysts sample mass. These mass-specic values show very similar results for all catalysts investigated. However, the value of catalyst RC is quite high, which can possibly be traced back to a measurement error. All these ndings indicate that SO2/ SO3-conversion is directly dependent on catalysts mass. However, referring SO2/SO3-conversion to catalysts surface, as performed at the conversion coefcient in Fig. 6, is expected to lead to an increase with increasing wall thickness. As a further consequence, comparison of non-mass-specic values of SO2/SO3-conversion for catalyst materials with different chemical composition can only be performed for identical catalyst wall thickness. 4.3. Mercury oxidation As the third reaction, mercury oxidation at the catalysts with different pitch was studied. In Fig. 9, mercury oxidation at the commercial reference catalyst at micro reactor test conditions (without NH3, NO and SO2) is related to ue gas HCl-concentration. Despite mercury ue gas concentration is tremendously lower compared to the ue gas HCl-concentration (cHCl/cHg = 1000), there is a dependency on the HCl-content. At HCl concentrations higher than 50 mg/m3, the increase in mercury oxidation reaches a limiting value. Therefore, the concentration of 100 mg/m3 was chosen as the upper limit of the experiments. Thus, the studied range of HCl-concentration covers almost the whole range of full scale power plant HCl-concentrations, which is strongly depended on coal origin. Kolker et al. [35] presented a range of 105000 mg Cl/ kg coal, resulting in ue gas concentrations of about 1500 mg HCl/m3. However, most of the coals red in boilers globally have low Cl-content, resulting in ue gas HCl-concentrations lower than 100 mg/m3. It is commonly accepted, that HCl plays an important role in mercury oxidation [13,14,36], but no evidence was given, why there is such an abundance of HCl needed, even if there are no other possibly disturbing ue gas components involved.

Fig. 10. Effect of catalysts wall thickness on mercury oxidation of SCR-DeNOx catalyst.

Fig. 10 shows the correlation of the mercury oxidation with catalysts wall thickness at different HCl-concentrations. For all investigated HCl-concentrations, there is a slight increase of mercury oxidation with catalysts wall thickness and pitch. As shown at the DeNOx-reaction, a fully diffusion controlled reaction results in decreasing or at least constant values for increasing pitch/wall thickness at the micro reactor. The results reveal that mercury oxidation does not only take place at the surface of the catalyst, indicating slow chemical reaction kinetics. Thus, the reactants (mercury and/or HCl) are able to penetrate into the catalysts macroporous system. These results are in contrast to the theoretical calculations performed by Niksa and Fujiwara [13], showing increased mercury oxidation at lower pitch sizes respectively low channel openings. This was explained by mass transport phenomena. Senior [37] developed a model for mercury oxidation at SCRDeNOx-catalysts and concluded, based on data of [9], that there is lower mercury oxidation at high dust catalysts with greater pitch compared to low dust catalysts with lower pitch. However, it has to be kept in mind that in [37], only two catalysts with a difference in wall thickness of 0.4 mm were considered. In this study, more catalysts with a range of over 0.6 mm were measured. Additionally, Seniors calculations have been performed at a NH3/NO-ratio of 1. Taking into account the results gained at the DeNOx-activity measurements above and the assumption, that DeNOx-activity and mercury oxidation takes place at the same active sites, it is obvious, that there is higher mercury oxidation at the low pitch catalyst, due to fewer active sites occupied by the DeNOx-reaction because of superior mass exchange. Different values of mercury oxidation in Seniors study compared to the values presented here can be referred to lower residence time in the catalyst at the experiments, leading to lower mercury oxidation at the samples. 4.4. Combined reactions In addition to the research on single reactions at the catalyst, which were performed in order to study the reactions in detail, experiments observing the interaction of the reactants involved were conducted. Fig. 11 shows the SO2/SO3-conversion during parallel NOx-reduction measured at catalyst P8.2 in the micro reactor. There is a linear increase of NOx-reduction for increasing ammonia/nitrogen oxide ratio, proving that the availability of ammonia is the limiting factor of the reaction up to the stoichiometric ratio of 1. At this point, reaction order with regard to NH3 becomes zero. NOx-reduction is not exactly proportional to NH3/NOratio, which can also be referred to the low residence time of the gas inside the catalyst. DeNOx-activity was also measured with ue gas mercury and HCl (100 mg/m3). The results showed no

Fig. 9. Effect of ue gas HCl-concentration on mercury oxidation.

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constant. Larger channels at P10 lead to lower pressure drop compared to P6. 5. Discussion There is a great inuence of honeycomb catalysts geometry on the main relevant reactions at the SCR-DeNOx-catalyst, but for the operation of SCR units of full scale power plants, there are several other factors to be considered. Due to the fact, that in this study a combined variation of pitch and wall thickness has been performed, the effect of the two factors has to be discussed separately. SCR-DeNOx-catalysts are -regarding the material usage- very ineffective related to DeNOx-performance. Only a very thin surface layer of around 50 lm is needed for the reaction to take place. Nevertheless, walls of commercial SCR-DeNOx-catalysts have a thickness of around 1 mm. As a result, the monolith wall thickness could be reduced signicantly without affecting the DeNOx-performance. Furthermore, it would be benecial to reduce the wall thickness in order to reduce the undesired SO2/SO3 conversion and catalyst cost. The pressure drop will also be lower due to higher void fraction. Unfortunately, mercury oxidation at the catalysts with lower wall thicknesses would be reduced simultaneously. On the other hand, regarding the pitch of the catalyst, it would be desirable for increased NOx-reduction to apply small pitch catalysts due to shorter distances of diffusion and gassolid mass transfer limitations of this fast reaction. However, there are several constraints from practical point of view, mainly related to application limitations and the catalyst production process. The applicable channel clear width (or pitch) is mainly determined by the particulate content of the ue gas, the characteristics of the dust, and the allowable pressure drop across the SCR reactor. The more dust, the larger the pitch size in order to avoid or minimize dust deposition and catalyst plugging. Catalyst channels in high-dust applications (where the catalyst is located immediately after the boiler, processing the full dust loading leaving the boiler) will therefore be signicantly larger than in a tail-end installation (the catalyst is located downstream of a particulate collection device and a ue gas desulphurization FGD system). The honeycomb catalyst wall thickness for high-dust applications at coal-red boilers shall be within a certain range (typically between 0.8 and 1.1 mm) to maintain mechanical resistance in operation and during a possible catalyst regeneration process. For tail-end or gas red applications small pitch catalysts (2 4 mm) with a reduced wall thickness (0.250.5 mm) can be used. Honeycomb catalysts are obtained by extruding a ceramic paste made by catalytic material followed by a delicate drying step. Therefore a certain ratio between inner wall thickness and channel clear width or respectively a certain range of the monolith void fraction (typically between 70% and 80%) shall be maintained for successful production. Also the (transversal) compression strength of the nal honeycomb catalyst is strongly affected by the number of cells and the inner wall thickness. Sufcient compression strength is required for packing of the catalyst monoliths into the steel frames. 6. Conclusion A systematical study on the effect of the variation of geometrical parameters of honeycomb catalysts has been performed. Although there are commonly accepted correlations for the comparison of different test conditions based on reaction kinetics (e.g. DeNOxactivity) available, the specic test conditions have to be considered. Micro reactor studies in laboratory with small samples are a suitable tool for systematic studies, especially regarding still not

Fig. 11. SO2/SO3-conversion at parallel NOx-reduction.

inuence of the reactants of the mercury oxidation reaction on DeNOx-activity, which can be explained by the low mercury concentration and the acidic nature of the active sites. However, SO2/SO3-conversion is inhibited by parallel DeNOx-reaction. For the NH3/NO-ratio of 0.8, the rate of SO3 formation is almost zero. Active sites are preferentially occupied by ammonia, hence SO2 cannot be converted to SO3. Moreover, it can be assumed, that adsorbed ammonia constrains the diffusion of SO2 through the catalysts walls. Measurements and calculations by Orsenigo et al. [24] showed the same behaviour, but the inhibition occurs rstly around NH3/NO = 1.0 at an area velocity of 10 m/h with a slight tendency to lower ratios at increased area velocities. Due to the high area velocities (AV = 27.5 m/h) in this study, the inhibition occurs at relatively low NH3/NO ratios because of the high NH3-coverage of the active sites. The interaction of DeNOxreaction and SO2/SO3-conversion will also take place in full scale SCR-reactors of coal red power plants. In the rst catalysts layer, corresponding to high NH3/NO ratios, the SO2/SO3-conversion is low and increases signicantly at the last catalyst layer where no ammonia is present. Thus, the values of SO2/SO3-conversion in Fig. 6 represent conditions in the last catalyst layer of the full scale high-dust SCR-DeNOx reactor.

4.5. Pressure drop In Fig. 12, pressure drop over the tested catalysts measured in bench reactor and normalised to 1000 mm length is shown. Pressure drop increases with decreasing clear width respectively cell opening. This will directly inuence the operating costs of the power plant by increased power consumption of the induced draught. Due to combined variation of pitch and wall thickness, the void fraction, which is also relevant for pressure drop, stays almost

Fig. 12. Pressure drop over tested catalysts measured at bench-reactor and normalised to 1000 mm length.

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fully claried reaction mechanisms and interactions of mercury oxidation. Bench reactor test of full scale monoliths are a commercial tool for suppliers and catalysts manufacturers to get reliable, near full scale comparison data in order to screen guarantee values. However, considering the results of micro reactor and bench reactor tests presented, the ow regime and the mass transfer has to be considered. DeNOx-activity decreases when catalysts clear width respectively the channel diameter increases. This effect could be traced back to mass transfer limitations. Increased wall thickness of catalysts could lead to higher mercury oxidation, but the drawback is a tremendously higher SO2/SO3-conversion which almost linearly increases with wall thickness in the studied range. Both reactions are to a certain extent limited by chemical reaction kinetics. The reactants use the whole catalysts bulk and not only the surface (unlike DeNOx reaction) for their reaction. SO2/SO3-conversion is signicantly inhibited by ue gas ammonia, which is adsorbed at the catalyst. Hence, the DeNOx-reaction takes place at the rst catalysts layers of the full scale catalyst reactor. Signicant conversion of ue gas SO2 to SO3 will only occur in the last catalyst layer where the ammonia concentration is almost zero. To enhance the desired reactions of DeNOx and mercury oxidation, the catalysts pitch of commercial catalysts could be slightly reduced and the wall thickness increased to a certain extent. However, this would increase the material costs due to higher amount of catalyst material needed and would also lead to higher pressure drop and a higher risk of catalyst blocking by y ash. Unfortunately, this would also boost SO2/SO3-conversion at the catalysts, which is highly undesired by power plant operators. Therefore, increasing of mercury oxidation by variation of catalysts pitch or wall thickness is not possible without drawbacks. However, further investigations on the interaction of the reactants with the catalysts material will be performed in order to gain a greater insight into the reaction mechanism and its dependencies. Still, there are methods available for selectively increasing mercury oxidation by variation of (chemical) composition of the catalyst, which are currently under research in the ongoing project. Acknowledgements The authors greatly thank IBIDEN Porzellanfabrik Frauenthal GmbH for providing the catalyst samples and E.ON New Build and Technology GmbH for performing the bench-reactor tests. The work was funded by the European Commission within the DEVCAT project under the Research Fund for Coal and Steel of the European Commission (RFCR-CT-2010-00012). References
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