Activity and characterization of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for the SCR of NO with CO in the presence of SO2 and HCl

SO₂ and HCl are major pollutants emitted from waste incineration processes. Both pollutants are difficult to remove completely and can enter the catalytic reactor. In this work, the effects of SO₂ and HCl on the performance of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for NO removal were investigated in simulated waste incineration conditions. The characterizations of the catalysts were analyzed by BET, SEM/EDS, XRD, and ESCA. Experimental results indicated the 1%Rh/Al₂O₃ catalyst was significantly deactivated for NO and CO conversions when SO₂ and HCl coexisted in the flue gas. The addition of between 2 and 10 wt.% Na promoted the activity of the 1%Rh/Al₂O₃ catalyst for NO removal, but decreased the CO oxidation and BET surface area. The catalytic activity for NO removal was inhibited by HCl as a result of the formation of RhCl₃. Adding Na to the Rh/Al₂O₃ catalyst decreased the inhibition of SO₂ because of the formation of Na₂SO₄, which was observed in the XRD and ESCA analyses. SEM mapping/EDS showed that more S was residual on the surface of the Rh-Na/Al₂O₃ catalyst than Cl.     

Catalytic role of vanadium(V) sulfate on activated carbon for SO2 oxidation and NH3-SCR of NO at low temperatures

Carbon-supported catalyst with vanadium(V) sulfate (V₂O₃(SO₄)₂) as active component was prepared, characterized and tested for SO₂ and NO catalytic removal. Result shows that this catalyst is very active towards SO₂ oxidation and selective catalytic reduction of NO with NH₃ in the low temperature range of 100–250 °C.     

Synergetic catalytic removal of Hg0 and NO over CeO2(ZrO2)/TiO2

A series of CeO₂(ZrO₂)/TiO₂ monolith catalysts were investigated for catalytic oxidation of Hg⁰ and NH₃-SCR of NO. Effect of flue gases components on catalytic oxidation of Hg⁰ was mainly studied. Results showed that the CeO₂(ZrO₂)/TiO₂ catalyst exhibited high efficiency for catalytic oxidation of Hg⁰ at 240–400 °C without adding other oxidant, and its catalytic performance for NH₃-SCR of NO was not affected. NH₃ had slight inhibitory effect while SO₂ and NO had no influence on catalytic oxidation of Hg⁰, but O₂ obviously improved catalytic oxidation of Hg⁰ for its oxidation susceptibility.     

Impacts of acid gases on mercury oxidation across SCR catalyst

A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO₂, and SO₃ on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O₂, CO₂, H₂O, NO, NO₂, and NH₃, and N₂. HCl, SO₂, and SO₃ were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5–50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO₂ and SO₃ showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO₂ and SO₃, by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO₂ (2000 ppm), and SO₃ (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst.     

Simultaneous removal of SO2 and NO by low cost sorbent-catalysts prepared by lime, fly ash and industrial waste materials

The potential of the sorbent-catalysts prepared from three low cost materials, i.e., the lime, fly ash and some industrial waste material containing iron oxide, have been investigated for simultaneous removal of SO₂ and NO _x from flue gas in the temperature range 700–850 °C. NH₃ was chosen as the reducing agent for NO reduction in this study. Experimental results showed that SO₂ and NO could be simultaneously removed efficiently in the absence of O₂ at the temperature window of 700–800 °C. The effect of product layer generated from SO₂ removal on NO removal was not obvious. NO removal efficiency was strongly inhibited by O₂, which was attributed to the partial oxidation of NH₃ to NO over the sorbent-catalysts in the presence of oxygen. Neither NO₂ nor N₂O by-product was detected both in the absence and presence of O₂. Three routes were suggested to overcome the negative effect of O₂. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Development of rate expressions for the catalytic decomposition of nitric oxide with ammonia on iron oxide

The reduction of nitric oxide with ammonia on iron oxide catalysts has been studied in a continuous-flow recycle reactor using simulated flue gas in the temperature range from 573 to 673 K. NO and HN₃ concentrations were varied between 0 and 1000 vpm, O₂ and H₂O concentrations between 0 and 9 vol.-%, the remainder being nitrogen. In the presence of oxygen, the formulated reaction rate equation describes the measured rates of the main reaction NO + 2/3 NH₃ ? 5/6 N₂ + H₂O. Its form corresponds to the Langmuir-Hinshelwood type. The rate equation well fits the data, which cover the whole industrial temperature and concentration range. In the absence of oxygen, the measured reaction rates can be best described by a power law.     

Vanadium-loaded carbon-based monoliths for on-board NO reduction: Influence of nature and concentration of the oxidation agent on activity

A series of polymeric carbon-coated monoliths oxidized with either concentrated or 2N HNO₃, H₂O₂ or H₂SO₄ and subsequently loaded with 3 wt.% vanadium were prepared. The influence of the different oxidation treatment conditions on the SCR (selective catalytic reduction) catalytic activity, texture and chemical surface properties were studied. Similar pore distribution and pore volumes were observed for the four oxidized samples, indicating that surface modification of carbon supports has been successfully made without disrupting the original textural structures of activated coated monoliths. The surface chemistry created by the oxidation treatments has two effects on the catalytic activity. One of these is that higher surface acidity results in higher NO reduction up to a certain extent. The highest acidities seem to promote a sufficiently strong NH₃ adsorption on the surface such that the lack of efficient desorption decreases the overall NO conversion efficiency. The other effect is that a low surface acidity does not seem to promote vanadium dispersion and fixation, thereby also resulting in decreased NO reduction efficiency.     

CO and NO adsorption for the IR characterization of Fe2+ cations in ferrierite: An efficient catalyst for NOx SCR with NH3 as studied by operando IR spectroscopy

Iron was introduced by ionic exchange inside the FER structure in order to yield a Fe-FER series with increasing metal loading. Characterization of the Fe²⁺ cations by adsorption of CO at liquid nitrogen temperature followed by infrared spectroscopy allowed to identify three distinct sites for iron. The most abundant iron species are located on easily accessible sites of the FER structure, whereas high metal loading is required to observe more confined Fe²⁺ species. According to the CO adsorption results, the main iron species appears to be coordinatively unsaturated whereas isotopic labelling upon NO adsorption indicates that two distinct iron sites almost give rise to the same mononitrosyl infrared signature. Studying the catalyst upon interaction with NO and O₂ in operando conditions leads to the observation of these mononitrosyl species who behave as reaction intermediates for the NO oxidation into NO₂. All our Fe-FER samples presenting these mononitrosyl complexes are active not only in NO-to-NO₂ reaction but also in the NOx selective catalytic reduction with ammonia. The effects of both NH₃ and SO₂ as adsorption competitor during the low temperature NH₃-SCR are also discussed.     

Activity and durability of iron-exchanged mordenite-type zeolite catalyst for the reduction of NO by NH3

NO removal activity and the durability of iron-exchanged mordenite type zeolite catalyst (FeHM) have been examined in a continuous fixed bed flow reactor. The catalytic activity for NO reduction by NH₃ in the presence of oxygen was much higher than that in the absence of oxygen, and it was fully reversible with respect to the presence of oxygen in the feed gas stream. The oxidation ability of SCR catalysts including FeHM was critical for both reactions of NH₃ and SO₂ oxidation, thus for the NO removal activity and its sulfur tolerance. The maximum conversion of NO for FeHM catalyst with respect to the reaction temperature shifted to the higher temperature due to its mild oxidation ability. The deactivation behaviors such as the changes of the physicochemical properties of the catalyst and the loss of NO removal activity induced by SO₂ could not be distinguished, regardless of the metals exchanged in zeolite. However, the amount of deactivating agents deposited on the catalyst surface depended on the species of metals exchanged on the mordenite type zeolite, which was mainly attributed to the oxidation ability of metals for SO₂ conversion to SO₃.     

Effects of water vapor, CO2 and SO2 on the NO reduction by NH3 over sulfated CaO

Gas effects on NO reduction by NH₃ over sulfated CaO have been investigated in the presence of O₂ at 700–850 °C. CO₂ and SO₂ have reversible negative effects on the catalytic activity of sulfated CaO. Although H₂O alone has no obvious effect, it can depress the negative effects of CO₂ and SO₂. In the flue gas with CO₂, SO₂ and H₂O co-existing, the sulfated CaO still catalyzed the NO reduction by NH₃. The in situ DRTFTS of H₂O adsorption over sulfated CaO indicated that H₂O generated Br?nsted acid sites at high temperature, suggesting that CO₂ and SO₂ competed for only the molecularly adsorbed NH₃ over Lewis acid sites with NO, without influencing the ammonia ions adsorbed over Br?nsted acid sites. Lewis acid sites shifting to Br?nsted acid sites by H₂O adsorption at high temperature may explain the depression of the negative effect on NO reduction by CO₂ and SO₂.     

CO-NO/O2 redox reactions over Cu substituted cobalt oxide spinels

Catalytic conversion of NO and CO over Cu substituted cobalt oxide spinels show excellent activity for CO-O₂ and NO-CO reactions. Lower concentration of Cu in cobalt oxide spinel is having an enhancing effect on the catalytic conversion. Best activity among the tested catalyst was found for Co_2.9Cu_0.1O₄ and complete conversion (100%) is observed at 93 °C for CO oxidation by O₂ and 209 °C for NO reduction by CO. Prepared catalysts show promising activity compared to few of the precious metal based catalysts reported in the literature. The influence of moisture and oxygen on catalytic conversion has been studied.     

Effects of Na, Cu, Ni and Co Modifications on the Activity and Characteristics of Rh/Al2O3 Catalysts for NO Reduction

This study used different metals to modify Rh/Al₂O₃ catalysts for NO reduction in a simulated waste incineration flue gas containing 6% O₂. The characteristics of the modified catalysts were analyzed using BET, TEM and XRD. The results of the experiment reveal that Na addition can significantly affect the properties of Rh/Al₂O₃ catalysts on the BET surface area and Rh metal dispersion. Furthermore, Na addition was found to significantly enhance the NO conversion of Rh/Al₂O₃ at 250–350 °C. On the contrary, Cu, Ni, and Co addition was found to have slight suppression effects.     

Catalytic removal of NO in waste incineration processes over Rh/Al2O3 and Rh–Na/Al2O3: Effects of particulates,heavy metals,SO2 and HCl

Two novel catalysts Rh/Al₂O₃ and Rh–Na/Al₂O₃ were prepared for NO removal and tested their practical performances in a laboratory-scale waste incineration system. The effects of particulates, heavy metals, and acid gases on the catalysts were evaluated and investigated through several characterization techniques, such as SEM, EA, XRPD, ESCA, and FTIR. The results indicated that the NO conversions were increased with the accumulation of particulates on the surface of catalysts, which was attributed to the increase in carbon content. However, the increase in heavy metals Cd and Pb contents on the surface of catalysts decreased the activity of catalyst for NO removal but did not change the chemical state of Rh and Na. The Rh/Al₂O₃ catalysts were poisoned when the acid gases SO₂ and HCl were present in the flue gas, because Rh and Al reacted with S and Cl to form inactive products. Adding Na to Rh/Al₂O₃ catalysts produced a promoting effect for SO₂ removal due to the formation of Na₂SO₄. The influence levels of different pollutants on the performances of Rh/Al₂O₃ and Rh–Na/Al₂O₃ catalysts for NO removal followed the sequence of HCl > heavy metals > SO₂ > particles.     

Carbon materials as catalyst supports for SO2 oxidation: catalytic activity of CuO-AC

Copper catalysts supported on acid treated activated carbon (AC) were prepared, characterized and tested in terms of their SO₂ oxidation activity. Reactions of CuO-AC in flow systems with sulfur dioxide, oxygen and nitrogen streams were investigated to determine the types of chemical interactions that occur on the sorbent surface. The effects of reaction temperature, acid treatment, metal loading, support particle size, SO₂ concentration and O₂ concentration on SO₂ oxidation activity were evaluated. It was found that carbon materials used as catalyst supports for copper oxide catalysts provided a high catalytic activity for adsorbing SO₂ from flue gas and oxidizing it. Acid pretreatment of the carbon supports increased the content of specific surface chemical groups to enhance the catalytic activity for SO₂ oxidation. Metal loading, as well as support particle size, have a significant influence on the SO₂ activity. The supported metals rather than surface oxygen functional groups on AC may be the active sites for adsorbing SO₂.     

Catalytic performance of CuCl<Subscript>2</Subscript>-modified V<Subscript>2</Subscript>O<Subscript>5</Subscript>-WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> catalyst for Hg<Superscript>0</Superscript> oxidation in simulated flue gas

CuCl₂-SCR catalysts prepared by an improved impregnation method were studied to evaluate the catalytic performance for gaseous elemental mercury (Hg⁰) oxidation in simulated flue gas. Hg⁰ oxidation activity of commercial SCR catalyst was significantly improved by the introduction of CuCl₂. Nitrogen adsorption, XRD, XRF and XPS were used to characterize the catalysts. The results indicated that CuCl₂ was well loaded and highly dispersed on the catalyst surface, and that CuCl₂ played an important role for Hg⁰ catalytic oxidation. The effects of individual flue gas components on Hg⁰ oxidation were also investigated over CuCl₂-SCR catalyst at 350 oC. The co-presence of NO and NH₃ remarkably inhibited Hg⁰ oxidation, while this inhibiting effect was gradually scavenged with the decrease of GHSV. Further study revealed the possibility of simultaneous removal of Hg⁰ and NO over CuCl₂-SCR catalyst in simulated flue gas. The mechanism of Hg⁰ oxidation was also investigated.     

Nanosized CeO2-supported metal oxide catalysts for catalytic reduction of SO2 with CO as a reducing agent

Nanosized CeO₂ was synthesized by sol–gel method and used as the support to prepare six kinds of supported metal oxide catalysts by incipient wetness impregnation method. These catalysts were investigated for the catalytic reduction of SO₂ to elemental sulfur with CO as a reducing agent. Experimental results indicate that Cr₂O₃/nano-CeO₂ was the most active catalyst. Using this catalyst, a kinetic study was performed on the reduction of SO₂ and the optimal feed ratio of CO/SO₂ was found to be 2.5/1, and low concentrations of SO₂ and CO provide a high SO₂ conversion and sulfur yield. We also found that the catalyst presulfided by CO + SO₂ exhibits a higher performance than those pretreated with CO, SO₂ or He. The discrepancy in the stability and activity resulted in the pretreatment has been rationally explained. The temperature-programmed desorption patterns of SO₂ and CO illustrate that Cr₂O₃/nano-CeO₂ can adsorb and desorb SO₂ and CO more easily than can other catalysts. These results may properly explain why Cr₂O₃/nano-CeO₂ has a higher activity for the reduction of SO₂.     

The activity of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for PAHs removal in the waste incineration processes: Effects of particulates, heavy metals, and acid gases

This study investigated the activity of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for polycyclic aromatic hydrocarbons (PAHs) removal and the influence of particulates, heavy metals, and acid gases (SO₂ and HCl) on the performance of catalysts. The experiments were carried out in a laboratory-scale waste incineration system. Experimental results show that the destruction removal efficiency (DRE) of PAHs by Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts were 80% and 59%, respectively when the flue gas did not contain any pollutants. The concentrations of PAHs increased by using a Rh/Al₂O₃ catalyst when the flue gas contained Cd, Pb, and SO₂ and also increased by using a Rh-Na/Al₂O₃ catalyst when the flue gas contained particulates, Cd, and HCl. Adding Na to the Rh/Al₂O₃ catalyst can inhibit the increases of 3-4 ring PAHs when the flue gas contained Pb. The influence of acid gases on the performance of the Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts followed the sequence SO₂ > HCl > SO₂ + HCl. The activity of the catalysts for PAHs removal was significantly suppressed by increased concentrations in particulates and Cd, yet promoted by a high Pb concentration. The results of ESCA analysis indicated that the presence of Cd and Pb did not change the chemical states of Rh and Na, but the presence of SO₂ and HCl did.     

WO3 and MoO3 addition effect on V2O5/TiO2 as promoters for removal of NOx and SOx from stationary sources

As an attempt to improve the catalytic activity at higher reaction temperatures between 300-450°C, various mole ratios of WO₃ were added to V₂O₅/TiO₂ catalytic systems. And also, in order to suggest a new mixed oxide catalyst system for simultaneous removal of NO_x and SO_x, from stationary sources, MoO₃-V₂O₅/TiO₂catalysts were prepared by a conventional impregnation method together with a newly introduced method of surface fixation (non-aqueous solution method). In case of WO₃ addition, at higher reaction temperature range (300–450°C), WO₃ and WO₃-V₂O₅/TiO₂ catalysts showed significant high conversion in NO reduction with NH₃ while V₂O₅/TiO₂ catalyst showed a significant change in selectivity mainly due to the excess side reaction of NH₃ oxidation. This difference in selectivity due to NH₃ oxidation at high temperature is supposed to be associated with the difference in values of surface excess oxygen between WO₃ and V₂O₅ on titania. The surface acidities of tested catalysts were relatively well correlated with the % conversion of NO at 400°C. In case of MoO₃ addition, the catalytic activity for the simultaneous removal of NO_x and SO_x were quite enhanced by the addition of MoO₃ into V₂O₅/TiO₂ catalysts. The enhanced activities were responsible for the formation of Mo=O bond on the intermediate species produced by solid solutions on MoO₃-V₂O₅/TiO₂ (aqueous). However, in the case of MoO₃-V₂O₅/TiO₂ (non-aqueous), the exact source of active site was not able to detect in IR spectra in spite of more enhanced activity was obtained in this study. After SO₂ contact, VOSO₄ is newly formed on the surface of catalyst, which supposed to be associated with the activity enhancement.     

In situ characterization of interaction of ammonia with carbon surface in oxygen atmosphere

The adsorption and oxidation of ammonia over carbons differing in the chemical structure of surface functional groups have been investigated by FTIR spectroscopy. The reactions of NH₃ with carbons have been studied both in the presence and in the absence of oxygen. As a result of NH₃ chemisorption, in addition to ammonium salts, there are formed surface amide and imide structures. At the higher temperature surface isocyanate species are formed. Thermal stabilities of surface structures, formed as a result of NH₃ chemisorption have been determined by means of FTIR spectroscopy. The activity and selectivity of carbons for the selective catalytic oxidation (SCO) of NH₃ to N₂ with excess O₂ has been shown by microreactor studies at 295-623 K. Carbon catalysts are very active for NH₃ oxidation. Nitrogen is generally the predominant product of ammonia oxidation. The selectivity to N₂, N₂O and NO is determined by the surface oxygen coverage and reaction temperature. The data obtained indicate that the N₂ is formed via selective catalytic reduction (SCR) between NH_x surface species and NO formed from NH₄⁺ oxidation. This implies that ammonia is activated in the form of NH₄⁺ species for both SCR and SCO processes.     

The effect of cobalt precursors on NO oxidation over supported cobalt oxide catalysts

The effect of cobalt precursors such as cobalt acetate and cobalt nitrate on NO oxidation was examined over cobalt oxides supported on various supports such as SiO₂, ZrO₂, and CeO₂. The N₂ physisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction with H₂ (H₂-TPR), NO chemisorptions, and temperature-programmed oxidation (TPO) with mass spectroscopy were conducted to characterize catalysts. The NO uptake as well as the catalytic activity for NO oxidation was dependent on the kinds of cobalt precursors and supports for supported cobalt oxides catalysts. Among tested catalysts, Co₃O₄/CeO₂ prepared from cobalt acetate showed the highest catalytic activity. The catalytic activity generally increased with the amount of chemisorbed NO. Reversible deactivation was observed over Co₃O₄/CeO₂ in the presence of H₂O. On the other hand, irreversible deactivation occurred over the same catalyst even in the presence of 5 ppm SO₂ in a feed. The strongly adsorbed SO₂ can prohibit NO from adsorbing on the active sites and also can prevent formed NO₂ from desorbing off the catalyst surface. The formation of SO₃ cannot be observed from the chemisorbed SO₂ on Co₃O₄/CeO₂ during TPO.