Studies on the deactivation of NOx storage-reduction catalysts by sulfur dioxide

The interaction of sulfur dioxide with a commercial NO_x storage-reduction catalyst (NSR) has been investigated using in situ IR and X-ray absorption spectroscopy. Two pathways of catalyst deactivation by SO₂ were identified. Under lean conditions (exposure to SO₂ and O₂) at 350 °C the storage component forms barium sulfates, which transform from surface to hardly reducible bulk sulfate species. The irreversible blocking of the Ba sites led to a decrease in NO_x storage capacity. Under fuel rich conditions (SO₂/C₃H₆) at 350–500 °C evidence for the formation of sulfides on the oxidation/reduction component (Pt) of the catalyst was found, which blocks the metal surface and thus hinders the further reduction of the sulfides.     

Investigation of simultaneous adsorption of SO2 and NOx on Na-γ-alumina with transient techniques

The simultaneous adsorption of SO₂ and NO_x on Na-γ-alumina was studied by means of step experiments in a fixed bed plug flow reactor at 387 K and atmospheric pressure. Typically the molar composition of the feed gas was 1.5% SO₂, 1% O₂, 4000 ppm NO, 500 ppm NO₂, and Ar. First the adsorption behavior of the pure components was measured. SO₂ and NO₂ adsorb easily, whereas NO and O₂ do not adsorb. Moreover there is no influence of O₂ on the adsorption behavior of the pure components.

NO and O₂ adsorption require the simultaneous presence of SO₂, NO, and O₂. The NO and O₂ adsorption rate is enhanced by an increasing SO₂/NO ratio. The total amount of SO₂ adsorbed is not affected by the simultaneous adsorption of NO and O₂. However, NO₂ adsorption increases the SO₂ adsorption capacity. In the presence of NO₂ most of the adsorbed NO_x is released as NO.     

Engineering practice and economic analysis of ozone oxidation wet denitrification technology

SO₂ and NO emitted from coal-fired power plants have caused serious air pollution in China. In this study, a test system for NO oxidation using O₃ is established. The basic characteristics of NO oxidation and products forms are studied. A separate test system for the combined removal of SO₂ and NO_x is also established, and the absorption characteristics of NO_x are studied. The characteristics of NO oxidation and NO_x absorption were verified in a 35 t·h^-1 industrial boiler wet combined desulfurization and denitrification project. The operating economy of ozone oxidation wet denitrification technology is analyzed. The results show that O₃ has a high rate and strong selectivity for NO oxidation. When O₃ is insufficient, the primary oxidation product is NO₂. When O₃ is present in excess, NO₂ continues to get oxidized to N₂O₅ or NO₃. The removal efficiency of NO₂ in alkaline absorption system is low (only about 15%). NO_x removal efficiency can be improved by oxidizing NO_x to N₂O₅ or NO₃ by increasing ozone ratio. When the molar ratio of O₃/NO is 1.77, the NO_x removal efficiency reaches 90.3%, while the operating cost of removing NO_x per kilogram is 6.06 USD (NO₂).     

Study of the reaction of NOx and soot on Fe2O3 catalyst in excess of O2

This study addresses the catalytic reaction of NO_x and soot into N₂ and CO₂ under O₂-rich conditions. To elucidate the mechanism of the soot/NO_x/O₂ reaction and particularly the role of the catalyst -Fe₂O₃ is used as model sample. Furthermore, a series of examinations is also made with pure soot for reference purposes. Temperature programmed oxidation and transient experiments in which the soot/O₂ and soot/NO reaction are temporally separated show that the NO reduction occurs on the soot surface without direct participation of the Fe₂O₃ catalyst. The first reaction step is the formation of CC(O) groups that is mainly associated with the attack of oxygen on the soot surface. The decomposition of these complexes leads to active carbon sites on which NO is adsorbed. Furthermore, the oxidation of soot by oxygen provides a specific configuration of active carbon sites with suitable atomic orbital orientation that enables the chemisorption and dissociation of NO as well as the recombination of two adjacent N atoms to evolve N₂. Moreover, carbothermal reaction, high resolution transmission electron microscopy and isotopic studies result in a mechanistic model that describes the role of the Fe₂O₃ catalyst. This model includes the dissociative adsorption of O₂ on the iron oxide, surface migration of the oxygen to the contact points of soot and catalyst and then final transfer of O to the soot. Moreover, our experimental data suggest that the contact between both solids is maintained up to high conversion levels thus resulting in continuous oxygen transfer from catalyst to soot. As no coordinative interaction of soot and Fe₂O₃ catalyst is evidenced by diffuse reflectance infrared Fourier transform spectroscopy a van der Waals type interaction is supposed.     

CO2, NOx and SO2 emissions from the combustion of coal with high oxygen concentration gases

The emissions of CO₂, NO_x and SO₂ from the combustion of a high-volatile coal with N₂- and CO₂-based, high O₂ concentration (20, 50, 80, 100%) inlet gases were investigated in an electrically heated up-flow-tube furnace at elevated gas temperatures (1123–1573 K). The fuel equivalence ratio, φ, was varied in the range of 0.4–1.6. Results showed that CO₂ concentrations in flue gas were higher than 95% for the processes with O₂ and CO₂-based inlet gases. NO_x emissions increased with φ under fuel-lean conditions, then declined dramatically after φ=0.8, and the peak values increased from about 1000 ppm for the air combustion process and 500 ppm for the O₂(20%)+CO₂(80%) inlet gas process to about 4500 ppm for the oxygen combustion process. When φ>1.4 the emissions decreased to the same level for different O₂ concentration inlet gas processes. On the other hand, NO_x emission indexes decreased monotonically with φ under both fuel-lean and fuel-rich combustion. SO₂ emissions increased with φ under fuel-lean conditions, then declined slightly after φ>1.2. Temperature has a large effect on the NO_x emission. Peak values of the NO_x emission increased by 50–70% for the N₂-based inlet gas processes and by 30–50% for the CO₂-based inlet gas process from 1123 to 1573 K. However, there was only a small effect of temperature on the SO₂ emission.     

The activity and characterization of sol–gel Sn/Al2O3 catalyst for selective catalytic reduction of NOx in the presence of oxygen

Catalytic performance of Sn/Al₂O₃ catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NO_x by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO₂ had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al₂O₃ (SG) catalyst, and the maximum NO₂ conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NO_x desorption accompanied with O₂ around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H₂O and SO₂ at low temperature, and the temperature window was also broadened in the presence of H₂O and SO₂, however the NO_x desorption and NO conversion decreased sharply on the 300 ppm SO₂ treated catalyst, the catalytic activity was inhibited by the presence of SO₂ due to formation of sulfate species (SO₄²⁻) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al₂O₃ (SG) was not decreased in the presence of large oxygen.     

Kinetic modelling of sulfur deactivation of Pt/BaO/Al2O3 and BaO/Al2O3 NOx storage catalysts

In this work, a kinetic model is constructed to simulate sulfur deactivation of the NO_x storage performance of BaO/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts. The model is based on a previous model for NO_x storage under sulfur-free conditions. In the present model the storage of NO_x is allowed on two storage sites, one for complete NO_x uptake and one for a slower NO_x sorption. The adsorption of SO_x is allowed on both of these NO_x storage sites and on one additional site which represent bulk storage. The present model is built-up of six sub-models: (i) NO_x storage under sulfur-free conditions; (ii) SO₂ storage on NO_x storage sites; (iii) SO₂ oxidation; (iv) SO₃ storage on bulk sites; (v) SO₂ interaction with platinum in the presence of H₂; (vi) oxidation of accumulated sulfur compounds on platinum by NO₂. Data from flow reactor experiments are used in the implementation of the model. The model is tested for simulation of experiments for NO_x storage before exposure to sulfur and after pre-treatments either with SO₂ + O₂ or SO₂ + H₂. The simulations show that the model is able to describe the main features observed experimentally.     

The combustion of carbon particulates using NO/O2 mixtures: The influence of SO4 and NOx trapping materials

The activity of several catalysts are studied in the soot combustion reaction using air and NO/air as oxidising agents. Over Al₂O₃-supported catalysts NO_(g) is a promoter for the combustion reaction with the extent of promotion depending on the Na loading. Over these catalysts SO₄²⁻ poisons this promotion by preventing NO oxidation through a site blocking mechanism. SiO₂ is unable to adsorb NO or catalyse its oxidation and over SiO₂-supported Na catalysts NO_(g) inhibits the combustion reaction. This is ascribed to a competition between NO and O₂. Over Fe-ZSM-5 catalysts the presence of a NO_x trapping component does not increase the combustion of soot in the presence of NO_(g) and it is proposed that this previously reported effect is only seen under continuous NO_x trap operation as NO₂ is periodically released during regeneration and thus available for soot combustion. Experiments during which the [NO]_(g) is varied show that CO, rather than an adsorbed carbonyl-like intermediate, is formed upon reaction between NO₂ (the proposed oxygen carrier) and soot.     

Co3O4 based catalysts for NO oxidation and NOx reduction in fast SCR process

Reaction activities of several developed catalysts for NO oxidation and NO_x (NO + NO₂) reduction have been determined in a fixed bed differential reactor. Among all the catalysts tested, Co₃O₄ based catalysts are the most active ones for both NO oxidation and NO_x reduction reactions even at high space velocity (SV) and low temperature in the fast selective catalytic reduction (SCR) process. Over Co₃O₄ catalyst, the effects of calcination temperatures, SO₂ concentration, optimum SV for 50% conversion of NO to NO₂ were determined. Also, Co₃O₄ based catalysts (Co₃O₄-WO₃) exhibit significantly higher conversion than all the developed DeNO_x catalysts (supported/unsupported) having maximum conversion of NO_x even at lower temperature and higher SV since the mixed oxide Co-W nanocomposite is formed. In case of the fast SCR, N₂O formation over Co₃O₄-WO₃ catalyst is far less than that over the other catalysts but the standard SCR produces high concentration of N₂O over all the catalysts. The effect of SO₂ concentration on NO_x reduction is found to be almost negligible may be due to the presence of WO₃ that resists SO₂ oxidation.     

The role of zeolite type on the lean NOx reduction by methane over Pd loaded pentasil zeolites

The lean selective catalytic reduction of NO_x by methane over protonic palladium loaded ZSM-5, FER and MOR, as well as, on bimetallic Pd–Pt-HMOR was examined. Special emphasis was paid on the combined effects of water and SO₂ in the feed stream. Under dry conditions and in the absence of SO₂, the degree of NO_x conversion at 450°C decreases as follows: Pd-HZSM-5>Pd-HMOR>Pd-HFER. Sulfur dioxide alone has no apparent effect on the activity for NO_x reduction, but the coexistence of water and SO₂ inhibits both NO_x and methane conversions. The extent of inhibition by water and SO₂ on NO_x reduction is Pd-HFER>Pd-HZSM-5>Pd-HMOR. Acid mordenite doped with low levels of Pt and Pd leads to an active catalyst that is more tolerant to the presence of either water or SO₂ than the corresponding monometallic Pt- and Pd-HMOR. Nevertheless, NO_x reduction is also inhibited at temperatures below 450°C when SO₂ and water are both present. TPD experiments of water over calcined samples of protonic Pd supported pentasil zeolites, Pd/γ-Al₂O₃ and Pt–Pd-HMOR with and without pretreatment in SO₂+O₂ indicate that sulfation of the surface increases water chemisorption by the support. Therefore, the observed decrease of NO_x reduction on Pd-loaded zeolite catalysts when SO₂ and H₂O coexist in the feed stream may be due to enhanced water inhibition and presumably active site poisoning.     

Analysis of the thermodynamic feasibility of NOx decomposition catalysis to meet next generation vehicle NOx emissions standards

Free energy minimization calculations are used to determine the thermodynamic equilibrium concentrations of NO_x and other species in stoichiometric and lean gas mixtures over a range of temperatures and compositions. Under lean (excess N₂ and O₂) conditions, the NO decomposition (NO↔(1/2)N₂+(1/2)O₂) and NO oxidation (NO+(1/2)O₂↔NO₂) equilibria impose lower bounds on the NO_x concentrations achievable by thermodynamic equilibration or NO_x decomposition, and these equilibrium NO_x concentrations can be practically significant. Assuming a perfect isothermal catalyst acting on a representative diesel exhaust stream collected over the federal test procedure (FTP) cycle, equilibrium NO_x levels exceed upcoming California Low Emission Vehicle II (LEV-II) and Tier II NO_x emissions standards for automobiles and trucks at temperatures above approximately 800 K. Consideration of a perfect adiabatic catalyst acting on the same diesel exhaust shows that equilibrium NO_x values can fall below NO_x emissions standards at lower temperatures, but to achieve these low concentrations would require the catalyst to attain 100% approach to equilibrium at very low temperatures. It is concluded that NO_x removal based on a thermodynamic equilibrating catalyst under lean exhaust conditions is not practically viable for automotive application, and that to achieve upcoming NO_x standards will require selective NO_x catalysts that vigorously promote NO_x reactions with reductant and do not promote NO decomposition or oxidation. Finally, the ability of a selective NO_x catalyst system to reduce NO_x concentrations to or below thermodynamic equilibrium values is proposed as a useful measure for selective catalytic reduction (SCR) activity.     

Catalytic NOx reduction by carbon supporting metals

Catalytic NO_x reduction by carbon supporting transition metals (Fe, Co, Ni, Cu) and potassium has been studied. The effect of oxygen on the catalytic properties of the metals has been analyzed. Temperature-programmed reactions and isothermal reactions have been conducted in a fixed bed flow reactor. Temperature-programmed reduction in hydrogen, XRD and XPS have been used to characterize the catalysts. All the metals studied catalyze the NO_x reduction by carbon in the presence of oxygen, but also the O₂–carbon reaction. Metal catalytic activity is the result of two factors, the tendency of the metal to be oxidized by NO and the easiness of the resulting oxide to be reduced by carbon. Among the metals studied, nickel exhibits the highest selectivity for NO_x reduction.

The results of this study strengthen the possible benefit of the lack of a gaseous reducing agent (such as ammonia or hydrocarbons) since the reduction of NO_x is performed by the carbon support itself.     

Novel low temperature NOx storage-reduction catalysts for diesel light-duty engine emissions based on hydrotalcite compounds

A series of Pt and Pt,Cu supported catalysts were prepared by wet impregnation of Mg–Al supports obtained from hydrotalcite-type (HT) precursor compounds. These novel NO_x storage-reduction (NO_xSR) catalysts show improved performances in NO_x storage than Pt,Ba/alumina NO_xSR catalysts at reaction temperatures lower than 200 °C. These catalysts show also improved resistance to deactivation by SO₂. The effect is attributed to the formation of well dispersed Mg(Al)O particles which show good NO_x storage properties. The promoted low temperature activity is explained by the lower basicity of the Mg(Al)O mixed oxide in comparison to BaO, which induces on one hand a lower inhibition on Pt activity (NO to NO₂ oxidation and/or hydrocarbon oxidation) due to electronic effect, and on the other hand a lower thermal stability of the stored NO_x. The presence of Cu slightly inhibits activity at low temperature, although improves activity and resistance to deactivation at 300 °C. On these catalysts FT-IR characterization evidences the formation of a Pt–Cu alloy after reduction.     

Temperature programmed desorption/surface-reaction study of an anodic alumina supported Ag catalyst for selective catalytic reduction of nitric oxide with propene

On an anodic alumina supported silver catalyst with a low Ag loading (1.68 wt.%), NO_x (NO/He, NO/O₂/He, NO₂/He) adsorption measurements and NO_x-temperature programmed decomposition (TPD)/temperature programmed surface-reaction (TPSR) measurements in different gas streams (He, C₃H₆/He, C₃H₆/O₂/He) were conducted to investigate the formation, consumption and reactivity of surface adsorbed NO_x species.

During NO adsorption, no noticeable uptake of NO was detected. Introducing oxygen greatly improved the formation of ads-NO_x species. A greater quantity of surface nitrate species was found after NO₂ adsorption, accompanied with gaseous NO release. The result of TPSR demonstrates the surface nitrate species can be effectively and preferentially reduced by propene. When introducing oxygen into the propene gas stream of TPSR test, the significantly increased amount of reacted nitrate undoubtedly shows the importance of oxygen in activating propene. The pathway for the selective reduction of NO_x in the presence of excess oxygen is proposed to pass through the selective reduction of the adsorbed nitrate species with the activated propene.

The enhanced NO_x conversion when replacing NO with NO₂ was attributed to the stronger NO_x adsorption capacity and oxidation ability of NO₂, than those for NO. With increasing oxygen concentration, the difference between NO and NO₂ would gradually decrease, and finally disappear in a high excess of oxygen.     

NOx adsorption on MnO2/NaY composite: an in situ FTIR and EPR study

The NO, NO/O₂, and NO/O₂/H₂O adsorption on MnO₂/NaY (5 and 15 wt.% MnO₂) composite catalyst and NaY has been studied by means of in situ FTIR and EPR spectroscopy at elevated temperatures and during heating under reaction-like conditions. NO adsorption and co-adsorption of NO and O₂ on NaY and MnO₂/NaY proceeds via oxidation of NO forming NO₂⁻ and NO₃⁻ species. Whereas the manganese dioxide preferably acts as oxidising agent, the zeolite stores the NO_x species as nitrite and nitrate ions in the solid. In the presence of oxygen, the nitrate formation is enhanced due to additional oxidation of NO through gaseous oxygen leading to NO₂. Dimerisation of NO₂ to N₂O₄ and following disproportionation of the latter causes the formation of NO⁺ and NO₃⁻ species which are associated with nucleophilic zeolitic oxygen and especially alkali cations of the zeolite, respectively. The presence of oxygen facilitates reoxidation of Mn²⁺ which keeps more Mn ions in the active state. Pre-adsorbed water and higher amounts of water vapour in the feed hinder the NO adsorption by blocking the adsorption sites and shift the nitrate formation to higher temperatures. The quantities and thermal stability of the nitrates formed during NO and NO/O₂ adsorption differs which points to a different mechanism of nitrate formation. In the absence of gaseous oxygen, nitrates are formed by participation of only lattice oxygen. In the presence of oxygen, nitrate formation by dimerisation and disproportionation reactions of NO₂ dominates. The manganese component of the composite catalyst supports the oxidation of NO to nitrite and subsequently to nitrate. During this process Mn⁴⁺ is reduced to Mn²⁺ as evidenced by in situ EPR measurements.     

Characterization and performance of Pt-USY in the SCR of NOx with hydrocarbons under lean-burn conditions

Pt-USY was used for the selective catalytic reduction of NO_x with hydrocarbons in the presence of excess oxygen. The catalyst was prepared by an ion-exchange method and characterized by XRD, TEM, CO chemisorption, and Ar adsorption at 87 K. The platinum particle size distribution was found to be broad (2–20 nm), with no apparent sintering of the active phase during the HC-SCR process after 25 h time-on-stream. Generally, large metal clusters (>15 nm) are situated at the external surface of the zeolite, while the smaller ones are located in the pores of the support. Pt-USY shows an excellent activity in the deNO_x reaction (molar NO_x conversion 90% at 475 K) with propene as the reductant in 5 kPa O₂, as well as stable operation during time-on-stream. Propane only yields a low NO_x conversion compared to propene. The presence of high oxygen contents (5–10 kPa O₂) slightly inhibits the reaction. No significant decrease in deNO_x activity was observed at high space velocities (up to 100,000 h⁻¹). The presence of SO₂ and H₂O in the feed stream did not significantly affect the deNO_x activity. Pt-USY performs better under lean-burn conditions than other Pt-catalysts supported on e.g. ZSM-5, Al₂O₃, or SiO₂. The selectivity to N₂ was similar to the other Pt-based catalysts (30%), the other major product being N₂O.     

NOx storage and reduction characteristics of Pd/MnOx–CeO2 at low temperature

The reaction between hydrogen and NO was studied over 1 wt.% Pd supported on NO_x-sorbing material, MnO_x–CeO₂, at low temperatures. The result of pulse mode reactions suggest that NO_x adsorbed as nitrate and/or nitrite on MnO_x–CeO₂ was reduced by hydrogen, which was spilt-over from Pd catalyst. The NO_x storage and reduction (NSR) cycles were carried out over Pd/MnO_x–CeO₂ in a conventional flow reactor at 150 °C. In a storage step, NO was removed by the oxidative adsorption from a stream of 0.04–0.08% NO, 5–10% O₂, and He balance. This was followed by a reducing step, where a stream of 1% H₂/He was supplied to ensure the conversion of nitrate/nitrite to N₂ and thus restore the adsorbability. It was revealed that the NSR cycle is much more suitable for the H₂–deNO_x process in excess O₂, compared to a conventional steady state reaction mode.     

Sulphur dioxide interaction with NOx storage catalysts

The effect of SO₂ on the NO_x storage capacity and oxidation and reduction activities of a model Pt/Rh/BaO/Al₂O₃ NO_x storage catalyst was investigated. Addition of 2.5, 7.5 or 25 vol. ppm SO₂ to a synthetic lean exhaust gas caused deactivation of the NO_x storage function, the oxidation activity and the reduction activity of the catalyst. The degree of deactivation of the NO_x storage capacity was found to be proportional to the total SO₂ dose that the catalyst had been exposed to. SO₂ was found to be accumulated in the catalyst as sulphate.     

Activity and stability of Ag–alumina for the selective catalytic reduction of NOx with methane in high-content SO2 gas streams

In this work, we investigated the activity and stability of Ag–alumina catalysts for the SCR of NO with methane in gas streams with a high concentration of SO₂, typical of coal-fired power plant flue gases. Ag–alumina catalysts were prepared by coprecipitation–gelation, and dilute nitric-acid solutions were used to remove weakly bound silver species from the surface of the as prepared catalysts after calcination. SO₂ has a severe inhibitory effect, essentially quenching the CH₄-SCR reaction on this type catalysts at temperatures <600 °C. SO₂ adsorbs strongly on the surface forming aluminum and silver sulfates that are not active for CH₄-SCR of NO_x. Above 600 °C, however, the reaction takes place without catalyst deactivation even in the presence of 1000 ppm SO₂. The reaction light-off coincides with the onset of silver sulfate decomposition, indicating the critical role of silver in the reaction mechanism. SO₂ is reversibly adsorbed on silver above 600 °C. While alumina sites remain sulfated, this does not hinder the reaction. Sulfation of alumina only decreases the extent of adsoption of NO_x, but adsorption of NO_x is not the limiting step. Methane activation is the limiting step, hence the presence of sulfur-free Ag–O–Al species is a requirement for the reaction. Strong adsorption of SO₂ on Ag–alumina decreases the rates of the reaction, and increases the activation energies of both the reduction of NO to N₂ and the oxidation of CH₄, the latter more than the former. Our results indicate partial contribution of gas phase reactions to the formation of N₂ above 600 °C. H₂O does not inhibit the reaction at 625 °C, and the effect of co-addition of H₂O and SO₂ is totally reversible.     

A combination of NOx trapping materials and urea-SCR catalysts for use in the removal of NOx from mobile diesel engines

Preliminary studies on a series of nanocomposite BaO–Fe ZSM-5 materials have been carried out to determine the feasibility of combining NO_x trapping and SCR-NH₃ reactions to develop a system that might be applicable to reducing NO_x emissions from diesel-powered vehicles. The materials are analysed for SCR-NH₃ and SCR-urea reactivity, their NO_x trapping and NH₃ trapping capacities are probed using temperature programmed desorption (TPD) and the activities of the catalysts for promoting the NH_{3 ads} + NO/O₂ → N₂ and NO_{x ads} + NH₃ → N₂ reactions are studied using temperature programmed surface reaction (TPSR).