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.     

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.     

High temperature catalytic combustion of methane and propane over hexaaluminate catalysts: NOx emission characteristics

Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH₄ and C₃H₈, in order to investigate the effect of the concentration of the fuels, O₂ and H₂O on NO_x emission and combustion characteristics. Among the hexaaluminate catalysts, Sr_0.8La_0.2MnAl₁₁O₁₉₋ prepared by the alkoxide method exhibited the highest activity for methane combustion and low NO_x emission capability. NO_x emission at 1500 °C was increased linearly with O₂ concentration, whereas water vapor addition decreased NO_x emission in CH₄ combustion over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst. In the catalytic combustion of C₃H₈ over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst, the amount of NO_x emitted was raised in the temperature range between 1000 and 1500 °C when the C₃H₈ concentration increased from 1 to 2 vol.%. It was found that NO_x emission in this temperature range was reduced effectively by adding water vapor.     

Application of numerical modeling of selective NOx reduction by hydrocarbon under diesel transient conditions in consideration of hydrocarbon adsorption and desorption process

A model of NO_x selective reduction by hydrocarbon (HC) was developed, which takes into account the adsorption and desorption of HC. The model was applied for predicting the performance of a De–NO_x catalytic reactor, working under transient conditions such as a legislative driving cycle. Diesel fuel was used as a supplemental reductant.

The behavior of HC and NO_x reactions and HC adsorption and desorption has been simulated successfully by our numerical approach under the transient conditions of the simulated Japanese 10–15 driving cycle. Our model is expected to optimize the design of selective diesel NO_x reduction systems using a diesel fuel as a supplemental reductant.     

Hysteresis in activity of microporous lean NOx catalysts in the presence of water vapor

Increasingly stringent ambient air quality standards coupled with the need to improve fuel economy has drawn significant attention to the search for emission control systems for lean burn engine vehicles. Much of the focus has been on zeolite-based catalysts for the conversion of NO_x to N₂ for automotive exhaust emission control. Under certain conditions, these catalysts are highly active catalysts for the reduction of NO_x using hydrocarbons as the reductant. However, many of these catalysts suffer from a variety of deactivation processes such as irreversible poisoning by SO_x or hydrothermal dealumination.

In addition to these deactivation processes, a recent focus of our research has been on the influence of water vapor on the activity of zeolite-based catalysts at low operating temperatures. We observe a hysteresis in catalytic activity of lean NO_x reduction (NO feed concentrations <100 ppm) upon increasing and decreasing temperature ramps at the low end of the operating window, that being from 100 to 300 °C using hydrocarbons as reductants. We describe these reversible influences of water vapor and the implications for this hysteresis in catalytic activity for the application of zeolite-based catalysts in lean NO_x catalysis, and compare these results to the instance of using ammonia as reductant.     

Mean field modelling of NOx storage on Pt/BaO/Al2O3

A mean field model, for storage and desorption of NO_x in a Pt/BaO/Al₂O₃ catalyst is developed using data from flow reactor experiments. This relatively complex system is divided into five smaller sub-systems and the model is divided into the following steps: (i) NO oxidation on Pt/Al₂O₃; (ii) NO oxidation on Pt/BaO/Al₂O₃; (iii) NO_x storage on BaO/Al₂O₃; (iv) NO_x storage on Pt/BaO/Al₂O₃ with thermal regeneration and (v) NO_x storage on Pt/BaO/Al₂O₃ with regeneration using C₃H₆. In this paper, we focus on the last sub-system. The kinetic model for NO_x storage on Pt/BaO/Al₂O₃ was constructed with kinetic parameters obtained from the NO oxidation model together with a NO_x storage model on BaO/Al₂O₃. This model was not sufficient to describe the NO_x storage experiments for the Pt/BaO/Al₂O₃, because the NO_x desorption in TPD experiments was larger for Pt/BaO/Al₂O₃, compared to BaO/Al₂O₃. The model was therefore modified by adding a reversible spill-over step. Further, the model was validated with additional experiments, which showed that NO significantly promoted desorption of NO_x from Pt/BaO/Al₂O₃. To this NO_x storage model, additional steps were added to describe the reduction by hydrocarbon in experiments with NO₂ and C₃H₆. The main reactions for continuous reduction of NO_x occurs on Pt by reactions between hydrocarbon species and NO in the model. The model is also able to describe the reduction phase, the storage and NO breakthrough peaks, observed in experiments.     

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.     

Transient behaviour of catalytic monolith with NOx storage capacity

Transient behaviour of catalytic monolith converter with NO_x storage is studied under conditions typical for automobiles with lean-burn engines (i.e., diesel and advanced gasoline ones). Periodical alternation of inlet concentrations is applied—NO_x are adsorbed on the catalyst surface during a long reductant-lean phase (2–3 min) and then reduced to N₂ within a short reductant-rich phase (2–6 s). Samples of industrial NO_x storage and reduction catalyst of NM/Ba/CeO₂/γ-Al₂O₃ type (NM = noble metal), washcoated on 400 cpsi cordierite substrate, are used in the study. Effects of the rich-phase length and composition on the overall NO_x conversions are examined experimentally. Reduction of NO_x by CO, H₂ and unburned hydrocarbons (represented by C₃H₆) in the presence of CO₂ and H₂O is considered.

Effective, spatially 1D, heterogeneous mathematical model of catalytic monolith with NO_x and oxygen storage capacity is described. The minimum set of experiments needed for the evaluation of relevant reaction kinetic parameters is discussed: (i) CO, H₂ and HC oxidation light-off under both lean and rich conditions, including inhibition effects, (ii) NO/NO₂ transformation, (iii) NO_x storage, including temperature dependence of effective NO_x storage capacity, (iv) water gas shift and steam reforming under rich conditions, i.e., in situ production of hydrogen, (v) oxygen storage and reduction, including temperature dependence of effective oxygen storage capacity, and (vi) NO_x desorption and reduction under rich conditions. The experimental data are compared with the simulation results.     

Regeneration of NOx trap catalysts

We have investigated the regeneration of a nitrated or sulphated model Pt/Ba-based NO_x trap catalyst using different reductants. H₂ was found to be more effective at regenerating the NO_x storage activity especially at lower temperature, but more importantly over the entire temperature window after catalyst ageing. When the model NO_x storage catalyst is sulphated in SO₂ under lean conditions at 650 °C almost complete deactivation can be seen. Complete regeneration was not achieved, even under rich conditions at 800 °C in 10% H₂/He. Barium sulphate formed after the high temperature ageing was partly converted to barium sulphide on reduction. However, if the H₂ reduced sample was exposed to a rich condition in a gas mixture containing CO₂ at 650 °C, the storage activity can be recovered. Under these rich conditions the S²⁻ species becomes less stable than the CO₃²⁻, which is active for storing NO_x. Samples which were lean aged in air containing 60 ppm SO₂ at <600 °C, after regeneration at λ=0.95 at 650 °C, have a similar activity window to a fresh catalyst. It is, therefore, important that CO₂ is present during the rich regenerations of the sulphated model samples (as of course it would be under real conditions), as suppression of carbonate formation can lead to sulphide formation which is inactive for NO_x storage.     

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).     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Impact of redox conditions on thermal deactivation of NOx traps for diesel

Performance of NO_x traps after high-temperature treatments in different redox environments was studied. Two types of treatments were considered: aging and pretreatment. Lean and rich agings were examined for a model NO_x trap, Pt–Ba/Al₂O₃. These were done at 950 °C for 3 h, in air and in 1% H₂/N₂, respectively. Lean aging had a severe impact on NO_x trap performance, including HC and CO oxidation, and NH₃ and N₂O formation. Rich aging had minimal impact on performance, compared to fresh/degreened performance. Deactivation from lean aging was essentially irreversible due to Pt sintering, but Pt remained dispersed with the rich aging. Pretreatments were examined for a commercially feasible fully formulated NO_x trap and two model NO_x traps, Pt–Ba/Al₂O₃ and Pt–Ba–Ce/Al₂O₃. Pretreatments were done at 600 °C for 10 min, and used feed gas that simulated diesel exhaust under several conditions. Lean pretreatment severely suppressed NO_x, HC, CO, NH₃ and N₂O activities for the ceria-containing NO_x traps, but had no impact on Pt–Ba/Al₂O₃. Subsequently, a relatively mild rich pretreatment reversed this deactivation, which appears to be due to a form of Pt–ceria interaction, an effect that is well known from early work on three-way catalysts. Practical applications of results of this work are discussed with respect to NO_x traps for light-duty diesel vehicles.     

Bench-scale demonstration of an integrated deSoot–deNOx system

A catalytic deSoot–deNO_x system, comprising Pt and Ce fuel additives, a Pt-impregnated wall-flow monolith soot filter and a vanadia-type monolithic NH₃-SCR catalyst, was tested with a two-cylinder DI diesel engine. The soot removal efficiency of the filter was 98–99 mass% with a balance temperature (stationary pressure drop) of 315 °C at an engine load of 55%. The NO_x conversion ranged from 40 to 73%, at a NH₃/NO_x molar ratio of 0.9. Both systems were measured at a GHSV of 52 000 l/(l h). The maximum NO_x conversion was obtained at 400 °C. The reason for the moderate deNO_x performance is discussed. No deactivation was observed after 380 h time on stream. The NO_x emission at high engine loads is around 15% lower than that of engines running without fuel additives.     

An examination of the role of plasma treatment for lean NOx reduction over sodium zeolite Y and gamma alumina Part 2: Formation of nitrogen

NO_x reduction with NO₂ as the NO_x gas in the absence of plasma was compared to plasma treated lean NO_x exhaust where NO is converted to NO₂ in the plasma. Product nitrogen was measured to prove true chemical reduction of NO_x to N₂. With plasma treatment, NO as the NO_x gas, and a NaY catalyst, the maximum conversion to nitrogen was 50% between 180 and 230 °C. The activity decreased at higher and lower temperatures. At 130 °C a complete nitrogen balance could be obtained, however between 164 and 227 °C less than 20% of the NO_x is converted to a nitrogen-containing compound or compounds not readily detected by gas chromatograph (GC) or Fourier transform infrared spectrometer (FT-IR) analysis. With plasma treatment, NO₂ as the NO_x gas, and a NaY catalyst, a complete nitrogen balance is obtained with a maximum conversion to nitrogen of 55% at 225 °C.

For γ-alumina, with plasma treatment and NO₂ as the NO_x gas, 59% of the NO_x is converted to nitrogen at 340 °C. A complete nitrogen balance was obtained at these conditions. As high as 80% NO_x removal over γ-alumina was measured by a chemiluminescent NO_x meter with plasma treatment and NO as the NO_x gas.

When NO is replaced with NO₂ and the simulated exhaust gases are not plasma treated, the maximum NO_x reduction activity of NaY and γ-alumina decreases to 26 and 10%, respectively. This is a large reduction in activity compared to similar conditions where the simulated exhaust was plasma treated. Therefore, in addition to NO₂, other plasma-generated species are required to maximize NO_x reduction.     

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.     

The removal of NOx from a lean exhaust gas using storage and reduction on H3PW12O40·6H2O

NO_x sorption and reduction capacities of 12-tungstophosphoric acid hexahydrate (H₃PW₁₂O₄₀·6H₂O, HPW) were measured under representative alternating conditions of lean and rich exhaust-type gas mixture. Under lean conditions, the sorption of NO_x is large and is equivalent to 37 mg of NO_x/g_HPW. Although a part of these NO_x remains unreduced, HPW is able to reduce some of the NO_x to produce N₂ by a reaction between the sorbed NO₂ and hydrocarbon (HC), but this process is slow. The addition of 1% Pt affects strongly the chemical behaviour occurring during the course of a rich operation. The NO desorption observed at the beginning of the rich phase is strongly accelerated. The direct correlation between NO₂ consumption and CO₂ production shows that the principal pathway is the reaction CO+NO₂→CO₂+NO. In a mixture of reducing gas (CO, HC, H₂), the competition is strongly in favour of CO though in its absence the reaction observed was the hydrogenation of propene to propane.     

An examination of the role of plasma treatment for lean NOx reduction over sodium zeolite Y and gamma alumina Part 1. Plasma assisted NOx reduction over NaY and Al2O3

The role of plasma processing on NO_x reduction over γ-alumina and a basic zeolite, NaY was examined. During the plasma treatment NO is oxidized to NO₂ and propylene is partially oxidized to CO, CO₂, acetaldehyde, and formaldehyde. With plasma treatment, NO as the NO_x gas, and a NaY catalyst, the maximum NO_x conversion was 70% between 180 and 230 °C. The activity decreased at higher and lower temperatures.

As high as 80% NO_x removal over gamma alumina was measured by a chemiluminescent NO_x meter with plasma treatment and NO as the NO_x gas.

For both catalysts a simultaneous decrease in NO_x and aldehydes concentrations was observed, which suggests that aldehyde may be important components for NO_x reduction in plasma-treated exhaust.     

Nature of nitrogen specie in coke and their role in NOx formation during FCC catalyst regeneration

NO_x emission during the regeneration of coked fluid catalytic cracking (FCC) catalysts is an environmental problem. In order to follow the route to NO_x formation and try to find ways to suppress it, a coked industrial FCC catalyst has been prepared using model N-containing compounds, e.g., pyridine, pyrrole, aniline and hexadecane–pyridine mixture. Nitrogen present in the FCC feed is incorporated as polyaromatic compounds in the coke deposited on the catalyst during cracking. Its functionality has been characterized using XPS. Nitrogen specie of different types, namely, pyridine, pyrrolic or quaternary-nitrogen (Q-N) have been discriminated. Decomposition of the coke during the catalyst regeneration (temperature programmed oxidation (TPO) and isothermal oxidation) has been monitored by GC and MS measurements of the gaseous products formed. The pyrrolic- and pyridinic-type N specie, present more in the outer coke layers, are oxidized under conditions when still large amount of C or CO is available from coke to reduced NO_x formed to N₂. “Q-N” type species are present in the inner layer, strongly adsorbed on the acid sites on the catalyst. They are combusted last during regeneration. As most of the coke is already combusted at this point, lack of reductants (C, CO, etc.) results in the presence of NO_x in the tail gas.     

Recent advances in automobile exhaust catalysts

Catalysts, which were recently developed by Toyota for the control of automobile exhaust, are reviewed. (1) For use in low emission vehicles, a CeO₂-ZrO₂ solid solution (CZ) with both high oxygen storage capacity and high heat resistance was developed as a support for a high performance three-way catalyst (TWC). (2) A novel three-way catalyst named the NO_x storage-reduction catalyst (NSR) was developed for automotive lean-burn engines. The NSR catalyst can store NO_x in an oxidizing atmosphere and then reduce stored NO_x at stoichiometric or reducing conditions. Also, it has high tolerance to sulfur poisoning which is the most stringent problem for the NSR catalyst.