On the catalytic nature of Mn/sulfated zirconia for selective reduction of NO with methane

In this work, the catalytic nature of Mn loaded sulfated zirconia (SZ) catalysts for the selective catalytic reduction (SCR) of NO with methane was investigated by a combination of reactions and characterizations such as FT-IR spectroscopy, H₂-TPR, UV–vis diffuse reflectance spectroscopy (DRS) and NO-TPD. It was found from the results of reactions and FT-IR spectra that the strong Brønsted and Lewis acid sites in the Mn/SZ catalysts were essential for the SCR of NO with methane. The loading of Mn increased the number of strong Lewis acid sites on the surface of SZ catalyst, which is one reason for its promoting effect. On the other hand, FT-IR spectra, H₂-TPR and UV–vis DRS of the catalysts demonstrated that the presence of the SO₄²⁻ species occupied the terminal OH sites on the surface of ZrO₂ support and thereby restrained the formation of more oxidative and nonstoichiometrically dispersed MnO_x (1.5 < x < 2) phase. Such an effect of SO₄²⁻ suppressed the combustion reaction of CH₄ by O₂ and increased the selectivity towards NO reduction. The NO-TPD showed that the loading of Mn increased the adsorption of NO over SZ catalyst, which is another reason for the promoting effect of Mn.     

Influence of sulphate doping on Pd/zirconia based catalysts for the selective catalytic reduction of nitrogen oxides with methane

The effect of sulphating zirconia on the selective catalytic reduction of NO by CH₄ in oxygen excess of Pd catalysts has been investigated. Since both the acidity and the Pd dispersion both contribute to the activity and selectivity of these catalysts a series of samples were prepared with different sulphate contents but maintaining the amount of Pd constant. Significant chemical and textural changes were caused by sulphating the zirconium hydroxide starting material, which lead to a clear improvement in the catalytic behaviour. A medium sulphate doping (≈4 wt.% expressed as SO₄²⁻) was found to be the most adequate to promote activity and selectivity in these Pd-sulphate zirconia based catalysts.     

Electrophilic chlorination of methane over superacidic sulfated zirconia

Catalytic chlorination of methane was studied over SO ₄ ^2– /ZrO₂, Pt/SO ₄ ^2– /ZrO₂, and Fe/Mn/SO ₄ ^2– /ZrO₂ solid superacid catalysts. The reactions were carried out in a continuous flow reactor under atmospheric pressure, at temperatures below 240°C, with a gaseous hourly space velocity of 1000 ml/g h and a methane to chlorine ratio of 4 to 1. At 200°C with 30% chlorine converted the selectivity in methyl chloride exceeds 90%. At more elevated temperatures, the selectivity decreases but stays above 80% in methyl chloride at 225°C using the sulfated zirconia catalysts. The selectivity can be enhanced by adding platinum to sulfated zirconia catalysts. An iron and manganese-doped catalyst exhibited excellent selectivities at somewhat lower conversions. Methyl chloride is obtained at 235°C in selectivities greater than 85%. No chloroform or carbon tetrachloride is formed. The electrophilic insertion involves electron-deficient metal-coordinated chlorine into the methane C-H bond.Catalysis by solid superacids, 29. For part 28 see ref. [14].     

NO reduction by CH4 in the presence of excess O2 over Mn/sulfated zirconia catalysts

Selective catalytic reduction (SCR) of NO with methane in the presence of excess oxygen has been investigated over a series of Mn-loaded sulfated zirconia (SZ) catalysts. It was found that the Mn/SZ with a metal loading of 2–3 wt.% exhibited high activity for the NO reduction, and the maximum NO conversion over the Mn/SZ catalyst was higher than that over Mn/HZSM-5. NH₃–TPD results of the catalysts showed that the sulfation process of the supports resulted in the generation of strong acid sites, which is essential for the SCR of NO with methane. On the other hand, the N₂ adsorption and the H₂–TPR of the catalysts demonstrated that the presence of the SO₄²⁻ species promoted the dispersion of the metal species and made the Mn species less reducible. Such an increased dispersion of metal species suppressed the combustion reaction of CH₄ by O₂ and increased the selectivity towards NO. The Mn/SZ catalysts prepared by different methods exhibited similar activities in the SCR of NO with methane, indicating the importance of SO₄²⁻. The most attractive feature of the Mn/SZ catalysts was that they were more tolerant to water and SO₂ poisoning than Mn/HZSM-5 catalysts and exhibited higher reversibility after removal of SO₂.     

Nanostructured macro-mesoporous zirconia impregnated by noble metal for catalytic total oxidation of toluene

Hierarchical bimodal macro-mesoporous zirconia oxide has been synthesized by a simple method in the presence of CTMABr surfactant. The synthesized zirconia having uniform macropores of 300–600 nm in diameter with wormhole-like mesoporous walls and high surface area was calcined at 400 and 600 °C and impregnated with 0.5 wt.% of palladium and compared with classical 0.5 wt.% Pd/ZrO₂ catalyst for toluene oxidation. The highest activity of 0.5 wt.%/macro-mesoporous zirconia calcined at 600 °C was mainly explained by a rather high Pd dispersion and by H₂-TPR measurements showing a higher quantity of PdO species easily reducible at 0 °C.     

Role of zeolite structure on reduction of NOx with methane over In- and Pd-based catalysts

Catalytic performances of ZSM-5 based catalysts containing indium or palladium were examined for NO reduction with CH₄ and NO_x chemisorption. The amounts of NO_x chemisorbed on In/H-ZSM-5 were well proportional to the catalytic activities for NO_x reduction. Pd/H-ZSM-5, on the other hand, hardly chemisorbed NO₂, while the catalytic activity for NO₂ reduction with CH₄ is very high. Furthermore, Pd loaded on SiO₂ showed comparably high catalytic activity for NO₂ reduction with CH₄ at 400°C in the absence of oxygen as Pd/H-ZSM-5. CH₄ combustion during NO_x reduction with CH₄ in the presence of oxygen significantly occurred over PdO on SiO₂, while less over Pd/H-ZSM-5. The role of zeolite might be slightly different between In/H-ZSM-5 and Pd/H-ZSM-5: the zeolitic porous structure is needed for In/H-ZSM-5 in order to concentrate NO₂ adspecies on InO⁺ sites, which is important for NO reduction with CH₄ on In/H-ZSM-5 based catalysts, while the ion-exchangeable ability of zeolite is needed for Pd/H-ZSM-5 in order to make Pd²⁺ located in a highly dispersed state, on which NO is strongly chemisorbed.     

The effect of sodium on the Pd-catalyzed reduction of NO by methane

The kinetics of NO reduction by methane over Pd catalysts supported on 8 mol% yttria-stabilised zirconia (YSZ) has been studied at atmospheric pressure in the 620–770 K temperature range. Langmuir–Hinshelwood type kinetics are found with characteristic rate maxima reflecting competitive adsorption of NO and methane: NO adsorption is much more pronounced than that of methane within the temperature range of this investigation. Pd is an effective catalyst: 100% selectivity towards N₂ can be achieved at 100% conversion of NO over this wide temperature range. Sodium causes strong poisoning of the reaction. The response of the system to variations in NO and methane concentrations, temperature, and sodium loading indicate that this is due to the Na-induced enhancement of NO chemisorption and dissociation relative to methane adsorption, i.e. sodium enhances oxygen poisoning of the catalyst. These results stand in revealing contrast to the strong promotional effect of sodium in the reduction of NO by propene over the same catalysts. The very different response of the two hydrocarbon reductants to Na doping of the Pd catalyst receives a consistent explanation.     

NOx reduction with methane over mordenite supported palladium catalyst

Catalytic reduction of NO_x with small amounts of hydrocarbons in the presence of excess oxygen and water vapor have been studied over mordenite supported metal catalysts. Pd/mordenite catalyst was found to be very active for the reduction of NO_x with methane.     

Co-ZSM-5催化剂上烃类选择性催化还原NOx机理研究进展

烃类选择性催化还原氮氧化物可能是富氧条件下脱除汽车尾气中氮氧化物污染的有效途径。以Co-ZSM-5催化剂为例,综述了国内外有关Co-ZSM-5催化剂及其在富氧条件下烃类选择还原氮氧化物的机理研究,并将烃类选择还原氮氧化物的过程概括为以下三个步骤：(1) (NO)ad + (O₂)ad (NOy)ad ( y ≥2 );(2) (NOy)ad + (CxHy)ad …… (NCaObHc )ad;(3) (NCaObHc )ad + NO + O₂ …… N₂ + CO₂ + CO + H₂O。     

Improvement in selective catalytic reduction of nitrogen oxides by using dielectric barrier discharge

The behavior of the selective catalytic reduction of nitrogen oxides (NO_x) assisted by a dielectric barrier discharge was investigated. The principal function of the dielectric barrier discharge in the present system is to generate ozone, which is continuously fed to a chamber where the ozone and NO-rich exhaust gas (NO forms the large majority of NO_x) are mixed. In the ozonization chamber, a part of NO contained in the exhaust gas is oxidized to NO₂, and then the mixture of NO and NO₂ enters the catalytic reactor. The ozonization method proposed in this study was found to be more energy-efficient for the oxidation of NO to NO₂ than the typical nonthermal plasma process. The degree of NO oxidation was approximately equal to the amount of ozone added to the exhaust gas, implying that the decomposition of ozone into molecular oxygen was relatively slow, compared to its reaction with NO. When the exhaust gas was first treated by ozone to produce a mixture of NO and NO₂, a remarkable enhancement in the catalytic reduction of nitrogen oxides was observed. Neither NO₃ nor N₂O₅ was formed in the present system, but small amounts of ozone and N₂O (less than 5 ppm) were detected in the outlet gas.     

Determination of active palladium species in ZSM-5 zeolite for selective reduction of nitric oxide with methane

The active site in ZSM-5 zeolite-supported palladium, which shows the catalytic activity for NO reduction with methane as a reducing agent, has been investigated qualitatively and quantitatively by means of NO chemisorption and NaCl titration, comparing with PdO supported on silica. Palladium species in 0.4 wt.% Pd loaded H-ZSM-5 can adsorb NO equimolarly after calcination at 773 K, and almost all the NO was desorbed at around 673 K, while the palladium species on PdO/SiO₂ hardly adsorbed NO. The palladium species in Pd(0.4)/H-ZSM-5 are ion-exchangeable with Na⁺ in NaCl solution, indicating that they exist in a cationic state of an isolated Pd²⁺. This method for quantitative analysis of the isolated Pd²⁺ cations is named as ‘NaCl titration’. The amount of the isolated Pd²⁺ cationic species increased with increasing palladium content on Pd/H-ZSM-5, and PdO co-existed above 1 wt.%. The amount of the isolated Pd²⁺ cation was unchanged after the reaction of NO₂–CH₄, NO₂–CH₄–O₂, or CH₄–O₂ at 673 K, while the adsorbed amount of NO per the Pd²⁺ as determined by NO-TPD decreased after the NO₂–CH₄–O₂ reaction. It was found by NaCl titration that the catalytic activity of Pd/H-ZSM-5 for NO₂–CH₄–O₂ reaction increased with increasing amount of the isolated Pd²⁺ cationic species up to 0.7 wt.%, while the increase in the amount of PdO led to decrease in selectivity towards NO₂ reduction. The palladium species that are active and selective for NO reduction with CH₄ will be proposed.     

Catalytic behavior of nanostructured sulfated zirconia promoted by alumina: Butane isomerization

Promotion of sulfated zirconia with alumina (ASZ) improves its catalytic activities in n-butane isomerization. The activity and stability of the sulfated zirconia catalysts are investigated in three different nanostructures: ASZ supported on MCM-41, ASZ nanoparticles, and Al-promoted mesoporous sulfated zirconia. The increase of activity was determined primarily by the amount of aluminum addition and the temperature of calcination. The remarkable activity and stability of the Al-promoted catalysts are due to an improved distribution of acid sites strength. The Al loadings in all three catalysts can be adjusted so that optimum catalytic activities for butane isomerization could be found. The increase of butane conversion can be as high as 6 times of that in un-promoted SZ catalysts. This is due to an enhanced amount of weak Brønsted acid sites with intermediate strength on the optimal catalysts. For nanoparticle form of sulfated zirconia, the activity is most steady which is related to the optimum distribution of weak Brønsted acid. On the other hand, too much strong Brønsted acid leads to rapid decay of activity because of coking and cracking. The overall reaction mechanism of the isomerization of n-butane over sulfated zirconia was discussed to understand the details in product distribution.     

Direct impregnation method for preparing sulfated zirconia supported on mesoporous silica

A new method has been developed to prepare sulfated zirconia (S–ZrO₂) supported on mesoporous silica. With direct exchange of metal containing precursors for the surfactants in the as-synthesized MCM-41 materials, the problem of fill-up of the mesoporous structure was avoided and high sulfur content was achieved. By using this method, the composite of S–ZrO₂/MCM-41 with ZrO₂ content higher than 60 wt.% can be easily obtained without serious blockage of the pore structure of MCM-41. Nevertheless, the pore size and pore volume of the resultant S–ZrO₂/MCM-41 composites were found to vary markedly with the loading of ZrO₂. The strong acidic character of the obtained composites was examined by using them as catalysts in n-butane isomerization. Introduction of other metals such as aluminum as promoter into S–ZrO₂/MCM-41 can be easily conducted by the direct impregnation method.     

Role of lanthanide elements on the catalytic behavior of supported Pd catalysts in the reduction of NO with methane

In this study, the role of lanthanide elements (Ce, Gd, La, and Yb) on Pd/TiO₂ catalysts in the catalytic reduction of NO with methane was investigated. Steady-state reaction experiments in the presence of oxygen showed that the addition of lanthanide elements increases the oxygen resistance of the catalyst. The post-reaction XPS characterization results revealed that majority of the Pd sites remained in the zero oxidation state in the presence of Ce or Gd. The effect of SO₂ (145 ppm) and H₂O (0–6.6%) in NO–CH₄–O₂ reaction over supported Pd and Gd–Pd catalysts was also investigated. Over the Gd–Pd catalyst with the presence of SO₂, more than 70% NO conversion was obtained for over 6 h while the Pd only catalyst showed a sharper drop in NO conversion. Over the Gd–Pd catalyst, the presence of H₂O showed no effect on NO conversion activity (>99% conversion) during the 18 h the catalyst was kept on stream. Among the lanthanide elements tested, Gd is the most effective, allowing the use of above stoichiometric oxygen concentration.     

Harmful by-products in selective catalytic reduction of nitrogen oxides by olefins over alumina

The selective reduction of nitrogen dioxide and nitrogen monoxide by olefins (ethene, propene) has been studied over two different -aluminium oxides in the temperature range 473–873 K. Nitrogen dioxide was reduced more effectively than nitrogen monoxide with both, ethene and propene, as a reductant. At temperatures exceeding 700 K, ammonia was formed as a by-product over one type of alumina. Concentrations in the range 30–40 ppm were determined for propene in combination with both, NO and NO₂, while no ammonia was produced with ethene as a reductant. In addition, significant formation of hydrogen cyanide up to 70 ppm was observed with propene over both aluminium oxides starting from either NO or NO₂. In contrast, hydrogen cyanide formation remained below 10 ppm with ethene as a reductant. Nitrous oxide formation did not exceed 10 ppm for all investigations. The results show that for alumina catalysts ethene is a more suitable reductant than propene due to its lower tendency to form undesired by-products.     

硫酸化NOx选择性催化还原脱硝催化剂的研究进

新型的硫酸化NOx选择性催化还原(SCR)催化剂，由于对催化性能具有良好的促进作用以及强抗碱金属中毒特性等日益受到关注，成为SCR研究的热点。概述了硫酸化SCR催化剂的研究现状，详细介绍其制备方法、物化性能、催化特性以及反应机理，并对今后的研究方向作了展望。     

NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

Stability of palladium-based catalysts during catalytic combustion of methane: The influence of water

The stability of methane conversion was studied over a Pd/Al₂O₃ catalyst and bimetallic Pd–Pt/Al₂O₃ catalysts. The activity of methane combustion over Pd/Al₂O₃ gradually decreased with time, whereas the methane conversion over bimetallic Pd–Pt catalysts was significantly more stable. The differences in combustion behavior were further investigated by activity tests where additional water vapor was periodically added to the feed stream. From these tests it was concluded that water speeds up the degradation process of the Pd/Al₂O₃ catalyst, whereas the catalyst containing Pt was not affected to the same extent. DRIFTS studies in a mixture of oxygen and methane revealed that both catalysts produce surface hydroxyls during combustion, although the steady state concentration on the pure Pd catalyst is higher for a fixed temperature and water partial pressure. The structure of the bimetallic catalyst grains with a PdO domain and a Pd–Pt alloy domain may be the reason for the higher stability, as the PdO domain appears to be more affected by the water generated in the combustion reaction than the alloy. Not all fuels that produce water during combustion will have stability issues. It appears that less strong binding in the fuel molecule will compensate for the degradation.     

Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen

We discovered a family of catalysts that can effectively reduce NO_x with methane in the presence of excess oxygen. This new catalytic chemistry offers an alternative means for controlling NO_x emissions. Complete reduction of nitric oxide was obtained at 400°C over a Co-ZSM-5 catalyst. The presence of oxygen in the feed greatly enhances the nitric oxide reduction activity on Co-ZSM-5, and the nitric oxide conversion is strongly related to the inlet methane level. On the other hand, Cu-ZSM-5, which is a unique catalyst for the direct nitric oxide decomposition, is a poor catalyst for nitric oxide reduction by methane in the presence of excess of oxygen.