Cooperation of Ag/Al2O3 and Sn/Al2O3 Catalysts for the Selective Reduction of NO by Propene

Compared to the Ag/Al₂O₃ catalyst, a two‐stage catalyst composed of an Ag/Al₂O₃ layer followed by a Sn/Al₂O₃ layer shows higher low‐temperature activity and a wider temperature window. Its activity below 350 °C is enhanced in the presence of SO₂. Even in the presence of H₂O and SO₂, the performance of the same catalytic system is still satisfactory.     

Influence of Al2O3 support on the activity of Ag/Al2O3 catalysts for SCR of NO with decane

The role of the Al₂O₃ support on the activity of supported Ag catalyst towards the selective catalytic reduction (SCR) of NO with decane is elucidated. A series of Ag/Al₂O₃ catalysts were prepared by impregnation method and characterized by N₂ pore size distribution, XRD, UV–Vis, in-situ FT-IR and acidity measurement by NH₃ and pyridine adsorption. The catalytic activity differences of Ag/Al₂O₃ are correlated with different properties of Al₂O₃ supports and the active Ag species formed. 4wt% Ag supported on sol-gel prepared Al₂O₃ (Ag/Al₂O₃ (SG), showed higher NO _x conversion (65% at 400 °C), compared with the respective catalysts made from commercial Al₂O₃ (Ag/Al₂O₃ (GB), Ag/Al₂O₃ (ALO), (∼26 and 7% at 400 °C). The higher surface area, acidity and pore size distribution in sol–gel prepared Al₂O₃ (SG) results in higher NO and hydrocarbon conversion. Based on the UV–vis characterization, the activity of NO reduction is correlated to the presence of Ag_n^δ+ clusters and acidity of Al₂O₃ support was found to be one of the important parameter in promoting the formation and stabilization of Ag_n^δ+ clusters. Furthermore from pyridine adsorption results, presence of more number of Bronsted acid sites in Ag/Al₂O₃ (SG) is confirmed, which could also contribute to low temperature hydrocarbon activation and improve NO conversion. In situ FT-IR measurements revealed the higher rate of –CN and –NCO intermediate species formation over 4wt% Ag/Al₂O₃ (SG). We conclude that the physico–chemical properties of Al₂O₃ play a crucial role in NO _x conversion over Ag/Al₂O₃ catalysts. Thus, the activity of the Ag/Al₂O₃ catalyst can be tailored by using a proper type of Al₂O₃ support.     

Enhanced NOx Conversion with Decane Over Ag/Al2O3 and Metal Supported ZSM-5 Composite SCR Catalysts

A combination of Ag/Al₂O₃ and a partial oxidation catalyst M/ZSM-5, M being different metal cations, were evaluated for selective catalytic reduction of NO with decane. Physical mixture of Ag/Al₂O₃ and M/ZSM-5 catalysts showed significant increase in NOx conversion compared to single component Ag/Al₂O₃ catalyst. M/ZSM-5 as a second catalyst component was found to generate more reactive hydrocarbons, such as unsaturated small chain hydrocarbons and oxygenates in situ, and enhance the NOx conversion over Ag/Al₂O₃ HC-SCR catalyst.     

Enhanced Sulfur Tolerance of Bimetallic PtPd/Al2O3 Catalysts for Hydrogenation of Tetralin by Addition of Fluorine

A series of mono- and bi-metallic Pt-Pd/Al₂O₃ samples with and without F were studied as aromatic hydrogenation catalysts. The effects of changing the order of impregnation of the Pt precursor and F as well as varying the calcination temperature (300–500 °C) were investigated. Temperature programmed reduction (TPR) results demonstrate the presence of a higher fraction of dispersed metal precursor species left on the surface from the impregnation (PtO _x Cl _y ) on the Pt/Al₂O₃ sample calcined at high temperature. The impregnation of F before the Pt precursor significantly decreases the interaction between the metal and the support. However, this decrease is not observed when F is impregnated after the metal precursor. For the bimetallic Pt-Pd catalysts, the sample prepared adding F before the metal show a higher degree of Pt-Pd interaction than either the parent Pt-Pd/Al₂O₃ catalyst or the one prepared with F added later. TPD of ammonia result show the increase in strong acid sites when F is present. Activity tests for tetralin hydrogenation in the presence of 350 ppm dibenzothiophene indicate a better sulfur tolerance for all F-promoted catalysts, especially Pt-Pd.     

Mechanistic Insight in the Ethane Dehydrogenation Reaction over Cr/Al2O3 Catalysts

A Cr/Al₂O₃ alkane dehydrogenation catalyst exhibits a maximum in ethylene yield during an ethane dehydrogenation cycle. Isotopic labelling experiments with monolabelled ¹³C-ethane and deuterium were used to elucidate whether the initial activity increase could be due to formation of an active, larger hydrocarbon intermediate on the surface. The results strongly indicate that this is not the case, and instead point to a traditional reaction cycle involving adsorption of ethane to form an ethyl species, followed by desorption of ethene and hydrogen. Transient kinetic data suggest that ethane adsorption is the rate-determining step of reaction.     

Promotional Effect of CO2 on Desulfation Processes for Pre-Sulfated Pt-BaO/Al2O3 Lean NOx Trap Catalysts

A combination of H₂ TPRX, TR-XRD and XPS analysis has been used to investigate the effects of CO₂ on the desulfation of pre-sulfated Pt-BaO/Al₂O₃ samples. The results demonstrate that the presence of CO₂ promotes the removal of sulfur species, especially at temperatures below 500 °C, with a corresponding suppression of BaS formation, thus resulting in a lower amount of residual sulfur on the sample after desulfation.     

超临界浸渍法制备CuO/Al_2O_3催化剂

应用超临界浸渍法制备CuO/γ-Al2O3催化剂。以Cu(NO3)2为前驱体,甲醇为助溶剂在载体Al2O3上于超临界二氧化碳中进行浸渍,研究了不同浸渍条件:超临界温度、压力、浸渍时间、前驱体和载体量之比,助溶剂量等因素对浸渍效果的影响。并以SEM和XRD分别对超临界与普通浸渍法制备的样品进行了表征。结果说明,超临界浸渍时吸附速度明显较快,吸附量大,浸渍物分布均匀且和载体作用较强。以亚甲基蓝的催化氧化降解为模型反应测定两种制法催化剂的活性,超临界条件制备的催化剂活性明显较好。所得结果表明,使用无机金属前驱体加助溶剂的方法可以代替有机金属前躯体在超临界浸渍中的使用。     

Ethylene Hydrogenation over Pt/Ga2O3/Al2O3 Catalysts

The effects of gallia addition on the Pt dispersion and the activity for ethylene hydrogenation at 0 °C were studied for Pt-supported catalysts as a function of the reduction temperature (350, 450, and 550 °C). The catalysts contained 0.5 wt.% Pt and were prepared by successive incipient wetness impregnations with Ga(NO₃)₃ and H₂PtCl₆ aqueous solutions. CO and H₂ chemisorption data indicated that, the addition of small amount of Ga₂O₃ caused an increase of the Pt dispersion and a decrease of ethylene conversion. Both of them decreased appreciably when Ga₂O₃ addition was increased, particularly, for the case where β-Ga₂O₃ was used as a support. The increase in reduction temperature magnified the negative effects of the gallia addition on dispersion and activity, although the addition of small amount of gallia improved the resistance to metal sintering. Results were interpreted in terms of the presence of reduced Ga species, which can encapsulate Pt particles.     

Reactivity of Surface Nitrates in H2-Assisted SCR of NO x Over Ag/Al2O3 Catalyst

The role of nitrate ad-species in H₂-assisted SCR over Ag/Al₂O₃ was compared in NH₃-SCR and n-C₆H₁₄-SCR processes. It was found that nitrates could be reduced by NH₃ or n-C₆H₁₄ at similar rates with H₂ co-feeding which indicates a common rate-limiting step. However, contributions of surface nitrate reduction to the overall NH₃-SCR or n-C₆H₁₄-SCR are different as revealed by comparing the rates of nitrate reduction with the rates of steady-state processes. The rate of the steady-state n-C₆H₁₄-SCR is virtually identical to the rate of surface nitrate reduction suggesting a significant contribution of the surface nitrates reduction to the overall n-C₆H₁₄-SCR process. On the other hand, the steady-state rate of NH₃-SCR is by ~15 times higher, which indicates that the reduction of surface nitrates plays a marginal role in the overall NH₃-SCR.     

用于邻苯基苯酚合成的Pt/Al2O3催化剂改性研究

考查了用于环己酮二聚物脱氢制备邻苯基苯酚(OPP)的Pt/Al2O3催化剂的改性研究。针对脱氢反应体系所存在的副反应特点,采用了载体碱改性〔使用了含钾矿物(KM)以及3种Mg-Al复合载体〕与助剂改性(使用K盐类)两种手段,开发出了二者结合的复合改性工艺。研究表明,矿物KM的载体改性效果较好(OPP选择性>80%),助剂改性以K2CO3的性能较好(OPP选择性>90%),而复合改性的Pt-K2CO3/KM-Al2O3〔w(Pt)=0.5%,w(K2O)=3.0%,w(KM)=15%〕催化剂在选定的反应条件下,最高活性可达二聚物转化率95.2%、OPP选择性95.0%,在100 h内,环己酮二聚物转化率和OPP选择性可分别保持在95.0%与92.0%以上。     

SCR of NO over Ir/Al2O3 Catalysts. Importance of the Activation Procedure and Influence of the Dispersion

For SCR of NO the study of Ir/Al₂O₃ solids shows the importance of the activation procedure under mixtures containing CO (NO–C₃H₆–CO–O₂ or NO–CO–O₂). The selective reductant remains C₃H₆, however. The activation goes with an iridium particles sintering without Ir loss.     

Dynamical Changes in Cu/ZnO/Al2O3 Catalysts

A combination of various transient and steady-state kinetic experiments was used to provide evidence for dynamical changes in a Cu/ZnO/Al₂O₃ catalyst of industrial interest. From these it can be deduced that the reversible structural alterations strongly depend on the reaction conditions as well as on the pretreatment. The pretreatment was found to induce changes in the morphology of the metallic Cu particles to some extent, and surface alloying under more severe reducing conditions.     

Differences Between Al2O3 and Ag/Al2O3 for Lean Reduction of NO x with Dimethyl Ether

Lean reduction of NO _x with DME occurs with high selectivity to N₂ over Al₂O₃ between 300 °C and 550 °C with a maximum of 47% at 380 °C, and with lower selectivity over Ag/Al₂O₃ between 250 °C and 400 °C due to the catalysts’ sensitivity to gas phase radical reactions and activity for NO _x reduction with methanol.     

Glycerol Hydrogenolysis to 1,2-Propanediol by Cu/ZnO/Al2O3 Catalysts

The effect of preparation methods on the Cu/ZnO/Al₂O₃ catalyst structure and catalytic activity on liquid glycerol hydrogenolysis to 1,2-propanediol has been investigated. The physicochemical properties of the catalysts were characterized by BET, XRD, TG/DTA, NH₃-TPD and TPR. The experimental results showed that the catalyst prepared by an oxalate gel–coprecipitation had the highest activity. At 200 °C and 400 psi hydrogen pressure, the glycerol conversion and 1,2-propanediol selectivity catalyzed by the Cu/ZnO/Al₂O₃ catalyst prepared via oxalate gel–coprecipitation were 92.3 and 94.5 % respectively. It was found that the 1,2-propanediol selectivity was dependent on hydrogen pressure and the un-desired by-products were mainly due to the side reactions caused by the presence of the intermediate acetol.     

Glycerol Hydrogenolysis to 1,2-Propanediol by Cu/ZnO/Al2O3 Catalysts

The effect of preparation methods on the Cu/ZnO/Al₂O₃ catalyst structure and catalytic activity on liquid glycerol hydrogenolysis to 1,2-propanediol has been investigated. The physicochemical properties of the catalysts were characterized by BET, XRD, TG/DTA, NH₃-TPD and TPR. The experimental results showed that the catalyst prepared by an oxalate gel–coprecipitation had the highest activity. At 200 °C and 400 psi hydrogen pressure, the glycerol conversion and 1,2-propanediol selectivity catalyzed by the Cu/ZnO/Al₂O₃ catalyst prepared via oxalate gel–coprecipitation were 92.3 and 94.5 % respectively. It was found that the 1,2-propanediol selectivity was dependent on hydrogen pressure and the un-desired by-products were mainly due to the side reactions caused by the presence of the intermediate acetol.

     

Unusual Activity Enhancement of NO Conversion over Ag/Al2O3 by Using a Mixed NH3/H2 Reductant Under Lean Conditions

Addition of H₂ to a NO/NH₃/O₂/H₂O feed for selective catalytic reduction of nitrogen oxide over Ag/Al₂O₃ catalysts causes an unusual enhancement of activity, e.g., the marginal activity (<10%) of 1 wt% Ag impregnated on γ-Al₂O₃ or mesoporous Al₂O₃ modifications is boosted to nearly 100% over a broad temperature range from 200 to 550°C at a space velocity of 30,000cm³g^?1h^?1). Contrary, silver on SiO₂ or α-Al₂O₃ shows no improvement of activity in the presence of H₂. The effect is tentatively attributed to a higher percentage of intermediary nano-sized Ag clusters on high-surface area Al₂O₃ in the presence of hydrogen. This promotes oxygen activation and hence NO oxidation to reactive intermediate nitrite species. The required dispersion of Ag cannot be stabilized on SiO₂ or α-Al₂O₃.     

沉淀法制备Al2O3-ZrO2-Y2O3复合粉体的固相反应

采用化学沉淀法制备了不同配比的Al2O3-ZrO2-Y2O3复合粉体.通过X射线衍射研究了热处理过程中各物质之间的反应顺序及复合粉体的物相组成,结果表明升温过程中Y2O3优先与ZrO2反应生成固溶体,温度较高时,剩余Y2O3与Al2O3反应生成钇铝石榴石YAG;不同的制备工艺没有改变各物质之间的固相反应顺序,但影响了复合粉体中各物相的相对含量.     

Role of Baria Dispersion in BaO/Al2O3 Catalysts for Transesterification

The transesterification of two vegetable oils containing different quantities of free fatty acid have been compared over a series of BaO/Al₂O₃ catalysts with a range of baria loadings/dispersions. Dispersion of baria on the alumina was determined by pulse chemisorption of carbon dioxide. Limited agreement was found between the numbers of exposed sites for CO₂ adsorption and the reaction rate and the rates measured were different for the two oils. The latter was unexpected as the rate determining step appears to involve only the activated adsorption of methanol, consistent with the change in rate measured when methanol was replaced by ethanol. Differences between the behaviour of the two oils and the lack of correlation between rates and available basic sites can both be accounted for by the strong dissociative adsorption of the free fatty acid which results in a less active catalyst for the transesterification of the triglyceride. Higher dispersed samples show less sensitivity to free fatty acid and give the highest rate per exposed surface site.     

Enhanced catalytic activity of Pt/Al2O3 on the CH4 SCR

In this study, we investigated the effect of mixing α-Al₂O₃ and γ-Al₂O₃ with a Pt catalyst on CH₄ selective catalytic reduction (SCR). Among the prepared catalysts, the Pt/α-Al₂O₃ catalyst was found to have the lowest catalytic activity, but the best adsorption characteristics for CH₄, which was used as the reductant. In contrast, the Pt/γ-Al₂O₃ catalyst was found to exhibit relatively high catalytic activity and moderate adsorption characteristics. To simultaneously enhance the catalytic activity and CH₄ adsorption characteristics, we developed a new catalyst, Pt/γ-Al₂O₃ + Pt/α-Al₂O₃, by mixing α-Al₂O₃ and γ-Al₂O₃ with a Pt catalyst. The catalytic activity test confirmed that mixing these catalysts led to enhanced catalytic activity.