Molecule sieving catalysts for NO reduction with hydrocarbons in exhaust of lean burn gasoline and diesel engines

NO oxidation catalysts with small pores and low hydrocarbon oxidation activity owing to molecular sieving were prepared by dispersing platinum in the pores of ferrierite and chabazite zeolites. These small pore platinum zeolite crystals were physically mixed with large pore silver mordenite zeolite crystals and evaluated as HC-SCR catalysts for selective catalytic reduction of NO in a synthetic gas mixture doped with octane or isooctane, mimicking exhaust from lean burning engines with unburned hydrocarbons. A synergetic effect on N₂ formation and hydrocarbon efficiency was obtained in these physical zeolite mixtures. In the pores of the small pore zeolite where the diffusion of NO, O₂ and NO₂ molecules with small kinetic diameters was rapid, NO was effectively oxidized by the platinum into NO₂, while the small window apertures suppressed the diffusion and reaction of the hydrocarbon. The silver plated large pore zeolite catalyzed the reaction between the NO₂ formed in the small pore zeolite and the hydrocarbon. The importance of molecular sieving was demonstrated in experiments with permutation of pore sizes and catalytic functions.     

The effect of NO2 on the activity of fresh and aged zeolite catalysts in the NH3-SCR reaction

The activity of fresh and hydrothermally aged zeolite-based catalysts in the NH₃-selective catalytic reduction (SCR) reaction with excess of oxygen were studied. In addition, the effect of NO₂ in the gas feed as well as the acidity of the catalysts for the SCR activity was investigated. The studied catalysts were hydrogen, copper, iron and silver ion exchanged ZSM-5, mordenite, beta, ferrierite, and Y-zeolites. The investigation verifies that the zeolite-based catalysts are very promising for the ammonia SCR reaction. Especially, the activity at low and high temperatures was higher than the activity of commercial vanadia-based catalysts. From the studied catalysts, Fe-beta was the most potential one. The presence of NO₂ in the inlet flow enhanced significantly the catalytic activity of fresh and hydrothermally aged zeolite catalysts. This suggests that the oxidation of NO to NO₂ is probably the rate-determining step for the SCR reaction.     

Catalytic combustion of methane over palladium exchanged zeolites

Palladium cation exchanged zeolites (ZSM-5, mordenite and ferrierite) were studied as catalysts for methane combustion. Pd-zeolites showed much higher activities than PdO/Al₂O₃. For comparable palladium loadings, PdO/Al₂O₃ requires a reaction temperature of ca. 70–80°C higher than Pd-ZSM-5 for conversions between 50–100%. The catalytic activity of Pd-ZSM-5 seems to be related to its reducibility. Temperature-programmed reduction experiments with carbon monoxide showed a lower reduction temperature (ca. 157°C) for Pd-ZSM-5 than for PdO/Al₂O₃ (225°C). Further, the positioning of the palladium by ion exchange offers a highly dispersed form of Pd^II supported on the high surface area zeolite.     

Disproportionation and Methylation of Toluene with Methanol Over Zeolite Catalysts

Zeolites TNU-9, SSZ-33, mordenite (MOR) and ZSM-5 were evaluated for their activities in toluene disproportionation and methylation reaction of toluene with methanol. The medium-pore zeolite TNU-9 was found to possess the highest conversion in toluene disproportionation as compared with SSZ-33, mordenite and ZSM-5 based catalyst. Zeolite mordenite with the highest Si/Al ratio of 135.9 (the lowest concentration of active sites) exhibited the highest toluene conversion and maximum xylene yield in toluene methylation. On mordenite, the presence of channel intersections allows more reaction space for the formation of bulky intermediates and/or products and the 12-ring channels on the other hand, allow diffusion without trapping, since the channel diameter is large enough. In toluene methylation, xylene selectivity at the same conversion level follows the order: ZSM-5 > TNU-9 > MOR > SSZ-33, which implies that xylene selectivity is directly related to the size of channels from medium to large pore zeolites. The medium-pore zeolite ZSM-5, with 10-ring channels, shows the lowest reactivity for further alkylation of xylene, while mordenite with 12-ring channel shows the highest reactivity for further alkylation of xylene.     

Effect of zeolite pore geometry on isomerization of n-butane

A comparative study of isomerization of n-butane over bifunctional catalysts based on zeolites with different pore geometry (ZSM-5 and mordenite) and with metal particles located inside and/or outside the zeolite main channel system has been carried out. 1,1,1,3,3,3-hexamethyldisilazane was used in order to obtain catalysts with external Brönsted acid sites poisoned. TPDA, FTIR, TPR and TEM techniques were used to characterize the catalysts. ZSM-5 catalysts were quite resistant to poisoning, mainly when metal sites were located inside the pore system. However, isomerization activity was virtually suppressed for the poisoned mordenite catalysts. It is proposed that the isomerization via C₈ formation cannot take place inside the one-dimensional pore system of mesopore-free mordenite catalysts, but this is not the case for isomerization on ZSM-5.     

Statistical analysis of Al distributions and metal ion pairing probabilities in zeolites

The distributions of Al tetrahedral sites are studied as a function of Si : Al ratio (from 11 to 95) in three zeolites: ZSM-5, ferrierite, and mordenite. Al configurations obeying Loewenstein’s rule are generated by a Monte Carlo procedure and analyzed in terms of accessibility to specific channels. The distribution of pairs of Al sites accessible to the same channel segregates into distinct nearest-neighbor and ring-bridging types. Such pairs provide favorable binding environments for extraframework MO_xM²⁺ cations in the metal-ion-exchanged forms of the zeolites. In all three zeolites, the probability of a given Al site having at least one suitable partner for pairing within 8.5 Å is close to unity for typical Si : Al ratios. The probability at shorter distances is more sensitive to the zeolite structure, reflecting the larger number of highly puckered five- and six-membered rings in ZSM-5. This sensitivity, and its implications for CuO_xCu²⁺ formation in the three Cu-exchanged forms, may explain why Cu-ZSM-5 is the most active of the three for catalytically decomposing NO.     

Gallium oxide promoted zeolite catalysts for oxidehydrogenation of propane

Novel gallium-containing catalysts for oxidehydrogenation of propane, based on zeolite Beta, ZSM-5 and ferrierite, have been prepared and characterised by scanning electron microscopy, IR, MAS NMR and Raman spectroscopies. The catalytic properties of zeolitic matrixes with B, Al, and both ions at tetrahedral sites have been studied. Transformation of propane on pure zeolites and promoted with gallium (III) oxide depended on the structure of the matrix, its morphology and the type of cations occupying zeolite framework sites. Formation of new hydroxyl groups has been evidenced for some MFI zeolites promoted with Ga₂O₃.     

Zeolite synthesis in the presence of flexible diquaternary alkylammonium ions (C2H5)3N(CH2)nN(C2H5)3 with n=3–10 as structure-directing agents

The use of flexible diquaternary alkylammonium ions (C₂H₅)₃N⁺(CH₂)_nN⁺(C₂H₅)₃ (Et₆-diquat-n with n=3–10) as structure-directing agents for zeolite synthesis in the presence of alkali metal cation is described. Among the organic structure-directing agents studied here, a considerable diversity in the phase selectivity was observed only for the Et₆-diquat-5 ion: this cation can produce five different zeolite structures (i.e., P1, SSZ-16, SUZ-4, ZSM-57, and mordenite), depending on the oxide composition of synthesis mixtures. Analysis of the variable-temperature ¹H CRAMPS NMR spectra obtained from the Et₆-diquat-5 molecules in these five zeolites reveals that the host–guest interactions occurring within the respective materials maintain in a manner different from one another even at 160 °C at which the zeolite hosts crystallize.     

Co-conversion of methanol and n-hexane into aromatics using intergrown ZSM-5/ZSM-11 as a catalyst

The conversion of n-hexane and methanol into value-added aromatic compounds is a promising method for their industrially relevant utilization. In this study, intergrown ZSM-5/ZSM-11 crystals were synthesized and their resulting catalytic performance was investigated and compared to those of the isolated ZSM-5 and ZSM-11 zeolites. The physicochemical properties of ZSM-5/ZSM-11 intergrown zeolite were analyzed using X-ray diffraction, N₂ isothermal adsorption-desorption, the temperature-programmed desorption of ammonium, scanning electron microscopy, Fourier transform infrared spectra of adsorbed pyridine, and nuclear magnetic resonance of ²⁷Al , and compared with those of the ZSM-5 and ZSM-11 zeolites. The catalytic performances of the materials were evaluated during the co-feeding reaction of methanol and n-hexane under the fixed bed conditions of 400°C, 0.5 MPa (N₂), methanol:꞉n-hexane=7꞉:3 (mass ratio), and weight hourly space velocity=1 h^–1 (methanol). Compared to the ZSM-5 and ZSM-11 zeolites, the ZSM-5/ZSM-11 zeolite exhibited the largest specific surface area, a unique crystal structure, moderate acidity, and suitable Brønsted/Lewis acid ratio. The evaluation results showed that ZSM-5/ZSM-11 catalyst exhibited better catalytic reactivity than the ZSM-5 and ZSM-11 catalysts in terms of methanol conversion rate, n-hexane conversion rate, and aromatic selectivity. The outstanding catalytic property of the intergrown ZSM-5/ZSM-11 was attributed to the enhanced diffusion associated with its unique crystal structure. The benefit of using zeolite intergrowth in the co-conversion of methanol and alkanes offers a novel route for future catalyst development.     

Effect of the support upon the behavior of Cu in NO decomposition exemplified on Cu-ZSM-5 containing Zr

ZSM-5 containing Zr in the lattice was prepared following the procedure for ZSM-5 using ZrCl₄ as zirconium precursor. Zr was substituted for Si in the ZSM-5 lattice and then this zeolite was loaded with Cu. Loading these catalysts with Cu was carried out following Iwamoto’s procedure. An increase in Zr results in a decrease in Cu loading, although the exchange solutions were the same. The increased Zr loading and, hence, decreased Cu loading resulted in a decreased NO decomposition activity relative to the Zr-free ZSM-5 loaded with Cu. NO conversions, obtained on Cu-ZSM-5 zeolites in which zirconium replaced Si, were below 40%, which is about 30% lower than those recorded on Cu-exchanged pure zeolites. The amount of NO₂ detected in the reaction products proved that, for total conversions lower than 20%, the reaction of NO takes place almost exclusively without decomposition to N₂ and O₂. The catalysts were characterized by DRIFTS and NO-DRIFTS, Raman spectroscopy, O₂ — TPD and XPS. The OH region observed in DRIFTS changed with an increase in Zr loading and, hence, Cu(II)–O–Cu(I) species cannot be formed. This may play a role in the decreased activity. Raman spectra showed that increased Zr also results in increased CuO which may lead to the decreased activity. Although the exposure of the samples with high Zr content to NO results in the apparent redispersion of CuO to isolated sites within the ZSM-5, the Cu moves to locations which are inactive and/or inaccessible to NO and, hence, the activity does not increase even though the Cu is dispersed. The formation of NO₂ follows the mechanism proposed by Shelef.     

无黏结剂ZSM-35沸石的制备与催化反应性能

考察了不同硅铝比无黏结剂ZSM-35沸石分子筛的合成条件及催化反应性能。以多种有机胺（乙二胺、环己胺、正丁胺）为模板剂,在SiO₂/Al₂O₃为30～40的情况下均可以水热合成无黏结剂ZSM-35沸石。在乙二胺模板剂体系中,ZSM-35合适的晶化温度为130～160℃。提高SiO₂/Al₂O₃至58时,在乙二胺和正丁胺模板剂体系下,合成产物易出现ZSM-5和石英相,而环己胺作为模板剂可以成功制备纯相的无黏结剂ZSM-35沸石。在SiO₂/Al₂O₃为72时,以乙二胺、环己胺、正丁胺为模板剂均难合成纯相ZSM-35沸石,易产生杂晶。在二甲苯异构化反应中,制备的ZSM-35沸石表现出比ZSM-5沸石更好的对二甲苯选择性和更低的二甲苯损失。     

The Effect of Zeolite Structure on the Activity and Selectivity in p-Xylene Alkylation with Isopropyl Alcohol

The effect of zeolite architecture and channel dimensionality on p-xylene conversion and selectivity to 1-isopropyl-2,5-dimethyl-benzene was investigated in p-xylene alkylation with isopropyl alcohol over novel zeolites SSZ-33 and SSZ-35. Catalytic behavior of these zeolites was compared with those of zeolites Beta, mordenite, ZSM-11 and ZSM-5. It was found that p-xylene conversion increases with increasing pore size and connectivity of the channel system of individual zeolites with the exception of SSZ-35, which possesses a system of one-dimensional 10-ring channels that periodically open into wide, shallow cavities circumscribed by 18-rings. SSZ-35 exhibited the highest conversion among all zeolites at the reaction temperature of 150 °C and also the highest selectivity to 1-isopropyl-2,5-dimethyl-benzene. Molecular modeling confirmed the dimensions of the 18-ring cages are optimal for the formation of this alkylation product.     

超声浸渍无机盐改性Hβ分子筛催化合成乙基蒽醌

采用超声浸渍法将无机盐Al₂(SO₄)₃、(NH₄)₂SO₄、Ce(NH₄)₂(NO₃)₆和Fe(NO₃)₃负载于Hβ分子筛上,通过NH₃-TPD、XRD和吡啶-IR对分子筛进行表征,考察改性前后分子筛酸性能和晶相的变化。将改性的Hβ分子筛用于催化乙苯和苯酐合成乙基蒽醌。结果表明,不同无机盐超声浸渍改性分子筛的催化效果差别较大,其中,每克分子筛负载0.2 g的Al₂(SO₄)₃的Alβ分子筛催化效果最好,苯酐转化率为45.67%,乙基蒽醌选择性为50.12%。分子筛的酸性能（包括酸量、酸种类和酸强度）对催化性能影响较大。     

Adsorption of Carbon Dioxide on High-Silica Zeolites with Different Framework Topology

Adsorption isotherms of carbon dioxide were measured on six high-silica zeolites TNU-9, IM-5, SSZ-74, ferrierite, ZSM-5 and ZSM-11 comprising three-dimensional 10-ring (8-ring for ferrierite) at 273, 293, 313 and 333 K. Based on the known temperature dependence of CO₂ adsorption, isosteric heats of adsorption were calculated. The obtained adsorption capacities and isosteric adsorption heats related to the amount of CO₂ adsorbed have provided detailed insight into the carbon dioxide interaction with zeolites of different framework topology. The zeolites TNU-9 and ferrierite are characterized by pronounced energetic heterogeneity whereas due to the location of Na⁺ cations in the same positions the isosteric adsorption heats of CO₂ adsorption on IM-5, ZSM-5 and ZSM-11 zeolites are rather constant for molecular ratio CO₂/Na⁺ < 1. As IM-5 zeolite has a maximum adsorption capacity, it appears to have optimum properties for carbon dioxide separation.     

On the exceptional time-on-stream stability of HZSM-12 zeolite: relation between zeolite pore structure and activity

ZSM-12 and several other 12-membered ring large-pore zeolites have been tested for the reforming of naphthenic hydrocarbon mixtures. It was found that ZSM-12 possesses a surprisingly higher coking resistance than other large pore zeolites tested such as USY, L-zeolite, mordenite, and β=zeolite for reforming of hydrocarbon mixtures. This superior performance is due to the unique non-interconnecting tubular-like linear channels of ZSM-12, which do not allow trapping/accumulation of coking precursors. ZSM-12 zeolite also demonstrated excellent structural stability even under severe acid dealumination. From this work, we found that the decrease of the aluminum content of a zeolite is not sufficient to ensure low rates of coke deposition. We also concluded that zeolites with channel intersections (cavities) of comparable size with the zeolite apertures do not favor coke formation. For these types of zeolites the strong acid sites carry out other acid-catalyzed reactions, rather than forming coke. In contrast, zeolites with relatively large supercages are inherently favorable to coking reactions, which in turn lead to the fast deactivation. The appropriate combination of the zeolite pore structure and acidity (controlled via dealumination) showed superior TOS behavior (time-stable activity and product selectivities). For zeolites which are susceptible to coking due to pore structure, the increase of the Brønsted acid strength results in fast deactivation. Contrary to what one would commonly expect and previous reports, we found that one-dimensional zeolites, such as, ZSM-12, can exhibit significantly higher tolerance to coking than multidirectional zeolites.     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Catalytic conversion of MTBE to biodegradable chemicals in contaminated water

The behavior of different acid zeolites in the hydrolysis at room temperature of methyl tert-butyl ether (MTBE) was studied with reference to the possibility of its conversion to more biodegradable products in underground water contaminated by MTBE. The effect of the structure of the zeolite and SiO₂/Al₂O₃ ratio was analyzed. The results indicate that acid H-MFI and H-BEA zeolites are effective in both adsorption and hydrolysis of MTBE and may be applied for both in situ underground water remediation and as protection barrier for wells or leaking tanks. However, other zeolites (mordenite and faujasite) result completely inactive. Furthermore, contrary to what was expected, the increase of the Si/Al ratio promotes the reactivity which is determined by the resistance to diffusion of MTBE in the pores of zeolites and the resistance of back-diffusion of the reaction products.     

Isomerization of α-Pinene Oxide Over Iron-Modified Zeolites

Fe-modified mordenite, ferrierite, Y, ZSM-5, ZSM-12 and beta zeolite catalysts were prepared by solid state ion-exchange and conventional liquid phase ion-exchange methods from aqueous solutions. Sn- modified H-beta-300 zeolite catalyst was prepared by the later method. The characterization of proton form, Fe and Sn modified zeolites was carried out using X-ray powder diffraction, scanning electron microscopy, Mössbauer spectroscopy with magnetic measurements, transmission electron microscopy, nitrogen adsorption, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma spectroscopy, thermo-gravimetric analysis and FTIR spectroscopy using pyridine as a probe molecule. Isomerization of α-pinene oxide over the Fe and Sn modified zeolite catalysts was carried out in the liquid phase using a batch-wise glass reactor. Formation of campholenic aldehyde and fencholenic aldehyde were observed to be influenced by the structure, acidity of zeolite and contents of Fe and Sn, reaction temperature and the catalysts pretreatment.     

Role of oxygen on NOx SCR catalyzed over Cu/ZSM-5 studied by FTIR, TPD, XPS and micropulse reaction

Pulse reaction, TPO/TPD (temperature programmed oxidation/temperature programmed desorption), XPS (X-ray photoelectron spectroscopy) and DRIFT (diffuse reflectance infrared transform spectroscopy) have been used to investigate the role of oxygen on SCR (selective catalytic reduction) of NO over Cu/ZSM-5 zeolites, especially during the early stage. Pulse reaction shows that propene is deposited on Cu ions and inhibits the adsorption of NO on them. It is necessary for oxygen to make Cu sites clean by deep oxidation of propene. In the presence of O₂, SCR at 623 K is accompanied by coke deposition on the zeolite. This coke can be discriminated from carbonaceous species formed on Cu in the absence of O₂ from the result of TPO. XPS results implies that Cu(II)–O species play a crucial role in forming Cu(II)–NO₂ species, and subsequently are well correlated with the activity of NO SCR.     

三元孔道结构纳米ZSM-5分子筛团聚体的合成

采用正丁胺和ZSM-5晶种双模板体系水热合成了一系列ZSM-5分子筛,考察了晶种、正丁胺添加量和晶化条件对分子筛物理化学性能、孔道结构和形貌的影响。对所得分子筛分别进行X射线衍射（XRD）、氮气吸-脱附、扫描电子显微镜（SEM）表征分析。结果表明：分子筛为三元孔道结构的纳米ZSM-5分子筛团聚体,正丁胺和晶种在合成过程中具有协同作用。在正丁胺与二氧化硅物质的量比为0.26、晶种添加量为3%（质量分数）、在120 ℃晶化24 h后再在170 ℃晶化48 h条件下合成的分子筛总比表面积和外比表面积分别为364 m²/g和59 m²/g。