Side chain alkylation of 2-picoline with formaldehyde over alkali modified zeolites

The catalytic side-chain alkylation of 2-picoline with formaldehyde (37 wt/v) was studied over alkali and alkaline earth metal ion modified zeolites in vapor phase conditions at atmospheric pressure, and at a reaction temperature of 300°C. A mixture of vinylpyridine and ethylpyridine were formed by the alkylation of the corresponding picoline over Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba metal ion modified zeolites. The catalytic activity of side-chain alkylation of 2-picoline was studied over various alkali modified zeolite molecular sieves like ZSM-5 (SiO₂/Al₂O₃ = 30), X, Y, Mordenite and MCM-41. Alkali modified ZSM-5 (30) catalyst was found more active in side-chain alkylation of 2-picoline when compared to other zeolites. Among all these catalysts studied K modified ZSM-5 (30) and K-Cs-ZSM-5 (30) gave best conversion of 2-picoline and selectivity to vinylpyridine. Cs-ZSM-5 (30) and K-ZSM-5 (30) were employed to study the reaction parameters like reaction temperature, weight hourly space velocity, molar ratio, and time on stream for 2-picoline independently. The effects of alkali metal ion content (K, Cs) and precursors of potassium ion on catalytic activity in side-chain alkylation was studied. An attempt has been made to correlate between the basicity with the activity of side-chain alkylation. The bifunctional catalyst is required containing medium or weak acidic centers and basic centers in the side-chain alkylation, which is understood through proposed reaction mechanism. The selectivities of 2-vinylpyridine were 81.7, 90.8, and 94.8% at 65.4, 62.1 and 57.2% conversions at 300°C from 2-picoline and formaldehyde over K-ZSM-5 (30), Rb-ZSM-5 (30) and K-Cs-ZSM-5 (30) respectively. Indian Institute of Chemical technology (IICT) communication no: 020707     

An inverse correlation of the enhancement effect of tetrachloromethane as a feedstream additive in the oxidative coupling of methane on silica-supported alkaline earth and alkali-alkaline earth catalysts with the polarizing ability of the alkaline earth cations

Results are reported for the oxidative coupling of methane on silica-supported alkaline earths prepared from either their acetates or chlorides with and without alkali metals as dopants and in the absence or presence of carbon tetrachloride (TCM). The addition of small quantities of TCM to the methane feedstream produces increases in the conversion of methane and the selectivities to C₂ hydrocarbons which correlate with the increase in cation size and thus are inversely related to the polarizing abilities of the cations.     

Side-chain alkylation of 2,6-lutidine to 2,6-divinylpyridine over basic zeolites

Synthesis of 2,6-divinylpyridine (2,6-DVP) and 2-methyl-6-vinylpyridine (2M6VP) was achieved for the first time by side-chain alkylation of 2,6-lutidine using formaldehyde (37 wt/v) as alkylating agent in heterogeneous conditions at atmospheric pressure, and at a reaction temperature of 300 °C over alkali and alkaline metal ion modified zeolites. A mixture of 2,6-divinylpyridine and 2-methyl,6-vinylpyridine were formed by the alkylation of the 2,6-lutidine over Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba metal ion modified zeolites. The catalytic activity of 2,6-lutidine was studied over various potassium metal ion modified zeolite molecular sieves like ZSM-5 (30), X, Y, mordenite and MCM-41. Alkali modified ZSM-5 (30) catalyst was found more active in side-chain alkylation of 2,6-lutidine when compared to other zeolites. Among all these catalysts studied K modified ZSM-5 (30) gave best conversion of 2,6-lutidine and selectivity to 2-methyl,6-vinylpyridine. K-ZSM-5 (30) catalyst was employed to study the reaction parameters like reaction temperature, weight hourly space velocity, molar ratio, and time on stream for 2,6-lutidine. The effect of potassium metal ion content and precursors of potassium ion on catalytic activity in side-chain alkylation of 2,6-lutidine was studied. The bifunctional catalyst is required containing medium or weak acidic centers and basic centers in the side-chain alkylation, which is understood through proposed mechanism. The selectivities of 2,6-DVP were 45.2, 40.0, and 30.7% at 73.4, 66.0 and 60.5% conversion at 300 °C from 2,6-lutidine and formaldehyde over K-ZSM-5 (30), Rb-ZSM-5 (30) and Cs-K-ZSM-5 (30), respectively.     

Nitrous oxide as an oxidant for ethane oxydehydrogenation

Waste nitrous oxide was used as an oxidant for ethane oxydehydrogenation performed at the range of temperature from 350 to 450 °C over iron modified zeolite catalysts. Different zeolite matrices (zeolite ZSM-5 of different Si/Al ratio, H-Y, mordenite) modified with iron cations introduced into zeolite by means of ionic exchange were applied as catalysts for the reaction under study. Additionally, amorphous silica and alumina silica as well as silicalite of MFI structure were also used as a matrix for iron ions accommodation and they were tested for oxydehydrogenation reaction. It was found that only iron modified zeolites showed activity for reaction under study. Amorphous oxide supports and crystalline neutral silicalite modified with iron cations by means of impregnation were completely inactive for oxydehydrogenation reaction. The best catalytic performance was found on iron modified zeolites of MFI structure. The Si/Al ratio of the ZSM-5 matrix influenced the activity for ethane oxydehydrogenation reaction insignificantly. N₂O oxidant was partly utilized for ethane oxidation (towards ethene or carbon oxides), while some part of the oxidant was decomposed to nitrogen and oxygen. Performing the reaction at 450 °C resulted in a high ethene yield and complete N₂O removal.     

硅源对ZSM-5分子筛合成和催化性能的影响

为了考察硅源对ZSM-5分子筛合成和催化性能的影响,分别采用白炭黑、硅胶、硅溶胶和单分散SiO₂为硅源合成ZSM-5分子筛,对合成的ZSM-5分子筛进行XRD、SEM、BET和NH₃-TPD表征,并以C₄烯烃为原料评价合成的ZSM-5分子筛的催化裂解性能。结果表明,以硅溶胶为硅源合成的ZSM-5分子筛具有较好的结晶度和催化活性。水热处理使分子筛酸量减少,孔容缩小,改善了分子筛的乙烯丙烯选择性。经600 ℃水热处理4 h的ZSM-5分子筛在常压、580 ℃和空速9 h^-1反应条件下,丁烯催化裂解为乙烯和丙烯平均转化率为90.2%,乙烯和丙烯总收率达61.1%。     

Hydrogen adsorption on M-ZSM-12 zeolite clusters (M = K,Na and Li): a density functional theory study

The molecular adsorption of hydrogen has been studied theoretically via DFT on additional framework with alkali metal atoms (K, Na and Li) in ZSM-12 zeolite. A 14T channel zeolite cluster model was used. Lewis acidity of alkali metals decreases with increasing atomic radius of alkali metal and H₂ adsorption. Adsorption enthalpy values were computed to be ?7.4 and ?5.1 kJ/mol on Li- and Na-ZSM-12 clusters, respectively. Hydrogen adsorption enthalpy values for Li- and Na-cases are meaningfully larger than the liquefaction enthalpy of hydrogen molecule. This designates that Li- and Na-ZSM-12 zeolites are potential cryoadsorbent materials for hydrogen storage.     

Catalytic cracking of 1-butene to propene and ethene on MCM-22 zeolite

Catalytic cracking of butene to propene and ethene was investigated over HMCM-22 zeolite. The performance of HMCM-22 zeolite was markedly influenced by time-on-stream (TOS) and reaction conditions. A rapid deactivation during the first 1 h reaction, followed by a quasi-plateau in activity, was observed in the process along with significant changes in product distributions, which can be attributed to the fast coking process occurring in the large supercages of MCM-22.

Properly selected reaction conditions can suppress the secondary reactions and enhance the production of propene and ethene. According to the product distribution under different butene conversion, we propose a simple reaction pathway for forming the propene, ethene and by-products from butene cracking.

HMCM-22 exhibited similar product distribution with the mostly used high silica ZSM-5 zeolite under the same conversion levels. High selectivities of propene and ethene were obtained, indicating that the 10-member ring of MCM-22 zeolite played the dominant role after 1 h of TOS. However, MCM-22 exhibited lower activity and stability than that on high silica ZSM-5 zeolite with longer time-on-stream.     

后处理改性对HZSM-5沸石丁烯裂解性能的影响

采用不同后处理手段(碱处理、水汽处理以及碱处理-水汽处理)对HZSM-5沸石的孔结构和酸性质进行了调变,并对其丁烯裂解性能进行了研究。运用N₂吸脱附、扫描电镜(SEM)、X射线衍射(XRD)以及吡啶吸附红外(Py-IR)对后处理改性前后的沸石样品的物理化学性质进行了表征。碱处理后HZSM-5的质子酸量增加,在5～20 nm处具有分布较宽的介孔,其反应活性升高,丙烯选择性下降,但失活速率没有加快。单独水汽处理在2～4 nm处产生介孔,但介孔体积较小。碱处理-水汽处理在2～4和5～20 nm处具有双分布介孔,前者分布较集中,后者分布较宽。单独水汽处理和碱处理-水汽处理的样品可以提高HZSM-5的丙烯选择性,主要归功于酸量的降低;反应2.5 h后具有较稳定的丙烯收率(高碱浓度处理-水汽处理的样品除外)。     

Methanol-to-Olefins Reaction over Large-Pore Zeolites: Impact of Pore Structure on Catalytic Performance

In the methanol-to-olefins (MTO) reaction, product flexibility is important for meeting the fluctuating chemicals demands. In this paper, the catalytic performance of recently reported zeolites having 12-ring pores, such as boroaluminosilicate CON-type zeolite ([Al,B]-CON), MCM-68, and YNU-5 zeolites, in the MTO reaction was compared to understand the relationship between zeolite framework and product selectivity. The catalytic performance of the synthesized zeolites was compared with that of Beta, mordenite, and ZSM-5. The highest selectivities for propylene and butylenes were achieved over MCM-68. The highest propylene-to-ethylene ratio in the products was obtained over [Al,B]-CON. ZSM-5 and [Al,B]-CON exhibited a superior ability to suppress coke formation compared to Beta, mordenite, MCM-68, and YNU-5.     

贵金属负载型核壳结构催化剂的制备及其催化性能

以十六烷基三甲基溴化铵(CTAB)为表面活性剂,尿素为碱源,正硅酸四乙酯(TEOS)为硅源,在环己烷和正戊醇组成的微乳体系中制备了以微孔ZSM-5分子筛为核,树枝状介孔SiO_2为壳的多级孔核壳结构分子筛。考察制备温度、时间、尿素添加量以及TEOS添加量等制备条件对制备催化剂所需载体的影响,并采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和N2吸附-脱附等手段对分子筛样品进行了表征。结果表明,制备温度为100~120℃,时间为4 h,尿素与TEOS物质的量之比为1和TEOS与ZSM-5物质的量之比为0.9~1.2时,得到的核壳结构分子筛呈现出优良的单分散性、完整性以及水热稳定性。最终在树枝状介孔SiO_2壳层负载高分散贵金属Pt,得到的双功能催化剂Pt/ZSM-5@MS在催化丙酮一锅法制备甲基异丁基酮(MIBK)反应中表现出较高的活性及良好的循环使用性能。     

The adsorption of fatty acids from vegetable oils with zeolites and bleaching clay/zeolite blends

The adsorption of model fatty acids (hepatnoic, oleic), using spiked vegetable oils, was studied using different kinds of zeolites (A-zeolite, X, Y-zeolites, mordenite), Y-zeolite exchanged with different cations (alkali, alkaline earth, transition metal ions), and with bleaching clay/zeolite blends. The adsorption process was shown to be governed by the molecular sieving properties of the zeolites involved as well as the electrostatic field strengths of the exchange cations. Facile interparticle diffusion of cations between clay and zeolite particles in the blends was verified by electron microprobe analysis and shown to cause unexpected results with respect to bleaching and fatty acid removal.     

Production of Propylene from Ethanol Over ZSM-5 Zeolites

In this work, we studied the conversion of ethanol to propylene over ZSM-5 zeolites. The catalytic performance of H-ZSM-5 (Si/Al₂ = 30, 80, and 280) and ZSM-5 (Si/Al₂ = 80) modified with various metals was investigated. H-ZSM-5(Si/Al₂ = 80) afforded high propylene yield, which indicates that a moderate surface acidity favored propylene production. Zr-modified ZSM-5(80) gave the highest yield (32%) of propylene at 773 K. Furthermore, the catalytic stability of the zeolite was improved by the modification of zirconium. The surface acidity and the presence of metal ions played important roles on the production of propylene.     

Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization

ZSM-5 and ZSM-11 zeolites with high crystallinity are synthesized and tested in the aromatization and isomerization reactions of 1-hexene at 370 °C in a continuous flow fixed bed. The results indicate that ZSM-5 and ZSM-11 zeolites possess similar acid site amount and strength, and most of the acid sites belong to Brønsted acid. When the ZSM-5 and ZSM-11 zeolites were used as catalysts, the aromatics selectivity over ZSM-11 catalyst was higher than that over ZSM-5 catalyst in contrast to i-paraffins selectivity, maybe attributed to that the C₇ and C₈ aromatics have an easier exit from the ZSM-11 zeolite. Moreover, the decrease of particle size can present superior aromatics selectivity and less i-paraffins selectivity in the aromatization and isomerization of 1-hexene over the ZSM-11 catalyst.     

Evidence for non-site-isolation in ZSM-5 from ion-exchange and catalytic studies

Ion exchange of HZSM-5 samples with alkali metal cations, using metal chloride solutions, results in partially exchanged zeolites, MHZSM-5, M = Li, Na, K or Cs. The degree of exchange is found to increase with increasing ionic radius of the cations. The catalytic properties of the alkalized zeolites were evaluated using the reaction conditions under which the catalytic activity of the HZSM-5 samples in terms of n-hexane cracking is proportional to the aluminium content. From the residual catalytic activity exhibited by the Na-, K- and CsHZSM-5 samples it is concluded that each of the larger Na⁺, K⁺ and Cs⁺ ions is influencing more than one AlO ₄ ^– tetrahedron, implying that the aluminium sites in ZSM-5 are not isolated. The ion-exchange results are then interpreted in terms of non-isolated aluminium sites. The ion-exchange and catalytic properties of the zeolites as a function of aluminium content are also discussed.     

Hierarchical ZSM-5 catalytic performance evaluated in the selective oxidation of styrene to benzaldehyde using TBHP

Hierarchical ZSM-5 catalysts with different Si/Al ratios (20, 60 and 100) were hydrothermally synthesized. The prepared samples were studied by several techniques, including X-ray diffraction (XRD), X-ray fluorescence (XRF) analysis, Fourier transform infrared (FTIR) spectroscopy, N₂ adsorption–desorption, high resolution transmission electron microscopy (HR-TEM), high resolution scanning electron microscopy (HR-SEM), and differential scanning calorimetry (DSC) technique. The average crystallite size and crystallinity decreases with increasing Si/Al ratio, which is confirmed by XRD. FTIR analysis further confirms the formation of ZSM-5 by the presence of characteristic bending, stretching and framework vibration. The HR-TEM images showed that all the samples having disc-like nanostructures are assembled by many primary nanocrystals. The as-synthesized ZSM-5 zeolites are thermally stable, which is confirmed by DSC. The catalytic activity of ZSM-5 zeolites was evaluated in the selective oxidation of styrene using tertiary-butyl hydroperoxide (TBHP) as the oxidant. Among the catalysts, ZSM-5(60) catalyst showed significantly higher yield of benzaldehyde at optimum conditions. The catalyst was recovered and recycled three times without a significant loss in activity and selectivity.     

Highly selective oxidative dehydrogenation of ethane to ethene over layered complex metal chloride oxide catalysts

Complex metal chloride oxides consisting of bismuth, alkali, alkaline earth, chlorine, and oxygen, were synthesized, characterized structurally, and tested as catalysts for the oxidative dehydrogenation of ethane to ethene with molecular oxygen. The catalysts were prepared by high-temperature solid-state reaction of appropriate mixtures of bismuth chloride oxide, bismuth oxide, alkali chloride, and alkaline earth chloride. We found that the catalysts containing strontium as the alkaline earth constituent and potassium as the alkali constituent were highly active and selective for the oxidative dehydrogenation of ethane. SrBi₃O₄Cl₃, which is a fundamental phase of the catalysts, was characterized by single and double chlorine sheets in its layer structure. The catalyst having the composition of KSr₂Bi₃O₄Cl₆ showed an extremely high ethene selectivity, more than 90%, even under high oxygen partial pressure conditions and at high molar ratios of oxygen to ethane, and gave 70% yield of ethene at 640°C under an optimized feed gas composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

Adsorption of CO<Subscript>2</Subscript> and CO on H-zeolites with different framework topologies and chemical compositions and a correlation to probing protonic sites using NH<Subscript>3</Subscript> adsorption

Adsorption of CO₂ and CO at 25 °C has been conducted using commercially-available (Y, ZSM-5) and laboratory-synthesized (SSZ-13, SAPO-34) H-zeolites with different framework topologies and chemical compositions, and their textual and surface properties have been characterized by N₂ sorption and NH₃ adsorption techniques. All the zeolites were microporous, although ZSM-5 and SSZ-13 apparently showed a mesoporous sorption behavior due to the interparticle spaces. The zeolites had Si/Al values in the order of SSZ-13 (16.44) > ZSM-5 (16.08) ? Y (2.82) ? SAPO-34 (0.19). Regardless, high CO₂ adsorption capacity was obtained for SSZ-13 and SAPO-34 with a CHA framework. The FAU zeolite Y with the highest micropore volume showed less CO₂ adsorption than the CHA zeolites and the MFI-type ZSM-5 yielded the poorest performance. Probing acid sites in the H-form zeolites using NH₃ disclosed that these all contain both weak and strong acid sites with significant dependence of their strengths and amounts on the topology. The acid strength of the weak acid sites in the CHA zeolites was the weakest, which might allow a stronger interaction with CO₂. The H-zeolites gave CO₂/CO selectivity factors that were in the range of 4.61–11.0, depending on the framework topology.     

Investigation on the morphology of hierarchical mesoporous ZSM-5 zeolite prepared by the CO2-in-water microemulsion method

A series of hierarchical mesoporous ZSM-5 zeolites with different morphology were successfully synthesized by the CO₂-in-water microemulsion method, and mesoporosity was formed without organotemplate. The different synthesis conditions, including silica alumina molar ratio, stirring time and compressed CO₂ pressure, were systematically investigated to discuss the influence of these conditions on the morphology of ZSM-5 zeolite. The resulting samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma (ICP) and nitrogen adsorption-desorption measurement. XRD results indicated that compressed CO₂ route for the synthesis of MFI zeolites had a fast crystallization rate and good crystallinity. SEM images showed that the ZSM-5 hierarchical mesoporous ZSM-5 zeolite had a uniform chain-like crystal morphology, whereas silicalite-1 displayed a monodisperse crystal morphology. In addition, the nitrogen adsorption-desorption measurement provided sufficient evidence for the presence of hierarchical mesopores in ZSM-5 zeolite.     

The Synthesis and Properties of Two Catalytically Important Zeolites

With his discovery of stilbite in 1756, Cronstedt [1] recognized the existence of a new group of minerals consisting of hydrated “aluminosilicates” of the alkali and alkaline earth cations. While several members of the group may have similar or nearly identical compositions, each possesses its own, unique crystal structure. At present there are 35 known naturally occurring zeolites. The crystal structures have been determined for 27 and all but about 10 have been prepared synthetically. This paper will present the definition of zeolites and focus on the synthesis and physicochemical properties of two catalytically and commercially important synthetic zeolites, zeolite Y and zeolite ZSM-5.     

Metal Exchanged ZSM-5 Zeolite Based Catalysts for Direct Decomposition of N2O

Co+Pt/ZSM-5 and Ag+Pt/ZSM-5 type catalysts were prepared by ion exchange method followed by calcination. These Co and Ag based catalysts, promoted by a small amount of Pt have been studied for their catalytic activity towards N₂O decomposition. Both the catalysts show high catalytic activity, however, cobalt–platinum based catalyst shows relatively better activity at higher temperature. At 550 °C almost 100% conversion of N₂O is achieved over Co+Pt/ZSM-5 with a maximum of 0.08479 mmole of N₂O decomposed per gram of the catalyst per unit time. These catalytic materials have been characterized for their structure, composition, morphology and other details, using XRD, SEM, EDX, ICP, BET techniques. Much improved catalytic activity for the bimetallic zeolite than the mono-metal containing compositions clearly demonstrate the synergistic effect of these transition metals, while high surface area of ZSM-5 is also responsible for the improved N₂O decomposition activity.