Benzene to phenol oxidation over iron exchanged zeolite ZSM-5

Zeolite ZSM-5 of different Si/Al ratio, templated and non-templated ones were modified with iron cations introduced by means of ionic exchange from aqueous solution and by solid state procedure. The modified samples calcined in the range of temperatures from 500 to 1000 °C were applied for benzene to phenol hydroxylation. Interaction of benzene and N₂O oxidant with Fe-ZSM-5 was searched by IR spectroscopy. The acidity of the samples was characterised by means of activity for cumene cracking and by IR spectra of adsorbed pyridine. Some correlations between oxidative activity, rate of deactivation and acidity of iron modified zeolites ZSM-5 were discussed.     

Direct partial oxidation of methane over ZSM-5 catalyst: Zn-ZSM-5 catalyst studies

Extended studies on Zn-ZSM-5 catalyst for the production of liquid hydrocarbons in the direct partial oxidation (DPO) of CH₄ with O₂ are reported. Previously, it was reported that metal-containing ZSM-5 catalysts could produce C₅₊ hydrocarbons from pure CH₄/O₂ feeds without feed additives. Zn-ZSM-5 produced the highest C₅₊ yields of the catalysts tested. This work shows that the method of introducing Zn onto the catalyst, ion-exchange versus impregnation, does not significantly alter C₅₊ yields if low Zn content is maintained ( 0.4–0.5 wt%). Liquid hydrocarbon yields in this system doubled after 8 h on stream while overall C₂₊ yields increased by over 300%. Mechanistic implications of these findings are discussed. Finally, processing a natural gas feed over Zn-ZSM-5 gave higher C₅₊ yields over CH₄ feed but these yields were not improved over previously published results using HZSM-5.     

乙醇在Pt/ZSM-5上催化氧化动力学

在内径为4 mm的石英管燃烧器中进行了富氧条件下乙醇在Pt/ZSM-5上的催化深度氧化动力学实验,反应温度控制在428 K以下,建立了Power-rate law模型和Langmuir-Hinshelwood模型来表征乙醇的低温深度氧化反应,Power-rate law模型和Langmuir-Hinshelwood模型的活化能分别为95.96和103.72 kJ·mol^-1,乙醇和氧气的反应级数分别为0.38和1.38。Langmuir-Hinshelwood模型中,乙醇的吸附常数比氧气的吸附常数大,说明乙醇在催化剂表面的吸附能力比氧气强,提高氧气的浓度比提高乙醇的浓度更有利于提高反应速率,这一点同样反映在氧气的反应级数比乙醇的反应级数大。     

Xylene isomerization by ZSM-5 zeolite catalyst

The larger pore LaY zeolite catalyst resembles homogeneous metal chloride and heterogeneous silica-alumina acid catalysts since the results are consistent with isomerization being a series of intramolecular 1,2 shifts. On the other hand, isomerization with the smaller pore zeolite, ZSM-5, is very different and the relative rate constants appear to be influenced by diffusion and/or shape selectivity. Disproportionation is a significant reaction with LaY but not with ZSM-5 in the temperature range used for the present study. The small amount of trimethylbenzene formed at low conversions using ZSM-5 is 1,2,4-trimethylbenzene, also providing evidence of shape selectivity influencing the reaction products.     

Kinetics of dimethyl ether oxidation over Pt/ZSM-5 catalyst

A kinetic study of dimethyl ether (DME) combustion over Pt/ZSM-5 was performed below 423 K. Power law model and Langmuir-Hinshelwood model were established to predict the reaction rate. Reaction orders for DME and O₂ were 0.28 and 2.30, respectively. Activation energies for the two models were 99.35 and 109.30 kJ/mol. The reaction orders and adsorption constants suggested DME was more strongly adsorbed on Pt/ZSM-5 than O₂ at low temperatures. The reliability of the models was confirmed by the comparison between the predicted and experimental conversions of DME.     

负载型ZSM-5分子筛催化剂再生方法研究

吡啶合成中所用的催化剂为负载铅ZSM-5分子筛（Pb-ZSM-5）,活性很好,但反应过程中催化剂很易发生积炭失活。通过对O₂烧炭再生、水蒸汽再生和甲醇再生处理的催化剂进行评价以及进行BET、XRD和TPD 表征,结果表明,甲醇再生方法效果明显,提高了催化剂的寿命。催化剂再生过程要抑制“飞温”现象发生。     

轻烃低温芳构化制取高辛烷值汽油

考察了反应温度、空速和高径比条件对轻烃在分子筛催化剂上低温芳构化制取高辛烷值汽油性能的影响。结果表明,反应温度和空速对催化剂的催化性能有明显影响,提高反应温度有利于提高芳烃收率,增加进料空速,催化剂芳构化性能下降,芳烃二次反应也减少。在450 ℃、1.0 h^-1和高径比为6.0的条件下,此轻烃在ZSM-5催化剂作用下,可得到高辛烷值汽油,其初馏点为49 ℃,干点为203 ℃,烯烃质量分数为13.42%,芳烃质量分数为84.24%,辛烷值为101,可作汽油调和组分,也可直接作汽油使用。     

ZSM-5催化剂催速失活的研究

分析了合成甲基叔丁基醚时结焦是ZSM-5失活的主要原因。本实验通过“连续试验法”对ZSM-5分子筛催化剂的失活规律进行了实验研究。通过检测不同温度下异丁烯的转化率来考察ZSM-5催化剂的稳定性，并得出最佳反应温度为75℃。     

Hexane activation over vanadium modified zeolite ZSM-5

The influence on the form of ZSM-5, vanadium content and the elimination of the exterior surface, on the activity and selectivity of n-hexane oxidation was studied using a fixed bed reactor. Blank reactor studies (carborundum packed reactor) showed no conversion below 450 °C with the highest conversion (8 %) at 500 °C. The dominant products were found to be carbon oxides (Sel./% = 90) with minor selectivities to the hexene isomers (7 %) with the remainder being cracked products, THF and benzene. H-ZSM-5 with different SiO₂/Al₂O₃ ratios (100 and 320) and Na-ZSM-5 (SiO₂/Al₂O₃ ratio of 100) were tested under non-oxidative conditions. As the ratio of the SiO₂/Al₂O₃ increased the aluminium content decreases and so too does the cracking ability of the zeolite (i.e. yield of cracked products dropped from 36 to 8 %). However, the use of the Na- form of the ZSM-5 zeolite completely eliminated acid cracking and therefore this system was further investigated. Na-V-ZSM-5 (~1 % loading) was synthesized using the solid state ion-exchange method. Time on stream experiments (fresh batch of catalyst for each experiment with sampling at the same time for a period of 24 h) were conducted and temperature (350, 400 and 450 °C), contact time (0.5, 0.8, 1.1 and 1.5 s) and fuel/air ratios (0.7, 1.3 and 2) were varied. The optimum conditions (Conv./% = 39) for terminal functionalised products were found to be at 400 °C at a contact time of 1.1 s and a fuel air ratio of 1.3. With the lower fuel air ratio of 0.7 (oxygen rich conditions), hexanal formation was favoured.     

纳米ZSM-5沸石上丁烯芳构化反应

用小型固定床加压反应器研究了液化石油气（C4 LPG）中的丁烯在纳米ZSM-5型催化剂DLG-1上的低温芳构化反应，重点考察了原料中二烯烃和碱性氮杂质，以及反应温度、压力和C4 LPG进料重量空速（WHSV LPG）条件对催化剂芳构化反应活性及稳定性的影响。结果表明：原料中的二烯烃和碱性氮杂质都能加速催化剂失活，其中碱性氮的失活作用比二烯烃大。反应温度、压力和进料重量空速都对催化剂性能有显著影响，最佳反应条件为450℃、2. 0 MPa和WHSV LPG=0. 83 h-1。反应温度、压力和进料空速过高都会导致催化剂积炭失活速度加快。     

CO oxidation over alumina supported platinum catalyst

The oxidation of CO over Pt/Al₂O₃ has been studied using combined FTIR andin situ reaction cell. During reaction the stretching frequency of the adsorbed carbonyl species remained constant over a temperature range during which a change in the CO conversion occurred. The range of conversion during which this invariance was observed was considerably greater for used catalyst than for fresh Pt/Al²O³. The formation of islands of CO and the role of these in the overall reaction mechanism is discussed.     

空气气氛下RuO2/ZSM-5催化醇的部分氧化反应

通过原位反应法制备了RuO₂/ZSM-5催化剂，并用XRD、XPS和TEM对合成的催化剂进行了表征，结果表明，RuO₂主要以20 nm左右的微晶分散在载体中，原位反应引入钌物种，没有改变载体ZSM-5的结构，大部分钌为四价。催化试验表明，在以空气为氧化剂的温和条件下，RuO₂/ZSM-5不仅可有效地催化芳香醇和带烯丙基的醇类（激活醇）氧化生成醛酮，而且对一些非激活醇也有较好的催化效果。     

Direct partial oxidation of methane over ZSM-5 catalyst: effects of additives

Previously, it was reported that the direct partial oxidation (DPO) of CH₄ with O₂ over HZSM-5 catalysts produces C₅₊ hydrocarbon liquids when the feed contains a propane or propene additive. This work studies additive effects on C₅₊ production in this system by processing a CH₄/C₃H₈ feed with subsequent removal of the C₃ additive and by processing natural gas feed. Results show C₅₊ production is maintained at constant yields for HZSM-5 catalysts having different zeolitic Al contents after removal of the C₃ additive. Mechanistic implications are discussed. Natural gas DPO consistently produced C₅₊ liquids due to the presence of C₂₊ components in the feed. While C₅₊ yields from natural gas DPO are higher than those observed for CH₄/C₃ feeds, increasing feed O₂ concentration, and thus conversion, deleteriously affected C₅₊ selectivity.     

ZSM-5分子筛负载金属氧化物催化剂催化燃烧含丙烯腈废气的性能

采用等体积浸渍法将过渡金属Cu负载到ZSM-5分子筛上,并与其他金属(Fe、Co、Ag、Pd、Ce)共浸渍得到负载型催化剂,将其用于全组分丙烯腈废气的催化脱除过程。催化活性评价结果表明,丙烯腈在Cu/ZSM-5催化剂上320℃可以实现完全转化;掺杂质量分数2%Ce后,丙烯腈的完全转化温度降低到300℃,高选择生成N2的温度窗口也变宽,催化剂稳定性高。通过X射线衍射、氮气吸附-脱附、氢气-程序升温还原、氨气-程序升温脱附和X射线光电子能谱等对催化剂的物化性能进行表征,结果表明,催化剂催化氧化丙烯腈尾气的性能依赖于Cu^2+的还原能力、催化剂表面弱酸与中强酸含量以及表面Cu^2+丰度。     

Enhanced selectivity to benzaldehyde in the liquid phase oxidation of benzyl alcohol using nanocrystalline ZSM-5 zeolite catalyst

In the present paper, nanocrystalline hierarchical ZSM-5 zeolites were successfully synthesized by the hydrothermal method in the presence of tetrapropylammonium hydroxide as a single template with the gel composition of 58SiO₂:Al₂O₃:20TPAOH:1,500H₂O. The prepared zeolite catalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Nitrogen adsorption–desorption (BET), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HR-TEM) techniques. The formation of pure and highly crystalline ZSM-5 zeolite phase is confirmed by XRD. The IR vibration band at 550 cm^?1 is assigned to the double 5-rings of MFI-type zeolites. N₂ adsorption–desorption isotherms showed that the synthesized product had high BET surface area and possessed composite pore structures with both micro and mesopores. The catalytic performance of hierarchical ZSM-5 zeolite was investigated in the selective oxidation of benzyl alcohol (BzOH) with hydrogen peroxide (H₂O₂) under mild conditions. The results showed that the conversion of BzOH and the selectivity to benzaldehyde were about 94 and about 99 % respectively, when using 0.08 g ZSM-5 catalyst with acetonitrile as the solvent and H₂O₂ as the oxidant at 90 °C. This catalyst can be retrieved and reprocessed for five times without a significant loss in its activity and selectivity.     

全结晶ZSM-5分子筛催化剂研究及工业应用

制备了全结晶ZSM-5分子筛催化剂,采用XRD、SEM、N2物理吸附-脱附及NH3-TPD等对催化剂进行表征,并考察其用于碳四烯烃催化裂解制丙烯(OCC)反应的催化性能。结果表明,制备的全结晶ZSM-5分子筛催化剂比常规成型的催化剂具有更高的结晶度、更大的比表面积、更丰富的孔结构以及更多的活性中心。高空速有利于反应的进行,提高压力对反应不利,升高温度有利于提高产物丙烯收率。在实验室研究的基础上,将全结晶ZSM-5分子筛催化剂用于OCC工业装置,取得良好的应用效果。     

用沸石分子筛ZSM-5型催化剂生产乙苯的技术分析

介绍了利用沸石分子筛催化剂生产乙苯的工艺技术，及开工情况，对其存在问题进行分析总结。     

Hydrodesulfurization over noble metals supported on ZSM-5 zeolites

Pt/HZSM-5 showed high and stable catalytic activity for the hydrodesulfurization of thiophene at 400°C and its catalytic activity was higher than that of commercial CoMo/Al₂O₃ catalyst. Pt/HZSM-5 zeolite was not poisoned by hydrogen sulfide in the hydrodesulfurization of thiophene and hydrocracking of hydrocarbons. The catalytic activity of Pt/HZSM-5 decreased with increase of SiO₂/Al₂O₃ ratio in HZSM-5. The Brønsted acid site of HZSM-5 and spillover hydrogen formed on Pt particle in Pt/HZSM-5 catalyst play an important role for the hydrodesulfurization of thiophene.     

Ethanol steam reforming study over ZSM-5 supported cobalt versus nickel catalyst for renewable hydrogen generation

The renewable hydrogen generation through ethanol steam reforming is one of the anticipated areas for sustainable hydrogen generation. To elucidate the role of Ni and Co with ZSM-5 support, catalysts were prepared by wet impregnation method and ethanol steam reforming(ESR) was performed. The catalysts were characterized by HR-XRD, ATR–FTIR, HR-SEM, TEM with SAED, EDAX, surface area analyzer and TPR. It had shown complete ethanol conversion at 773 K, but the selectivity in hydrogen generation was found higher for 10% Ni/ZSM-5 catalyst as compared to 10% Co/ZSM-5. The 10% Ni/ZSM-5 catalyst has about 72% hydrogen selectivity at temperature 873 K. It indicates that Ni is a more sustainable catalyst as compared to Co with ZSM-5 support for ESR. The C_2H_4 was found major undesirable products up to 823 K temperature. Nevertheless, the 10% Ni/ZSM-5 catalyst had shown its stability for high temperature(873 K) ESR performance.