Ethane aromatization on Ru/H-ZSM-5 zeolite

The influence of the reaction temperature and of the space velocity on the activity and selectivity in the aromatization of ethane on Ru/H-ZSM-5 was investigated in a flow reactor.

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Ru/H-ZSM-5 .

     

Influence of lead on propane aromatization over Pt/ZSM5 catalysts

Aromatization of propane has been investigated over Pt-Pb/ZSM5. Addition of Pb decreases propane conversion with a corresponding increase in the aromatic selectivity. Hydrogenolysis reactions are inhibited by the presence of lead.

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Pt–Pb/ZSM-5. Pb . .

     

Influence of catalyst binder on the acidity and activity/selectivity of Ga/H-ZSM-5 zeolite in propane aromatization

The acidity and initial and time-on-stream activity in propane aromatization (at 550°C, space velocity of 3100 cm³g⁻¹ _(zeolite)h⁻¹) of Ga-impregnated H-ZSM-5 zeolite without or with binders (50 wt%), such as silica, alumina and kaolin, have been investigated. Both the acidity and catalytic activity of the zeolite are influenced by the presence of binder in the catalyst, depending upon the binder. The influence is found to be lowest for alumina and highest for kaolin. Among the binders, alumina is the most preferred binder for the zeolite catalyst.     

Increasing the yield of aromatic hydrocarbons in aromatization of n-butane over Ga/H-ZSM-5 zeolite using a palladium membrane

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Nature of the metal-support interaction in bifunctional catalytic Pt/H-ZSM-5 zeolite

The metal-support interaction of a dispersed Pt atom on H-ZSM-5 zeolite has been investigated by using an embedded cluster and cluster models with the density functional theory/B3LYP functional method. We found that the Pt atom interacts with a Br?nsted proton and a nearby framework oxygen. Interaction with the framework oxygen causes electron transfer from the zeolite to the Pt atom. Concurrently, a Br?nsted proton stabilizes the Pt atom on the zeolite surface by withdrawing excess electron density from the Pt atom. These charge transfers result in a zero net charge on the Pt atom while changing its orbital occupation. The binding energy of Pt on the Br?nsted acid was 15 kcal/mol. Inclusion of the Madelung potential by Surface Charge Representation of the Electrostatic Embedded Potential method (SCREEP) had small effects on structure and charge density of Pt/H-ZSM-5 but it shifted the stretching mode of CO toward a higher frequency by almost 40 cm(-1). The frequency shift of absorbed CO calculated with embedded cluster models was from 8 to 11 cm(-1) red shift, compared to 20 cm(-1) red shift from experiment. This implies that not only the electronic state of the Pt atom but also the Madelung potential of the support is responsible for the observed small red shift of CO on the Pt-H-ZSM-5.     

Propane aromatization over Pt?Sn/ZSM-5 catalysts

Addition of Sn modifies the catalytic performance of Pt/ZSM-5. Total conversions decrease with increasing Sn/Pt ratio. Selectivity to aromatics is higher on the Pt–Sn samples. A Pt–Sn interaction has been confirmed by H₂ chemisorption and TPR experiments.

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Sn Pt/ZSM5. Sn/Pt . Pt–Sn. Pt–Sn H₂ .

     

Hydrogenolysis reactions during propane aromatization over Pt/ZSM-5

Propane aromatization has been investigated over Pt/ZSM-5 in the temperature range of 400–500°C. Hydrogenolysis of propane to methane occurs mainly on the platinum sites and becomes an important route in propane transformation when reactions leading to aromatics tend to reach thermodynamic equilibrium.

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Pt/ZSM-5 400–500°C. , .

     

CVD modified KL zeolite supported Pt for n-hexane aromatization

Modification of non-acidic KL zeolite by chemical vapor deposition (CVD) of Si(OEt)₄ and (CH₃)₃Si–O–Si(CH₃)₃ followed by Pt loading was used to study the influence of zeolite support on the aromatization of n-hexane. Deposited on the framework oxygen ions of the non-acidic zeolite, the silica layer effectively narrowed the pores of KL zeolite. But owing to the appearance of new basic sites, such as potassium oxide (K₂O), the interaction between Pt metal and zeolite support was strengthened, causing Pt particles to be more electron-excess. n-Hexane pulse-flow microreactions were carried out to study the effects on the aromatization reactivity and sulfur poisoning properties.     

Zinc-containing zeolite catalysts for ethane aromatization prepared by solid-state modification

Solid-state modification was used to prepare zinc-containing zeolite catalysts based on pentasils with different framework SiO₂/Al₂O₃ ratios. The catalysts were studied by X-ray diffraction analysis and IR spectroscopy. The activity and selectivity of the Zn—pentasil systems prepared by the solid-state modification and impregnation methods were compared in the aromatization of ethane. The active and stable zeolite catalysts modified by transition metal ions can be obtained by the topochemical method.     

Generation of protonic acid sites originating from molecular hydrogen over H-ZSM-5

Infrared studies of adsorbed pyridine and OH groups on H-ZSM-5 zeolite demonstrate that protonic acid sites are generated on the surfaces by exposure to molecular hydrogen above 373 K. By evacuation of gas phase hydrogen, the protonic acid sites are eliminated.

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, H-ZSM-5 373 . .

     

亚微米ZSM-5负载Cr催化剂上乙烷CO2气氛下脱氢制乙烯

石油资源的日趋短缺使天然气和页岩气的开发利用受到重视,因而低碳烷烃脱氢制取低碳烯烃也随之引起了人们越来越多的关注.由于乙烷纯脱氢反应的平衡收率低,能耗高,而氧气氧化脱氢又易将乙烷深度氧化为CO2或CO,因此开发具有反应条件温和、装置投资和操作费用低等优势的CO2气氛下乙烷脱氢的技术路线日益得到重视. CrOx是该反应理想的催化剂之一, CO2的加入可使CrOx对乙烷脱氢的催化活性提升3倍,然而受困于CrOx过小的比表面积,通常将CrOx制备成负载型催化剂使用. CrOx的常见载体有Al2O3, ZrO2和SiO2等氧化物及MCM-41, SBA-15, SBA-1和MSU-x等介孔硅材料, ZSM-5作为载体负载CrOx用于低碳烷烃脱氢的研究则较少,所得结果也不甚理想.我们采用亚微米尺寸的ZSM-5作为载体制备了负载型CrOx催化剂,研究了其在CO2气氛下催化乙烷脱氢反应,发现该催化剂具有非常优异的脱氢活性,高硅铝比和Na型的ZSM-5作载体对反应更加有利,而且在反应进行50 h后,催化剂依然保持很好的活性和很高的乙烯收率,这是在一般负载型CrOx催化剂上所不能实现的.
　　X射线光电子能谱(XPS)表征发现, Na型ZSM-5载体制得的催化剂具有更高的Cr6+/Cr3+比.一般认为, Cr6+是Cr系催化剂进行低碳烷烃脱氢反应时的活性位(或活性位前驱体),因此可以初步判定, Na型载体具有很好催化效果的原因可能是由它制得的催化剂具有更多的反应活性位.程序升温还原(H2-TPR)表征结果证实了这一点, Na型载体明显具有更高的H2消耗量;也就是说, Na型载体制得的催化剂具有更多的可还原Cr物种,即脱氢活性位.进一步表征发现,反应活性还与Cr物种存在形式有关.文献报道,低聚态的Cr物种和孤立态的Cr物种比Cr2O3有更好的催化活性.通过漫反射紫外-可见光谱(UV-Vis)对Cr物种的存在形态进行表征后发现, Na型载体上Cr主要以四配位形式存在,而在H型载体上出现了对应于六配位的Cr物种;激光Raman表征结果表明, Na型载体上出现的都是低聚态Cr物种和孤立态Cr物种,而H型载体上出现了明显的对应于α-Cr2O3的峰,说明相较于H型载体, Na型载体更有利于Cr组分分散,这也是Na型ZSM-5载体催化剂具有更高活性的原因之一.
　　CO2引入后对乙烷脱氢反应具有明显的促进作用,特别是在CO2/C2H6=5时,催化剂上C2H6转化率是非CO2气氛下的3.2倍;同时, CO2的引入也提高了脱氢反应的稳定性.在非CO2气氛下,反应进行6 h后, C2H6转化率降低到初活性的60%左右,而在CO2/C2H6=5时,相同时间内催化剂活性下降仅有5%左右.实验分析了CO2对脱氢反应具有促进作用的原因.在脱氢反应温度650 oC下, CO2/H2=1时进行了逆水煤气反应测试,发现CO2的转化率达到22.5%,说明引入CO2后可以通过逆水煤气反应有效地消耗掉乙烷脱氢反应生成的H2,从而促进反应向脱氢方向进行; CO2的引入也可以促进Cr物种的CrOx/CrOx-1循环,从而提高催化剂效率,减缓催化剂失活; CO2还可与反应中生成的积碳类物质发生Boudouard反应,将反应活性位暴露出来,从而提高催化剂的稳定性. CO2气氛下反应6 h后催化剂的积碳量为3.0%,低于非CO2气氛下的3.4%,同时在脱氢反应中生成的CO量与消耗掉的CO2量的比值约为1.4,也有力地说明Boudouard反应的存在.     

Zn/H-ZSM-5催化剂上的二甲醚芳构化反应

 考察了 H-ZSM-5 和 Zn/H-ZSM-5 催化剂的二甲醚芳构化性能. 结果表明, H-ZSM-5 分子筛催化剂酸性的增强和酸中心的增多有利于二甲醚芳构化. 当在 H-ZSM-5 催化剂中加入 2% Zn 时, 在 360 oC 下反应时总芳烃收率从 50.0% 增加至 66.2%, C8 芳烃收率从 28.6% 增加到 39.0%. 反应温度升高到 480 oC 时, 总芳烃收率增加至 78.0%.     

Transformation of light paraffins into aromatic hydrocarbons over H-ZSM-11 zeolite

H-ZSM-11, the proton-exchanged form of ZSM-11 zeolite has been studied for conversion of n-pentane, n-hexane, n-heptane and a mixture of light paraffins to aromatic hydrocarbons, at 400–540 °C and WHSV=1 h^–1, giving high selectivity to BTX (80%). The aromatic yields are apparently limited only by the hydrogen content of the feed and products.

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H-ZSM-11, - ZSM-11, -, -, - 400–540°C 1 ^–1. BTX (80%). .

     

Palladium species in Pd/H-ZSM-5 zeolite catalysts for CH4-SCR

The active state of palladium for NO reduction with methane (CH₄-SCR) was investigated by comparing the catalytic activity of Pd/H-ZSM-5 with that of PdO/SiO₂. High catalytic activity for CH₄-SCR was given by Pd/H-ZSM-5 in the temperature range of 300–500 °C. PdO/SiO₂ catalyzed the reaction between NO₂ and CH₄ in the absence of oxygen, which retarded the reaction by consuming CH₄ in combustion. CH₄ combustion occurred on either zeolite-supported or silica-supported catalyst, while NO preferentially retarded the combustion on Pd/H-ZSM-5. NO was found to be chemisorbed on the palladium sites in zeolite, while it was hardly chemisorbed on PdO/SiO₂. NaCl titration showed that the palladium species in zeolite are Pd²⁺ cations content, on which NO is strongly chemisorbed resulting in high selectivity for CH₄-SCR.     

H-ZSM-5分子筛形貌对ZnCr2O4/H-ZSM-5双功能催化剂合成气制芳烃催化性能的影响

采用水热法，通过改变合成条件选择性制备出具有球状堆积、薄片状、中空和海绵条状结构的四种不同形貌的H-ZSM-5分子筛，并采用XRD、SEM、Py-FTIR、NH₃-TPD、ICP和N₂物理吸附等手段对其结构性质进行了表征。将具有尖晶石结构的ZnCr₂O₄复合氧化物与不同形貌的H-ZSM-5分子筛组成ZnCr₂O₄/H-ZSM-5双功能催化剂，应用于合成气直接制芳烃（STA）的反应过程，研究了H-ZSM-5分子筛形貌对该双功能催化剂STA性能的影响。结果表明，H-ZSM-5分子筛形貌对ZnCr₂O₄/H-ZSM-5的合成气制芳烃催化性能具有重要影响；不同形貌H-ZSM-5分子筛的芳烃选择性由高到低顺序依次为球状堆积 > 海绵条状 > 中空结构 > 薄片状结构。其中，ZnCr₂O₄氧化物与具有球状堆积结构的H-ZSM-5分子筛组成的ZnCr₂O₄/H-ZSM-5（sphere）双功能催化剂在STA反应过程中表现出最佳的催化性能：在350℃和3.0 MPa条件下，CO转化率为12.6%，芳烃选择性高达68.8%，而甲烷、C_2-4⁰烷烃和CO₂选择性分别降低至1.3%、14.3%和41.4%。这是由于球状堆积H-ZSM-5分子筛粒径适中（约350 nm），孔道长度适宜，适合芳烃产物的扩散但又能避免低碳烃类过早扩散出酸性分子筛孔道，从而有利于合成气转化中间产物的芳构化，提高芳烃产物的选择性。     

Isomerization of n-hexane over Pt/NH4NaY zeolite

Isomerization of n-hexane over Pt/NH₄NaY follows the reaction scheme k₁, k₂, k_c linearly increase with increasing ammonia exchange degree in the zeolite and no significant changes in selectivity occur. During activation Al is partially removed from the lattice framework with the formation of HAlNaY.

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- Pt/NH₄NaY . k₁, k₂ k_c , . Al HAlNaY.

     

Structures and reaction mechanisms of glycerol dehydration over H-ZSM-5 zeolite: a density functional theory study

The initial stage of glycerol conversion over H-ZSM-5 zeolite has been investigated using density functional theory (DFT) calculations on an embedded cluster model consisting of 128 tetrahedrally coordinated atoms. It is found that glycerol dehydration to acrolein and acetol proceeds favourably via a stepwise mechanism. The formation of an alkoxide species upon the first dehydration requires the highest activation energy (42.5 kcal mol(-1)) and can be considered as the rate determining step of the reaction. The intrinsic activation energies for the first dehydration are virtually the same for both acrolein and acetol formation, respectively, suggesting the competitive removal of the primary and secondary OH groups. A high selectivity to acrolein at moderate temperatures can be attributed to the selective activation of the stronger adsorption mode of glycerol through the secondary OH group and the kinetically favoured subsequent consecutive steps. In addition, the less reactive nature of acrolein relative to acetol precludes it from being converted to other products upon conversion to glycerol. In accordance with typical endothermic reactions, the forward rate constant for glycerol dehydration significantly increases with increasing reaction temperature.     

高性能Pt/La-Ba-Al2O3/H-ZSM-5氢燃料汽车尾气处理催化剂

采用胶溶法制备了La-Ba-Al2O3(LBA)材料,以此为载体采用浸渍法制备了两种整体式催化剂Pt/LBA和Pt/LBA/H-ZSM-5,并评价了它们去除NO的性能.采用N2吸附-脱附和X射线衍射对载体材料进行了表征.结果表明,所制备的LBA仅有γ-Al2O3晶相存在,比表面积和孔容分别为144 m2/g和0.45 ml/g,具有较好的抗高温老化性能.在106～356 ℃间,催化剂Pt/LBA/H-ZSM-5上NO转化率很高,在153℃时达到最高为98.8%,此时N2选择性为81.3%.该催化剂有很大的潜在应用价值.     

The effect of the nature of a modifying additive (Pt,Zn, Ga) on the activity of oxide and zeolite catalysts in ethane dehydrogenation and aromatization

The catalytic properties of Pt, Zn, and Ga deposited on supports of various natures (Al₂O₃, SiO₂, NaZSM, and HZSM) in the dehydrogenation and aromatization of ethane were investigated. Pt-containing catalysts are the most active in the conversion of ethane: the selectivity with respect to ethylene is 25–87 % depending on the nature of the support. In the presence of Zn- and Ga-containing catalysts the yield of ethylene is 2–3 times lower than with Pt-catalysts. With HZSM modified by Pt, Zn, or Ga aromatic hydrocarbons (ArH) and methane are the main products of ethane transformation. Ga/HZSM is the most efficient catalyst of the aromatization of ethane under the conditions studied (550 °C, 120 h^–1).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 606–609, April, 1994.