Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route

Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and s...     

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.     

中空Pt/ZSM-5催化剂用于愈创木酚加氢脱氧合成环烷烃

采用溶解-重结晶方法合成了不同硅铝比具有级孔壳的中空ZSM-5分子筛,并对其负载Pt催化剂（Pt/HZ-x）催化愈创木酚加氢脱氧制备环烷烃性能进行了探究。通过X射线晶体衍射（XRD）、场发射扫描电子显微镜（SEM）、场发射透射电子显微镜（TEM）、氮气吸附脱附（N₂-BET）、氨气程序升温脱附（NH₃-TPD）和X射线光电子能谱（XPS）对合成的系列催化剂进行了物化性质表征。得益于特殊的中空级孔结构,中空ZSM-5分子筛具有高外比表面积和介孔孔容,有利于促进活性金属Pt的分散和增强反应物的传质。Pt/HZ-x催化剂表现出了优异的催化性能和愈创木酚加氢脱氧活性,在220℃的低温即可以达到100%的环烷烃选择性。另外,随着分子筛载体酸性的减弱,愈创木酚加氢脱氧产物的二次反应程度降低,增大了环己烷的选择性。     

Hierarchical ZSM-5 zeolite designed by combining desilication and dealumination with related study of n-heptane cracking performance

The effect of the basic (NaOH) and/or acid (citric acid and EDTA-2Na) treatment of ZSM-5 zeolite has been studied comparing the structural and acidic features and their catalytic performance in n-heptane cracking. The properties of the catalysts have been elucidated using XRD, N₂ low-temperature sorption, ²⁷Al and ²⁹Si NMR, pyridine adsorbed FTIR, NH₃–TPD, SEM and TEM analysis. The results showed that the degree of desilication and dealumination of ZSM-5 zeolites was greatly dependent on the agents. NaOH obviously created new mesopores on parent ZSM-5 zeolites by desilication. Citric acid contributed to the removal of nonframework Al species, causing the increase of micropore surface area. EDTA-2Na promoted desilication and simultaneously converted part of removed framework Al species into nonframework Al species. The treatment of ZSM-5 combined with those three agents was very effective to obtain a hierarchical structure with partial breakdown of the crystallites and high acid amounts of both Brönsted and Lewis acid sites. Catalytic tests showed that the post-treated ZSM-5 catalysts had higher activity and stability than parent ZSM-5 catalyst at the same reaction temperature. The synergetic effect of Brönsted acid and Lewis acid of ZSM-5 catalyst (Z5-ACE) probably facilitated n-heptane conversion, while more clean micropore and newly created mesopores facilitated the slight increase of olefin selectivity and suppressing the formation of coke deposition in its inherent micropores to some extent.     

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。     

Novel utilization of MCM-22 molecular sieves as supports of cobalt catalysts in the Fischer–Tropsch synthesis

Cobalt catalysts (2–10 wt% Co) supported on silica-rich MCM-22 zeolites have been prepared by impregnation with aqueous Co(NO₃)₂ solutions. The catalysts are characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), nitrogen adsorption, solid state nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The catalytic properties for the Fischer–Tropsch synthesis (FTS) at 280 °C, 12.5 bar and H₂/CO = 2 are evaluated. The catalysts supported on MCM-22 exhibit the highest selectivity to long-chain (C₅₊) hydrocarbons when MCM-22 supports are synthesized with the appropriate Si/Al ratio.     

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.     

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study, various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5. The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied. The results of XRD, TEM N₂-adsorption-desorption, NH₃-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals, and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5. Catalytic cracking of n-dodecane (550 ℃, 4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance, with the improvement higher than 87% in the catalytic activities and 21% in the deactivation rate compared with untreated zeolites. This could be ascribed to their suitable pore structure, which enhanced the diffusion of reactant molecules in pores of catalysts.     

Optimization of conditions for preparation of ZSM-5@silicalite-1 core–shell catalysts via hydrothermal synthesis

Although the preparation of ZSM-5@silicalite-1 (ZS) core-shell catalysts has been reported in the literature, their selectivity to para-xylene (PX) in the toluene alkylation with methanol is difficult to control. Here we present the effects of water and ZSM-5 adding amounts in the synthesis solution, the hydrothermal synthesis time, and the Si/Al ratio of core ZSM-5 on the catalytic performance of ZS core-shell catalysts. The ZS core-shell catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption, and NH₃ temperature-programmed desorption (NH₃-TPD) techniques. The highest PX selectivity of 95.5% was obtained for the ZS (Si/Al=140) catalyst prepared in the synthesis solution with a molar ratio of 0.2TPAOH:1TEOS:250H₂O at 175℃ and 10 r·min^-1 for only 2 h and the corresponding toluene conversion is as high as 22.8% for the alkylation of toluene with methanol.     

Al-SBA-15固体酸催化合成硬脂酸三乙醇胺酯

制备了一系列Si/Al比(均为摩尔比,下同)从15到50的Al-SBA-15固体酸催化剂,并将其应用于硬脂酸与三乙醇胺的酯化反应中。结果表明,Si/Al比为25的Al-SBA-15固体酸催化剂的催化活性和选择性较高,反应6 h酯胺的酸值可降至1.78 mg KOH/g,单双酯总质量分数可达84.79%;该催化剂重复使用6次,催化活性没有明显降低,说明该催化剂具有高的稳定性。采用XRD、N2吸附脱附、透射电镜和吸附吡啶的红外光谱对催化剂的结构、比表面积和表面酸性进行了表征,结果表明,Si/Al比为25的Al-SBA-15催化剂保持了SBA-15的结构,具有大的比表面积和均一的孔径,在催化剂表面同时存在Lewis酸和Brnsted酸。     

Thermal-catalytic degradation kinetics of polypropylene over BEA, ZSM-5 and MOR zeolites

In this study, thermal degradation of additive-free polypropylene powder over different type of zeolite catalysts was investigated. BEA, ZSM-5 and MOR with different surface areas, pore structures, acidities and Si/Al molar ratios were used as solid catalysts for degradation of polypropylene (PP). Degradation rate of the PP over zeolites was studied by thermogravimetric analysis (TGA) employing four different heating rates and apparent activation energies of the processes were determined by the Kissinger equation. The catalytic activity of zeolites decreases as BEA > ZSM-5a (Si/Al = 12.5) > ZSM-5b (Si/Al = 25) > MOR depending on pore size and acidity of the catalysts. On the other hand, initial degradation is relatively faster over MOR and BEA than that over both ZSM-5 catalysts depending on the apparent activation energy. It can be concluded that acidity of the catalyst is the most important parameter in determining the activity for polymer degradation process as well as other structural parameters, such as pore structure and size.     

Ga改性的HZSM-5分子筛甲醇芳构化催化反应性能

以浸渍法和水热合成法向ZSM-5分子筛中引入Ga助剂对其进行改性。采用XRD、XPS、NH₃-TPD和SEM等技术对改性前后的分子筛进行了表征。结果表明,采用两种不同引入方式引入Ga助剂对分子筛的晶体结构、孔径及形貌影响均很小,而对分子筛酸性的影响与Ga的引入方式有关。其中,浸渍法引入Ga对分子筛的酸性影响不明显,只是其中的强酸位略有减少。而水热合成法引入Ga会显著增加分子筛的弱酸及强酸的酸量。在固定床反应器上考察了Ga的引入对HZSM-5催化剂甲醇芳构化催化性能的影响。结果表明,水热合成法引入Ga较浸渍法引入Ga更能提高甲醇芳构化反应的活性和芳烃选择性。此外,Ga改性HZSM-5分子筛对其甲醇芳构化反应中积炭反应的抑制起到积极作用。     

采用不同模板剂控制合成较大晶粒的ZSM-5分子筛

采用不同模板剂以及模板剂组合比较,研究了合成较大晶粒ZSM-5分子筛的过程。通过XRD表征产物的晶相结构,采用SEM观察了产物分子筛的晶粒大小。在分析不同模板剂的模板效应以及合成较大晶粒分子筛影响因素的基础上,提出了能够控制合成中等粒度ZSM-5分子筛的合成方法。结果表明,采用模板剂的不同组合可以控制合成出晶粒粒径在10 μm左右的均匀的较大晶粒分子筛。     

正丁烷及丁烯-1在不同硅铝比ZSM-5分子筛上吸附的实验与模型

Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gravimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir（DL）model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory（IAST）,the IAST-DL model was applied to model the butene-1（1）/n-butane（2）binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorption over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.     

Synthesis of nanosized ZSM-2 zeolite with potential acid catalytic properties

Nanosized ZSM-2 zeolite crystals (～100 nm) with suitable surface acid properties were prepared. ZSM-2 zeolite forms with improved acidity were obtained through thermal deammoniation and steam treatment. Detailed characterization of acidic ZSM-2 zeolite was carried out by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), diffuse reflectance infrared Fourier transform (DRIFT), nitrogen sorptometry, dynamic light scattering (DLS), thermogravimetry (TGA), potentiometric acidity measurements, and FTIR analysis of pyridine adsorption. Acid properties of ZSM-2 zeolite were significantly improved by conversion into its protonated (H-ZSM-2) and dealuminated (DEAL-ZSM-2) forms, in which bridged Si(OH)Al groups with Brönsted acidity (H-ZSM-2) and aluminium extraframework species with Lewis acid character (DEAL-ZSM-2) are generated. These acidic ZSM-2 zeolite forms also maintain adequate crystalline order and high surface area values, making this nanosized zeolite attractive for catalytic applications.In the context of catalyst supporting materials for the polymerization of olefins, the DEAL-ZSM-2 zeolite form showed Lewis acid properties similar to those of a traditional MAO-modified silica support. Thus, DEAL-ZSM-2 zeolite appears as a promising material to be evaluated as polymerization catalyst support when a reduction of the amount of high-cost MAO cocatalyst is desired.     

高分散纳米Y型分子筛负载Ni_2P催化剂的制备及其加氢脱硫性能

以无模板剂法合成的纳米Y型分子筛(35 nm左右)为载体,采用低温还原法制备了高分散Ni_2P/NY催化剂,同时制备了普通Y型分子筛担载的Ni_2P/Y催化剂作为对比。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和X射线光电子能谱(XPS)等手段对载体和催化剂进行了表征,并在固定床反应器中考察了不同催化剂对4,6-二甲基二苯并噻吩(4,6-DMDBT)的加氢脱硫反应性能。结果表明,该催化剂的高活性来自纳米Y型分子筛上Ni_2P分散度的提高和高活性中心的暴露。在反应温度为340℃,反应压力为3.0 MPa的条件下,以Ni_2P/NY为催化剂,4,6-DMDBT的转化率达到了96.0%,高于CoMoS/Al_2O_3商业催化剂(77.2%)和Ni_2P/Y催化剂(67.0%)。     

不同硅铝比ZSM-5分子筛催化剂一步法甲醇制汽油

分别使用硅铝比为26、38、60和90的ZSM-5分子筛原粉制备4种催化剂ZSM-5-26、ZSM-5-38、ZSM-5-60和ZSM-5-90,用于一步法甲醇制汽油实验,并对催化剂进行XRD、IR、BET和NH3-TPD表征。利用100 m L微反固定床实验装置,在反应温度380℃、系统压力2.0 MPa和空速1.0 h-1条件下,考察4种催化剂一步法合成汽油过程的甲醇转化率、产物分布和产品组成等性质。结果表明,ZSM-5-60分子筛催化剂性能相对较好,拥有32.2%较为理想的汽油收率和产物组成。     

A structural study of the Fe/ZSM-5 catalyst by through-focus exit-wavefunction reconstruction in HRTEM

Through-focus exit-wavefunction reconstruction in high-resolution transmission electron microscopy has been applied to process the image series obtained from both the simple ZSM-5 catalyst and an iron-loaded one prepared by impregnation. In conventional high-resolution transmission electron microscopic observations, artificial patches due to electron optical effects always appear in the centers of the ten-member ring channels of the ZSM-5 structures, preventing the atomic details in the channels to be revealed, which are crucial information for understanding the catalytic properties of this type of catalysts. Our study shows that such artificial patches can be removed in the retrieved exit-wavefunctions, allowing the projected structures of the ZSM-5 zeolites to be imaged. Together with X-ray energy dispersive spectroscopy, through-focus exit-wavefunction reconstruction confirmed the existence of iron atoms in the ten-member ring channels of the iron-loaded ZSM-5 catalyst.     

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.     

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.