Shear-thickening behavior of Fe-ZSM5 zeolite slurry and its removal with alumina/boehmites

Science.gov (United States)

Liu, Xiao-guang; Li, Yan; Xue, Wen-dong; Sun, Jia-lin; Tang, Qian

2018-06-01

A cryogenic scanning electron microscopy (cryo-SEM) technique was used to explore the shear-thickening behavior of Fe-ZSM5 zeolite pastes and to discover its underlying mechanism. Bare Fe-ZSM5 zeolite samples were found to contain agglomerations, which may break the flow of the pastes and cause shear-thickening behaviors. However, the shear-thickening behaviors can be eliminated by the addition of halloysite and various boehmites because of improved particle packing. Furthermore, compared with pure Fe-ZSM5 zeolite samples and its composite samples with halloysite, the samples with boehmite (Pural SB or Disperal) additions exhibited network structures in their cryo-SEM images; these structures could facilitate the storage and release of flow water, smooth paste flow, and avoid shear-thickening. By contrast, another boehmite (Versal 250) formed agglomerations rather than network structures after being added to the Fe-ZSM5 zeolite paste and resulted in shear-thickening behavior. Consequently, the results suggest that these network structures play key roles in eliminating the shear-thickening behavior.

Hierarchical ZSM-5 Zeolite: Synthesis and Application in Oil Refinery%多级孔ZSM-5分子筛的制备及其在炼油领域中的应用

Institute of Scientific and Technical Information of China (English)

郑步梅; 方向晨; 郭蓉; 王振宇

2017-01-01

The hierarchical ZSM-5 zeolite integrates the merits of both microporous zeolite and mesoporous materi al.It possesses not only adjustable acidity and high hydrothermal stability,but also excellent diffusivity.Consequently,the hierarchical ZSM-5 zeolite has a wide application prospect in catalytic fields.The research progress of hierarchical ZSM-5 zeolite was reviewed,with the main focus on the synthesis strategies including post-treatment method,hard-templating method and soft-templating method.Meanwhile the applications of hierarchical ZSM-5 zeolite in oil refining field were introduced.Finally,the development trends of hierarchical ZSM-5 are prospected.%多级孔ZSM-5分子筛结合了微孔分子筛可调变的酸性、良好的水热稳定性以及介孔材料优异的传质扩散性能,在催化领域有着广阔的应用前景.我们综述了近年来多级孔ZSM-5分子筛的研究进展,重点概述了多级孔ZSM-5分子筛的不同制备方法,包括后处理法、硬模板法和软模板法等,同时介绍了多级孔ZSM-5分子筛在炼油领域的应用研究,并在上述基础上对多级孔ZSM-5分子筛的研究趋势进行了展望.

Transalkylation of ethyl benzene with triethylbenzene over ZSM-5 zeolite catalyst

KAUST Repository

Akhtar, M. Naseem; Tukur, Nasiru M.; Al-Yassir, Nabil; Al-Khattaf, Sulaiman; Čejka, Jiří

2010-01-01

Transalkylation of 1,3,5-triethylbenzene (TEB) with ethylbenzene (EB) has been studied over ZSM-5 zeolite using a riser simulator reactor with respect to optimizing DEB yield. The reaction temperature was varied from 350 to 500°C with contact time

Catalytic conversion of 11C-labeled methanol over Cs-ZSM-5 zeolite

International Nuclear Information System (INIS)

Sarkadi-Priboczki, E.; Kovacs, Z.; Kumar, N.; Salmi, T.; Murzin, D.Yu.

2004-01-01

Reaction mechanism of the conversion of 11 C labeled methanol over basic Cs-ZSM-5 zeolite catalyst was investigated and the reaction products obtained were compared with that of H-ZSM-5 acidic catalyst. The catalytic experiments were carried out by passing 11 C-labeled methanol with He as a carrier gas over Cs-ZSM-5 packed in a micro reactor. After adsorption of the radio methanol, the catalyst was heated up to 330 deg C. The products of the catalytic conversion of the 11 C-labeled methanol were analyzed by radio-gas chromatography (gas chromatograph with thermal conductivity detector on-line coupled with a radioactivity detector). (N.T.)

Desilication of ZSM-5 zeolites for mesoporosity development using microwave irradiation

International Nuclear Information System (INIS)

Hasan, Zubair; Jun, Jong Won; Kim, Chul-Ung; Jeong, Kwang-Eun; Jeong, Soon-Yong; Jhung, Sung Hwa

2015-01-01

Highlights: • Microwaves have beneficial effects on desilication of zeolites. • Produced mesopores with microwaves have narrow pore-size distribution. • Advantages and disadvantages of various desilicating agents were also reported. - Abstract: Mesoporous ZSM-5 zeolite was obtained by desilication in alkaline solutions with microwave (MW) and conventional electric (CE) heating under hydrothermal conditions. Both methods were effective in the production of mesoporous zeolites; however, MW was more efficient than CE as it led to well-defined mesopores with relatively small sizes and a narrow size distribution within a short treatment time. Moreover, the mesoporous ZSM-5 obtained through this method was effective in producing less bulky products from an acid-catalyzed reaction, specifically the butylation of phenol. Finally, various bases were found to have advantages and disadvantages in desilication. NaOH was the most reactive; however, macroporosity could develop easily under a severe condition. Ammonia water was weakly reactive; however, it could be used to precisely control the pore architecture, and no ion exchange is needed for acid catalysis. Organic amines such as ethylenediamine can also be used in desilication

Cu-ZSM-5, Cu-ZSM-11, and Cu-ZSM-12 Catalysts for Direct NO Decomposition

DEFF Research Database (Denmark)

Kustova, Marina; Kustov, Arkadii; Christiansen, Sofie E.

2006-01-01

Cu-ZSM-5 has for many years been recognized as a unique catalyst for direct NO decomposition. Here, it is discovered that both Cu-ZSM-11 and Cu-ZSM-12 are about twice as active as Cu-ZSM-5. This difference is attributed to the active sites located almost exclusively in the straight zeolite pores...

Construction of Bifunctional Co/H-ZSM-5 Catalysts for the Hydrodeoxygenation of Stearic Acid to Diesel-range Alkanes.

Science.gov (United States)

Wu, Guangjun; Zhang, Nan; Dai, Weili; Guan, Naijia; Li, Landong

2018-04-27

Bifunctional Co/H-ZSM-5 zeolites were prepared by surface organometallic chemistry grafting route, namely by the stoichiometric reaction between cobaltocene and the Brønsted acid sites in zeolites, and applied to the model reaction of stearic acid catalytic hydrodeoxygenation. Cobalt species existed in the form of isolated Co2+ ions at exchange positions after grafting, transformed to CoO species on the surface of zeolite and stabilized inside zeolite channels upon calcination in air, and finally reduced to metallic cobalt species of homogeneous clusters of ca. 1.5 nm by hydrogen. During this process, the Brønsted acid sites of H-ZSM-5 zeolites could be preserved with acid strength slightly reduced. The as-prepared bifunctional catalyst exhibited a ~16 times higher activity in stearic acid hydrodeoxygenation (2.11 gSAgcat-1h-1) than the reference catalyst (0.13 gSAgcat-1h-1) prepared by solid-state ion exchange, and a high C18/C17 ratio of ~24 was achieved as well. The remarkable hydrodeoxygenation performance of bifunctional Co/H-ZSM-5 could be explained from the effective synergy between the uniformed metallic cobalt clusters and the Brønsted acid sites in H-ZSM-5 zeolite. The simplified reaction network and kinetics of stearic acid hydrodeoxygenation catalyzed by the as-prepared bifunctional Co/H-ZSM-5 zeolites were also investigated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of metal coating methods on the activity of bimetal-containing zeolite catalysts of Co, Pd-ZSM-5 in carbon monoxide oxidation

Science.gov (United States)

Oleksenko, L. P.; Lutsenko, L. V.; Yatsimirskii, V. K.

2011-07-01

It has been established that catalytic activity in the CO oxidation of bimetal-containing zeolite Co,Pd-systems based on ZSM-5 and obtained via ion exchange and impregnation at different orders of the introduction of metal cations is higher than that of monometal-containing systems Co-ZSM-5 and Pd—ZSM-5. Through TPD of NH3, it was determined that coordination-unsaturated bicationic associates are formed in Co,Pd/ZSM-5 zeolites obtained by ion exchange. It was found that the activity of bimetal-containing systems depends on the relation of the active components.

Study on the Synthesis and Characterization of Nano Silver Loaded ZSM-5 Zeolite for Bacterial Elimination.

Science.gov (United States)

Nam, Le Thi Hoai; Vinh, Tran Quang; Loan, Nguyen Thi Thanh; Nhiem, Nguyen Thi; Trang, Nguyen Thi Thu; Tan, Nguyen Minh; Radnik, Jörg

2015-09-01

The synthesis of nano silver coated ZSM-5 zeolite (Ag/ZSM-5) by ion exchange method combined with anaerobic thermal treatment and its bacterial elimination performance were studied. The various Ag content of different samples was analysed by atomic absorption spectroscopy method. The Ag/ZSM-5 sample with 0.251 wt% Ag (denoted as ZAg3) was characterized by using atomic absorption spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and pulsed CO chemisorption methods. The results showed that silver nanoparticles with a small nano-size of 2-3 nm were formed and distributed on the surface of ZSM-5 zeolite with a dispersion value of 59%. The samples denoted as ZAg1, ZAg2, ZAg3, ZAg4 correspond to a Ag content of 0.064; 0.128; 0.251; 0.253 wt% Ag. In the evaluation series, after 10 min of contact time between bacterial and Ag/ZSM-5, over 99% of E.coli (initial concentration was 10(6) cfu/ml) could be eliminated by Ag/ZSM-5 with the Ag content of at least 0.251 wt% (ZAg3). In addition, over 99% of Coliform (initial concentration was 10(5) cfu/ml) could be eliminated by Ag/ZSM-5 with Ag content of at least 0.128 wt% (ZAg2). In a further evaluation series varying the contact time, ZAg3 sample could eliminate over 99% and 100% of Ecoli after 10 min and 60 min, respectively (initial concentrations of both E.coli and Coliform were 10(5) cfu/ml). In addition, it could eliminate 100% of Coliform in only 10 min of contact time.

Highly Oriented Growth of Catalytically Active Zeolite ZSM-5 Films with a Broad Range of Si/Al Ratios

NARCIS (Netherlands)

Fu, Donglong|info:eu-repo/dai/nl/412516918; Schmidt, Joel E.|info:eu-repo/dai/nl/413333736; Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Chowdhury, Abhishek Dutta|info:eu-repo/dai/nl/412438003; Meirer, Florian; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

2017-01-01

Highly b-oriented zeolite ZSM-5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films.

Preparation, characterization and antimicrobial property of ag+- nano Chitosan/ZSM-5: novel Hybrid Biocomposites

Directory of Open Access Journals (Sweden)

Maasoumeh Khatamiana

2016-10-01

Full Text Available Objective(s: Binary hybrids of chitosan-zeolite have many interesting applications in separation and bacteriostatic activity. Materials and Methods: Template free ZSM-5 zeolite was synthesized by hydrothermal method, physical hydrogels of nano chitosan in the colloidal domain were obtained in the absence of toxic organic solvent and then nano chitosan/ZSM-5 hybrid composites with nano chitosan contents of 0.35%, 3.5%, 35% wt.% were prepared. The as prepared hybrid composites were ion-exchanged with Ag cations. Results: XRD and FT-IR results revealed a good crystalinity of as synthesized template frees ZSM-5 with BET surface area of 307 m2g-1. Presence of chitosan in composites was confirmed by XRD patterns and FT-IR spectroscopic analysis, the chitosan content in composite was obtained with TG analysis. SEM analysis of composites shows that chitosan particles were dispersed within the nanometer scale. The antimicrobial activity of different samples was investigated and the results showed that the Ag+-exchanged samples have the highest antibacterial properties. Cancer cell line A549 cell line were cultured in designated medium treated with Ag+-exchanged samples at the concentration of 0.01 to 0.5 mg/ml. After 24 and 48 hours incubation, the efficacy of Ag+-exchanged samples to treat cancer cell lines were measured by means of cell viability test via MTT assay. Concentrations of 0.05 and 0.1 mg/ml of Ag+-exchanged samples induced a very low toxicity. Conclusion: These hybrid composite materials have potential applications on tissue engineering and antimicrobial food packaging.

Photodegradation of Methyl Green by Nickel-Dimethylglyoxime/ZSM-5 Zeolite as a Heterogeneous Catalyst

Directory of Open Access Journals (Sweden)

Alireza Nezamzadeh-Ejhieh

2013-01-01

Full Text Available Ni-DMG/ZSM-5 zeolite was prepared by ion exchange and complexation procedures. FT-IR, XRD, SEM, TG, and DTG methods were used for characterization of the raw and modified samples. The prepared composite was used as a catalyst in the photodegradation process of an aqueous solution methyl green (MG dye under UV irradiation. The effect of key operating parameters such as catalyst dosage, temperature, the initial concentration of the dye, and pH of the samples was studied on the degradation extent of the dye. UV-Vis spectrophotometric measurements were performed for determination of the decolorization and mineralization extents. The optimal operation parameters were found as follows: , temperature of 60°C, 0.6 g L−1 of the catalyst, and 40 ppm of the dye concentration. The Ni-DMG particles out of zeolite framework did not show significant degradation efficiency. The degradation process obeys the first-order kinetic.

Alkaline leaching for synthesis of improved Fe-ZSM5 catalysts

NARCIS (Netherlands)

Espinosa, S; Mentruit, C; Kapteijn, F; Moulijn, JA; Melián-Cabrera, I.

Fe-ZSM5 catalysts were fully Fe-exchanged by pretreating the parent zeolite with base a solution prior to the Fe-exchange. The catalysts prepared in this way showed very low amount of inactive FeOx and improved performance in N2O decomposition. Alkaline leaching breaks down the zeolite crystals -

Synthesis of hierarchical porous materials with ZSM-5 structures via template-free sol–gel method

Directory of Open Access Journals (Sweden)

Wei Han et al

2007-01-01

Full Text Available Interests are focused on preparation of hierarchical porous materials with zeolite structures by using soft or rigid templates in order to solve diffusion and mass transfer limitations resulting from the small pore sizes of zeolites. Here we develop a convenient template-free sol–gel method to synthesize hierarchical porous materials with ZSM-5 structures. This method involves hydrothermal recrystallization of the xerogel converted from uniform ZSM-5 sol by a vacuum drying process. By utilizing this method we can manipulate the size of zeolite nanocrystals as building units of porous structures based on controlling temperature of recrystallization, consequently obtain hierarchical porous materials with different intercrystalline pore sizes and ZSM-5 structures.

Coke burning behavior of a catalyst of ZSM-5/ZSM-11 co-crystallized zeolite in the alkylation of benzene with FCC off-gas to ethylbenzene

Energy Technology Data Exchange (ETDEWEB)

Song, Yi; Zhai, Yuchun [Northeastern University, Shenyang, 110006 (P. R. China); Liu, Shenglin; Wang, Qingxia; Xu, Longya [State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P. O. Box 110, Dalian 116023 (P. R. China)

2006-04-15

Since the commercialization of ethylbenzene production via alkylation of benzene with the dilute ethene in FCC off-gas over a ZSM-5/ZSM-11 co-crystallized zeolite catalyst in China, the catalyst has been regenerated several times and showed good regeneration performance. During the alkylation process, the catalytic activity decreases, some of the catalyst pores are blocked and the acid centers are partly covered by coke deposition. Influence of the factors such as catalyst particle size, temperature, etc. on the burning rate of the coke was investigated by the TG technique, and a rate equation for coke burning on the ZSM-5/ZSM-11 co-crystallized catalyst was established. (author)

Ion exchange in ZSM-5 zeolite

International Nuclear Information System (INIS)

Matthews, D.P.; Rees, L.V.C.

1986-01-01

The ion exchange properties of Na-ZSM5 have been studied using a number of univalent and divalent cations at 25degC and 65degC. All the univalent cations studied achieved 100 per cent exchange. The thermodynamic affinity sequence Cs > Rb=NH 4 =H 3 O>K>Na>Li was found at both temperatures for a sample with Si/Al=39. Standard enthalpies of exchange ΔH o were calculated using the van't' Hoff isochore and standard entropies of exchange were then calculated from ΔH o and ΔG o . Multivalent cations were unable to achieve 100 per cent exchange. The maximum exchange was found to increase through the series Ca 2+ cations ( 57 Fe enriched) on dehydration and rehydration following sorption and desorption of ethanol. At least 3 sites for Fe 2+ were observed in the dehydrated zeolite. (author)

Utilization of biomass: Conversion of model compounds to hydrocarbons over zeolite H-ZSM-5

DEFF Research Database (Denmark)

Mentzel, Uffe Vie; Holm, Martin Spangsberg

2011-01-01

Zeolite catalyzed deoxygenation of small oxygenates present in bio-oil or selected as model compounds was performed under Methanol-to-Hydrocarbons (MTH) like reaction conditions using H-ZSM-5 as the catalyst. Co-feeding of the oxygenates with methanol generally decreases catalyst lifetime due...

Adsorption of carbon monoxide on Ag(I)-ZSM-5 zeolite: An ab initio density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Qiu Zhenzhen [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Yu Yangxin, E-mail: yangxyu@mail.tsinghua.edu.cn [Department of Chemical Engineering, Tsinghua University, Beijing 100084 (China); Mi Jianguo [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

2012-10-01

Highlights: Black-Right-Pointing-Pointer Significant difference in adsorption energy is found for CO adsorbed on different Ag{sup +}-exchange sites. Black-Right-Pointing-Pointer Energetically stable sites in Ag-ZSM-5 are found. Black-Right-Pointing-Pointer Introduction of the two Al atoms to the site of Ag-ZSM-5 results in a reduction of CO adsorption energy. Black-Right-Pointing-Pointer Comparison of CO adsorption energy on the corresponding charge-exchange sites of Ag-ZSM-5 and Cu-ZSM-5 is made. - Abstract: Adsorption of carbon monoxide on different Ag{sup +}-exchange sites of Ag-ZSM-5 zeolite has been investigated using density functional theory. The coordination and local geometry of the Ag{sup +} ion in Ag-ZSM-5 as well as adsorption structures and energies of CO adsorbed on these sites are explored extensively. The structure of Ag{sup +}-exchange sites, location of the Al atom on the T site, and number of the Al atoms contained in the sites are considered in the theoretical calculations. The calculated results show that the Ag-O coordination number of two is strongly preferred before and after CO adsorption. The Ag-O bond lengths are in a broad range of 2.2-2.9 Angstrom-Sign , and the Ag-C bond lengths for CO adsorbed on Ag-ZSM-5 zeolite are calculated to be 2.0-2.2 Angstrom-Sign . Both Ag-O and Ag-C bond lengths for CO-Ag-ZSM-5 complex are longer than those for CO-Cu-ZSM-5 complex. The calculated adsorption energy of CO adsorbed on the I2 sites is between 28.5 and 29.6 kcal/mol, and that on the Z5, Z6, M5 and M6 sites containing one Al atom on the T position is between 11.3 and 18.9 kcal/mol whereas the calculated adsorption energy of CO adsorbed on the M7 site containing one Al atom is 19.9 kcal/mol. The introduction of the two Al atoms to the Ag{sup +}-exchange site results in a reduction of CO adsorption energy. In general, the adsorption energy of CO on Ag-ZSM-5 is lower than that on Cu-ZSM-5. The predicted coordination of the Ag{sup +} ion, bond lengths

Synthesis of ZSM-5 zeolite from coal fly ash and rice husk: characterization and application for partial oxidation of methane to methanol

Science.gov (United States)

Krisnandi, Y. K.; Yanti, F. M.; Murti, S. D. S.

2017-04-01

Indonesian fly ash (SiO2/Al2O3 mole ratio = 3.59) was used together with rice husk (SiO2 92%) as raw material for mesoporous ZSM-5 zeolite synthesis. Prior being used, coal fly ash and rice husk were subjected to pre-treatment in order to extract silicate (SiO4 4-) and aluminate (AlO4 5-) and to remove the impurities. Then the ZSM-5 zeolite were synthesized through hydrothermal treatment using two types of templates (TPAOH and PDDA). The as-synthesized ZSM-5 was characterized using FTIR, XRD, SEM-EDX, and BET. The result of FTIR showed peaks at 1250-950 cm-1 (v asymetric T-O), 820-650 cm-1 (v symetric T-O), and at 650-500 cm-1 confirming the presence of the five number ring of the pentasil structure. The result of XRD showed the appearance of certain peaks in the position 2 theta between 7-9° and 22-25° indicative of ZSM-5 structure, but also showed the pattern of low intensity magnetite and hematite. The SEM image showed the rough surface of hexagonal crystals from ZSM-5 structure, indicative of mesoporosity in the structure. EDX result showed Si/Al ratio of 20, while surface area analysis gave SA of 43.16. The ZSM-5 zeolites then was modified with cobalt oxide through impregnation method. The catalytic activity as heterogeneous catalysts in partial oxidation of methane was tested. The result showed that hence the catalytic activity of ZSM-5 and Co/ZSM-5 from fly ash and rice husk were still inferior compared to the pro-analysis sourced-counterpart, they were potential to be used as catalyst in the partial oxidation of methane to methanol.

Síntese da zeólita ZSM-5 e suas propriedades estruturais após troca iônica com cobre Synthesis of the ZSM-5 zeolite and its structural properties after copper ion-exchange

Directory of Open Access Journals (Sweden)

E. L. Foletto

2000-12-01

Full Text Available A zeólita ZSM-5 foi sintetizada utilizando sílica "Aerosil-Degussa -- 380 m²/g" como fonte de silício, em substituição ao trisilicato de sódio, que é normalmente utilizado na síntese dessa zeólita. Subseqüentemente, foi incorporado cobre à ZSM-5 através do método convencional de troca iônica. Técnicas de difração de raios X, microscopia eletrônica de varredura, área superficial e análise elementar por absorção atômica foram utilizadas para verificar a formação da zeólita sintetizada e suas propriedades após troca com cobre. Os resultados mostraram que houve a formação da ZSM-5 nas condições de síntese empregadas e que a amostra modificada pelo processo de troca manteve as propriedades da zeólita original.The ZSM-5 zeolite was synthesized using silica "Aerosil-Degussa -- 380 m²/g" as silicon source, in substitution to the sodium trisilicate, which is usually employed in the zeolite synthesis. Subsequently, the copper was incorporated to ZSM-5 by conventional ion-exchange method. X-ray diffraction, scanning electron microscopy, surface area and elemental analysis by atomic absorption have been used to verify ZSM-5 formation and its properties after copper exchange. The results presented ZSM-5 formation in the employed synthesis conditions. The ion-exchanged sample conserved the original ZSM-5 properties.

Mechanistic insights into aqueous phase propanol dehydration in H-ZSM-5 zeolite

Energy Technology Data Exchange (ETDEWEB)

Mei, Donghai [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate & Institute for Integrated Catalysis, Richland WA 99352; Lercher, Johannes A. [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate & Institute for Integrated Catalysis, Richland WA 99352; Dept. of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 Garching 85748 Germany

2016-10-06

Aqueous phase dehydration of 1-propanol over H-ZSM-5 zeolite was investigated using density functional theory (DFT) calculations. The water molecules in the zeolite pores prefer to aggregate via the hydrogen bonding network and be protonated at the Brønsted acidic sites (BAS). Two typical configurations, i.e., dispersed and clustered, of water molecules were identified by ab initio molecular dynamics simulation of the mimicking aqueous phase H-ZSM-5 zeolite unit cell with 20 water molecules per unit cell. DFT calculated Gibbs free energies suggest that the dimeric propanol-propanol, the propanol-water complex, and the trimeric propanol-propanol-water are formed at high propanol concentrations, which provide a kinetically feasible dehydration reaction channel of 1-propanol to propene. However, calculation results also indicate that the propanol dehydration via the unimolecular mechanism becomes kinetically discouraged due to the enhanced stability of the protonated dimeric propanol and the protonated water cluster acting as the BAS site for alcohol dehydration reaction. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5.

Science.gov (United States)

Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

2016-08-25

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

Catalytic Efficiency of Titanium Dioxide (TiO2) and Zeolite ZSM-5 Catalysts in the in-situ Epoxidation of Palm Olein

Science.gov (United States)

Yunus, M. Z. Mohd; Jamaludin, S. K.; Abd. Karim, S. F.; Gani, A. Abd; Sauki, A.

2018-05-01

Titanium dioxide and zeolite ZSM-5 are the commonly used heterogeneous catalysts in many chemical reactions. They have several advantages such as low cost and environmental friendly. In this study, titanium dioxide and zeolite ZSM-5 act as catalyst in the in-situ epoxidation of palm olein. Epoxidation of palm olein was carried out by using in-situ generated performic acid to produce epoxidized palm olein in a semi-batch reactor at different temperatures (45°C and 60°C) and agitation speed of 400 rpm. The effects of both catalysts are studied to compare their efficiency in catalyzing the in-situ epoxidation. Epoxidized palm olein was analyzed by using percent of relative conversion to oxirane (RCO%) and fourier transform infrared spectroscopy (FTIR). Surface area of the catalysts used were then characterized by using BET. The results indicated that titanium dioxide is a better catalyst in the in-situ epoxidation of palm olein since it provides higher RCO% compared to Zeolite ZSM-5 at 45°C.

Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

Energy Technology Data Exchange (ETDEWEB)

Eraenen, K; Kumar, N; Lindfors, L E [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

1997-12-31

Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

Energy Technology Data Exchange (ETDEWEB)

Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

1996-12-31

Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

Encapsulation of ferro- and ferricyanide complexes inside ZSM-5 zeolite synthesized from rice straw: Implications for synthesis of Prussian blue pigment

International Nuclear Information System (INIS)

Ali, Ibraheem O.; Salama, Tarek M.; Thabet, Mohamed S.; El-Nasser, Karam S.; Hassan, Ali M.

2013-01-01

Encapsulation of [Fe(CN) 6 ] 4− and [Fe(CN) 6 ] 3− complexes in the intracrystalline pores of ZSM-5 zeolite, Fe II L/Z and Fe III L/Z respectively, by the zeolite synthesis method was reported. The modified zeolites were characterized by powder XRD, FT-IR and UV–vis spectroscopy. The nitrogen adsorption isotherms allow for the evaluation of pore structure of the complex-modified zeolites, whereas the thermal analysis (TGA/DTA) measurements provide insight into the decomposition products of the immobilized complexes. The modified zeolites exhibited smaller pore volumes and surface areas as compared with those of unpromoted ZSM-5, suggesting the inclusion of iron cyanides inside the interconnecting channels of ZSM-5. While the ferricyanide complex enhanced the formation of highly crystalline zeolite, the ferrocyanide one resulted in a lesser effect. The electronic spectra of the colloidal species developed when Fe III L/Z brought in contact with an aqueous solution of [Fe(CN) 6 ] 3− exhibit absorptions attributed to CN − → iron charge-transfer. New bands at 294 and 319 nm due to d–d transitions of Fe III tetrahedral monomeric moieties were emitted concurrently under successive adsorption of [Fe(CN) 6 ] aq 3− over Fe III L/Z, along with a broad band at 555 nm assigned to polymeric [Fe II –C–N–Fe III ] of Prussian blue (PB). The FT-IR spectra of Fe III/II L/Z devoted to the adsorption of an aqueous solution of [Fe(CN) 6 ] 3− showed a band at 2092 cm −1 assigned to the C–N stretch in the Fe II –CN–Fe III linkages. The vibrations attributable to Fe–O–Si bonding along with hydrocarbon and nitroprusside appeared only in the spectrum of Fe III L/Z, thus was found to be strong evidence for the mutual interaction between [Fe(CN) 6 ] 3− and the latter sample. - Highlights: • We synthesized ferrous and ferric cyanide complexes inside ZSM-5 zeolite. • The decomposition of the encapsulated complexes occurred at high temperatures. �

Influence of the Zeolite ZSM-5 on Catalytic Pyrolysis of Biomass via TG-FTIR

Directory of Open Access Journals (Sweden)

Ze Wang

2015-06-01

Full Text Available Bio-oil from the pyrolysis of biomass is an important renewable source for liquid fuel. However, the application of bio-oil has been severely restricted due to its high viscosity, acidity, and low heating value. Thus, it has been necessary to upgrade bio-oil for automobile fuel via catalytic deoxygenation reactions. Herein, the effects of the zeolite ZSM-5 on the pyrolysis of four biomass materials (corn cob, corn straw, pine powder, and cellulose were investigated via TG-FTIR (thermogravimetric analyzer coupled with a Fourier transform infrared spectrometer to better understand the working mechanism of ZSM-5. The contents of the products of H2O, CO, CO2, and the C-O, C=O, and OH groups evolved with increasing pyrolytic temperature were monitored by FTIR. It was found that the relative contents of the C-O and C=O groups were decreased under the catalysis of ZSM-5, while the formations of CO, H2O, and the OH containing compounds were promoted. To explain the regulations, reaction routes were speculated and the catalytic conversion mechanisms were deduced.

Facile synthesis of hierarchical nanocrystalline ZSM-5 zeolite under mild conditions and its catalytic performance.

Science.gov (United States)

Ni, Youming; Sun, Aiming; Wu, Xiaoling; Hai, Guoliang; Hu, Jianglin; Li, Tao; Li, Guangxing

2011-09-15

Hierarchical nanocrystalline ZSM-5 zeolite (NZ5) was synthesized at 100 °C under atmospheric pressure using methylamine as a mineralizing agent. The crystallization process of NZ5 was characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), and infrared spectroscopy (FTIR). The results of contrastive experiments showed that evaporation of the solvent promoted the aggregation of primary particles, and the addition of methylamine accelerated the crystallization process. The NZ5 aggregate consisted of 20 nm individual particles, as shown in scanning electron microscope (SEM). The lattice fringes in the transmission electron microscope (TEM) images and the XRD results indicated that individual particles of NZ5 were highly crystalline. N(2) adsorption-desorption isotherms showed that NZ5 had high BET surface areas with mesopores having a mean diameter of about 9 nm. NZ5 exhibited a long lifetime, a stable and high yield of liquid hydrocarbons, and a high anti-coking performance in methanol-to-hydrocarbons reaction. Catalytic testing and TGA results showed that the lifetime of NZ5 was about ten times longer than that of micro-sized ZSM-5 zeolite (MZ5), and the average coking rate with NZ5 was one fifth over that of MZ5. Copyright © 2011 Elsevier Inc. All rights reserved.

Hexane cracking over steamed phosphated zeolite H-ZSM-5 : Promotional effect on catalyst performance and stability

NARCIS (Netherlands)

Van Der Bij, Hendrik E.; Meirer, Florian; Kalirai, Samanbir; Wang, Jian; Weckhuysen, Bert M.

2014-01-01

The nature behind the promotional effect of phosphorus on the catalytic performance and hydrothermal stability of zeolite H-ZSM-5 has been studied using a combination of 27Al and 31P MAS NMR spectroscopy, soft X-ray absorption tomography and n-hexane catalytic cracking, complemented with NH3

Co2+ Ions as Probes of Al Distribution in the Framework of Zeolites. ZSM-5 Study

Czech Academy of Sciences Publication Activity Database

Dědeček, Jiří; Kaucký, Dalibor; Wichterlová, Blanka; Gonsiorová, O.

2002-01-01

Roč. 4, - (2002), s. 5406-5413 ISSN 1463-9076 R&D Projects: GA MŠk OC D15.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : Al distribution in zeolites * ZSM-5 * Vis spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.838, year: 2002

Photoionization and Electron Transfer of Biphenyl within the Channels of Al-ZSM-5 Zeolites.

Science.gov (United States)

Gener, Isabelle; Buntinx, Guy; Brémard, Claude

1999-06-14

Evidence of the photogenerated long-lived biphenyl radical and a trapped electron in the void space of aluminated nonacidic ZSM-5 zeolites has been obtained from the time-resolved UV/Vis absorption, Raman scattering, and EPR spectra. The restoration of the ground states implicates the existence of long-lived positive holes in the framework. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Generación de mesoporosidad en zeolitas ZSM-5 sintetizadas en medio inorgánico

Directory of Open Access Journals (Sweden)

Carmen M. López

2011-10-01

Full Text Available In this work we presented a study over the generation of mesoporosity in ZSM-5 zeolites with ratio Si/Al of 10 and 35 synthesized in inorganic medium. A mesoporous phase with hexagonal arrangement that coexists with the zeolite ZSM-5 remnant, was obtained after alkaline treatment of zeolite followed by hydrothermal treatment in the presence of CTAB surfactant micelles. The acidity and catalytic activity of the zeolite ZSM-5 with higher relation Si/Al were kept after the treatment, whereas a notable decrease of these properties was obtained for the zeolite with minor relation Si/Al

Encapsulation of ferro- and ferricyanide complexes inside ZSM-5 zeolite synthesized from rice straw: Implications for synthesis of Prussian blue pigment

Energy Technology Data Exchange (ETDEWEB)

Ali, Ibraheem O.; Salama, Tarek M., E-mail: tm_salama@yahoo.com; Thabet, Mohamed S.; El-Nasser, Karam S.; Hassan, Ali M.

2013-06-15

Encapsulation of [Fe(CN){sub 6}]{sup 4−} and [Fe(CN){sub 6}]{sup 3−} complexes in the intracrystalline pores of ZSM-5 zeolite, Fe{sup II}L/Z and Fe{sup III}L/Z respectively, by the zeolite synthesis method was reported. The modified zeolites were characterized by powder XRD, FT-IR and UV–vis spectroscopy. The nitrogen adsorption isotherms allow for the evaluation of pore structure of the complex-modified zeolites, whereas the thermal analysis (TGA/DTA) measurements provide insight into the decomposition products of the immobilized complexes. The modified zeolites exhibited smaller pore volumes and surface areas as compared with those of unpromoted ZSM-5, suggesting the inclusion of iron cyanides inside the interconnecting channels of ZSM-5. While the ferricyanide complex enhanced the formation of highly crystalline zeolite, the ferrocyanide one resulted in a lesser effect. The electronic spectra of the colloidal species developed when Fe{sup III}L/Z brought in contact with an aqueous solution of [Fe(CN){sub 6}]{sup 3−} exhibit absorptions attributed to CN{sup −} → iron charge-transfer. New bands at 294 and 319 nm due to d–d transitions of Fe{sup III} tetrahedral monomeric moieties were emitted concurrently under successive adsorption of [Fe(CN){sub 6}]{sub aq}{sup 3−} over Fe{sup III}L/Z, along with a broad band at 555 nm assigned to polymeric [Fe{sup II}–C–N–Fe{sup III}] of Prussian blue (PB). The FT-IR spectra of Fe{sup III/II}L/Z devoted to the adsorption of an aqueous solution of [Fe(CN){sub 6}]{sup 3−} showed a band at 2092 cm{sup −1} assigned to the C–N stretch in the Fe{sup II}–CN–Fe{sup III} linkages. The vibrations attributable to Fe–O–Si bonding along with hydrocarbon and nitroprusside appeared only in the spectrum of Fe{sup III}L/Z, thus was found to be strong evidence for the mutual interaction between [Fe(CN){sub 6}]{sup 3−} and the latter sample. - Highlights: • We synthesized ferrous and ferric cyanide

Enhanced catalytic performance for light-olefins production from chloromethane over hierarchical porous ZSM-5 zeolite synthesized by a growth-inhibition strategy

Science.gov (United States)

Liu, Qing; Wen, Dafen; Yang, Yanran; Fei, Zhaoyang; Zhang, Zhuxiu; Chen, Xian; Tang, Jihai; Cui, Mifen; Qiao, Xu

2018-03-01

Hierarchical porous ZSM-5 (HP-ZSM-5) zeolites were synthesized by hydrothermal crystallization method adding triethoxyvinylsilane as the growth-inhibitor at different hydrothermal crystallized temperatures. The properties of the obtained samples were characterized by XRD, SEM, N2-sorption, uptake of ethylene, 27Al MAS NMR, NH3-TPD, and Py-IR. It was found that the mesopore was introduced and the acidity was adjusted over HP-ZSM-5 samples successfully. The hydrothermal crystallized temperature had an important influence on the porous structure and surface properties. The catalytic performance for chloromethane to light-olefins (CMTO) were also investigated. Compared with ZSM-5 samples, HP-ZSM-5 samples exhibited enhanced stability and increased selectivity of light-olefins for CMTO reaction because of the introduction of the abundant mesopore and appropriate acidity. The lifetime (the duration of chloromethane conversion >98%) and selectivity of light-olefins reached 115 h and 69.3%, respectively.

Probing the porosity of cocrystallized MCM-49/ZSM-35 zeolites by hyperpolarized 129Xe NMR.

Science.gov (United States)

Liu, Yong; Zhang, Weiping; Xie, Sujuan; Xu, Longya; Han, Xiuwen; Bao, Xinhe

2008-01-31

One- and two-dimensional 129Xe NMR spectroscopy has been employed to study the porosity of cocrystallized MCM-49/ZSM-35 zeolites under the continuous flow of hyperpolarized xenon gas. It is found by variable-temperature experiments that Xe atoms can be adsorbed in different domains of MCM-49/ZSM-35 cocrystallized zeolites and the mechanically mixed counterparts. The exchange of Xe atoms in different types of pores is very fast at ambient temperatures. Even at very low temperature two-dimensional exchange spectra (EXSY) show that Xe atoms still undergo much faster exchange between MCM-49 and ZSM-35 analogues in the cocrystallized zeolites than in the mechanical mixture. This demonstrates that the MCM-49 and ZSM-35 analogues in cocrystallized zeolites may be stacked much closer than in the physical mixture, and some parts of intergrowth may be formed due to the partially similar basic structure of MCM-49 and ZSM-35.

Adsorption of butyl acetate in air over silver-loaded Y and ZSM-5 zeolites: experimental and modelling studies.

Science.gov (United States)

Bhatia, Subhash; Abdullah, Ahmad Zuhairi; Wong, Cheng Teng

2009-04-15

Adsorption behaviours of butyl acetate in air have been studied over silver-loaded Y (Si/Al=40) and ZSM-5 (Si/Al=140) zeolites. The silver metal was loaded into the zeolites by ion exchange (IE) and impregnation (IM) methods. The adsorption study was mainly conducted at a gas hourly space velocity (GHSV) of 13,000 h(-1) with the organic concentration of 1000 ppm while the desorption step was carried out at a GHSV of 5000 h(-1). The impregnated silver-loaded adsorbents showed lower uptake capacity and shorter breakthrough time by about 10 min, attributed to changes in the pore characteristics and available surface for adsorption. Silver exchanged Y (AgY(IE)) with lower hydrophobicity showed higher uptake capacity of up to 35%, longer adsorbent service time and easier desorption compared to AgZSM-5(IE). The presence of water vapour in the feed suppressed the butyl acetate adsorption of AgY(IE) by 42% due to the competitive adsorption of water on the surface and the effect was more pronounced at lower GHSV. Conversely, the adsorption capacity of AgZSM-5(IE) was minimally affected, attributed to the higher hydrophobicity of the material. A mathematical model is proposed to simulate the adsorption behaviour of butyl acetate over AgY(IE) and AgZSM-5(IE). The model parameters were successfully evaluated and used to accurately predict the breakthrough curves under various process conditions with root square mean errors of between 0.05 and 0.07.

Performance of modified H-ZSM-5 zeolite for dehydration of methanol to dimethyl ether

Energy Technology Data Exchange (ETDEWEB)

Hassanpour, Samaneh; Taghizadeh, Majid [Department of chemical engineering, Babol University of Technology, P.O. Box 484, 4714871167 Babol (Iran); Yaripour, Fereydoon [Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company, Tehran (Iran)

2010-10-15

The conversion of methanol to dimethyl ether was carried out over various commercial zeolites and modified H-ZSM-5 catalysts to evaluate their catalytic performance. A series of commercially available zeolite samples were used for vapor-phase dehydration of methanol to DME. Catalyst screening tests were performed in a fixed-bed reactor under the same operating conditions (T = 300 S, P = 16 barg, WHSV = 3.8 h{sup -1}). It was found that all the H-form zeolite catalysts in this study were active and selective for DME synthesis. According to the experimental results MDHC-1 catalyst exhibited the highest activity in dehydration of methanol. After finding the most active catalyst, the H-MFI90 zeolite was modified with Na content varying from 0 to 120 mol%, via wet-impregnation method to further improve its selectivity. All of catalysts were characterized by BET, XRD, NH{sub 3}-TPD, ICP, TGA, SEM, FT-IR and TPH techniques. It was found that these materials affected activity of MDHC-1 zeolite by changing its acidity. Ultimately, among all the catalysts studied, Na{sub 100}-modified H-MFI90 zeolite exhibited optimum activity, selectivity and stability at methanol dehydration reaction. (author)

The study of methanol transformation over Cu-modified ZSM-5, Beta zeolite and MCM-41 mesoporous silica using 11C-radioisotope labeling

International Nuclear Information System (INIS)

Sarkadi-Priboczki, E.; Kovacs, Z.

2004-01-01

Complete text of publication follows. The copper-containing zeolites and mesoporous silica, among other metals, are suitable for dehydrogenation of methanol. The Cu transition metal determines the route of methanol conversion on supports of ZSM-5 and Beta zeolite as well as MCM-41 mesoporous silica. The catalysis mechanism and the catalytic property are concluded from the composition of methanol derivates over Cu-modified catalysts. The Cu ion-exchanged ZSM-5 and Beta zeolite and MCM-41 mesoporous silica were synthesized and characterized using X-ray power diffraction, scanning electron microscope, nitrogen and pyridine adsorption, X-ray fluorescency and FTIR spectroscopy. The 11 C-radioactive labeling method ( 11 C radioisotope, T 1/2 = 20 min, is a gamma emitter by annihilation of its positron) is suitable for following the process of 11 C-methanol con- version i.e. adsorption, desorption and catalytic transformation as well as for investigation of small amounts of molecules over catalysts by very sensitive radioactivity detectors.The 11 C radioisotope was produced at cyclotron and the 11 C-methanol was synthesized by a classical radiochemical method. After catalysis the 11 C-radioactive and non radioactive volatile products were identified by radiogas chromatography hereby radiolabeled compound and -derivates were distinguished from other participant natural, nonradioactive carbon compounds. Along radioactive products dimethyl ether and small hydrocarbons products were formed by Bronsted acid sites of catalysts while formaldehyde and small methyl formate were formed by Cu metal over bifunctional Cu-ZSM-5, Cu-Beta zeolite and mesoporous Cu-MCM-41 silica at 240 deg C. The detection of methoxy methanol and dimethoxy methane confirmed the simultaneous presence of acid and basic sites of catalysts. At higher temperature (400 deg C) the CO and CO 2 final products were dominated. In our previous works, methanol conversion to hydrocarbons was observed by dehydration

Mesoporous ZSM-5 Zeolites in Acid Catalysis: Top-Down vs. Bottom-Up Approach

Directory of Open Access Journals (Sweden)

Pit Losch

2017-07-01

Full Text Available A top-down desilication of Al-rich ZSM-5 zeolites and a bottom-up mesopores creating method were evaluated in this study. Three liquid–solid and one gas–solid heterogeneously-catalysed reactions were chosen to establish relationships between zeolites textural properties and their catalytic behavior in acid-catalysed model reactions that are influenced by shape selectivity: Diels-Alder cyclization between isoprene and methylacrylate, Methanol-to-Olefins (MTO reaction, chlorination of iodobenzene with trichloroisocyanuric acid (TCCA, and Friedel-Crafts acylation of anisole by carboxylic acids with differing sizes. It is found amongst others that no optimal mesoporosity for all the different reactions can be easily obtained, but depending on the chosen application, a specific treatment has to be set to achieve high activity/selectivity and stability.

Small-angle neutron scattering studies of the template-mediated crystallization of ZSM-5 type zeolite

International Nuclear Information System (INIS)

Iton, L.E.; Brun, T.O.; Epperson, J.E.

1988-03-01

Small-angle neutron scattering is a useful new approach to the study of zeolite crystallization from aluminosilicate gels and the action of template molecules. It has been applied to gels for synthesis of zeolite ZSM-5 using tetrapropylammonium ions as templates where the scattering length densities of the gel particles and their texture were determined using contrast variation methods. Gels formulated from soluble silicate incorporate template molecules promptly into an amorphous ''embryonic'' structure and crystallization ensues via a solid hydrogel transformation mechanism. Gels formulated from colloidal silica show different scattering behavior, and a liquid phase transport mechanism is inferred. 8 refs., 4 figs., 2 tabs

Transformation of South African coal fly ash into ZSM-5 zeolite and its application as an MTO catalyst

CSIR Research Space (South Africa)

Missengue, RNM

2017-01-01

Full Text Available This study presents a way of using South African coal fly ash by extracting metals such as Al and Fe with concentrated sulphuric acid, and then using the solid residue as a feedstock for the synthesis of ZSM-5 zeolite. The percentage of aluminium...

Direct NO decomposition over conventional and mesoporous Cu-ZSM-5 and Cu-ZSM-11 catalysts

DEFF Research Database (Denmark)

Kustova, Marina; Rasmussen, Søren Birk; Kustov, Arkadii

2006-01-01

Conventional Cu-ZSM-5 has for many years been recognized as a unique catalyst for direct NO decomposition. Zeolite-based catalysts have a crystallographically well-defined microporous structure. In such microporous catalysts, the creation and accessibility of the active sites is often influenced...... that ZSM-11 has only straight microporous channels, while ZSNI-5 has both straight and sinusoidal channels. Apparently, there is a preferential formation of active sites and/or improved accessibility in the straight channels compared to the sinusoidal channels, which make the ZSM-11 material a better...

Nafion®/H-ZSM-5 composite membranes with superior performance for direct methanol fuel cells

NARCIS (Netherlands)

Yildirim, M.H.; Curos, Anna Roca; Motuzas, Julius; Motuzas, J.; Julbe, Anne; Stamatialis, Dimitrios; Wessling, Matthias

2009-01-01

Solution cast composite direct methanol fuel cell membranes (DEZ) based on DE2020 Nafion® dispersion and in-house prepared H-ZSM-5 zeolites with different Si/Al ratios were prepared and thoroughly characterized for direct methanol fuel cell (DMFC) applications. All composite membranes have indeed

High Yield of Liquid Range Olefins Obtained by Converting i-Propanol over Zeolite H-ZSM-5

DEFF Research Database (Denmark)

Mentzel, Uffe Vie; Shunmugavel, Saravanamurugan; Hruby, S.L.

2009-01-01

Methanol, ethanol, and i-propanol were converted under methanol-to-gasoline (MTH)-like conditions (400 degrees C, 1-20 bar) over zeolite H-ZSM-5. For methanol and ethanol, the catalyst lifetimes and conversion capacities are comparable, but when i-propanol is used as the reactant, the catalyst...... lifetime is increased dramatically. In fact, the total conversion capacity (calculated as the total amount of alcohol converted before deactivation in g(alcohol)/g(zeolite)) is more than 25 times higher for i-propanol compared to the lower alcohols. Furthermore, when i-propanol is used as the reactant...

Conversion of straight-run gas-condensate benzenes into high- octane gasolines based on modified ZSM-5 zeolites

International Nuclear Information System (INIS)

Erofeev, V; Reschetilowski, V; Khomajakov, I; Egorova, L; Volgina, T; Tatarkina, A

2014-01-01

This paper describes the conversion of straight-run benzene of gas condensate into high-octane gasoline based on zeolite catalyst ZSM-5, modified in binary system oxide- based Sn (III) and Bi (III). It was defined that the introduction of the binary system oxide-based Sn(III) and Bi (III) into the basic zeolite results in the 2-fold increase of its catalytic activity.High-octane gasoline converted from straight-run benzene is characterized by a low benzol content in comparison to the high-octane benzenes produced during the catalytic reforming

Paraselectivity and Formation of Aromatic Hydrocarbons over ZSM-5 Type Catalysts

Energy Technology Data Exchange (ETDEWEB)

Unneberg, E

1997-12-31

The zeolite ZSM-5, patented by Mobil Oil Corporation in 1972, is able to convert methanol to gasoline (MTG) and water. Due to the size of the channels, undesired hydrocarbons larger than C{sub 11} are not present in the mixture, and a high octane gasoline is obtained. This has aroused a great deal of interest in the ZSM-5. Rather than being concerned with energy considerations, this doctoral thesis describes syntheses of ZSM-5 and discusses the ZSM-5 as such and studies the possible paraselectivities in various reactions over the catalyst ZSM-5. 774 refs., 113 figs., 54 tabs.

Paraselectivity and Formation of Aromatic Hydrocarbons over ZSM-5 Type Catalysts

Energy Technology Data Exchange (ETDEWEB)

Unneberg, E.

1996-12-31

The zeolite ZSM-5, patented by Mobil Oil Corporation in 1972, is able to convert methanol to gasoline (MTG) and water. Due to the size of the channels, undesired hydrocarbons larger than C{sub 11} are not present in the mixture, and a high octane gasoline is obtained. This has aroused a great deal of interest in the ZSM-5. Rather than being concerned with energy considerations, this doctoral thesis describes syntheses of ZSM-5 and discusses the ZSM-5 as such and studies the possible paraselectivities in various reactions over the catalyst ZSM-5. 774 refs., 113 figs., 54 tabs.

Oxidative desulfurization of thiophene on TiO2/ZSM-12 zeolite

OpenAIRE

Santos,Marília Ramalho Figueiredo dos; Pedrosa,Anne Michelle Garrido; Souza,Marcelo José Barros de

2016-01-01

In this work the hydrothermal synthesis of ZSM-12 zeolite was performed, varying the MTEACl/SiO2 ratio, where the synthesis temperature was 140 ºC and the crystallization time was 144 hours. The catalysts were characterized by XRD, FTIR and TG. TiO2/ZSM-12 catalysts were used with titanium ions concentrations of 5, 10 and 15%. The oxidative desulfurization (ODS) reactions were performed using a model mixture containing n-heptane as solvent and thiophene as sulfur compound, H2O2 as an oxidizin...

Transalkylation of ethyl benzene with triethylbenzene over ZSM-5 zeolite catalyst

KAUST Repository

Akhtar, M. Naseem

2010-09-01

Transalkylation of 1,3,5-triethylbenzene (TEB) with ethylbenzene (EB) has been studied over ZSM-5 zeolite using a riser simulator reactor with respect to optimizing DEB yield. The reaction temperature was varied from 350 to 500°C with contact time ranging from 3 to 15s to report on the effect of reaction conditions on TEB conversion, DEB selectivity and isomerization of TEB. The transalkylation of TEB with EB was compared with the reactions of pure 1,3,5-TEB and EB (disproportionation, isomerization and cracking). A synergistic effect was observed on the conversion of 1,3,5-TEB and DEB yield. The 1,3,5-TEB conversion increased from 40% to 50% with simultaneous increase in the DEB selectivity from 17% to 36% in transalkylation reaction (EB+1,3,5-TEB) as compared with the reaction of pure 1,3,5-TEB. It was found that pure 1,3,5-TEB underwent cracking reaction to produce DEB and EB. The isomerization of 1,3,5-TEB was more active at low temperature while cracking was more active at high temperature. The temperature of 350°C was observed as the optimum for production of maximum amount of DEB. Kinetic parameters for the disappearance of 1,3,5-TEB during its transformation reaction via cracking and isomerization pathways were calculated using the catalyst activity decay function based on time-on-stream (TOS). The apparent activation energies decrease in order E secondary cracking>E primary racking>E isomerization for ZSM-5 catalysts. © 2010 Elsevier B.V.

Partial oxidation of methane to methanol over catalyst ZSM-5 from coal fly ash and rice husk ash

Directory of Open Access Journals (Sweden)

Mirda Yanti Fusia

2017-01-01

Full Text Available Methane is one of the greenhouse gases that can be converted into liquid fuels such as methanol to retain most of the energy of methane and produce a cleaner environment. The conversion of methane to methanol using ZMS-5 represents a breakthrough in the utilization of methane. However, material sources for zeolite synthesis as catalyst usually are pro-analysis grade materials, which are expensive. Therefore, in this research, coal fly ash and rice husk ash were used as raw materials for mesoporous ZSM-5 zeolite synthesis. First, coal fly ash and rice husk were subjected to pre-treatment to extract silicate (SiO44− and aluminate (AlO45− and impurities separation. The ZSM-5 zeolite was synthesized through hydrothermal treatment using two types of templates. After ZSM-5 was synthesized, it was modified with Cobalt through impregnation method. The catalytic activity of both ZSM-5 and Co/ZSM-5 zeolites as heterogeneous catalysts in partial oxidation of methane were preliminary tested and compared with that commercial one. The result showed that the zeolite catalyst ZSM-5 from fly ash coal and rice husk ash has the potential to be used as catalysts in the partial oxidation of methane to methanol.

Multinuclear MAS NMR studies on coked zeolites H-ZSM-5

International Nuclear Information System (INIS)

Ernst, H.; Freude, D.; Hunger, M.; Pfeifer, H.

1991-01-01

During the cracking process carbonaceous materials are deposited on the outer or inner surface of the catalyst. These deposits are in many cases the main cause of catalyst deactivation. Magic angle spinning (MAS) NMR investigations and catalytic n-hexane cracking were carried out on H-ZSM-5 zeolites after a mild hydrothermal de-alumination. By 13 C CP MAS NMR it could be shown that the enhanced catalytic activity does not enhance the coke formation and that the chemical nature of these deposits is essentially aromatic. From 1 H MAS NMR studies performed on shallow-bed activated sealed samples and 27 Al and 29 Si MAS NMR on rehydrated samples it follows that for high coke concentrations the catalyst deactivation is caused mainly by blocking of Broensted acid sites. (author). 27 refs.; 3 figs.; 2 tabs

Facile synthesis of mesostructured ZSM-5 zeolite with enhanced mass transport and catalytic performances

Energy Technology Data Exchange (ETDEWEB)

Li, Chao; Ren, Yanqun [School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Tianhe District, Guangzhou 510641 (China); Gou, Jinsheng [College Material Science and Technology, Beijing Forestry University, Key Laboratory of Wooden Material Science and Application, Ministry of Education, 35 Tsinghua East Road, Haidian District, Beijing 100083 (China); Liu, Baoyu [School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Tianhe District, Guangzhou 510641 (China); Xi, Hongxia, E-mail: cehxxi@scut.edu.cn [School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Tianhe District, Guangzhou 510641 (China)

2017-01-15

Highlights: • A mesostructured MFI zeolite was synthesized via dual-functional surfactant approach. • Mass transport was investigated by applying zero length column technique. • The catalyst exhibited excellent catalytic activity and long lifetime. • Gaussian DFT was employed to study the role of surfactant in crystallization process. - Abstract: A mesostructured ZSM-5 zeolite with multilamellar structure was successfully synthesized by employing a tetra-headgroup rigid bolaform quaternary ammonium surfactant. It was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), nitrogen adsorption/desorption isotherms, amines temperature programmed desorption (amines-TPD), and computer simulation. These results indicated that the dual-functional amphiphilic surfactants play a critical role for directing the multilamellar structure with high mesoporosity. The mass transport and catalytic performances of the zeolite were investigated by zero length column (ZLC) technique and aldol condensation reactions to evaluate the structure-property relationship. These results clearly indicated that the mass transport of selected molecules in hierarchical zeolite can be accelerated by introducing mesoporous structure with mesostructure with reduced diffusion length and an overall enhanced resistance against deactivation in reactions involving large molecules. Furthermore, the dual-functional surfactant approach of making hierarchical zeolite with MFI nanosheets framework would open up new opportunities for design and synthesis of hierarchical zeolites with controllable mesoporous structures.

Facile synthesis of mesostructured ZSM-5 zeolite with enhanced mass transport and catalytic performances

International Nuclear Information System (INIS)

Li, Chao; Ren, Yanqun; Gou, Jinsheng; Liu, Baoyu; Xi, Hongxia

2017-01-01

Highlights: • A mesostructured MFI zeolite was synthesized via dual-functional surfactant approach. • Mass transport was investigated by applying zero length column technique. • The catalyst exhibited excellent catalytic activity and long lifetime. • Gaussian DFT was employed to study the role of surfactant in crystallization process. - Abstract: A mesostructured ZSM-5 zeolite with multilamellar structure was successfully synthesized by employing a tetra-headgroup rigid bolaform quaternary ammonium surfactant. It was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), nitrogen adsorption/desorption isotherms, amines temperature programmed desorption (amines-TPD), and computer simulation. These results indicated that the dual-functional amphiphilic surfactants play a critical role for directing the multilamellar structure with high mesoporosity. The mass transport and catalytic performances of the zeolite were investigated by zero length column (ZLC) technique and aldol condensation reactions to evaluate the structure-property relationship. These results clearly indicated that the mass transport of selected molecules in hierarchical zeolite can be accelerated by introducing mesoporous structure with mesostructure with reduced diffusion length and an overall enhanced resistance against deactivation in reactions involving large molecules. Furthermore, the dual-functional surfactant approach of making hierarchical zeolite with MFI nanosheets framework would open up new opportunities for design and synthesis of hierarchical zeolites with controllable mesoporous structures.

Synthesis and catalytic performance of ZSM-5/MCM-41 composite molecular sieve from palygorskite

Science.gov (United States)

Jiang, Jinlong; Wu, Mei; Yang, Yong; Duanmu, Chuansong; Chen, Jing; Gu, Xu

2017-10-01

ZSM-5/MCM-41 composite molecular sieve has been hydrothermally synthesized through a two-step crystallization process using palygorskite (PAL) as silicon and aluminum source. The products were characterized by various means and their catalytic properties for acetalization of cyclohexanone and esterification of acetic acid and n-butanol were also investigated. In the first step ZSM-5 zeolite could be formed from the acid-treated PAL after hydrothermal treatment using tetrapropylammonium bromide as template. XRD patterns, N2 adsorption and desorption data, and TEM images show that the composite obtained in the secondary step had a well-ordered mesoporous MCM-41 phase and a microporous ZSM-5 zeolite phase. Compared with ZSM-5, ZSM-5/MCM-41 composite possessed more total acid amount, weak acid sites and large pore structure due to the formation of MCM-41 and exhibited higher catalytic activity for the acetalization and esterification reaction.

Synthesis and characterization of ZSM-5 and calcined kaolin evaluation using the content of structure-directing

International Nuclear Information System (INIS)

Rodrigues, J.J.; Silva, V.J. da; Rodrigues, M.G.F.

2012-01-01

This study aims to evaluate the effect of the structure-directing content, tetrapropylammonium bromide, on the structural and morphological characteristics of ZSM-5 zeolite obtained using calcined kaolin as silicon and aluminum. The samples were characterized by XRD, EDX, SEM and Physics Adsorption N 2 . Trough X ray diffraction patterns was possible to observed the formation of the structure of ZSM-5 with intense peaks and well-defined characteristic of crystalline. The micrographs showed that the samples consist of agglomerates and/or aggregates of particles characteristic of the MFI structure typical of ZSM-5 zeolite. And through the adsorption-desorption isotherms physical N2 was possible to observe that the samples show hysteresis type I typical of microporous materials with specific surface areas of 218 and 222 m 2 /g. Therefore, the use of calcined kaolin to obtain ZSM-5 zeolite was effective. (author)

The Fabrication of Ga2O3/ZSM-5 Hollow Fibers for Efficient Catalytic Conversion of n-Butane into Light Olefins and Aromatics

Directory of Open Access Journals (Sweden)

Jing Han

2016-01-01

Full Text Available In this study, the dehydrogenation component of Ga2O3 was introduced into ZSM-5 nanocrystals to prepare Ga2O3/ZSM-5 hollow fiber-based bifunctional catalysts. The physicochemical features of as-prepared catalysts were characterized by means of XRD, BET, SEM, STEM, NH3-TPD, etc., and their performances for the catalytic conversion of n-butane to produce light olefins and aromatics were investigated. The results indicated that a very small amount of gallium can cause a marked enhancement in the catalytic activity of ZSM-5 because of the synergistic effect of the dehydrogenation and aromatization properties of Ga2O3 and the cracking function of ZSM-5. Compared with Ga2O3/ZSM-5 nanoparticles, the unique hierarchical macro-meso-microporosity of the as-prepared hollow fibers can effectively enlarge the bifunctionality by enhancing the accessibility of active sites and the diffusion. Consequently, Ga2O3/ZSM-5 hollow fibers show excellent catalytic conversion of n-butane, with the highest yield of light olefins plus aromatics at 600 °C by 87.6%, which is 56.3%, 24.6%, and 13.3% higher than that of ZSM-5, ZSM-5 zeolite fibers, and Ga2O3/ZSM-5, respectively.

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

International Nuclear Information System (INIS)

Quartieri, Simona; Montagna, Gabriele; Arletti, Rossella; Vezzalini, Giovanna

2011-01-01

The elastic behavior of H-ZSM-5 was investigated by in-situ synchrotron X-ray powder diffraction, using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.) as 'non-penetrating' and 'penetrating' pressure transmitting media, respectively. From P amb to 6.2 GPa the volume reduction observed in s.o. is 16.6%. This testifies that H-ZSM-5 is one of the most flexible microporous materials up to now compressed in s.o. Volume reduction observed in m.e.w. up to 7.6 GPa is 14.6%. A strong increase in the total electron number of the extraframework system, due to the penetration of water/alcohol molecules in the pores, is observed in m.e.w. This effect is the largest up to now observed in zeolites undergoing this phenomenon without cell volume expansion. The higher compressibility in s.o. than in m.e.w. can be ascribed to the penetration of the extra-water/alcohol molecules, which stiffen the structure and contrast the channel deformations. - Graphical abstract: High-pressure behavior of H-ZSM-5 compressed in (16:3:1) methanol:ethanol:water: (a) projection of the structure along the [0 1 0] direction at P amb , 2 GPa and after pressure release to original ambient conditions (P amb (rev)), and (b) P-dependence of the extraframework content expressed as total number of electrons (gray square represents the number of the extraframework electrons at P amb after decompression). Highlights: → X-ray powder diffraction study of H-ZSM-5 compressibility. → H-ZSM-5 is one of the softest porous material compressed in silicon oil. → Penetration of additional water/alcohol molecules upon compression in m.e.w. → Extra molecules contribute to stiffen the structure and to contrast HP effects.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

Directory of Open Access Journals (Sweden)

Candelaria Leal Marchena

2015-05-01

Full Text Available Materials based on tungstophosphoric acid (TPA immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH43PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

N2O decomposition over Fe/ZSM-5: reversible generation of highly active cationic Fe species

NARCIS (Netherlands)

Zhu, Q.; Hensen, E.J.M.; Mojet, B.L.; Wolput, van J.H.M.C.; Santen, van R.A.

2002-01-01

Fe-oxide species in Fe/ZSM-5 (prepared by chemical vapor deposition of FeCl3)-active in N2O decomposition-react with zeolite protons during high temperature calcination to give highly active cationic Fe species, this transformation being reversible upon exposure to water vapor at lower temperature

One-step preparation of zeolite silicalite-1 microspheres with adjustable macroporosity

KAUST Repository

Hua, Jia

2009-06-23

A facile one-step method was developed for the preparation of zeolite silicalite-1 (or ZSM-5) microspheres without the need of pre-synthesizing zeolite nanocrystals. In this method, Pluronic triblock copolymer F127 was added into a homogeneous silicalite-1 synthesis solution. During the hydrothermal synthesis, zeolite nanocrystals (∼ 100 nm) were formed and spontaneously assembled into uniform micrometer-sized (3-5 μm) spheres due to the presence of F127. The obtained microspheres possess significant textual porosity (up to 0.24 cm 3/g), which can be adjusted by simply adding different amounts of styrene in the synthesis. The zeolite microspheres are useful for enzyme immobilization, and the enzyme loading is proportional to the textual porosity. © 2009 American Chemical Society.

The Effect of Zeolite Composition and Grain Size on Gas Sensing Properties of SnO2/Zeolite Sensor

Directory of Open Access Journals (Sweden)

Yanhui Sun

2018-01-01

Full Text Available In order to improve the sensing properties of tin dioxide gas sensor, four kinds of different SiO2/Al2O3 ratio, different particle size of MFI type zeolites (ZSM-5 were coated on the SnO2 to prepared zeolite modified gas sensors, and the gas sensing properties were tested. The measurement results showed that the response values of ZSM-5 zeolite (SiO2/Al2O3 = 70, grain size 300 nm coated SnO2 gas sensors to formaldehyde vapor were increased, and the response to acetone decreased compared with that of SnO2 gas sensor, indicating an improved selectivity property. The other three ZSM-5 zeolites with SiO2/Al2O3 70, 150 and 470, respectively, and grain sizes all around 1 μm coated SnO2 sensors did not show much difference with SnO2 sensor for the response properties to both formaldehyde and acetone. The sensing mechanism of ZSM-5 modified sensors was briefly analyzed.

Infrared spectra and stability of CO and H2O sorption over Ag-exchanged ZSM-5 zeolite: DFT study

International Nuclear Information System (INIS)

Jiang Shujun; Huang Shiping; Tu Weixia; Zhu Jiqin

2009-01-01

The infrared spectra and stability of CO and H 2 O sorption over Ag-exchanged ZSM-5 zeolite were investigated by using density function theory (DFT). The changes of NBO charge show that the electron transfers from CO molecule to the Ag + cation to form an σ-bond, and it accompanies by the back donation of d-electrons from Ag + cation to the CO (π*) orbital as one and two CO molecules are adsorbed on Ag-ZSM-5. The free energy changes ΔG, -5.55 kcal/mol and 6.52 kcal/mol for one and two CO molecules, illustrate that the Ag + (CO) 2 complex is unstable at the room temperature. The vibration frequency of C-O stretching of one CO molecule bonded to Ag + ion at 2211 cm -1 is in good agreement with the experimental results. The calculated C-O symmetric and antisymmetric stretching frequencies in the Ag + (CO) 2 complex shift to 2231 cm -1 and 2205 cm -1 when the second CO molecule is adsorbed. The calculated C-O stretching frequency in CO-Ag-ZSM-5-H 2 O complex shifts to 2199 cm -1 , the symmetric and antisymmetric O-H stretching frequencies are 3390 cm -1 and 3869 cm -1 , respectively. The Gibbs free energy change (ΔG H 2 O ) is -6.58 kcal/mol as a H 2 O molecule is adsorbed on CO-Ag-ZSM-5 complex at 298 K. The results show that CO-Ag-ZSM-5-H 2 O complex is more stable at room temperature

New insight in the template decomposition process of large zeolite ZSM-5 crystals: an in situ UV-Vis/fluorescence micro-spectroscopy study

NARCIS (Netherlands)

Karwacki, L.|info:eu-repo/dai/nl/304824283; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

2011-01-01

A combination of in situ UV-Vis and confocal fluorescence micro-spectroscopy was used to study the template decomposition process in large zeolite ZSM-5 crystals. Correlation of polarized light dependent UV-Vis absorption spectra with confocal fluorescence emission spectra in the 400–750 nm region

Mesoporous Fe-containing ZSM-5 zeolite single crystal catalysts for selective catalytic reduction of nitric oxide by ammonia

DEFF Research Database (Denmark)

Kustov, Arkadii; Egeblad, Kresten; Kustova, Marina

2007-01-01

Mesoporous and conventional Fe-containing ZSM-5 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnationmethod and tested in NO selective catalytic reduction (SCR) with NH3. It was found that mesoporous Fe-ZSM-5 catalysts exhibit higher SCR activities than comparable conventional cataly...

Location of Framework Al Atoms in the Channels of ZSM-5: Effect of the (Hydrothermal) Synthesis.

Science.gov (United States)

Pashkova, Veronika; Sklenak, Stepan; Klein, Petr; Urbanova, Martina; Dědeček, Jiří

2016-03-14

(27) Al 3Q MAS NMR and UV/Vis spectroscopy with bare Co(II) ions as probes of Al pairs in the zeolite framework were employed to analyze the location of framework Al atoms in the channel system of zeolite ZSM-5. Furthermore, the effect of Na(+) ions together with tetrapropylammonium cation (TPA(+)) in the ZSM-5 synthesis gel on the location of Al in the channel system was investigated. Zeolites prepared using exclusively TPA(+) as a structure-directing agent (i.e., in the absence of Na(+) ions) led to 55-90% of Al atoms located at the channel intersection, regardless the presence or absence of Al pairs [Al-O-(Si-O)2 -Al sequences in one ring] in the zeolite framework. The presence of Na(+) ions in the synthesis gel did not modify the Al location at the channel intersection (55-95% of Al atoms) and led only to changes in i) the distribution of framework Al atoms between Al pairs (decrease) and single isolated Al atoms (increase), and ii) the siting of Al in distinguishable framework tetrahedral sites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran

DEFF Research Database (Denmark)

Sádaba, Irantzu; Gorbanev, Yury; Kegnæs, Søren

2013-01-01

on the four different zeolite supports H-beta, H-Y, H-mordenite, and H-ZSM-5 with 1–10 wt% vanadia loading were prepared and characterized by nitrogen physisorption, X-ray powder diffraction, scanning electron  microscopy, ammonia temperature-programmed desorption, Raman spectroscopy and UV...

Fe-BEA Zeolite Catalysts for NH3-SCR of NOx

DEFF Research Database (Denmark)

Frey, Anne Mette; Mert, Selcuk; Due-Hansen, Johannes

2009-01-01

Iron-containing zeolites are known to be promising catalysts for the NH3-SCR reaction. Here, we will investigate the catalytic activity of iron-based BEA catalysts, which was found to exhibit improved activities compared to previously described iron-containing zeolite catalysts, such as ZSM-5...... and ZSM-12. Series of Fe-BEA zeolite catalysts were prepared using a range of different preparation methods. Furthermore, we found that an iron concentration around 3 wt% on BEA showed a small optimum in SCR activity compared to the other iron loadings studied....

The direct hydroxylation of benzene to phenol catalyzed by Fe-ZSM-5 zeolite : a DFT and hybrid MP2:DFT calculation

NARCIS (Netherlands)

Yang, Z.; Yang, G.; Liu, X.; Han, Xiuwen

2013-01-01

The title reactions over Fe-III and Fe-II-ZSM-5 zeolites are divided into seven and six steps, wherein the M06L:B3LYP energy barriers of N2O decomposition to form active site, benzene activation to form C-O bond and proton transfer to form phenol are equal to 37.0, 13.7, 17.2 and 33.7, 3.0, 19.1

Zeolite synthesis from the pyrrolidine containing system and their catalytic properties in the methanol conversion reaction

Energy Technology Data Exchange (ETDEWEB)

Suzuki, Kunio; Kiyozumi, Yoshimichi; Shin, Shigemitsu; Ogawa, Kiyoshi; Yamazaki, Yasuyoshi; Watanabe, Hideo

1987-12-18

Systhesis of zeolite from a system containing cheaper pyrrolidine as a crystallization regulator than quaternary ammonium ion was carried out and the methanol conversion reaction was studied over the systhesized zeolite to get C/sub 2/ and C/sub 3/ olefins. Hydrous gels were prepared by adding and agitating pyrrolidine, water glass and sulfuric acid to aluminum sulfate solution; and aluminum nitrate, colloidal silica and pyrrolidine to NaOH solution. Five zeolite, that is, ZSM-5, ZSM-35, ZSM-39, ZSM-48 and KZ-1 were synthesized by changing gel components. X-ray powder diffraction, BET specific surface areas, micropore diameters, micropore volumes, oxygen contents by scanning electron photomicrographs and infra-red spectra were examined. The organic base in hydrous gels influenced greatly on the zeolite composition and structure. The ZSM-5 zeolite exhibited the superior performance as to a high selectivity of light olefins over the target of development. (12 figs, 1 tab, 20 refs)

Active sites in Fe/ZSM-5 for nitrous oxide decomposition and benzene hydroxylation with nitrous oxide

NARCIS (Netherlands)

Sun, K.; Xia, H.; Feng, Z.; Santen, van R.A.; Hensen, E.J.M.; Li, Can

2008-01-01

The effect of the iron content and the pretreatment conditions of Fe/ZSM-5 catalysts on the Fe speciation and the catalytic activities in nitrous oxide decomposition and benzene hydroxylation with nitrous oxide has been investigated. Iron-containing ZSM-5 zeolites with varying iron content (Fe/Al =

Synthesis, structural characterization, and catalytic properties of tungsten-exchanged H-ZSM5

International Nuclear Information System (INIS)

Ding, Weiping; Meitzner, George D.; Marler, David O.; Iglesia, Enrique

2001-01-01

W-exchanged H-ZSM5 was prepared by sublimation of WCl6 at 673 K followed by hydrolysis of exchanged WClx species at 523 K. D2 exchange with residual OH groups showed that each W initially replaced about two zeolitic protons for W/Al ratios of 0.29 and 0.44, consistent with the formation of (WO2)2+ containing W6+ species bridging two cation exchange sites. As temperatures reached973 K during D2-OH exchange, these species reduced to (WO2)+ with the concurrent formation of one OD group. CH4 conversion turnover rates (per W) and C2-C1 2 selectivities are very similar to those observed on a Mo/H-ZSM5 sample with similar cation exchange level. As in the case of Mo/H-ZSM5, WOx/H-ZSM5 precursors are initially inactive in CH4 reactions, but they activate during induction with the concurrent evolution of CO, H2O, and an excess amount of H2. The reduction and carburization processes occurring during CH4 reactions and the structure of the exchanged WOx precursors was probed using in situ X-ray absorption spectroscopy (XAS). XAS studies confirmed the isolated initial nature of the exchanged WOx precursors after hydrolysis and dehydration and the formation of WCx clusters 0.6 nm in diameter during CH4 reactions at 973 K. The structural and catalytic resemblance between W- and Mo-exchanged H-ZSM5 is not unexpected, in view of chemical similarities between oxides or carbides of Mo and W. The synthesis of exchanged WOx precursors and their subsequent carburization during CH4 reactions, however, are more difficult than the corresponding processes for the MoOx counterparts. This may account for previous reports of lower CH4 reaction rates and aromatics selectivities on W/H-ZSM5 compared with those observed on Mo/H-ZSM5 and with those reported here for rigorously exchanged W/H-ZSM5

Thermogravimetry of alpha, omega-diaminoalkanes used in synthesizing zsm-5

CSIR Research Space (South Africa)

Howden, MG

1993-04-01

Full Text Available Thermogravimetry was determined on a series of alpha, omega-diaminoalkanes, in which the alkane chain contained from three to eight carbon atoms that were located in zeolite ZSM-5 during synthesis. Of the series, 1, 6-diaminohexane functions best...

Characteristics of supported nano-TiO2/ZSM-5/silica gel (SNTZS): Photocatalytic degradation of phenol

International Nuclear Information System (INIS)

Zainudin, Nor Fauziah; Abdullah, Ahmad Zuhairi; Mohamed, Abdul Rahman

2010-01-01

Photocatalytic degradation of phenol was investigated using the supported nano-TiO 2 /ZSM-5/silica gel (SNTZS) as a photocatalyst in a batch reactor. The prepared photocatalyst was characterized using XRD, TEM, FT-IR and BET surface area analysis. The synthesized photocatalyst composition was developed using nano-TiO 2 as the photoactive component and zeolite (ZSM-5) as the adsorbents, all supported on silica gel using colloidal silica gel binder. The optimum formulation of SNTZS catalyst was observed to be (nano-TiO 2 :ZSM-5:silica gel:colloidal silica gel = 1:0.6:0.6:1) which giving about 90% degradation of 50 mg/L phenol solution in 180 min. The SNTZS exhibited higher photocatalytic activity than that of the commercial Degussa P25 which only gave 67% degradation. Its high photocatalytic activity was due to its large specific surface area (275.7 m 2 /g), small particle size (8.1 nm), high crystalline quality of the synthesized catalyst and low electron-hole pairs recombination rate as ZSM-5 adsorbent was used. The SNTZS photocatalyst synthesized in this study also has been proven to have an excellent adhesion and reusability.

X-ray emission spectroscopy study of iron silicate catalyst FeZSM-5

International Nuclear Information System (INIS)

Csencsits, R.; Lyman, C.E.; Gronsky, R.

1988-03-01

Iron silicate analogs of the zeolite ZMS-5 may be directly synthesized from iron silicate gels in a manner which differs slightly from the alumino-silicate ZSM-5. The resultant white, crystalline iron silicate is referred to as FeZSM-5 in the as-synthesized form. Thermal treatment removes the organic crystal-directing agent and moves some of the framework iron into non-framework sites producing the calcined form of the molecular sieve FeZSM-5. Homogeneity in the distribution of catalytic iron throughout the particles is desired in an optimal catalyst. Distribution of the iron throughout the framework in the as-synthesized forms would affect the final distribution of catalytic iron in the calcined and steamed forms; thus, the iron distribution throughout the as-synthesized and calcined forms of FeZSM-5 were studied using the high spatial resolution on the analytical electron microscope. 7 refs., 3 figs

Characteristics of supported nano-TiO{sub 2}/ZSM-5/silica gel (SNTZS): Photocatalytic degradation of phenol

Energy Technology Data Exchange (ETDEWEB)

Zainudin, Nor Fauziah; Abdullah, Ahmad Zuhairi [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Penang (Malaysia); Mohamed, Abdul Rahman, E-mail: chrahman@eng.usm.my [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Penang (Malaysia)

2010-02-15

Photocatalytic degradation of phenol was investigated using the supported nano-TiO{sub 2}/ZSM-5/silica gel (SNTZS) as a photocatalyst in a batch reactor. The prepared photocatalyst was characterized using XRD, TEM, FT-IR and BET surface area analysis. The synthesized photocatalyst composition was developed using nano-TiO{sub 2} as the photoactive component and zeolite (ZSM-5) as the adsorbents, all supported on silica gel using colloidal silica gel binder. The optimum formulation of SNTZS catalyst was observed to be (nano-TiO{sub 2}:ZSM-5:silica gel:colloidal silica gel = 1:0.6:0.6:1) which giving about 90% degradation of 50 mg/L phenol solution in 180 min. The SNTZS exhibited higher photocatalytic activity than that of the commercial Degussa P25 which only gave 67% degradation. Its high photocatalytic activity was due to its large specific surface area (275.7 m{sup 2}/g), small particle size (8.1 nm), high crystalline quality of the synthesized catalyst and low electron-hole pairs recombination rate as ZSM-5 adsorbent was used. The SNTZS photocatalyst synthesized in this study also has been proven to have an excellent adhesion and reusability.

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons.

Science.gov (United States)

Narula, Chaitanya K; Li, Zhenglong; Casbeer, Erik M; Geiger, Robert A; Moses-Debusk, Melanie; Keller, Martin; Buchanan, Michelle V; Davison, Brian H

2015-11-03

Direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10-15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C2 (dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

Bidimensional ZSM-5 zeolites probed as catalysts for polyethylene cracking

Czech Academy of Sciences Publication Activity Database

Peral, A.; Escola, J. M.; Serrano, D. P.; Přech, Jan; Ochoa-Hernández, Cristina; Čejka, Jiří

2016-01-01

Roč. 6, č. 8 (2016), s. 2754-2765 ISSN 2044-4753 R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : PILLARED MOLECULAR -SIEVE * NANOCRYSTALLINE ZSM-5 * PROTOZEOLITIC UNITS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.773, year: 2016

Hydronium-Ion-Catalyzed Elimination Pathways of Substituted Cyclohexanols in Zeolite H-ZSM5

Energy Technology Data Exchange (ETDEWEB)

Hintermeier, Peter H. [Department; Eckstein, Sebastian [Department; Mei, Donghai [Institute; Olarte, Mariefel V. [Institute; Camaioni, Donald M. [Institute; Baráth, Eszter [Department; Lercher, Johannes A. [Department; Institute

2017-10-02

Hydronium ions in the pores of zeolite H-ZSM5 show high catalytic activity in the elimination of water from cyclohexanol in aqueous phase. Substitution induces subtle changes in rates and reaction pathways, which are concluded to be related to steric effects. Exploring the reaction pathways of 2-, 3-, and 4-methylcyclohexanol (2-McyOH, 3-McyOH, and 4-McyOH), 2- and 4-ethylcyclohexanol (2-EcyOH and 4-EcyOH), 2-n-propylcyclohexanol (2-PcyOH), and cyclohexanol (CyOH) it is shown that the E2 character increases with closer positioning of the alkyl and hydroxyl groups. Thus, 4-McyOH dehydration proceeds via an E1-type elimination, while cis-2-McyOH preferentially reacts via an E2 pathway. The entropy of activation decreased with increasing alkyl chain length (ca. 20 J mol^-1 K^-1 per CH₂ unit) for 2-substituted alcohols, which is concluded to result from constraints influencing the configurational entropy of the transition states.

One-Step Synthesis of Hierarchical ZSM-5 Using Cetyltrimethylammonium as Mesoporogen and Structure-Directing Agent

OpenAIRE

Meng, Lingqian; Mezari, Brahim; Goesten, Maarten G.; Hensen, Emiel J. M.

2017-01-01

Hierarchical ZSM-5 zeolite is hydrothermally synthesized in a single step with cetyltrimethylammonium (CTA) hydroxide acting as mesoporogen and structure-directing agent. Essential to this synthesis is the replacement of NaOH with KOH. An in-depth solid-state NMR study reveals that, after early electrostatic interaction between condensed silica and the head group of CTA, ZSM-5 crystallizes around the structure-directing agent. The crucial aspect of using KOH instead of NaOH lies in the faster...

Synthesis of ZSM-5 and Co-ZSM-5 starting from inorganic systems

International Nuclear Information System (INIS)

Zapata N, Mauren; Montes Consuelo; Villa Aida Luz

1995-01-01

ZSM-5 was obtained in a completely inorganic system. Besides, several experiments were carried out to introduce Co+2 in the Framework of inorganic ZSM-5. The addition of a cobalt source to the precursor gel increased the time to obtain ZSM-5 crystals compared to the gel without a cobalt source. Furthermore, thermal stability over 500 was lower in Co-ZSM-5. Chemical analysis suggests that some cobalt was in the channels, since it was removed by ion exchange

Nanocrystalline Hierarchical ZSM-5: An Efficient Catalyst for the Alkylation of Phenol with Cyclohexene.

Science.gov (United States)

Radhika, N P; Selvin, Rosilda; Kakkar, Rita; Roselin, L Selva

2018-08-01

In this paper, authors report the synthesis of nanocrystalline hierarchical zeolite ZSM-5 and its application as a heterogeneous catalyst in the alkylation of phenol with cyclohexene. The catalyst was synthesized by vacuum-concentration coupled hydrothermal technique in the presence of two templates. This synthetic route could successfully introduce pores of higher hierarchy in the zeolite ZSM-5 structure. Hierarchical ZSM-5 could catalyse effectively the industrially important reaction of cyclohexene with phenol. We ascribe the high efficiency of the catalyst to its conducive structural features such as nanoscale size, high surface area, presence of hierarchy of pores and existence of Lewis sites along with Brønsted acid sites. The effect of various reaction parameters like duration, catalyst amount, reactant mole ratio and temperature were assessed. Under optimum reaction conditions, the catalyst showed up to 65% selectivity towards the major product, cyclohexyl phenyl ether. There was no discernible decline in percent conversion or selectivity even when the catalyst was re-used for up to four runs. Kinetic studies were done through regression analysis and a mechanistic route based on LHHW model was suggested.

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbons Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

DEFF Research Database (Denmark)

Nordvang, Emily Catherine; Borodina, Elena; Ruiz-Martínez, Javier

2015-01-01

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ...... single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics...... at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during...

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

NARCIS (Netherlands)

Nordvang, Emily C.; Borodina, Elena; Ruiz-Martinez, Javier; Fehrmann, Rasmus; Weckhuysen, Bert M.

2015-01-01

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ

Catalytic reduction of NO and N20 for CO on Co-ZSM-5

International Nuclear Information System (INIS)

Rios, Luis Alberto; Aristizabal, Gladys Liliana; Ruiz, Julio Fernando; Montes Consuelo

1996-01-01

Several catalysts with the help of ZSM-5 with Co were tested in the catalytic reduction of NO and N2O using CO like agent reducer and in presence of variable quantities of O2 The cobalt incorporated in the zeolite ZSM-5 for the methods of ionic exchange, impregnation and substitution. ZSM-5 exchanged with Co presented the highest conversions of NO (80% to 5OO oC), in presence of 3000 ppm of O2; When adding 25.700 ppm of O2 the conversion it diminished notably, that which shows an effect inhibitor of the O2. The substituted catalysts and impregnated they were less active for the reduction of the NO. With all the catalysts conversions of 70-90% were achieved for the N2O; Additionally, marked deactivation of the catalyst was not presented with the time

HYDROPHOBIC ZEOLITE-SILICONE RUBBER MIXED MATRIX MEMBRANES FOR ETHANOL-WATER SEPARATION: EFFECT OF ZEOLITE AND SILICONE COMPONENT SELECTION ON PERVAPORATION PERFORMANCE

Science.gov (United States)

High-silica ZSM 5 zeolites were incorporated into poly(dimethyl siloxane) (PDMS) polymers to form mixed matrix membranes for ethanol removal from water via pervaporation. Membrane formulation and preparation parameters were varied to determine the effect on pervaporation perform...

Mechanistic studies on the transformation of ethanol into ethene over Fe-ZSM-5 zeolite.

Science.gov (United States)

Maihom, Thana; Khongpracha, Pipat; Sirijaraensre, Jakkapan; Limtrakul, Jumras

2013-01-14

Ethanol, through the utilization of bioethanol as a chemical resource, has received considerable industrial attention as it provides an alternative route to produce more valuable hydrocarbons. Using a density functional theory approach incorporating the M06-L functional, which includes dispersion interactions, a large 34T nanocluster model of Fe-ZSM-5 zeolite in which T is a Si or Al atom is employed to examine both the stepwise and concerted mechanisms of the transformation of ethanol into ethene. For the stepwise mechanism, ethanol dehydration commences from the first hydrogen abstraction of the ethanol OH group to form the ethoxide-hydroxide intermediate with a low activation energy of 17.7 kcal mol(-1). Consequently, the ethoxide-hydroxide intermediate is decomposed into ethene through hydrogen abstraction from the ethoxide methyl carbon to either the OH group of hydroxide or the oxygen of the ethoxide group with high activation energies of 64.8 and 63.5 kcal mol(-1), respectively. For the concerted mechanism, ethanol transformation into the ethene product occurs in a single step without intermediate formation, with an activation energy of 32.9 kcal mol(-1). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CONVERSION OF (±-CITRONELLAL AND ITS DERIVATIVES TO (--MENTHOL USING BIFUNCTIONAL NICKEL ZEOLITE CATALYSTS

Directory of Open Access Journals (Sweden)

Indri Badria Adilina

2015-06-01

Full Text Available (±-Citronellal and its derivatives were converted to (--menthol by a one-pot reaction system using zeolite based nickel catalysts. The catalysts were prepared by immobilization of nickel on natural zeolite (NZ or synthetic zeolite (ZSM-5 by a simple cation exchange method. Calcination and hydrogen treatment procedures were able to significantly increase the surface area and pore volume of NZ based catalysts whereas negligible changes in the properties were observed for that of ZSM-5. Catalytic reactions were carried out at 70ºC by stirring the mixture in the air for cyclization of (±-citronellal to (±-isopulegol followed by hydrogenation towards the desired (--menthol at 2 Mpa of H2 pressure. The Ni/NZ catalyst was able to convert a (±-citronellal derivative yielding 9% (--menthol (36% selectivity with conversion up to 24%, whereas Ni/ZSM5 catalyst directly converted 65% (±-citronellal to give 4% menthol (6% selectivity. These zeolite based catalysts are therefore potential materials for the conversion of biomass feed stock to value-added chemicals.

Location of Framework Al Atoms in the Channels of ZSM-5: Effect of the (Hydrothermal) Synthesis

Czech Academy of Sciences Publication Activity Database

Pashková, Veronika; Sklenák, Štěpán; Klein, Petr; Urbanová, Martina; Dědeček, Jiří

2016-01-01

Roč. 22, č. 12 (2016), s. 3937-3941 ISSN 1521-3765 R&D Projects: GA ČR GA15-13876S Institutional support: RVO:61388955 Keywords : ZSM-5 * synthesis * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry

Deactivation of Zeolite Catalyst H-ZSM-5 during Conversion of Methanol to Gasoline: Operando Time- and Space-Resolved X-ray Diffraction.

Science.gov (United States)

Rojo-Gama, Daniel; Mentel, Lukasz; Kalantzopoulos, Georgios N; Pappas, Dimitrios K; Dovgaliuk, Iurii; Olsbye, Unni; Lillerud, Karl Petter; Beato, Pablo; Lundegaard, Lars F; Wragg, David S; Svelle, Stian

2018-03-15

The deactivation of zeolite catalyst H-ZSM-5 by coking during the conversion of methanol to hydrocarbons was monitored by high-energy space- and time-resolved operando X-ray diffraction (XRD) . Space resolution was achieved by continuous scanning along the axial length of a capillary fixed bed reactor with a time resolution of 10 s per scan. Using real structural parameters obtained from XRD, we can track the development of coke at different points in the reactor and link this to a kinetic model to correlate catalyst deactivation with structural changes occurring in the material. The "burning cigar" model of catalyst bed deactivation is directly observed in real time.

Synthesis of novel perfluoroalkylglucosides on zeolite and non-zeolite catalysts.

Science.gov (United States)

Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

2015-04-08

Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 °C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts.

Linkage isomerism of carbonyl coordination complexes formed upon CO adsorption on the zeolite Li-ZSM-5: variable-temperature FTIR studies

Science.gov (United States)

Otero Areán, C.; Rodríguez Delgado, M.; Manoilova, O. V.; Turnes Palomino, G.; Tsyganenko, A. A.; Garrone, E.

2002-08-01

Carbon monoxide adsorbed at a low-temperature on the zeolite Li-ZSM-5 forms Li +⋯CO and Li +⋯(CO) 2 species characterized by C-O stretching bands at 2195 and 2187 cm-1, respectively. These C-bonded carbonyls are in a temperature-dependent equilibrium with Li +⋯OC and CO⋯Li +⋯CO species having O-bonded CO. By means of variable-temperature FTIR spectroscopy, the enthalpy change involved in the corresponding isomerization process was found to be ΔH°=7.8 kJ mol-1 for the monocarbonyl and ΔH°=5.1 kJ mol-1 for the dicarbonyl. Therefore, although C-bonded species were always found to show a higher cation-CO interaction energy than O-bonded species, the difference is smaller in the case of dicarbonyls.

The improvement of gas-sensing properties of SnO2/zeolite-assembled composite

Science.gov (United States)

Sun, Yanhui; Wang, Jing; Li, Xiaogan; Du, Haiying; Huang, Qingpan

2018-05-01

SnO2-impregnated zeolite composites were used as gas-sensing materials to improve the sensitivity and selectivity of the metal oxide-based resistive-type gas sensors. Nanocrystalline MFI type zeolite (ZSM-5) was prepared by hydrothermal synthesis. Highly dispersive SnO2 nanoparticles were then successfully assembled on the surface of the ZSM-5 nanoparticles by using the impregnation methods. The SnO2 nanoparticles are nearly spherical with the particle size of 10 nm. An enhanced formaldehyde sensing of as-synthesized SnO2-ZSM-5-based sensor was observed whereas a suppression on the sensor response to other volatile organic vapors (VOCs) such as acetone, ethanol, and methanol was noticed. The possible reasons for this contrary observation were proposed to be related to the amount of the produced water vapor during the sensing reactions assisted by the ZSM-5 nanoparticles. This provides a possible new strategy to improve the selectivity of the gas sensors. The effect of the humidity on the sensor response to formaldehyde was investigated and it was found the higher humidity would decrease the sensor response. A coating layer of the ZSM-5 nanoparticles on top of the SnO2-ZSM-5-sensing film was thus applied to further improve the sensitivity and selectivity of the sensor through the strong adsorption ability to polar gases and the "filtering effect" by the pores of ZSM-5.

Catalytic properties of extraframework iron-containing species in ZSM-5 for N2O decomposition

NARCIS (Netherlands)

Li, G.; Pidko, E.A.; Filot, I.A.W.; Santen, van R.A.; Li, Can; Hensen, E.J.M.

2013-01-01

The reactivity of mononuclear and binuclear iron-containing complexes in ZSM-5 zeolite for catalytic N2O decomposition has been investigated by periodic DFT calculations and microkinetic modeling. On mononuclear sites, the activation of a first N2O molecule is favorable. The rate of catalytic N2O

Carbon/H-ZSM-5 composites as supports for bi-functional Fischer-Tropsch synthesis catalysts

NARCIS (Netherlands)

Valero-Romero, M.J.; Sartipi, S.; Sun, X.; Rodríguez-Mirasol, J.; Cordero, T.; Kapteijn, F.; Gascon, J.

2016-01-01

Mesoporous H-ZSM-5–carbon composites, prepared via tetrapropylammonium hydroxide (TPAOH) post treatment of H-ZSM-5 followed by deposition of pyrolytic carbon, have been used as the support for the preparation of Co-based Fischer–Tropsch catalysts. The resulting catalysts display an improved

Catalytic transformation of methyl benzenes over zeolite catalysts

KAUST Repository

Al-Khattaf, S.

2011-02-01

Catalytic transformation of three methyl benzenes (toluene, m-xylene, and 1,2,4-trimethyl benzene) has been investigated over ZSM-5, TNU-9, mordenite and SSZ-33 catalysts in a novel riser simulator at different operating conditions. Catalytic experiments were carried out in the temperature range of 300-400 °C to understand the transformation of these alkyl benzenes over large pore (mordenite and SSZ-33) in contrast to medium-pore (ZSM-5 and TNU-9) zeolite-based catalysts. The effect of reaction conditions on the isomerization to disproportionation product ratio, distribution of trimethylbenzene (TMB) isomers, and p-xylene/o-xylene ratios are reported. The sequence of reactivity of the three alkyl benzenes depends upon the pore structure of zeolites. The zeolite structure controls primarily the diffusion of reactants and products while the acidity of these zeolites is of a secondary importance. In the case of medium pore zeolites, the order of conversion was m-xylene > 1,2,4-TMB > toluene. Over large pore zeolites the order of reactivity was 1,2,4-TMB > m-xylene > toluene for SSZ-33 catalyst, and m-xylene ∼ 1,2,4-TMB > toluene over mordenite. Significant effect of pore size between ZSM-5 and TNU-9 was observed; although TNU-9 is also 3D 10-ring channel system, its slightly larger pores compared with ZSM-5 provide sufficient reaction space to behave like large-pore zeolites in transformation of aromatic hydrocarbons. We have also carried out kinetic studies for these reactions and activation energies for all three reactants over all zeolite catalysts under study have been calculated. © 2011 Elsevier B.V.

Stability and activity of doped transition metal zeolites in the hydrothermal processing

Directory of Open Access Journals (Sweden)

Thomas François Robin

2015-12-01

Full Text Available This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper and iron in under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered as a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds which have an impact on the physical and chemical propriety of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts but their stability and activity under hydrothermal conditions is not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350 °C. Catalysts have been characterised before and after treatment using XRD, BET physisorption and STEM microscopy. Metal leaching was determined by analysis of the water phase following hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5 for example molybdenum improves the crystallinity of the zeolite. In general, metal doped zeolites were relatively stable under subcritical water. Activity of the catalysts for processing lipids, protein and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella and P. ellipsoidea. The catalysts exhibited greater activity towards converting lipids for example MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.

Stability and Activity of Doped Transition Metal Zeolites in the Hydrothermal Processing

International Nuclear Information System (INIS)

Robin, Thomas François; Ross, Andrew B.; Lea-Langton, Amanda R.; Jones, Jenny M.

2015-01-01

This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper, and iron under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion-exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds that have an impact on the physical and chemical properties of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts, but their stability and activity under hydrothermal conditions are not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350°C. Catalysts have been characterized before and after treatment using X-ray diffraction, BET physisorption, and scanning transmission electronic microscopy. Metal leaching was determined by the analysis of the water phase following the hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5, for example, molybdenum improves the crystallinity of the zeolite. In general, metal-doped zeolites were relatively stable in subcritical water. The activity of the catalysts for processing lipids, protein, and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella, and Pseudochoricystis ellipsoidea. The catalysts exhibited greater activity toward converting lipids, for example, MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.

Stability and Activity of Doped Transition Metal Zeolites in the Hydrothermal Processing

Energy Technology Data Exchange (ETDEWEB)

Robin, Thomas François, E-mail: thomas.cognac@gmail.com; Ross, Andrew B.; Lea-Langton, Amanda R.; Jones, Jenny M. [School of Chemical and Process Engineering, University of Leeds, Leeds (United Kingdom)

2015-12-14

This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper, and iron under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion-exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds that have an impact on the physical and chemical properties of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts, but their stability and activity under hydrothermal conditions are not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350°C. Catalysts have been characterized before and after treatment using X-ray diffraction, BET physisorption, and scanning transmission electronic microscopy. Metal leaching was determined by the analysis of the water phase following the hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5, for example, molybdenum improves the crystallinity of the zeolite. In general, metal-doped zeolites were relatively stable in subcritical water. The activity of the catalysts for processing lipids, protein, and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella, and Pseudochoricystis ellipsoidea. The catalysts exhibited greater activity toward converting lipids, for example, MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.

Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH_3

International Nuclear Information System (INIS)

Zhang, Tao; Shi, Juan; Liu, Jian; Wang, Daxi; Zhao, Zhen; Cheng, Kai; Li, Jianmei

2016-01-01

Highlights: • The hydrothermal stability of Cu-ZSM-5 catalyst was enhanced after surface modification. • An inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer. • The contact between Si and Cu and Al atoms could form Si-O-Al and Si- O−Cu bonds. • The redox and acidity properties of Cu-ZSM-5-CLD-Aged catalyst were largely retained. • The adsorption and activation of NO and NH_3 was almost unchanged over Cu-ZSM-5-CLD catalyst before and after hydrothermal treatment. - Abstract: The surface of Cu-ZSM-5 catalyst was modified by chemical liquid deposition (CLD) of tetraethoxysilane (TEOS) for enhancing its hydrothermal stability in the selective catalytic reduction of NO with NH_3. After hydrothermal aging at 750 °C for 13 h, the catalytic performance of Cu-ZSM-5-Aged catalyst was significantly reduced for NO reduction in the entire temperature range, while that of Cu-ZSM-5-CLD-Aged catalyst was affected very little. The characterization results indicated that an inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer, which prevents the detachment of Cu"2"+ from ZSM-5 ion-exchange positions and the dealumination of zeolite during the hydrothermal aging process. Based on the data it is hypothesized to be the primary reason for the high hydrothermal stability of Cu-ZSM-5-CLD catalyst.

1 - Aromatization of n-hexane and natural gasoline over ZSM-5 zeolite, 2- Wet catalytic oxidation of phenol on fixed bed of active carbon; 1 - Aromatisation de n-hexane et d'essence sur zeolithe ZSM-5, 2 - Oxydation catalytique en voie humide du phenol sur charbon actif

Energy Technology Data Exchange (ETDEWEB)

Suwanprasop, S.

2005-04-15

I - The production of aromatic hydrocarbons from n-hexane and natural gasoline over Pd loaded ZSM-5 zeolite in a tubular reactor was achieved under the suitable conditions at 400 deg. C, and 0.4 ml/min reactant feeding rate, employing ZSM-5 (0.5% Pd content) as a catalyst. Under these conditions, n-hexane and natural gasoline conversions were found to be 99.7% and 94.3%, respectively (with respective aromatic selectivity of 92.3% and 92.6%). II - Wet catalytic air oxidation of phenol over a commercial active carbon was studied in a three phase fixed bed reactor under mild temperature and oxygen partial pressure. Exit phenol concentration, COD, and intermediates were analysed. Oxidation of phenol was significantly improved when increasing operating temperature, oxygen partial pressure, and liquid space time, while up or down flow modes had only marginal effect. A complete model involving intrinsic kinetics and all mass transfer limitations gave convenient reactor simulation. (author)

Fabrication of novel chitosan/PAN/magnetic ZSM-5 zeolite coated sponges for absorption of oil from water surfaces.

Science.gov (United States)

Samadi, Saman; Yazd, Shabnam Sharif; Abdoli, Hossein; Jafari, Pooya; Aliabadi, Majid

2017-12-01

In the present study, the chitosan (bottom layer)/polyacrylonitrile (top layer, PAN) nanofibers were coated on the sponge surface. The synthesized magnetic Fe 3 O 4 - ZSM-5 nanozeolites have been loaded into the chitosan/PAN nanofibers to increase the performance of nanofibers toward absorption of lubricating oil, motor oil and pump oil from water surfaces. Scanning electron microscope (SEM), Transmission electron microscope (TEM) and X-ray diffraction (XRD) analysis were used to characterize the synthesized nanozeolites. The morphology and wettability of nanofibers were determined using SEM and water contact angle tests. The influence of Fe 3 O 4 - ZSM-5 nanozeolite content and chitosan/PAN/Fe 3 O 4 - ZSM-5 nanofiber thickness was evaluated on the potential of sponges for oils absorption. The maximum capacity of the chitosan/PAN/Fe 3 O 4 - ZSM-5 nanofibers coated sponges for absorption of motor oil, lubricating oil and pump oil was found to be 99.4, 95.3 and 88.1g/g, in Fe 3 O 4 - ZSM-5 2wt.% and nanofiber thickness of 12μm (chitosan layer of 2μm and PAN layer of 10μm). The reusability of nanofibrous sponges showed that the hydrophobic chitosan/PAN/Fe 3 O 4 - ZSM-5 nanofibers coated sponges can be easily reused in water-oil separation for many cycles. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of crystallite size and shape of zeolite ZSM-22 on its activity and selectivity in the catalytic cracking of n-octane

Energy Technology Data Exchange (ETDEWEB)

Bager, F.; Ernst, S. [Kaiserslautern Univ. (Germany). Dept. of Chemistry, Chemical Technology

2013-11-01

Light olefins belong to the major building blocks for the petrochemical industry, particularly for the production of polymers. It has become necessary to increase the production of light olefins specifically in the case for propene with so called 'on-purpose propene' technologies. One possible route is to increase the amount of propene that can be obtained from Fluid Catalytic Cracking (FCC) by optimizing the catalyst through introducing new additives, which offer a high selectivity to propene. Zeolite ZSM-22 samples with different crystallite sizes and morphologies have been synthesized via hydrothermal syntheses and characterized by powder X-Ray diffraction, nitrogen physisorption, atomic absorption spectroscopy, scanning electron microscopy and solid-state NMR spectroscopy. The zeolites in the Broensted-acid form have been tested as catalysts in the catalytic cracking of n-octane as a model hydrocarbon. Clear influences of the crystallite size on the deactivation behavior have been observed. Larger crystals of zeolite ZSM-22 produce an increased amount of coke deposits resulting in a faster deactivation of the catalyst. The experimental results suggest that there is probably some influence of pore diffusion on the catalytic activity of the ZSM-22 sample with the large crystallite size. However a noticeable influence on the general product distribution could not be observed. (orig.)

Co-conversion of Ethane and Methanol into Higher Hydrocarbons over Ga/H-ZSM-5, Mo/H-ZSM-5 and Ga-Mo/H-ZSM-5

DEFF Research Database (Denmark)

Mentzel, Uffe Vie; Rovik, Anne; Christensen, Claus H.

2009-01-01

Ethane and methanol are converted simultaneously over Ga/H-ZSM-5, Mo/H-ZSM-5 and Ga-Mo/H-ZSM-5 to produce light olefins and aromatics. The presence of methanol in the reactant stream is intended to facilitate activation of ethane following literature reports on co-conversion of methane and methan...... and in the carbonaceous compounds deposited on the catalysts. This indicates that both reactants take part in the formation of the hydrocarbon pool, which is the origin of all products....

Thermochemical properties of copper forms of zeolite ZSM5 containing dimethylethylenediamine

Czech Academy of Sciences Publication Activity Database

Čuvanová, S.; Reháková, M.; Finocchiaro, P.; Pollicino, A.; Bastl, Zdeněk; Nagyová, S.; Fajnor, V. Š.

2007-01-01

Roč. 452, č. 1 (2007), s. 13-19 ISSN 0040-6031 R&D Projects: GA AV ČR 1ET400400413 Grant - others:GA SR(SK) 1/1385/04; GA SR(SK) 1/1373/04 Institutional research plan: CEZ:AV0Z40400503 Keywords : ZSM-5 * dimethylethylenediamine * copper * thermal analysis * XPS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.562, year: 2007

A green route to methyl acrylate and acrylic acid by an aldol condensation reaction over H-ZSM-35 zeolite catalysts.

Science.gov (United States)

Ma, Zhanling; Ma, Xiangang; Liu, Hongchao; He, Yanli; Zhu, Wenliang; Guo, Xinwen; Liu, Zhongmin

2017-08-10

A one-step aldol condensation reaction to produce MA and AA is a green and promising strategy. Here, the aldol condensation reaction was first conducted with DMM and MAc over different types of zeolite catalysts. The H-ZSM-35 zeolite demonstrates excellent catalytic performance with a DMM conversion of 100% and a MA + AA selectivity of up to 86.2% and superior regeneration ability, with great potential for industrial operation.

Determining the efficiency of ZSM-5 zeolite impregnated with nanoparticles of titanium dioxide in the photocatalytic removal of styrene vapors

Directory of Open Access Journals (Sweden)

Mojtaba Nakhaei pour

2017-03-01

Full Text Available Introduction: Styrene monomer is a volatile organic compound that has many applications particularly in plastic, rubber and paint industries. According to the harmful effects of these compounds on human and environment, reducing and controling of them seem necessary. Therefore, in this study removal of styrene was investigated using photocatalytic process of titanium dioxide nanoparticles stabilized on ZSM-5. Methods: After stabilization of titanium dioxide nanoparticles on ZSM-5 zeolite, BET, SEM and XRD analysis were used to determine the characteristics of nanoparticles. Experiments were conducted at ambient temperature in laboratory scale. Concentration of produced styrene in the experiments was 50 and 300 ppm, and input flow rate was 1 l/min. Results: images and spectra obtained through XRD and SEM-EDAX showed that  nano-catalysts are well- stabilized. The results showed that by increasing of input concentration of styrene from 50 to 300 ppm, photocatalytic removal efficiency are reduced. Also, adsorption capacity of the catalyst bed in concentrations of 50 and 300 ppm was calculated 16.3 and19.4 mg/gr of adsorbent respectively. Conclusion: The results show that the use of hybrid bed can increase the removal efficiency of contaminants. And due to low cost of application of these systems compared to conventional methods, it is recommended that more comprehensive studies to be done regarding the optimization of the parameters affecting the process of photocatalytic removal.

Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Zhang, Tao; Shi, Juan; Liu, Jian, E-mail: liujian@cup.edu.cn; Wang, Daxi; Zhao, Zhen, E-mail: zhenzhao@cup.edu.cn; Cheng, Kai; Li, Jianmei

2016-07-01

Highlights: • The hydrothermal stability of Cu-ZSM-5 catalyst was enhanced after surface modification. • An inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer. • The contact between Si and Cu and Al atoms could form Si-O-Al and Si- O−Cu bonds. • The redox and acidity properties of Cu-ZSM-5-CLD-Aged catalyst were largely retained. • The adsorption and activation of NO and NH{sub 3} was almost unchanged over Cu-ZSM-5-CLD catalyst before and after hydrothermal treatment. - Abstract: The surface of Cu-ZSM-5 catalyst was modified by chemical liquid deposition (CLD) of tetraethoxysilane (TEOS) for enhancing its hydrothermal stability in the selective catalytic reduction of NO with NH{sub 3}. After hydrothermal aging at 750 °C for 13 h, the catalytic performance of Cu-ZSM-5-Aged catalyst was significantly reduced for NO reduction in the entire temperature range, while that of Cu-ZSM-5-CLD-Aged catalyst was affected very little. The characterization results indicated that an inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer, which prevents the detachment of Cu{sup 2+} from ZSM-5 ion-exchange positions and the dealumination of zeolite during the hydrothermal aging process. Based on the data it is hypothesized to be the primary reason for the high hydrothermal stability of Cu-ZSM-5-CLD catalyst.

Production of furfural from waste aqueous hemicellulose solution of hardwood over ZSM-5 zeolite.

Science.gov (United States)

Gao, Hongling; Liu, Haitang; Pang, Bo; Yu, Guang; Du, Jian; Zhang, Yuedong; Wang, Haisong; Mu, Xindong

2014-11-01

This study aimed to produce furfural from waste aqueous hemicellulose solution of a hardwood kraft-based dissolving pulp production processing in a green method. The maximum furfural yield of 82.4% and the xylose conversion of 96.8% were achieved at 463K, 1.0g ZSM-5, 1.05g NaCl and organic solvent-to-aqueous phase ratio of 30:15 (V/V) for 3h. The furfural yield was just 51.5% when the same concentration of pure xylose solution was used. Under the optimized condition, furfural yield was still up to 67.1% even after the fifth reused of catalyst. Catalyst recycling study showed that ZSM-5 has a certain stability and can be efficiently reused. Copyright © 2014 Elsevier Ltd. All rights reserved.

Catalytic para-xylene maximization. Part X: Toluene disproportionation on HF promoted H-ZSM-5 catalysts

Directory of Open Access Journals (Sweden)

Ahmed K. Aboul-Gheit

2012-12-01

Full Text Available H-ZSM-5 zeolite catalysts were doped with 2%, 3% and 4%HF to be used for investigating their activities and selectivities for xylenes production and for para-xylene maximization at temperatures of 300–500 °C via toluene disproportionation. This doping caused pore size modification of the H-ZSM-5 catalyst. The reaction was carried out in a fixed bed flow type reactor. The ratio of produced para-xylene relative to its thermodynamic composition reached as high as 3.29 at 300 °C on the 4%HF doped H-ZSM-5 catalyst although this catalyst possessed the lowest amount of the largest pores (3.0–5.7 nm and the smallest pores (0.4–1.7 nm. The overall activities of the catalysts were decreased with an increase in HF doping because of diffusion restriction. The kinetics of the reaction were simply treated and found to give Ea and ΔS∗ values compatible with the characterization data of the catalysts.

Effect of aluminium distribution in the framework of ZSM-5 on hydrocarbon transformation. Cracking of 1-butene

Czech Academy of Sciences Publication Activity Database

Sazama, Petr; Dědeček, Jiří; Gábová, Vendula; Wichterlová, Blanka; Spoto, G.; Bordiga, S.

2008-01-01

Roč. 254, č. 2 (2008), s. 180-189 ISSN 0021-9517 R&D Projects: GA AV ČR IAA4040308; GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : H-ZSM-5 * Al destribution * catalytic cracking * zeolite acidity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.167, year: 2008

Ultrasound assisted dispersion of different amount of Ni over ZSM-5 used as nanostructured catalyst for hydrogen production via CO2 reforming of methane

International Nuclear Information System (INIS)

Vafaeian, Yaser; Haghighi, Mohammad; Aghamohammadi, Sogand

2013-01-01

Graphical abstract: A series of Ni/ZSM-5 nanocatalysts with different amount of Ni were prepared via ultrasound assisted method and characterized with XRD, FESEM, TEM, BET and FTIR techniques. The research deals with catalyst development for dry reforming of methane with the aim of reaching the most stable catalyst specifically over nano-sized catalysts. About more than 99% of Ni particles size is less than 100 nm for the sample prepared with 8% Ni, which is essential to the relative suppression of the carbon formation on catalysts. Catalyst prepared with 8% Ni content showed superior activity in process expected due to its better catalytic properties. - Highlights: • Using ZSM-5 zeolite in dry reforming of methane. • Employing ultrasound energy in synthesis of Ni/ZSM-5 nanocatalyst. • Enhancement of Ni particles size to meet desired catalyst at lower amount of Ni loading. • Dry reforming of methane over Ni/ZSM-5 nanocatalyst with different Ni-loading. • Superior activity of Ni/ZSM-5 nanocatalyst synthesized with 8% Ni content. - Abstract: Carbon dioxide reforming of methane is an interesting route for synthesis gas production especially over nanostructured catalysts. The present research deals with nanocatalyst development by sonochemical method for dry reforming of methane with the aim of reaching the most efficient nanocatalyst. Effect of Ni metal content, one of the most significant variables, on the properties of the ZSM-5 supported nanocatalysts was taken into account. The Ni/ZSM-5 nanocatalysts were prepared via assisted traditional impregnation method via ultrasound irradiation and characterized with XRD, FESEM, TEM, BET and FTIR techniques. Comparison of XRD patterns implies that the peaks related to NiO become sharper by increasing metal content over the support. In the case of nanocatalysts with lower metal content (3% and 8%), the beneficial influence of ultrasound assisted procedure become more pronounced and the observed reduction in

Xenon capture on silver-loaded zeolites: characterization of very strong adsorption sites

International Nuclear Information System (INIS)

Daniel, Cecile; Elbaraoui, Adnane; Aguado, Sonia; Schuurman, Yves; Farrusseng, David; Springuel-Huet, Marie-Anne; Nossov, Andrei; Fontaine, Jean-Pierre; Topin, Sylvain; Taffary, Thomas; Deliere, Ludovic

2013-01-01

The number and strength of adsorption sites for Xe in silver-modified zeolites are estimated from isotherm measurements at various temperatures over a broad range of pressure (from 1 ppm to atmospheric pressure). Fully and partially exchanged silver zeolites were synthesized starting from Na-ZSM-5(25), Na-ZSM-5(40), Na-Beta, NaX, and NaY. We have discovered that silver-modified zeolites may present one or two distinct adsorption sites depending on the nature of the material and silver loadings. The strongest adsorption sites are characterized by isosteric heat of adsorption in the order of -40 to -50 kJ.mol -1 . For Pentasil-type zeolites, we observe a linear 2:1 correlation between the total amount of silver and the number of strong sites. The highest concentration of strong sites is found for fully silver exchanged ZSM-5 (5.7 * 10 -4 mol/g), which presents the largest silver content for Pentasil-type zeolite. The equilibrium constant of Ag-ZSM-5 at low pressure is about 50 times larger than that of AgX. Qualitative correlations were established between Xe adsorption isotherms and Xe NMR signals. We show that Xe NMR could be used as a quantitative method for the characterization of the strength and of the number of strong Xe adsorption sites on silver-exchanged zeolites. The numbers of strong adsorption sites responsible for the Xe adsorption at 10-1000 ppm can be determined by the length of the plateau observed at low Xe uptake. In practice, our findings give guidelines for the discovery and optimization of silver-loaded zeolites for the capture of Xe at ppm levels. It appears that the amount of silver is a key parameter. Silver-modified ZSM-5 shows adsorption capacities 2-3 orders of magnitude larger than currently applied adsorbents for atmospheric Xe capture. (authors)

Decomposition of NO on Cu-loaded zeolites

Energy Technology Data Exchange (ETDEWEB)

Sepulveda-Escribano, A; Marquez-Alvarez, C; Rodriquez-Ramos, I; Fierro, J L.G. [Instituto de Catalisis y Petroleoquimica, Madrid (Spain); Guerrero-Ruiz, A [Departamento de Quimica Inorganica, UNED, Madrid (Spain)

1993-05-26

Two copper ion-exchanged zeolites, Cu/NaY and Cu/NaZSM-5 have been studied by several techniques (TPR, TPD of NO, IR spectroscopy of adsorbed NO and XPS) and their catalytic activity for NO-decomposition have been determined under dynamic conditions. The results obtained here show that copper is stabilized as Cu[sup +] in Cu/NaZSM-5 after calcination in air at 673K, while in Cu/NaY the initial Cu[sup +]-ions are easier oxidized to Cu[sup 2+], this leading to a completely different catalytic behavior in the reaction of NO-decomposition. So, whereas the Cu/NaZSM-5 exhibits a high NO-conversion at the reaction temperatures (573 and 873K), the parent Cu/NaY zeolite becomes deactivated in the first stages of reaction.

Removal of pyridine from liquid and gas phase by copper forms of natural and synthetic zeolites

International Nuclear Information System (INIS)

Rehakova, Maria; Fortunova, Lubica; Bastl, Zdenek; Nagyova, Stanislava; Dolinska, Silvia; Jorik, Vladimir; Jona, Eugen

2011-01-01

Zeoadsorbents on the basis of copper forms of synthetic zeolite ZSM5 and natural zeolite of the clinoptilolite type (CT) have been studied taking into account their environmental application in removing harmful pyridine (py) from liquid and gas phase. Sorption of pyridine by copper forms of zeolites (Cu-ZSM5 and Cu-CT) has been studied by CHN, X-ray photoelectron spectroscopy, X-ray powder diffractometry, FTIR spectroscopy, thermal analysis (TG, DTA and DTG) and analysis of the surface areas and the pore volumes by low-temperature adsorption of nitrogen. The results of thermal analyses of Cu-ZSM5, Cu-(py) x ZSM5, Cu-CT and Cu-(py) x CT zeolitic products with different composition (x depends on the experimental conditions of sorption of pyridine) clearly confirmed their different thermal properties as well as the sorption of pyridine. In the zeolitic pyridine containing samples the main part of the pyridine release process occurs at considerably higher temperatures than is the boiling point of pyridine, which proves strong bond and irreversibility of py-zeolite interaction. FTIR spectra of Cu-(py) x zeolite samples showed well resolved bands of pyridine. The results of thermal analysis and FTIR spectroscopy are in a good agreement with the results of other used methods.

Occluded cobalt species over ZSM-5 matrix: Design, preparation, characterization and magnetic behavior

International Nuclear Information System (INIS)

Pierella, Liliana B.; Saux, Clara; Bertorello, Hector R.; Bercoff, Paula G.; Botta, Pablo M.; Rivas, J.

2008-01-01

Co-containing molecular sieves with MFI structure was synthesized by the hydrothermal crystallization method and cobalt was incorporated in it by wet impregnation at different percentages. Thermal post-treatments were applied to Co-ZSM-5: calcination and reduction. X ray diffraction (XRD) and FTIR studies confirmed crystallinity, structure and orthorhombic symmetry of the obtained samples (Co-ZSM-5 calcined and Co-ZSM-5 reduced). The XRD, Raman spectroscopy, SEM and TPR techniques for the calcined samples showed the presence of Co 3 O 4 which diminished in the reduced samples and Co 0 appeared. The magnetic behavior of the materials was evaluated by magnetization (M) variation with applied magnetic field (H) at different temperatures. Low magnetization is observed in the calcined samples while high values are attained in the reduced samples, due to the presence of metallic Co

Carbon dioxide adsorption on micro-mesoporous composite materials of ZSM-12/MCM-48 type: The role of the contents of zeolite and functionalized amine

Energy Technology Data Exchange (ETDEWEB)

Santos, S.C.G. [Federal University of Sergipe, Materials Science and Engineering Postgraduate Program P" 2CEM, São Cristovão/SE (Brazil); Pedrosa, A.M.Garrido [Federal University of Sergipe, Departament of Chemistry (DQI), São Cristovão/SE (Brazil); Souza, M.J.B., E-mail: mjbsufs@gmail.com [Federal University of Sergipe, Department of Chemical Engineering (DEQ), Av. Marechal Rondon S/N, 49100-000, São Cristovão/SE (Brazil); Cecilia, J.A.; Rodríguez-Castellón, E. [University of Málaga, Department of Inorganic Chemistry, Crystallography and Mineralogy, Faculty of Sciences, 29071, Málaga (Spain)

2015-10-15

Highlights: • Synthesis of the micro-mesoporous composite materials of ZSM-12/MCM-48 type. • Application of these adsorbents in the carbon dioxide adsorption. • Effects of the contents of zeolite and amino group in the material surface on the CO{sub 2} capture efficiency. - Abstract: In this study ZSM-12/MCM-48 adsorbents have been synthesized at three ZSM-12 content, and also were functionalizated with amine groups by grafting. All the adsorbents synthesized were evaluated for CO{sub 2} capture. The X-ray diffraction analysis of the ZSM-12/MCM-48 composite showed the main characteristic peaks of ZSM-12 and MCM-48, and after the functionalization, the structure of MCM-48 on the composite impregnated was affected due amine presence. For the composites without amine, the ZSM-12 content was the factor determining in the adsorption capacity of CO{sub 2} and for the composites with amine the amount of amine was that influenced in the adsorption capacity.

Carbon dioxide adsorption on micro-mesoporous composite materials of ZSM-12/MCM-48 type: The role of the contents of zeolite and functionalized amine

International Nuclear Information System (INIS)

2CEM, São Cristovão/SE (Brazil))" data-affiliation=" (Federal University of Sergipe, Materials Science and Engineering Postgraduate Program P2CEM, São Cristovão/SE (Brazil))" >Santos, S.C.G.; Pedrosa, A.M.Garrido; Souza, M.J.B.; Cecilia, J.A.; Rodríguez-Castellón, E.

2015-01-01

Highlights: • Synthesis of the micro-mesoporous composite materials of ZSM-12/MCM-48 type. • Application of these adsorbents in the carbon dioxide adsorption. • Effects of the contents of zeolite and amino group in the material surface on the CO 2 capture efficiency. - Abstract: In this study ZSM-12/MCM-48 adsorbents have been synthesized at three ZSM-12 content, and also were functionalizated with amine groups by grafting. All the adsorbents synthesized were evaluated for CO 2 capture. The X-ray diffraction analysis of the ZSM-12/MCM-48 composite showed the main characteristic peaks of ZSM-12 and MCM-48, and after the functionalization, the structure of MCM-48 on the composite impregnated was affected due amine presence. For the composites without amine, the ZSM-12 content was the factor determining in the adsorption capacity of CO 2 and for the composites with amine the amount of amine was that influenced in the adsorption capacity

Synthesis of Nd-doped ZSM-5 and its application to treating slightly polluted water

Directory of Open Access Journals (Sweden)

Mang Lu

2018-03-01

Full Text Available In this study, ZSM-5 zeolite was synthesized using diatomaceous mud as the raw material, and then doped with different amounts of Nd2O3. The orthogonal experiments were performed to investigate the influence of Nd:Si molar ratio, zeolite dosage, contact time, solution pH and temperature on the removal of humic acid (HA. The removal of HA was comprehensively evaluated by chemical oxygen demand (COD, UV254 and UV410 of the solution. The results demonstrate that solution pH and zeolite dosage are the two most important factors influencing HA adsorption. The optimum experimental conditions were determined to be: 35 °C, Nd:Si molar ratio of 1:100, 2.0 g/L zeolite, pH 4 and 50 min contact time. Under these conditions, the removal efficiencies of UV254, UV410 and COD are 82.70%, 76.00% and 82.10%, respectively, corresponding to a comprehensive removal of 81.02%.

Recovery of the heavy elements by NaY AND NaZSM-5 sorbant materials

International Nuclear Information System (INIS)

Nibou, D.; Lebail, S.

1997-04-01

Porous sorbants as zeolites have a several applications in differents fiels: industrial gas purification, catalysis, transformation hydrocarbures prosesses and exchange ions. The hiogh capacity to exchange their cations with those of aqueous solutions was known (1). Since the accession of synthetic zeolites, these silicates have invaded the market and the firstindustrial applications were in exchange field. Studies at Battelle Northwest in Rchland, Washington have shown that zeolites may be used in treatment of radioactive wastes (2). The used method for storing the isotopes is based on selective removal by ion exchange. Clinoptilolite, zeolite (modernite), NaA, and AW-500 have been used. In this context, the present work deals with the recovery of heavy metals like lead and uranium using some microporous materials. The obtained results show that NaY faujasite and NaZSM-5 of the FAU- and MFI-type structure respectively are very effective in removing these elements from waste water

The potential of medium-pore zeolites for improved propene yields from catalytic cracking

Energy Technology Data Exchange (ETDEWEB)

Bager, F.; Salas, N.; Ernst, S. [Technische Univ. Kaiserslautern (Germany). Dept. of Chemistry, Chemical Technology

2011-07-01

The medium-pore zeolites ZSM-5 (MFI), ZSM-22 (TON), ZSM-23 (MTT), and EU-1 (EUO) were synthesized under hydrothermal conditions and modified by ion exchange to obtain the Broensted-acid forms. The activity and selectivity of these catalysts in catalytic cracking of a model compound, viz. n-octane, was studied in a fixed-bed flow-type reactor. The catalytic results clearly reflect the differences in the pore architectures of the tested zeolites on n-octane conversion and on the product selectivities. Over the zeolites with one-dimensional pore systems and without large intracrystalline cavities, a remarkable increase of the contribution of the monomolecular cracking mechanism could be observed as compared to the standard catalyst zeolite ZSM-5. This is indicated by a high selectivity for unsaturated products and, hence, increasing yields of propene. Large cavities in the pore system, viz. in the case of zeolite EU-1, increase the conversion in particular at lower temperatures. However, the large cavities also favor the formation of large transition states required for the classical bimolecular cracking mechanism, resulting in decreased selectivities for unsaturated products, increased selectivities for aromatics formation and faster deactivation. (orig.)

Hollow ZSM-5 encapsulated Pt nanoparticles for selective catalytic reduction of NO by hydrogen

Science.gov (United States)

Hong, Zhe; Wang, Zhong; Chen, Dan; Sun, Qiang; Li, Xuebing

2018-05-01

Pt nanoparticles were successfully encapsulated in hollow ZSM-5 single crystals by tetrapropylammonium hydroxide (TPAOH) hydrothermal treatment with an "dissolution-recrystallization" process. The prepared Pt/hollow ZSM-5 (Pt/h-ZSM-5re) sample exhibited the best activity and a maximum NO conversion of 84% can be achieved at 90 °C with N2 selectivity of 92% (GHSV = 50,000 h-1). Meanwhile, Pt/h-ZSM-5re catalyst exhibited excellent SO2, H2O resistance and durability, which was related to the stabilization of Pt active sites by hollow structure during H2-SCR. It was found that the increase of NO2 concentration in the feed gas mixture led to an activity decline. In addition, the H2-SCR reaction routes over Pt/hollow ZSM-5 catalyst at different temperature were investigated.

Zeolites for nitrosamine and pharmaceutical removal from demineralised and surface water: Mechanisms and efficacy

KAUST Repository

De Ridder, David J.

2012-03-01

Zeolites with a high Si/Al ratio can be used as selective adsorbents in water treatment, targeting organic micropollutants which are removed poorly with activated carbon. Due to size exclusion, many Natural Organic Matter (NOM) components cannot access the pores, thus limiting adsorption competition between organic micropollutant and NOM. Furthermore, zeolite channel diameters are close to molecule diameters, which results in strong van der Waals interaction. MOR200 and ZSM5, the two most hydrophobic zeolites, showed the highest removal of neutral nitrosamines in demineralised water, with higher efficacy than activated carbon. DAY and MOR30, which were relatively hydrophilic zeolites, did not show appreciable removal of any of the nitrosamines. When nitrosamines were adsorbed from surface water, there was no influence of competition with, or pore blockage by, NOM components on nitrosamine removal for ZSM5 zeolite, in contrast to activated carbon. Repulsion of negatively charged pharmaceuticals was significant for ZSM5, which had a Si/Al ratio of 80. MOR200 had a Si/Al ratio of 200, indicating a lower Al content than ZSM5 and, as such, a lower negative surface charge. Charge effects were not observed for MOR200. A relationship was found between the Stokes diameter of the pharmaceuticals and nitrosamines, and their removal by ZSM5 and MOR200, indicating that a "close fit" adsorption mechanism is more likely than hydrophobic interaction in these zeolites. Due to their selective nature, adsorption on zeolites should only be considered as an additional treatment step to existing processes, dedicated for the removal of specific organic micropollutants. Less specific treatment techniques, such as activated carbon filtration, are still required to ensure a broad barrier for organic micropollutants in water treatment. © 2012 Elsevier B.V. All rights reserved.

The Catalytic Conversion of Thiophenes over Large H-ZSM-5 Crystals: An X-Ray, UV/Vis, and Fluorescence Microspectroscopic Study

NARCIS (Netherlands)

Kox, M.H.F.; Mijovilovich, A.E.; S ättler, J.J.H.B.; Stavitski, I.; Weckhuysen, B.M.

2013-01-01

X-ray absorption, UV/Vis, and fluorescence microspectroscopy have been used to characterize the catalytic conversion of thiophene derivatives within the micropores of an individual H-ZSM-5 zeolite crystal. Space-resolved information into the Si/ Al ratios and sulfur content was provided by X-ray

Zeolite ZSM-57

International Nuclear Information System (INIS)

Valyocsik, E.W.; Page, N.M.; Chu, C.T.W.

1989-01-01

This patent describes a synthetic porous crystalline zeolite having a molar ratio of XO 2 ; Y 2 O 3 of at least 4. Wherein X represents silicon and/or germanium and Y represents aluminum, boron, chromium, iron and/or gallium. The porous crystalline zeolite having at least the X-ray diffraction lines as set forth in the text

Structure and critical function of Fe and acid sites in Fe-ZSM-5 in propane oxidative dehydrogenation with N2O and N2O decomposition

Czech Academy of Sciences Publication Activity Database

Sazama, Petr; Sathu, Naveen Kumar; Tabor, Edyta; Wichterlová, Blanka; Sklenák, Štěpán; Sobalík, Zdeněk

2013-01-01

Roč. 299, MAR 2013 (2013), s. 188-203 ISSN 0021-9517 R&D Projects: GA ČR GAP106/11/0624; GA ČR GA203/09/1627 Institutional support: RVO:61388955 Keywords : Fe-ZSM-5 zeolite * Structure of Fe species * Steamed Fe-zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.073, year: 2013

Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

International Nuclear Information System (INIS)

Barnabas, M.V.; Trifunac, A.D.

1994-01-01

Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

Effect of Metal Addition and Silica/Alumina Ratio of Zeolite on the Ethanol-to-Aromatics by Using Metal Supported ZSM-5 Catalyst

International Nuclear Information System (INIS)

Kim, Han-Gyu; Yang, Yoon-Cheol; Jeong, Kwang-Eun; Kim, Tae-Wan; Jeong, Soon-Yong; Kim, Chul-Ung; Jhung, Sung Hwa; Lee, Kwan-Young

2013-01-01

The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/Al 2 ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption (NH3-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/Al 2 ratio of ZSM-5 is about 50-80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of 437 .deg. C and WHSV of 0.8 h −1

Study on antimony oxide self-assembled inside HZSM-5

International Nuclear Information System (INIS)

Li Bin; Li Shijie; Wang Yingxia; Li Neng; Liu Xiyao; Lin Bingxiong

2005-01-01

Sb/ZSM-5 was obtained by solid-state reaction with the mixture of Sb 2 O 3 and zeolite HZSM-5 under a dry nitrogen flow at 773K. Characterization of the treated zeolite was undertaken with XRD, 27 Al MAS NMR, BET, TGA and FT-IR. The results revealed that part of the antimony oxides migrated into the channels of zeolite, and decreased the Bronsted acid sites in Sb/ZSM-5 remarkably. The other part of antimony oxides together with the amorphous alumino-silicate in the products distributed on the external surface of zeolite ZSM-5 and modified it, while the framework of ZSM-5 in crystal phase was retained. The structure of occluded antimony oxide inside the channels of ZSM-5 was studied by XRD Rietveld method. The result showed that their structure can be described as a chain of non-perfect [Sb 5 O 5 (H 2 O) 2 ] n 5n+ , which is parallel to the straight channel of ZSM-5. There is about 0.6 [Sb 5 O 5 (H 2 O) 2 ] 5+ unit in every cell of the ZSM-5 on an average

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

Science.gov (United States)

Narula, Chaitanya K; Yang, Xiaofan

2015-03-24

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Preparação e caracterização de compósitos poliméricos baseados em amido termoplástico e materiais de alta área superficial: zeólita ZSM-5 e sílica coloidal Preparation and characterization of polymeric composites based on thermoplastic starch and high surface area materials: ZSM-5 zeolite and colloidal silica

Directory of Open Access Journals (Sweden)

Fábio Plotegher

2013-01-01

Full Text Available Foram produzidas amostras de amido termoplástico (TPS reforçadas com materiais de alta área superficial, com o intuito de verificar a variação nas propriedades do polímero, com especial enfoque na sua permeabilidade a vapor d'água. Foram utilizadas como carga a sílica coloidal (área superficial de 122,7 m²/g e uma zeólita do tipo ZSM-5, produzida em laboratório (área superficial de 261,3 m²/g, em teores de 2 a 10% em massa. Os resultados demonstraram que a adição de ambos os materiais melhorou as propriedades mecânicas do TPS, embora nos maiores teores houve redução da qualidade das interfaces e dessas propriedades, principalmente para a ZSM-5. Em todos os casos a introdução da carga inorgânica reduziu a permeabilidade ao vapor d'água em até 20% quando comparada à permeabilidade do TPS, porém a melhor dispersão da sílica coloidal na matriz permitiu as maiores reduções, apesar da área superficial inferior.Compositions of thermoplastic starch (TPS reinforced by high surface area materials were produced, intending to study the variation in polymer properties, focusing on the permeability to water vapor. Colloidal silica (surface area 122.7 m²/g and a ZSM-5 zeolite (surface area 261.3 m²/g were used, in loadings from 2 to 10% weight. The results demonstrated that the addition of both materials was favorable to the TPS mechanical properties, however in higher loadings the quality of polymer interfaces and these properties were negatively affected, especially for ZSM-5. In all the cases the inorganic particles reduced the permeability to water vapor in levels below 20% when compared to pure TPS, although the best dispersion of colloidal silica determined better reductions, despite its lower surface area.

CALCULATION OF CATALYTIC REACTIVITY FOR PREPARING DICHLORODIMETHYLSILANE UTILIZING PRE- AND POST-MODIFIED 24T AlCl3/ZSM-5

Directory of Open Access Journals (Sweden)

Wenyuan Xu

Full Text Available Dichlorodimethylsilane is the most important raw material for the preparation of organic silicon materials. Currently, the preparation of dichlorodimethylsilane is mainly based on disproportionation method. This method can turn wastes (by-products into treasures but the mechanism is still indeterminate. In this study, MP2/6-311++G (3df, 2pd basis set was used to study the mechanism of the disproportionation for producing dichlorodimethylsilane. Dichlorodimethylsilane is catalyzed by 24T cluster AlCl3/ZSM-5 catalyst and modified by (AlCl2+, and (BCl2+. The calculation results show that the rate-determining step is the reaction of the catalyst with trimethylchlorosilane . The activation energy of the rate-determining step of main reaction is: 393.83, 427.73, and 527.61 kJ mol-1, respectively. The structure analysis, activation energy analysis and LOL analysis for different catalysts all show that the catalytic effect of unmodified AlCl3/ZSM-5 is better.

Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process.

Science.gov (United States)

Gusev, Andrey A; Psarras, Antonios C; Triantafyllidis, Konstantinos S; Lappas, Angelos A; Diddams, Paul A

2017-10-21

ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC) process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam), FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives) are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated) activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n -Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C 12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F) ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas) olefins as the nature (Brønsted-to-Lewis ratio) of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at higher

Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process

Directory of Open Access Journals (Sweden)

Andrey A. Gusev

2017-10-01

Full Text Available ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam, FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n-Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas olefins as the nature (Brønsted-to-Lewis ratio of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at

Kinetics and thermodynamic for sorption of arsenate by Lanthanum-exchanged zeolite

International Nuclear Information System (INIS)

Mohd Jelas Haron; Saiful Adli Masdan; Mohd Zobir Hussein; Zulkarnain Zainal; Anuar Kassim

2007-01-01

Zeolites are crystalline, hydrated aluminosilicate containing exchangeable alkaline and alkaline earth cations in their structural frameworks. Since zeolites have permanent negative charges on their surfaces, they have no affinity for anions. However recent studies have shown that modification of zeolites with certain surfactants or metal cations yield sorbents with a strong affinity for many anions. In this paper, modification of zeolites (zeolite A, X and ZSM5) were performed by exchange of naturally occurring cations with lanthanum ion that forms low solubility arsenate salt. The exchanged zeolites were used to sorb arsenate from aqueous solution. Among parameters investigated were effect of pH, arsenate initial concentrations, contact time and temperature. The maximum exchanged capacity of La (III) ion was obtained when using solution with initial pH of 4. Zeolite X gives the highest La (III) exchanged capacity compared to other zeolites. The results showed that As (V) sorption by La-zeolites occurred at about pH 6.5 and increased as pH increased and reaching maximum at equilibrium pH about 7.8. On the other hand, almost no arsenate sorption occurred on un exchanged zeolites. This indicates that La (III) ion on the exchanged zeolites is taking part on the As(V) sorption via surface precipitation. The results also showed that the sorption capacities increased with increasing initial As (V) concentrations. The sorption followed Langmuir model with maximum sorption capacities of 0.41, 0.21 and 0.19 mmol/g at 25 degree Celsius for La exchanged zeolite X (La-ZX), La exchanged zeolite ZSM5 (La-ZSM) and La exchanged zeolite A (La-ZA), respectively. The amounts of sorption of As (V) by La exchanged zeolite increased as temperature increased from 25 to 70 degree Celsius indicating that the process is endothermic. The free energy changes ( ΔG degree) for the sorption at 25 degree Celsius were -10.25, -9.65 and -8.49 kJ/ mol for La-ZX, La-ZSM and La-ZA, respectively. The

Catalytic Flash Pyrolysis of Biomass Using Different Types of Zeolite and Online Vapor Fractionation

KAUST Repository

Imran, Ali; Bramer, Eddy; Seshan, Kulathuiyer; Brem, Gerrit

2016-01-01

-staged condensation of the pyrolysis vapor. Zeolite-based catalysts are investigated to study the effect of varying acidities of faujasite Y zeolites, zeolite structures (ZSM5), different catalyst to biomass ratios and different catalytic pyrolysis temperatures. Low

Aromatization of alkanes over Pt promoted conventional and mesoporous gallosilicates of MEL zeolite

KAUST Repository

Akhtar, M. N.; Al-Yassir, N.; Al-Khattaf, S.; Čejka, Jiří

2012-01-01

Aromatization of hexane and propane was investigated over Pt promoted mesoporous gallium-containing HZSM-11 with controlled mesoporosity generated by desilication. Prepared catalysts were characterized by nitrogen adsorption, X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared of chemisorbed pyridine, and NH 3 temperature programmed desorption confirming the development of intracrystalline mesoporosity of Ga-containing HZSM-11. The catalytic activities, which were compared in the aromatization of n-hexane and propane, increased upon desilication. The aromatization of n-hexane decreased in the following order, Pt/mesoporous GaZSM-11 Pt/conventional GaZSM-11 mesoporous GaZSM-11 > conventional GaZSM-11. Hexane conversion reached 70.1% over mesoporous Pt/GaZSM-11 with Si/Ga of 61, as compared with 29.6 and 24.9% for corresponding mesoporous and conventional GaZSM-11 (Si/Ga = 94), respectively, for experiments at liquid hour space velocity of 3.6 h -1, and 540 °C. Comparison of BTX (benzene-toluene-xylene) selectivity at the conversion level of ∼21.0% revealed that Pt/mesoporous GaZSM-11 is more selective than corresponding mesoporous and conventional GaZSM-11. The BTX selectivity over Pt/mesoporous GaZSM-11 (Si/Ga = 94), which showed strong dependence on the conversion, reached 28.2%, whereas over corresponding mesoporous and conventional GaZSM-11catalysts reached 19.1% and 5.5%, respectively. A higher conversion and better selectivity can be attributed to the improved accessibility to the active extra-framework Ga species owing to the generation of mesopores inside the zeolite particles and shortening the contact time. It is worth mentioning that the prepared catalysts exhibited quite low activity in propane aromatization but exhibiting similar trends as for hexane aromatization. © 2011 Elsevier B.V. All rights reserved.

The investigation of order–disorder transition process of ZSM-5 induced by spark plasma sintering

Energy Technology Data Exchange (ETDEWEB)

Wang, Liang [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 2999 North Renmin Road, Songjiang, Shanghai 201620 (China); Wang, Lianjun, E-mail: wanglj@dhu.edu.cn [State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, 2999 North Renmin Road, Songjiang, Shanghai 201620 (China); Jiang, Wan [Engineering Research Center of Advanced Glasses Manufacturing Technology, MOE, Donghua University, 2999 North Renmin Road, Songjiang, Shanghai 201620 (China); Lin, He, E-mail: linhe@sinap.ac.cn [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 239 Zhangheng Road, Pudong, Shanghai 200120 (China)

2014-04-01

Based on the amorphization of zeolites, an order–disorder transition method was used to prepare silica glass via Spark Plasma Sintering (SPS). In order to get a better understanding about the mechanism of amorphization induced by SPS, the intermediate products in this process were prepared and characterized by different characterization techniques. X-ray diffraction and High-energy synchrotron X-ray scattering show a gradual transformation from ordered crystal to glass. Local structural changes in glass network including Si–O bond length, O–Si–O bond angle, size of rings, coordination were detected by Infrared spectroscopy and {sup 29}Si magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy. Topologically ordered, amorphous material with a different intermediate-range structure can be obtained by precise control of intermediate process which can be expected to optimize and design material. - Graphical abstract: Low-density, ordered zeolites collapse to the rigid amorphous glass through spark plasma sintering. The intermediate-range structure formed in the process of order–disorder transition may give rise to specific property. - Highlights: • Order–disorder transition process of ZSM-5 induced by spark plasma sintering was investigated using several methods including XRD, High-energy synchrotron X-ray scattering, SAXS, IR, NMR, ect. • Order–disorder transition induced by SPS was compared with TIA and PIA. • Three stages has been divided during the whole process. • The collapse temperature range which may give rise to intermediate-range structure has been located.

Ethylene formation by dehydration of ethanol over medium pore zeolites

Science.gov (United States)

Gołąbek, Kinga; Tarach, Karolina A.; Filek, Urszula; Góra-Marek, Kinga

2018-03-01

In this work, the role of pore arrangement of 10-ring zeolites ZSM-5, TNU-9 and IM-5 on their catalytic properties in ethanol transformation were investigated. Among all the studied catalysts, the zeolite IM-5, characterized by limited 3-dimensionality, presented the highest conversion of ethanol and the highest yields of diethyl ether (DEE) and ethylene. The least active and selective to ethylene and C3 + products was zeolite TNU-9 with the largest cavities formed on the intersection of 10-ring channels. The catalysts varied, however, in lifetime, and their deactivation followed the order: IM-5 > TNU-9 > ZSM-5. The processes taking place in the microporous zeolite environment were tracked by IR spectroscopy and analysed by the 2D correlation analysis (2D COS) allowing for an insight into the nature of chemisorbed adducts and transition products of the reaction. The cage dimension was found as a decisive factor influencing the tendency for coke deposition, herein identified as polymethylated benzenes, mainly 1,2,4-trimethyl-benzene.

Aluminium distribution in ZSM-5 revisited: The role of Al–Al interactions

International Nuclear Information System (INIS)

Ruiz-Salvador, A. Rabdel; Grau-Crespo, Ricardo; Gray, Aileen E.; Lewis, Dewi W.

2013-01-01

We present a theoretical study of the distribution of Al atoms in zeolite ZSM-5 with Si/Al=47, where we focus on the role of Al–Al interactions rather than on the energetics of Al/Si substitutions at individual sites. Using interatomic potential methods, we evaluate the energies of the full set of symmetrically independent configurations of Al siting in a Si 94 Al 2 O 192 cell. The equilibrium Al distribution is determined by the interplay of two factors: the energetics of the Al/Si substitution at an individual site, which tends to populate particular T sites (e.g., the T14 site), and the Al–Al interaction, which at this Si/Al maximises Al–Al distances in general agreement with Dempsey’s rule. However, it is found that the interaction energy changes approximately as the inverse of the square of the distance between the two Al atoms, rather than the inverse of the distance expected if this were merely charge repulsion. Moreover, we find that the anisotropic nature of the framework density plays an important role in determining the magnitude of the interactions, which are not simply dependent on Al–Al distances. - Graphical abstract: Role of Al–Al interactions in high silica ZSM-5 is shown to be anisotropic in nature and not dependent solely on Coulombic interactions. Highlights: ► Si–Al distribution in ZSM-5 is revisited, stressing the role of the Al–Al interaction. ► Coulomb interactions are not the key factors controlling the Al siting. ► Anisotropy of the framework is identified as a source of departure from Dempsey’s rule.

Conversion of methanol to hydrocarbons over conventional and mesoporous H-ZSM-5 and H-Ga-MFI: Major differences in deactivation behavior

DEFF Research Database (Denmark)

Mentzel, Uffe Vie; Højholt, Karen Thrane; Holm, Martin Spangsberg

2012-01-01

. In the methanol-to-hydrocarbons (MTH) process, H-ZSM-5 is subjected to coke formation leading to catalyst deactivation. Here we show that when the gallium containing zeotypes are employed in the MTH process, only insignificant amounts of coke are present in the deactivated catalysts, indicating distinct...... (hydrolysis) of the Ga&sbnd;O bonds in the zeolite structure rather than coke deposition....

Adsorption of nicotine on different zeolite types, from aqueous solutions

Directory of Open Access Journals (Sweden)

Stošić Dušan K.

2007-01-01

Full Text Available The plant alkaloid, nicotine, is a strongly toxic heterocyclic compound: the lethal dose for an adult human being (40-60 mg is importantly lower in comparison with the other known poisons such as arsenic or strychni­ne. Cigarettes represent "the most toxic and addictive form of nicotine". Besides the negative effects of nicotine on public health produced by self-administration, recently another potentially very dangerous effect has been recognized: because of its miscibility with water, nicotine can be found in industrial wastewaters, and consequently, in groundwater. Therefore, the problem of nicotine removal from aqueous solutions has became an interesting topic. In this work, the removal of nicotine has been probed by adsorption on solid materials. Adsorption of nicotine on different zeolites (clinoptilolite, ZSM-5 and β zeolite and on activated carbon was investigated from aqueous solutions, at 298 K. The obtained results are presented as adsorption isotherms: the amount of adsorbed nicotine as a function of equilibrium concentration. These data were obtained from the residual amount of nicotine in the aqueous phase, by the use of UV spectroscopy. The highest amounts of adsorbed nicotine was found for activated carbon and p zeolite (~ mmol·g-1. The attempt to modify the adsorption properties of ZSM-5 zeolite has been also done: ZSM-5 was modified by ion-exchange with VIII group metal (Cu2+ and Fe3+. In addition, the adsorption of nicotine on ZSM-5 zeolite with different Si/Al ratios has been done. It has been noticed that ion-exchange did not improve the adsorption possibilities, while the adsorption was importantly lower in the case of higher silicon content in ZMS-5 structure. 13C NMR spectra were collected for suspensions formed of solid adsorbent and aqueous solution of nicotine; in this way, the part of nicotine molecule which is most probably connected with the adsorbent was recognized.

Study of (Fe/HZM-5) catalyst be used in the Fischer-Tropsch synthesis: preparation and characterization; Estudo do catalisador (Fe/HZSM-5) a ser utilizado na sintese de Fischer-Tropsch: preparacao e caracterizacao

Energy Technology Data Exchange (ETDEWEB)

Gonzaga, Arthur C. [Universidade Estadual do Maranhao (UEMA0), MA (Brazil); Sousa, Bianca V. de; Lima, Wellington S.; Rodrigues, Meiry G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica

2008-07-01

In this work it was developed an iron catalyst supported on the ZSM-5 zeolite to be used in the Fischer-Tropsch Synthesis (FTS). The NH{sub 4}{sup +}ZSM-5 zeolitic support was submitted to the wet impregnation, using the 0.1 M of the Fe(NO{sub 3}){sub 3}.9H{sub 2}O solution to obtain the Fe/NH{sub 4}{sup +}ZSM-5 sample in the content of iron 5% wt. After, the material was submitted for the drying process and in the following, for the calcination one, obtaining the Fe/HZSM-5 form. The EDS characterization analyses showed that in the Fe/HZSM-5 sample the iron is in the Fe{sub 2}O{sub 3} form and that the impregnation and calcination processes did not cause significant exchanges in the zeolitic support framework. The results of the N{sub 2} physical adsorption of the 5% Fe/HZSM-5 showed the presence of the micropores and mesopores. From these results, the obtained material (5% Fe/HZSM-5) presents a great potential to be used like a catalyst in the FTS. (author)

Studies of N{sub 2}0 adsorption and decomposition on Fe-ZSM-5

Energy Technology Data Exchange (ETDEWEB)

Wood, Benjamin R.; Reimer, Jeffrey A.; Bell, Alexis T.

2002-03-08

The interactions of N2O with H-ZSM-5 and Fe-ZSM-5 have been investigated using infrared spectroscopy and temperature-programmed reaction. Fe-ZSM-5 samples with Fe/Al ratios of 0.17 and 0.33 were prepared by solid-state exchange. It was determined that most of the iron in the samples of Fe-ZSM-5 is in the form of isolated cations, which have exchanged with Bronsted acid H+ in H-ZSM-5. The infrared spectrum of N2O adsorbed on H-ZSM-5 at 298 K exhibits bands at 2226 and 1308 cm-1 associated with vibrations of the N-N and N-O bonds, respectively. The positions of these bands relative to those seen in the gas phase suggest that N2O adsorbs through the nitrogen end of the molecule. The heat of N2O adsorption in H-ZSM-5 is estimated to be 5 kcal/mol. In the case of Fe-ZSM-5, additional infrared bands are observed at 2282 and 1344 cm-1 due to the interactions of N2O with the iron cations. Here too, the directions of the shifts in the vibrational features relative to those for gas-phase N2O suggest that the molecule adsorbs through its nitrogen end. The heat of adsorption of N2O on the Fe sites is estimated to be 16 kcal/mol. The extent of N2O adsorption on Fe depends on the oxidation state of Fe. The degree of N2O adsorption is higher following pretreatment of the sample in He or CO at 773 K, than following pretreatment in O2 or N2O at the same temperature. Temperature-programmed decomposition of N2O was performed on the Fe-ZSM-5 samples and revealed that N2O decomposes stoichiometrically to N2 and O2. A higher activity was observed if the catalysts were pretreated in He than if they were pretreated in N2O. For the He-pretreated samples, the activation energy for N2O decomposition was estimated to be 42 kcal/mol and the preexponential factor of the rate coefficient for this process was found to increase with Fe/Al ratio. This trend was attributed to the increasing auto reducibility of Fe3+ cations to Fe2+ cations with increasing Fe/Al ratio.

Characterization of zeolites by magic-angle-spinning NMR

International Nuclear Information System (INIS)

Brunner, E.; Ernst, H.; Freude, D.; Hunger, M.; Pfeifer, H.

1988-01-01

Magic-angle-spinning nuclear magnetic resonance (MAS NMR) has been used to study structure defects in TPA/ZSM-5, the dealumination process caused by hydrothermal treatment and acid leaching of zeolites, the influence of Lewis sites upon water as a probe molecule, the boron incorporation into the ZSM-5 framework, and the acid sites and structure defects in SAPO-5. The nuclei under study are 1 H, 11 B, 27 Al, 29 Si, and 31 P. 24 refs.; 7 figs.; 1 table

The effect of the pore structure of medium-pore zeolites on the dehydroisomerization of n-butane: A comparison of Pt-FER, Pt-TON and Pt-ZSM5

NARCIS (Netherlands)

Pirngruber, G.D.; Zinck, O.P.E.; Seshan, Kulathuiyer; Lercher, J.A.

2000-01-01

The catalytic dehydroisomerization of n-butane over Pt–ZSM5, Pt–TON, and Pt–FER was investigated. Pt–ZSM5 showed the highest yield and selectivity to isobutene. Most of the by-products of Pt–ZSM5 were formed by oligomerization/cracking of butene, while acid-catalyzed cracking and metal-catalyzed

Cu-ZSM-5 zeolite highly active in reduction of NO with decane - Effect of zeolite structural parameters on the catalyst performance

Czech Academy of Sciences Publication Activity Database

Čapek, Libor; Dědeček, Jiří; Wichterlová, Blanka; Cider, L.; Jobson, E.; Tokarová, V.

2005-01-01

Roč. 60, 3-4 (2005), s. 147-153 ISSN 0926-3373 R&D Projects: GA ČR GD203/03/H140; GA AV ČR 1ET400400413 Grant - others:European Union(XE) GR5D-CT2001-00595 Institutional research plan: CEZ:AV0Z40400503 Keywords : Cu-ZSM-5 * NO reduction * SCR-NOx * lean burn conditions * decane Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.809, year: 2005

Towards a methanol economy: Zeolite catalyzed production of synthetic fuels

DEFF Research Database (Denmark)

Mentzel, Uffe Vie

The main focus of this thesis is zeolite catalyzed conversion of oxygenates to hydrocarbon fuels and chemicals. Furthermore, conversion of ethane to higher hydrocarbons has also been studied. After a brief introduction to the concept of “the methanol economy” in the first chapter, the second...... a commercial H-ZSM-5 zeolite impregnated with gallium and/or molybdenum is described. The object was to investigate if the presence of methanol in the feed could enhance the conversion of ethane, but in all cases the opposite is observed; the presence of methanol actually suppresses the conversion of ethane...... various zeolite catalysts is studied in Chapter 4. When 2-propanol or 1-butanol is converted over H-ZSM-5, the total conversion capacities of the catalyst are more than 25 times higher than for conversion of methanol and ethanol. Furthermore, for conversion of C3+ alcohols, the selectivity shifts during...

Influence of oxalate ligand functionalization on Co/ZSM-5 activity in Fischer Tropsch synthesis and hydrodeoxygenation of oleic acid into hydrocarbon fuels.

Science.gov (United States)

Ayodele, Olumide Bolarinwa

2017-08-30

Achieving high degree of active metal dispersions at the highest possible metal loading and high reducibility of the metal remains a challenge in Fischer Tropsch synthesis (FTS) as well as in hydrogeoxygenation (HDO).This study therefore reports the influence of oxalic acid (OxA) functionalization on the metal dispersion, reducibility and activity of Co supported ZSM-5 catalyst in FTS and HDO of oleic acid into paraffin biofuel. The Brunauer-Emmett-Teller (BET) results showed that cobalt oxalate supported ZSM-5 catalyst (CoOx/ZSM-5) synthesized from the incorporation of freshly prepared cobalt oxalate complex into ZSM-5 displayed increase in surface area, pore volume and average pore size while the nonfunctionalized cobalt supported on ZSM-5 (Co/ZSM-5) catalyst showed reduction in those properties. Furthermore, both XRD and XPS confirmed the presence of Co° formed from the decomposition of CoOx during calcination of CoOx/ZSM-5 under inert atmosphere. The HRTEM showed that Co species average particle sizes were smaller in CoOx/ZSM-5 than in Co/ZSM-5, and in addition, CoOx/ZSM-5 shows a clear higher degree of active metal dispersion. The FTS result showed that at CO conversion over Co/ZSM-5 and CoOx/ZSM-5 catalysts were 74.28% and 94.23% and their selectivity to C 5+ HC production were 63.15% and 75.4%, respectively at 4 h TOS. The HDO result also showed that the CoOx/ZSM-5 has higher OA conversion of 92% compared to 59% over Co/ZSM-5. In addition CoOx/ZSM-5 showed higher HDO and isomerization activities compared to Co/ZSM-5.

Adsorption of Water and Ethanol in MFI-Type Zeolites

KAUST Repository

Zhang, Ke

2012-06-12

Water and ethanol vapor adsorption phenomena are investigated systematically on a series of MFI-type zeolites: silicalite-1 samples synthesized via both alkaline (OH -) and fluoride (F -) routes, and ZSM-5 samples with different Si/Al ratios as well as different charge-balancing cations. Full isotherms (0.05-0.95 activity) over the range 25-55 °C are presented, and the lowest total water uptake ever reported in the literature is shown for silicalite-1 made via a fluoride-mediated route wherein internal silanol defects are significantly reduced. At a water activity level of 0.95 (35 °C), the total water uptake by silicalite-1 (F -) was found to be 0.263 mmol/g, which was only 12.6%, 9.8%, and 3.3% of the capacity for silicalite-1 (OH -), H-ZSM-5 (Si/Al:140), and H-ZSM-5 (Si/Al:15), respectively, under the same conditions. While water adsorption shows distinct isotherms for different MFI-type zeolites due to the difference in the concentration, distribution, and types of hydrophilic sites, the ethanol adsorption isotherms present relatively comparable results because of the overall organophilic nature of the zeolite framework. Due to the dramatic differences in the sorption behavior with the different sorbate-sorbent pairs, different models are applied to correlate and analyze the sorption isotherms. An adsorption potential theory was used to fit the water adsorption isotherms on all MFI-type zeolite adsorbents studied. The Langmuir model and Sircar\\'s model are applied to describe ethanol adsorption on silicalite-1 and ZSM-5 samples, respectively. An ideal ethanol/water adsorption selectivity (α) was estimated for the fluoride-mediated silicalite-1. At 35 °C, α was estimated to be 36 for a 5 mol % ethanol solution in water increasing to 53 at an ethanol concentration of 1 mol %. The adsorption data demonstrate that silicalite-1 made via the fluoride-mediated route is a promising candidate for ethanol extraction from dilute ethanol-water solutions. © 2012

An operando optical fiber UV–vis spectroscopic study of the catalytic decomposition of NO and N2O over Cu-ZSM-5

NARCIS (Netherlands)

Weckhuysen, B.M.; Groothaert, M.H.; Lievens, K.; Leeman, H.; Schoonheydt, R.A.

2003-01-01

The role of the bis(μ-oxo)dicopper core, i.e., [Cu2(μ-O)2]2+, in the decomposition of NO and N2O by the Cu-ZSM-5 zeolite has been studied with combined operando UV–vis monitoring of the catalyst and on-line GC analysis. An optical fiber was mounted on the outer surface of the quartz wall of the

Hydrogen output from radiolytic split of water in the presence of some zeolites

International Nuclear Information System (INIS)

Cecal, A.; Colisnic, D.; Popa, K.; Paraschivescu, A.; Bilba, N.

2002-01-01

Radiolytic decomposition of water under the action of gamma rays in the presence of some zeolites such as ZSM-5, SAPO-5 and MOR was studied. The irradiation was performed using a gamma 60 Co source at an activity of 3 . 10 4 Ci and dose rate 8.3 KGy/h. The stable products of radiolysis as well as the other chemical species were identified by mass spectrometry. The calculated radiochemical yield decreased in order: H-ZSM-5 > Na-ZSM-5 > H-SAPO-5 > MOR and was higher in the presence of these catalysts than in their absence

Effect of varied quantities of zeolite on the reduction of polycyclic ...

African Journals Online (AJOL)

This research was carried out to determine the possibility of total and selective reduction of polycyclic aromatic hydrocarbons (PAHs) content in cigarette smoke by applying different amounts of zeolite directly to the cigarette blend. Zeolite catalysts CuZSM-5 were applied in the form of suspension to the cut tobacco blend in ...

Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NOx with methane

International Nuclear Information System (INIS)

Pieterse, J.A.Z.; Van den Brink, R.W.; Booneveld, S.; De Bruijn, F.A.

2003-01-01

Selective catalytic reduction of NO with CH 4 was studied over ZSM-5, MOR, FER and BEA zeolite-based cobalt (Co) and palladium (Pd) catalysts in the presence of oxygen and water. As compared to other catalytic systems reported in literature for CH 4 -SCR in the presence of water, zeolite supported Co-Pd combination catalysts are very active and selective. The most active catalysts, based on MOR and ZSM-5, are characterised by well-dispersed Pd ions in the zeolite that activate methane. Wet ion exchange is a good method to achieve high dispersion of Pd provided that it is carried out in a competitive manner. The presence of cobalt (Co 3 O 4 , Co-oxo ions) boosts SCR activity by oxidising NO to NO 2 . The activity of the zeolite-based Co-Pd combination catalysts decreases with prolonged times on stream. The severity of the deactivation was found to be different for different zeolite topologies. The characterisation and evaluation of freshly calcined catalysts and spent catalysts show two things that occur during reaction: (1) zeolite solvated metal cations disappear in favour of (inactive) metal oxides and presumably larger metal entities, i.e. loss of dispersion; (2) loss of crystallinity affiliated with steam-dealumination and the concomitant formation of extra-framework aluminium (EFAL) in the presence of water. Both phenomena strongly depend on the (reaction) temperature. The deactivation of Co-Pd-zeolite resembles the deactivation of Pd-zeolite. Hence, future research could encompass the stabilisation of Pd (cations) in the zeolite pores by exploring additives other than cobalt. For this, detailed understanding on the siting of Pd in zeolites is important

Redox properties of phenosafranine at zeolite-modified electrodes-Effect of surface modification and solution pH

International Nuclear Information System (INIS)

Easwaramoorthi, S.; Natarajan, P.

2008-01-01

Redox properties of cationic dye phenosafranine (3,7-diamino-5-phenylphenazenium chloride) (PS + ) were studied at zeolite-modified electrodes using Zeolite-Y and NaZSM-5. The peak current and peak potential of phenosafranine-adsorbed zeolite were found to be influenced by the pH of the electrolyte solution. Observation of a second redox couple is suggested to be due to formation of new species at low concentration from the reduced phenosafranine at the zeolite-modified electrodes. Titanium dioxide nanoparticles encapsulated in the cavities of the zeolite or anchored on the external surface of the zeolite do not seem to affect the redox properties of adsorbed PS + . When the cyclic voltammograms are recorded immediately after the electrode is immersed into the solution, the redox potential of PS + is found to be sensitive to the nature of the zeolite surface. The peak potential shifts towards positive region under continuous cycles as the surface hydroxyl groups get protonated in acidic electrolyte solution thereby forcing the movement of dye molecules from the zeolite surface to the zeolite electrode solution interface. The electron transfer rate constants for the adsorbed dye at the electrode are calculated to be 2.5 ± 0.2 s -1 and 3.5 ± 0.2 s -1 for the zeolite-Y electrode and the ZSM-5 electrode, respectively by the Laviron equation

Elastic behavior of MFI-type zeolites: 3 - Compressibility of silicalite and mutinaite

Energy Technology Data Exchange (ETDEWEB)

Quartieri, Simona, E-mail: squartieri@unime.it [Dipartimento di Scienze della Terra, Universita di Messina, Viale Ferdinando Stagno d' Alcontres 31, 98166 Messina S. Agata (Italy); Arletti, Rossella [Dipartimento di Scienze Mineralogiche e Petrologiche, Via Valperga Caluso 35, 10125 Torino (Italy); Vezzalini, Giovanna [Dipartimento di Scienze della Terra, Universita di Modena e Reggio Emilia, Via S. Eufemia 19, 41100 Modena (Italy); Di Renzo, Francesco [Institut Charles Gerhardt de Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, 8 rue Ecole Normale, 34296 Montpellier (France); Dmitriev, Vladimir [Swiss-Norwegian Beam Line at ESRF, BP220, 38043 Grenoble Cedex (France)

2012-07-15

We report the results of an in-situ synchrotron X-ray powder diffraction study - performed using silicone oil as 'non-penetrating' pressure transmitting medium - of the elastic behavior of three zeolites with MFI-type framework: the natural zeolite mutinaite and two silicalites (labeled A and B) synthesized under different conditions. While in mutinaite no symmetry change is observed as a function of pressure, a phase transition from monoclinic (P2{sub 1}/n) to orthorhombic (Pnma) symmetry occurs at about 1.0 GPa in the silicalite samples. This phase transition is irreversible upon decompression. The second order bulk moduli of silicalite A and silicalite B, calculated after the fulfillment of the phase transition, are: K{sub 0}=18.2(2) and K{sub 0}=14.3 (2) GPa, respectively. These values makes silicalite the most compressible zeolite among those up to now studied in silicone oil. The structural deformations induced by HP in silicalite A were investigated by means of complete Rietveld structural refinements, before and after the phase transition, at P{sub amb} and 0.9 GPa, respectively. The elastic behaviors of the three MFI-type zeolites here investigated were compared with those of Na-ZSM-5 and H-ZSM-5, studied in similar experimental conditions: the two silicalites - which are the phases with the highest Si/Al ratios and hence the lowest extraframework contents - show the highest compressibility. On the contrary, the most rigid material is mutinaite, which has a very complex extraframework composition characterized by a high number of cations and water molecules. - Graphical abstract: High-pressure behavior of silicalite compressed in silicone oil: projection of the structure along the [0 1 0] direction at Pamb(a), 0.9 GPa (b). (c) Comparison of the unit-cell volume variations as a function of pressure for mutinaite, H-ZSM5, Na-ZSM5, silicalite A, and silicalite B compressed in silicone oil. Highlights: Black-Right-Pointing-Pointer X-ray powder

Design and fabrication of zeolite macro- and micromembranes

Science.gov (United States)

Chau, Lik Hang Joseph

2001-07-01

The chemical nature of the support surface influences zeolite nucleation, crystal growth and elm adhesion. It had been demonstrated that chemical modification of support surface can significantly alter the zeolite film and has a good potential for large-scale applications for zeolite membrane production. The incorporation of titanium and vanadium metal ions into the structural framework of MFI zeolite imparts the material with catalytic properties. The effects of silica and metal (i.e., Ti and V) content, template concentration and temperature on the zeolite membrane growth and morphology were investigated. Single-gas permeation experiments were conducted for noble gases (He and Ar), inorganic gases (H2, N2, SF6) and hydrocarbons (methane, n-C4, i-C4) to determine the separation performance of these membranes. Using a new fabrication method based on microelectronic fabrication and zeolite thin film technologies, complex microchannel geometry and network (supported zeolite films. The zeolite micropatterns were stable even after repeated thermal cycling between 303 K and 873 K for prolonged periods of time. This work also demonstrates that zeolites (i.e., Sil-1, ZSM-5 and TS-1) can be employed as catalyst, membrane or structural materials in miniature chemical devices. Traditional semiconductor fabrication technology was employed in micromachining the device architecture. Four strategies for the manufacture of zeolite catalytic microreactors were discussed: zeolite powder coating, uniform zeolite film growth, localized zeolite growth, and etching of zeolite-silicon composite film growth inhibitors. Silicalite-1 was also prepared as free-standing membrane for zeolite membrane microseparators.

Crystal dimension of ZSM-5 influences on para selective disproportionation of ethylbenzene.

Science.gov (United States)

Hariharan, Srinivasan; Palanichamy, Muthaiahpillai

2014-03-01

Crystal size and crystal dimensions are vital role in shape selective feature. Para selective disproportionation of EthylBenzene (Dip-EB) was investigated over ZSM-5 synthesized in acidic medium. The catalysts were prepared by hydrothermal process with various Si/Al ratios (50, 75 and 100) using fluoride ion precursor. This fluoride ion precursor dissolves the ZSM-5 nutrients below it neutral pH between 4 and 6. The synthesized material was subjected into various physico chemical characterizations such as XRD, SEM, TGA and BET analyses. The XRD patterns showed high crystalline nature and their resulting SEM images were also indicate thin prismatic crystals of large dimension compared with alkaline medium synthesized one. The BET results earned good textural property. Catalytic activity of vapor phase Dip-EB was carried out between 523 and 673 K. As their result, diethylbenzene (DEB) isomers were obtained, but para selective Diethylbenzene (p-DEB) was observed higher than others. The high selectivity towards p-DEB was due to large crystal dimension of ZSM-5 catalysts synthesized in fluoride medium. Hence it is good commercial application for petrochemical feed stock production.

Theoretical evidence of the observed kinetic order dependence on temperature during the N(2)O decomposition over Fe-ZSM-5.

Science.gov (United States)

Guesmi, Hazar; Berthomieu, Dorothee; Bromley, Bryan; Coq, Bernard; Kiwi-Minsker, Lioubov

2010-03-28

The characterization of Fe/ZSM5 zeolite materials, the nature of Fe-sites active in N(2)O direct decomposition, as well as the rate limiting step are still a matter of debate. The mechanism of N(2)O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [Fe(II)(mu-O)(mu-OH)Fe(II)](+) inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches. The overall calculated path of N(2)O decomposition involves the oxidation of binuclear Fe(II) core sites by N(2)O (atomic alpha-oxygen formation) and the recombination of two surface alpha-oxygen atoms leading to the formation of molecular oxygen. Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N(2)O decomposition are strongly dependent on the temperature. This theoretical result was compared to the experimentally observed steady state kinetics of the N(2)O decomposition and temperature-programmed desorption (TPD) experiments. A switch of the reaction order with respect to N(2)O pressure from zero to one occurs at around 800 K suggesting a change of the rate determining step from the alpha-oxygen recombination to alpha-oxygen formation. The TPD results on the molecular oxygen desorption confirmed the mechanism proposed.

Temperature-Induced Desorption of Methyl tert-Butyl Ether Confined on ZSM-5: An In Situ Synchrotron XRD Powder Diffraction Study

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Elisa Rodeghero

2017-02-01

Full Text Available The temperature-induced desorption of methyl tert-butyl ether (MTBE from aqueous solutions onto hydrophobic ZSM-5 was studied by in situ synchrotron powder diffraction and chromatographic techniques. This kind of information is crucial for designing and optimizing the regeneration treatment of such zeolite. The evolution of the structural features monitored by full profile Rietveld refinements revealed that a monoclinic (P21/n to orthorhombic (Pnma phase transition occurred at about 100 °C. The MTBE desorption process caused a remarkable change in the unit-cell parameters. Complete MTBE desorption was achieved upon heating at about 250 °C. Rietveld analysis demonstrated that the desorption process occurred without any significant zeolite crystallinity loss, but with slight deformations in the channel apertures.

Adsorption of Water and Ethanol in MFI-Type Zeolites

KAUST Repository

Zhang, Ke; Lively, Ryan P.; Noel, James D.; Dose, Michelle E.; McCool, Benjamin A.; Chance, Ronald R.; Koros, William J.

2012-01-01

Water and ethanol vapor adsorption phenomena are investigated systematically on a series of MFI-type zeolites: silicalite-1 samples synthesized via both alkaline (OH -) and fluoride (F -) routes, and ZSM-5 samples with different Si/Al ratios as well

A solvent evaporation route towards fabrication of hierarchically porous ZSM-11 with highly accessible mesopores

DEFF Research Database (Denmark)

Song, Wen; Liu, Zhiting; Liu, Liping

2015-01-01

A route to generate hierarchically porous zeolite ZSM-11 has been paved via solvent evaporation induced self-assembly assisted by hexadecyltrimethoxysilane to produce a preformed dry gel, followed by its subsequent transformation into zeolite via steam-assisted-crystallization. The crystallization...

Elastic behavior of MFI-type zeolites: 3 – Compressibility of silicalite and mutinaite

International Nuclear Information System (INIS)

Quartieri, Simona; Arletti, Rossella; Vezzalini, Giovanna; Di Renzo, Francesco; Dmitriev, Vladimir

2012-01-01

We report the results of an in-situ synchrotron X-ray powder diffraction study – performed using silicone oil as “non-penetrating” pressure transmitting medium – of the elastic behavior of three zeolites with MFI-type framework: the natural zeolite mutinaite and two silicalites (labeled A and B) synthesized under different conditions. While in mutinaite no symmetry change is observed as a function of pressure, a phase transition from monoclinic (P2 1 /n) to orthorhombic (Pnma) symmetry occurs at about 1.0 GPa in the silicalite samples. This phase transition is irreversible upon decompression. The second order bulk moduli of silicalite A and silicalite B, calculated after the fulfillment of the phase transition, are: K 0 =18.2(2) and K 0 =14.3 (2) GPa, respectively. These values makes silicalite the most compressible zeolite among those up to now studied in silicone oil. The structural deformations induced by HP in silicalite A were investigated by means of complete Rietveld structural refinements, before and after the phase transition, at P amb and 0.9 GPa, respectively. The elastic behaviors of the three MFI-type zeolites here investigated were compared with those of Na-ZSM-5 and H-ZSM-5, studied in similar experimental conditions: the two silicalites – which are the phases with the highest Si/Al ratios and hence the lowest extraframework contents – show the highest compressibility. On the contrary, the most rigid material is mutinaite, which has a very complex extraframework composition characterized by a high number of cations and water molecules. - Graphical abstract: High-pressure behavior of silicalite compressed in silicone oil: projection of the structure along the [0 1 0] direction at Pamb(a), 0.9 GPa (b). (c) Comparison of the unit-cell volume variations as a function of pressure for mutinaite, H-ZSM5, Na-ZSM5, silicalite A, and silicalite B compressed in silicone oil. Highlights: ► X-ray powder diffraction study of silicalite and mutinaite

Effect of ZSM-5 on the production of reformulated gasoline. Comparison between FCC pilot plant and commercial results

International Nuclear Information System (INIS)

Lappas, A.A.; Iatridis, D.; Vasalos, I.A.; Phyxogios, G.

1999-01-01

One of the more interesting ways for production of light olefins and for minimization of Gasoline olefins is the use of catalytic additives in the FCC (fluid catalytic cracking) inventory. The most widely used additive for the FCC process is the ZSM-5 which is a shape selective zeolite. When this additive is added to FCC units, it boosts the yields of LPG's olefins at the expense of gasoline, while increasing gasoline RON. The addition of ZSM-5 offers a great flexibility to a refinery since, in a relatively simple and cheap way, it can increase the RON and produces higher yields of light olefins. For all the above reasons the last years more studies are carried out in order to investigate the effect of this additive. In study presented in this paper, main emphasis was given, for the investigation of the effect of ZSM- 5 addition on FCC product distribution and especially on gasoline olefins. Moreover, in the previous literature works the ZSM-5 influences were examined using mainly fixed bed reactors. In the present study the investigation was carried out in a FCC pilot plant. The additive was also added in a commercial FCC unit of a Greek refinery (Hellenic Aspropyrgos Refinery - HAR) and thus comparison results of commercial and pilot plant test are also presented. The above study is part of a research collaboration which exists the last 10 years between the laboratory of Environmental Fuels and hydrocarbons of Chemical Process Engineering Research Institute (LEFH/CPERI) and the main Greek refineries (HEL.PETROLEUM, Motor Oil Hellas Refinery). The target of this research collaboration is i) the development of technology for the production of reformulated fuels and hydrocarbons and ii) to assist the Greek refineries to face the new regulations for environmental friendly fuels

Radioactive (14C) tracer studies of methanol conversion over a Ni-ZSM-5 zeolite

International Nuclear Information System (INIS)

Hwu, F.S.; Hightower, J.W.

1983-01-01

Secondary reactions have been identified in the overall conversion of methanol to hydrocarbons over a Ni-ZSM-5 catalyst. The major conclusions are: (1) The alkylation of light olefins with methanol or methyl ether is one pathway for the formation of larger olefins with one more carbon atom. (2) Paraffins are produced primarily by hydrogen transfer to the corresponding olefin. (3) Except for minor cracking reactions, paraffins with no more than 7 carbon atoms, are final stable products; isomerization among paraffin isomers does not take place at 368 0 C. (4) Light olefins, e.g. ethylene, propylene, and butenes, are reactive intermediates for aromatics formation. (5) Aromatic compounds may also be produced by methanol- methyl ether-alkylation of benzene and subsequent alkylated benezenes. 2 figures, 3 tables

Preparation and Characterization of Zeolite Membrane for Bioethanol Purification

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Aprilina Purbasari

2013-06-01

Full Text Available The use of bioethanol as an alternative fuel with a purity of more than 99.5% wt has prompted research on bioethanol purification. One of the promising methods used for bioethanol purification is pervaporation membrane. This research is aimed to prepare and characterize zeolite membranes for pervaporation membrane. The membrane preparation consisted of two stages, namely support preparation and zeolite deposition on the support. In support preparation, α- alumina and kaolin with specific composition (50:30; 40:40; 50:30 was mixed with additives and water. After pugging and aging process, the mixture became paste and extruded into tubular shape. The tube was then calcined at temperature of 1250 °C for 3 hours. After that, zeolite 4A was deposited on the tubes using clear solution made of 10 %wt zeolite and 90 %wt water and heated at temperature of 80 °C for 3 hours. Furthermore, the resulting zeolite membranes was washed with deionized water for 5 minutes and dried in oven at temperature of 100 °C for 24 hours. Characterization of zeolite membranes included mechanical strength test, XRD, and SEM. In the mechanical strength test, the membrane sample with α- alumina:kaolin = 50:30 (membrane A has the highest mechanical strength of 46.65 N/mm2. Result of XRD analysis for the membrane A indicated that mullite and corundum phases were formed, which mullite phase was more dominant. Meanwhile the result of SEM analysis shows that zeolite crystals have been formed and covered the pores support, but the deposition of zeolite has not been optimal yet. The performance examination for bioethanol purification showed that the membrane could increase the purity of bioethanol from 95% to 98.5% wt. © 2013 BCREC UNDIP. All rights reservedReceived: 23rd October 2012; Revised: 15th February 2013; Accepted: 16th February 2013[How to Cite: Purbasari, A., Istirokhatun, T., Devi, A.M., Mahsunnah, L. , Susanto, H. (2013. Preparation and Characterization of Zeolite

Catalytic transformation of methyl benzenes over zeolite catalysts

KAUST Repository

Al-Khattaf, S.; Akhtar, M. N.; Odedairo, T.; Aitani, A.; Tukur, N. M.; Kubů, M.; Musilová -Pavlačková , Z.; Čejka, J.

2011-01-01

experiments were carried out in the temperature range of 300-400 °C to understand the transformation of these alkyl benzenes over large pore (mordenite and SSZ-33) in contrast to medium-pore (ZSM-5 and TNU-9) zeolite-based catalysts. The effect of reaction

Hydrogen production by steam reforming of bio-oil aqueous fraction over Co-Fe/ZSM-5

Science.gov (United States)

Chen, Mingqiang; Wang, Yishuang; Liang, Tian; Yang, Zhonglian

2018-02-01

A series of Co-Fe/ZSM-5 catalysts were prepared by impregnation method and their catalytic performance under steam reforming bio-oil aqueous fraction (SRBAF). The as-prepared catalysts were characterized by XRD, BET, and SEM. The characterization results revealed the Co-Fe alloy phase was formed in Co0.5Fe0.5/ZSM-5 catalyst, and this catalyst exhibited unique pore volume (0.28 cm3/g) and pore size (8.4 nm). The results of experiment demonstrated the addition of Fe species could significantly increase C conversion and H2 yield, and the formation of Co-Fe alloy effectively inhibited methanation reaction and improved water-gas shift (WGS) reaction. The highest H2 yield (81%) and C conversion (85%) was obtained at the following reaction conditions: 2.5 g of C0.5F0.5/Z catalyst, T = 700 °C, S/C = 10-14,.feed flow rate was 10.0 gbio-oil/h, N2 flow rate was 0.16 L/min.

The nature of cationic adsorption sites in alkaline zeolites-single, dual and multiple cation sites

Czech Academy of Sciences Publication Activity Database

Nachtigall, P.; Delgado, M. R.; Nachtigallová, Dana; Arean, C. O.

2012-01-01

Roč. 14, č. 5 (2012), s. 1552-1569 ISSN 1463-9076 R&D Projects: GA ČR GA203/09/0143 Institutional research plan: CEZ:AV0Z40550506 Keywords : exchanged ZSM-5 zeolites * carbon-monoxide adsorption * low-temperature CO * solid-state NMR * high-silica zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.829, year: 2012

Beyond Creation of Mesoporosity: The Advantages of Polymer-Based Dual-Function Templates for Fabricating Hierarchical Zeolites

KAUST Repository

Tian, Qiwei

2016-02-05

Direct synthesis of hierarchical zeolites currently relies on the use of surfactant-based templates to produce mesoporosity by the random stacking of 2D zeolite sheets or the agglomeration of tiny zeolite grains. The benefits of using nonsurfactant polymers as dual-function templates in the fabrication of hierarchical zeolites are demonstrated. First, the minimal intermolecular interactions of nonsurfactant polymers impose little interference on the crystallization of zeolites, favoring the formation of 3D continuous zeolite frameworks with a long-range order. Second, the mutual interpenetration of the polymer and the zeolite networks renders disordered but highly interconnected mesopores in zeolite crystals. These two factors allow for the synthesis of single-crystalline, mesoporous zeolites of varied compositions and framework types. A representative example, hierarchial aluminosilicate (meso-ZSM-5), has been carefully characterized. It has a unique branched fibrous structure, and far outperforms bulk aluminosilicate (ZSM-5) as a catalyst in two model reactions: conversion of methanol to aromatics and catalytic cracking of canola oil. Third, extra functional groups in the polymer template can be utilized to incorporate desired functionalities into hierarchical zeolites. Last and most importantly, polymer-based templates permit heterogeneous nucleation and growth of mesoporous zeolites on existing surfaces, forming a continuous zeolitic layer. In a proof-of-concept experiment, unprecedented core-shell-structured hierarchical zeolites are synthesized by coating mesoporous zeolites on the surfaces of bulk zeolites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biotemplating of Luffa cylindrica sponges to self-supporting hierarchical zeolite macrostructures for bio-inspired structured catalytic reactors

International Nuclear Information System (INIS)

Zampieri, Alessandro; Mabande, Godwin T.P.; Selvam, Thangaraj; Schwieger, Wilhelm; Rudolph, Alexander; Hermann, Ralph; Sieber, Heino; Greil, Peter

2006-01-01

Biomorphic self-supporting MFI-type zeolite frameworks with hierarchical porosity and complex architecture were prepared using a 2-step (in-situ seeding and secondary crystal growth) hydrothermal synthesis in the presence of a biological template (Luffa sponge), employed as a macroscale sacrificial structure builder. The bio-inspired zeolitic replica inherited the complex spongy morphology and the intricate open-porous architecture of the biotemplate. Moreover, it exhibited reasonable mechanical stability in order to study the applicability of the biomorphic catalyst in a technical catalytic process. A bio-inspired catalytic reactor utilising the self-supporting ZSM-5 scaffold in monolithic configuration was developed in order to test the catalytic performance of the material

Caracterização termogravimétrica e espectroscópica das propriedades ácidas da zeólita ZSM-22 Thermogravimetric and spectroscopic characterization of acidic properties of ZSM-22 zeolite

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A. R. Loiola

2010-07-01

Full Text Available A acidez da estrutura da zeólita ZSM-22 foi determinada por análise térmica. A energia de ativação, calculada pelo método de Ozawa, envolveu uma energia de termodecomposição de 18,44 kJ.mol-1. O valor do fator pré-exponencial A foi de 2,2746. Suas propriedades texturais foram determinadas por análise de dessorção/adsorção de nitrogênio, cujos resultados indicaram a existência de microporosidade, com área de superfície de 257 m².g-1, volume de microporos de 0,041 cm³.g-1 e diâmetro de poros de 32,6 Å. Análises de luminescência, utilizando európio como sonda, sugerem que a acidez é distribuída uniformemente dentro da estrutura da zeólita.The acidity and stability of ZSM-22 zeolite structure have been studied by thermal analysis. The activation energy calculated by Ozawa method to the events related to thermodecomposition was 18.44 kJ.mol-1. The value of the pre-exponential factor A was 2.2746. Its textural properties have been determined by nitrogen adsorption desorption analysis, whose results indicated microporous properties, with surface area 257 m².g-1, micropore volume 0.041 cm³.g-1 and pore diameter 32.6 Å. Luminescence analyses, using europium as probe, suggest that the acidity is distributed uniformly within the zeolite structure.

Catalytic pyrolysis of woody biomass in a fluidized bed reactor: influence of the zeolite structure

Energy Technology Data Exchange (ETDEWEB)

A. Aho; N. Kumar; K. Eranen; T. Salmi; M. Hupa; D.Yu. Murzin [Aabo Akademi University, Aabo/Turku (Finland). Process Chemistry Centre, Laboratory of Industrial Chemistry and Reaction Engineering

2008-09-15

Catalytic pyrolysis of biomass from pine wood was carried out in a fluidized bed reactor at 450{sup o}C. Different structures of acidic zeolite catalysts were used as bed material in the reactor. Proton forms of Beta, Y, ZSM-5, and Mordenite were tested as catalysts in the pyrolysis of pine, while quartz sand was used as a reference material in the non-catalytic pyrolysis experiments. The yield of the pyrolysis product phases was only slightly influenced by the structures, at the same time the chemical composition of the bio-oil was dependent on the structure of acidic zeolite catalysts. Ketones and phenols were the dominating groups of compounds in the bio-oil. The formation of ketones was higher over ZSM-5 and the amount of acids and alcohols lower than over the other bed materials tested. Mordenite and quartz sand produced smaller quantities of polyaromatic hydrocarbons than the other materials tested. It was possible to successfully regenerate the spent zeolites without changing the structure of the zeolite. 12 refs., 9 figs., 5 tabs.

for zeolite coating

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Carlos Renato Rambo

2006-01-01

Full Text Available Biotemplating is the processing of microcellular ceramics by reproduction of natural morphologies, where the microstructural features of the biotemplate are maintained in the biomorphic ceramic. Different biotemplates with distinct pore anatomies were used to produce biomorphic supports for the zeolite coating: wood, cardboard, sea-sponge and sisal. The biomorphic ceramics were produced by distinguished processing routes: Al-gas infiltration-reaction, liquid-metal infiltration, dip-coating and sol-gel synthesis, in order to produce nitrides, carbides and oxides, depending on the processing conditions. The zeolite coating was performed by hydrothermal growth of MFI-type (Silicalite-1 and ZSM-5 zeolite crystals onto the internal pore walls of the biomorphic templates. The final biomorphic ceramic-zeolite composites were physically characterized, evaluated in terms of their gas adsorption capabilities and correlated to their microstructure and specific pore anatomy. The combination of the properties of the biomorphic ceramics with the adsorption properties of zeolites results in materials with distinct properties as potential candidates for adsorption and catalytic applications due to their characteristic porosity, molecular sieving capabilities and high thermo-mechanical strength.

Theoretical study on the nitration of methane by acyl nitrate catalyzed by H-ZSM5 zeolite.

Science.gov (United States)

Silva, Alexander Martins; Nascimento, Marco Antonio Chaer

2008-09-25

A theoretical study on the nitration of methane by acyl nitrate catalyzed by HZSM-5 zeolite is reported. The zeolite was represented by a "double ring" 20T cluster. The calculations were performed at the DFT/X3LYP/6-31G** and MP2/6-31G** levels. The first step of the mechanism involves the protonation of the acyl nitrate by the zeolite and the formation of a nitronium-like ion. The reaction proceeds through a concerted step with the attack of the methane molecule by the nitronium-like ion and the simultaneous transfer of a proton from the methane molecule to the zeolite, thus reconstructing the acidic site. The activation energies for the first and second steps of this reaction are, respectively, 14.09 and 10.14 kcal/mol at X3LYP/6-31G** level and 16.68 and 13.85 kcal/mol at the MP2/6-31G**.

Influence of the desilication process on the acidity of HZSM-5 zeolite

Energy Technology Data Exchange (ETDEWEB)

Rac, Vladislav, E-mail: vrac@ffh.bg.ac.rs [Faculty of Agriculture, Department of Chemistry, University of Belgrade, Belgrade (Serbia); Rakić, Vesna [Faculty of Agriculture, Department of Chemistry, University of Belgrade, Belgrade (Serbia); Miladinović, Zoran [Institute of General and Physical Chemistry, Belgrade (Serbia); Stošić, Dušan; Auroux, Aline [Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), Villeurbanne (France)

2013-09-10

Highlights: ► Mesopore creation in three different HZSM-5 zeolites was performed via desilication. ► Acidity was assessed by microcalorimetric and thermokinetic data. ► ZSM-5 with SiO{sub 2}/Al{sub 2}O{sub 3} = 23 proved to be the least susceptable to mesopore creation. ► Acidity of samples with SiO{sub 2}/Al{sub 2}O{sub 3} = 50 and 80 remained mostly unchanged by desilication, while the surface diffusion was improved. - Abstract: The influence of the alkaline treatment on the acidity of zeolite ZSM-5 (SiO{sub 2}/Al{sub 2}O{sub 3} = 23, 50 and 80) modified by desilication was investigated. The samples were characterized by X-ray diffraction, low temperature adsorption of nitrogen and solid-state {sup 27}Al MAS NMR. Acidity of the samples was investigated using microcalorimetry-volumetry of ammonia adsorption at 423 K. Acid sites accessibility and intracrystalline diffusion were estimated by the thermokinetic parameter. The desilication process was shown to be Si/Al ratio dependant. Relative enhancement of mesopore surface decreased in the following order of SiO{sub 2}/Al{sub 2}O{sub 3}: 50 > 8 0 >23. Pore size distribution broadened and mesopore sizes increased with increasing Si/Al ratio. For samples with SiO{sub 2}/Al{sub 2}O{sub 3} = 50 and 80 almost full preservation of acid sites strength and distribution was achieved. Significant alteration of the acidity was found for the mesoporous sample with SiO{sub 2}/Al{sub 2}O{sub 3} = 23. Thermokinetic parameter values indicate facilitated intracristalline diffusion for mesoporous samples.

STUDY OF EPOXIDE DECYCLISATION OF CARYOPHYLENE OXIDE WITH SYNTHETIC ZEOLITE AS CATALYSTS

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Winarto Haryadi

2010-06-01

Full Text Available The reaction of epoxide ring opening of caryophillene oxide has been done using zeolite H-Y, H-sodalit, and H-ZSM-5 as catalysts. The reactions were done in two types, there were in dioxane solvent at temperature of 110 oC and without solvent at temperature of 175 oC. The catalyst weight was 10 % from caryophillene oxide weight, and the time of reaction was four hours. The product of reaction was analyzed using GC, FTIR, and GC-MS. The reactions of caryophillene oxide in dioxane solvent with the three kinds of zeolites did not give any targeted product. Whereas, the reactions without solvent gave three main products, there was one compound with one group of secondary hidroxyl (secondary alcohol, and two compounds of ketone from caryophillene. The reaction product of caryophillene oxide obtained without using solvent with the three type of catalysts were then compared. Conversion of three main products produced by H-ZSM-5 catalyst, H-sodalit catalyst and H-Y catalyst were 82.11 %, 54.92 % and 38.53 % respectively. For that reason, the transformation of caryophillene oxide using H-ZSM-5 catalyst was considered to be the best selective product. The alcohol product was resulted from reaction between caryophillene oxide and Bronsted acid, and  the ketone products was resulted from the reaction with Lewis acid in zeolite.   Keywords: Epoxide ring opening, HY, H-sodalit and HZSM-5

Assessing the acid properties of desilicated ZSM-5 by FTIR using CO and 2,4,6-trimethylpyridine (collidine) as molecular probes

DEFF Research Database (Denmark)

Holm, Martin Spangsberg; Svelle, S.; Joensen, F.

2009-01-01

Lewis acid sites were generated, presumably from dislodged framework aluminium. Collidine, which is too bulky to enter the micropore system of ZSM-5, could access Lewis acidity, suggesting that these sites were predominantly generated on the external surface or in the newly created mesopores....... Additionally, by first saturating the zeolite surface with collidine and subsequently adsorbing CO, we show that barely any Lewis acidity was uncoordinated post-collidine saturation while the Bronsted acidity continuously was protected behind the micropore system. It is hypothesized from the present study...

Proton proximity – New key parameter controlling adsorption, desorption and activity in propene oligomerization over H-ZSM-5 zeolites

Czech Academy of Sciences Publication Activity Database

Bernauer, Milan; Tabor, Edyta; Pashková, Veronika; Kaucký, Dalibor; Sobalík, Zdeněk; Wichterlová, Blanka; Dědeček, Jiří

2016-01-01

Roč. 344, DEC 2016 (2016), s. 157-172 ISSN 0021-9517 R&D Projects: GA ČR GA15-13876S; GA MŠk(CZ) LM2015073 Institutional support: RVO:61388955 Keywords : ZSM-5 * Al siting * Single Al Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.844, year: 2016

FTIR study of the relation between extra-framework aluminum species and the adsorbed molecular water, and its effect on the acidity in ZSM-5 steamed zeolite

Energy Technology Data Exchange (ETDEWEB)

Isernia, Luis Fioravanti, E-mail: luis.isernia@gmail.com [Laboratorio de Tamices Moleculares, Universidad de Oriente - UO, Maturin, Monagas (Venezuela, Bolivarian Republic of)

2013-11-01

The infrared spectroscopy study of zeolite samples, obtained by steam treatment at 560-960 Degree-Sign C of the ZSM-5 catalyst (framework Si/Al ratio of 13), suggests an association between adsorbed molecular water and extra-framework aluminum hydroxyls generated after treatment. Moreover, infrared spectroscopy of adsorbed pyridine shows the reduction of the densities of Broensted and Lewis sites, when treatment temperature rises, with contradicts the frequently accepted mechanism of the transformation of two bridged Si-OH-Al groups for each Lewis site generated. The gradual conversion of the octahedral extra-framework aluminum (Lewis-associated) in polymeric species with low acidity is the most probable cause of this behavior. On the other hand, the apparent decline of the acid Broensted strength, with the increase in the temperature of the hydrothermal treatment, has two possible causes: a) the decreasing accessibility, of the pyridine molecular probe to bridged Si-OH-Al groups with the strongest Broensted acidity, inside the channels, and b) the gradual transformation of these groups into extra framework species of weak acidity. (author)

Comparative study of the active sites in zeolites by different probe molecules

Directory of Open Access Journals (Sweden)

ALINE AUROUX

2005-03-01

Full Text Available This review summarizes some of the recently published results concerning the acid sites in the zeolites ZSM-5 and Y studied by temperature-programmed desorption (TPD and adsorption calorimetry using different probe molecules NH3, CO, N2O and n-hexane. For the first time it has been shown that the acid sites in hydrated zeolites are accessible for n-hexane adsorption

Effects of different level addition of zeolite ZSM-5 additive on quality and composition of the dry gas, LPG (Liquefied Petroleum Gas) and gasoline, produced in FCC (Fluid Catalytic Cracking); Efeito dos diferentes niveis de adicao de aditivos de ZSM-5 na qualidade e composicao do gas combustivel, GLP e gasolina produzidos em FCC

Energy Technology Data Exchange (ETDEWEB)

Bastiani, Raquel; Pimenta, Ricardo D.M.; Almeida, Marlon B.B.; Lau, Lam Y. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil)

2004-07-01

The effects of the addition of different level of ZSM-5 additives on different FCC catalysts formulations have been studied on laboratory scale FST (Fluidized Simulation Test). The main objective of the present work is to perform a qualitative identification of the main parameters of FCC catalyst which affect the ZSM-5 additives performance concerning quality and composition of Dry Gas, LPG and Gasoline. The product composition of each test was analyzed by PIANO groups separated by carbon number. The effect of ZSM-5 on products composition was evaluated. The results showed that the ZSM-5 additive cracks gasoline range olefins and isoparaffins into Dry Gas and LPG, favoring the formation of ethylene, propylene and butylenes, while the absolute yield of gasoline aromatics changes little. The aromatics fraction in gasoline, MON and RON numbers in gasoline increase. The ZSM-5 effectiveness is negatively affected by high levels of rare earth on FCC catalyst (RE-USY). Higher hydrogen transfer provides lower olefins (higher than C6) formation, which are the most reactive species for ZSM-5 cracking. (author)

On the location, strength and accessibility of Brønsted acid sites in hierarchical ZSM-5 particles

DEFF Research Database (Denmark)

Tzoulaki, Despina; Jentys, Andreas; Pérez-Ramírez, Javier

2012-01-01

Microporous and mesoporous (hierarchical) ZSM-5 samples, prepared by desilication, dealumination and templating with carbon nanoparticles have been characterized by adsorbing benzene, cyclohexane and 1,3,5-trimethylbenzene (mesitylene) to probe the location, the strength and the accessibility...

Tailoring of the structure of Fe-cationic species in Fe-ZSM-5 by distribution of Al atoms in the framework for N2O decomposition and NH3-SCR-NOx

Czech Academy of Sciences Publication Activity Database

Sazama, Petr; Wichterlová, Blanka; Tabor, Edyta; Šťastný, Petr; Sathu, Naveen Kumar; Sobalík, Zdeněk; Dědeček, Jiří; Sklenák, Štěpán; Klein, Petr; Vondrová, Alena

2014-01-01

Roč. 312, APR 2014 (2014), s. 123-138 ISSN 0021-9517 R&D Projects: GA ČR GAP106/11/0624; GA TA ČR TA01021377 Institutional support: RVO:61388955 Keywords : Fe-ZSM-5 zeolite * Structure of Fe species * Fe(III)-oxo species Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.921, year: 2014

Spontaneous dispersion of PdO onto acid sites of zeolites studied by in situ DXAFS

CERN Document Server

Okumura, K; Niwa, M; Yokota, S; Kato, K; Tanida, H; Uruga, T

2003-01-01

The generation of highly dispersed PdO over zeolite supports was studied using in situ energy-dispersive XAFS (DXAFS) technique. From the comparison with the Na-ZSM-5, it was found that the oxidation as well as the spontaneous dispersion of Pd was promoted through the interaction between PdO and acid sites of H-form zeolites. (author)

A bioscaffolding strategy for hierarchical zeolites with a nanotube-trimodal network.

Science.gov (United States)

Li, Guannan; Huang, Haibo; Yu, Bowen; Wang, Yun; Tao, Jiawei; Wei, Yingxu; Li, Shougui; Liu, Zhongmin; Xu, Yan; Xu, Ruren

2016-02-01

Hierarchical zeolite monoliths with multimodal porosity are of paramount importance as they open up new horizons for advanced applications. So far, hierarchical zeolites based on nanotube scaffolds have never been reported. Inspired by the organization of biominerals, we have developed a novel precursor scaffolding-solid phase crystallization strategy for hierarchical zeolites with a unique nanotube scaffolding architecture and nanotube-trimodal network, where biomolecular self-assembly (BSA) provides a scaffolding blueprint. By vapor-treating Sil-1 seeded precursor scaffolds, zeolite MFI nanotube scaffolds are self-generated, during which evolution phenomena such as segmented voids and solid bridges are observed, in agreement with the Kirkendall effect in a solid-phase crystallization system. The nanotube walls are made of intergrown single crystals rendering good mechanical stability. The inner diameter of the nanotube is tunable between 30 and 90 nm by varying the thickness of the precursor layers. Macropores enclosed by cross-linked nanotubes can be modulated by the choice of BSA. Narrow mesopores are formed by intergrown nanocrystals. Hierarchical ZSM-5 monoliths with nanotube (90 nm), micropore (0.55 nm), mesopore (2 nm) and macropore (700 nm) exhibit superior catalytic performance in the methanol-to-hydrocarbon (MTH) conversion compared to conventional ZSM-5. BSA remains intact after crystallization, allowing a higher level of organization and functionalization of the zeolite nanotube scaffolds. The current work may afford a versatile strategy for hierarchical zeolite monoliths with nanotube scaffolding architectures and a nanotube-multimodal network leading to self-supporting and active zeolite catalysts, and for applications beyond.

Catalytic Flash Pyrolysis of Biomass Using Different Types of Zeolite and Online Vapor Fractionation

KAUST Repository

Imran, Ali

2016-03-11

Bio-oil produced from conventional flash pyrolysis has poor quality and requires expensive upgrading before it can be used as a transportation fuel. In this work, a high quality bio-oil has been produced using a novel approach where flash pyrolysis, catalysis and fractionation of pyrolysis vapors using two stage condensation are combined in a single process unit. A bench scale unit of 1 kg/h feedstock capacity is used for catalytic pyrolysis in an entrained down-flow reactor system equipped with two-staged condensation of the pyrolysis vapor. Zeolite-based catalysts are investigated to study the effect of varying acidities of faujasite Y zeolites, zeolite structures (ZSM5), different catalyst to biomass ratios and different catalytic pyrolysis temperatures. Low catalyst/biomass ratios did not show any significant improvements in the bio-oil quality, while high catalyst/biomass ratios showed an effective deoxygenation of the bio-oil. The application of zeolites decreased the organic liquid yield due to the increased production of non-condensables, primarily hydrocarbons. The catalytically produced bio-oil was less viscous and zeolites were effective at cracking heavy molecular weight compounds in the bio-oil. Acidic zeolites, H-Y and H-ZSM5, increased the desirable chemical compounds in the bio-oil such as phenols, furans and hydrocarbon, and reduced the undesired compounds such as acids. On the other hand reducing the acidity of zeolites reduced some of the undesired compounds in the bio-oil such as ketones and aldehydes. The performance of H-Y was superior to that of the rest of zeolites studied: bio-oil of high chemical and calorific value was produced with a high organic liquid yield and low oxygen content. H-ZSM5 was a close competitor to H-Y in performance but with a lower yield of bio-oil. Online fractionation of catalytic pyrolysis vapors was employed by controlling the condenser temperature and proved to be a successful process parameter to tailor the

The Effect of Mesoporous H-ZSM-5 Crystallinity as a CaO Support on the Transesterification of Used Cooking Oil

Directory of Open Access Journals (Sweden)

Amalia Putri Purnamasari

2017-10-01

Full Text Available Transesterification of used cooking oil was carried out over calcium oxide supported on mesoporous H-ZSM-5 prepared from kaolin as solid base catalysts. Solid basic catalysts investigated in this study were characterized by XRD, FTIR spectroscopy, and N2 adsorption-desorption techniques. The XRD pattern showed peaks corresponding to the CaO and mesoporous ZSM-5 in the sample. The peak intensity of the CaO increased as CaO loading in ZSM-5 was increased. The characterization based on FTIR spectroscopy revealed that CaO/H-ZSM-5 solids have functional groups characteristics of both CaO and mesoporous H-ZSM-5 which appeared in the band at around  550 cm-1 and 480 cm-1. The isotherm of N2 adsorption-desorption of CaO/H-ZSM-5 indicated the type IV isotherm with the presence of hysteresis loop. For the catalytic activity, the biodiesel yield using catalyst of 10 % CaO/HZSM-5 (100 %, 30 % CaO/HZSM-5 (100 %, 50 % CaO/HZSM-5 (100 % were 24.34, 27.37, and 29.73 %, respectively. It also related with the basic active site, when loading CaO increased, the basic active site also increased. Copyright © 2017 BCREC Group. All rights reserved Received: 21st November 2016; Revised: 8th March 2017; Accepted: 9th March 2017; Available online: 27th October 2017; Published regularly: December 2017 How to Cite: Purnamasari, A.P., Sari, M.E.F., Kusumaningtyas, D.T., Suprapto, S., Hamid, A., Prasetyoko, D. (2017. The Effect of Mesoporous H-ZSM-5 Crystallinity as a CaO Support on the Transesterification of Used Cooking Oil. Bulletin of Chemical Reaction Engineering & Catalysis, 12(3: 329-336 (doi:10.9767/bcrec.12.3.802.329-336

Factors affecting alcohol-water pervaporation performance of hydrophobic zeolite-silicone rubber mixed matrix membranes

Science.gov (United States)

Mixed matrix membranes (MMMs) consisting of ZSM-5 zeolite particles dispersed in silicone rubber exhibited ethanol-water pervaporation permselectivities up to 5 times that of silicone rubber alone and 3 times higher than simple vapor-liquid equilibrium (VLE). A number of conditi...

Synthesis and characterization of ZSM-12 type zeolytic catalysts by using different aluminium sources in the petroleum industry; Sintese e caracterizacao de catalisadores zeoliticos do tipo ZSM-12 utilizando diferentes fontes de aluminio na industria do petroleo

Energy Technology Data Exchange (ETDEWEB)

Moraes, Marilia R.F.S.; Jesus, Daniela B.; Souza, Marcelo J.B. [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Dept. de Engenharia Quimica; Santos, Consuelo D.; Machado, Sanny W.M.; Pedrosa, Anne M. Garrido [Universidade Federal de Sergipe (UFS), Sao Cristovao, SE (Brazil). Dept. de Quimica

2010-12-15

The main objective was to synthesize and characterize ZSM-12 zeolites from different sources of aluminium, using hydrothermal method and characterize the catalysts synthesized by X-ray diffractions, thermal analysis and infrared absorption spectroscopy. The X-ray diffractogram showed the formation of zeolites of the family pantasil crystalline. Thermogravimetric curves and FTIR spectra were utilized by monitoring the removal of template and by monitoring the maintenance of zeolite structure. (author)

Hierarchical ZSM-5 zeolite catalysts for the selective oxidation of benzene

NARCIS (Netherlands)

Koekkoek, A.J.J.

2011-01-01

Zeolites are widely used as catalysts, especially in oil refining and the petrochemical industries. Nowadays the cracking of heavy oil feeds as well as the processing of larger (bio)molecules demands for improved catalysts that can overcome the pore size constraints and diffusion limitations of the

Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5.

Science.gov (United States)

Zhang, Huiyan; Luo, Mengmeng; Xiao, Rui; Shao, Shanshan; Jin, Baosheng; Xiao, Guomin; Zhao, Ming; Liang, Junyu

2014-03-01

Chemical liquid deposition (CLD) with KH550, TEOS and methyl silicone oil as the modifiers was used to modify ZSM-5 and deposit its external acid sites. The characteristics of modified catalysts were tested by catalytic conversion of biomass pyrolysis-derived compounds. The effects of different modifying conditions (deposited amount, temperature, and time) on the product yields and selectivities were investigated. The results show KH550 modified ZSM-5 (deposited amount of 4%, temperature of 20°C and time of 6h) produced the maximum yields of aromatics (24.5%) and olefins (16.5%), which are much higher than that obtained with original ZSM-5 catalyst (18.8% aromatics and 9.8% olefins). The coke yield decreased from 44.1% with original ZSM-5 to 26.7% with KH550 modified ZSM-5. The selectivities of low-molecule-weight hydrocarbons (ethylene and benzene) decreased, while that of higher molecule-weight hydrocarbons (propylene, butylene, toluene, and naphthalene) increased comparing with original ZSM-5. Copyright © 2013 Elsevier Ltd. All rights reserved.

Redox Catalysis over Metallo-Zeolites. Contribution to Environmental Catalysis

Czech Academy of Sciences Publication Activity Database

Wichterlová, Blanka; Sobalík, Zdeněk; Dědeček, Jiří

2003-01-01

Roč. 41, - (2003), s. 97-114 ISSN 0926-3373 R&D Projects: GA AV ČR IBS4040016; GA AV ČR IAA4040007 Institutional research plan: CEZ:AV0Z4040901 Keywords : metallo-zeolites * Co-beta * Fe-ZSM-5 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.476, year: 2003

Investigation of zeolites by solid state quadrapole NMR

International Nuclear Information System (INIS)

Janssen, R.

1990-01-01

The subject of this thesis is the NMR investigation of zeolites. The nature and properties of zeolites are discussed. Some of the basic priniples of NMR techniques on quadrupole nuclei are presented. A special technique, namely a two-dimensional nutation experiment is discussed in detail. The theory of the nutation experiment for quadrupole spin species with spin quantum number 3/2 as well as 5/2 is presented. For both spin spcies the theoretical spectra are compared with experimental results. It is also shown that the nutation expeirment can be performed with several pulse schemes. It is shown how phase-sensitive pure-absorption nutation spectra can be obtained and an NMR-probe is presented that is capable of performing NMR experiments at high (up to 500 degree C) temperatures. The two-dimensional nutation NMR technique has been applied to sodium cations in zeolite NaA. For this purpose a numbre of zeolite samples were prepared that contained different amounts of water. With the aid of nutation NMR the hydration of the zeolite can be studied and conclusions can be drawn about the symmetry of the surrounding of the sodium cations. With the aid of an extension of the nutation NMR experiment: Rotary Echo Nutation NMR, it is shown that in zeolite NaA, in various stages of hydration, the sodium cations or water molecules are mobile. Proof is given by means of high-temperature 23 Na-NMR that dehydrates zeolite NaA undergoes a phase transition at ca. 120 degree C. In a high-temperature NMR investigation of zeolite ZSM-5 it is shown that the sodium ions start to execute motions when the temperature is increased. (author). 198 refs.; 72 figs.; 6 tabs

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

Science.gov (United States)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

Organic iodide capture using a zeolite dry filtration

International Nuclear Information System (INIS)

Park, Sanggil; Sung, Joonyoung; Kim, Gi-ppeum; Lee, Jaeyoung

2017-01-01

An organic iodide, especially, methyl iodide (CH 3 I) would generated non-negligibly from a severe accident in a nuclear power plant. This CH 3 I will be dangerous for human when it was inhaled, it is highly toxic and causes a serious nerve disorder. Even it is a major contributor to a thyroid cancer. In order to prevent its environmental release, it is required to decontaminate using a filtration system. For the removal of CH 3 I from the release gases, wet-type is not ideal due to a high re-volatile characteristics of CH 3 I. It may become volatile after dissolving in a pool and forms CH 3 I again at the surface of water pool. Therefore, a dry-filtration should be installed to remove the CH 3 I. In this study, we preliminary investigate the characteristics of zeolite filtration methods for the removal of CH 3 I. We used both silver ion exchanged ZSM-5-zeolite (Ag+-ZSM-5) to study the effect of silver ion for the removal of iodine from CH 3 I. In summary, the CH 3 I capture tests using a silver ion exchanged zeolite was conducted in the coupled TGAGC test set-up. The mass change of the sample and concentration of CH 3 I were measured. The samples were investigated by the SEM/EDS to see its surface characteristics.

Comparative study of the methane and methanol mass transfer in the mesoporous H-ZSM-5/alumina extruded pellet

Science.gov (United States)

Zhokh, Alexey A.; Strizhak, Peter E.

2018-07-01

H-ZSM-5/alumina catalyst pellet was prepared using extrusion method. The as-prepared mesoporous material was characterized using nitrogen adsorption, IR, XRD, and TEM methods. Transport of methane and methanol in the obtained H-ZSM-5/alumina extruded grain was studied. We demonstrate that the methanol transport may be described by the time-fractional diffusion equation in a fairly good manner. The measured value of the fractional order of the time-fractional derivative reveals the fast super-diffusive regime of the methanol transport in the mesoporous solid. Contrary, the methane transport has been found to follow a standard diffusion and described by the second Fick's law. These findings show that mass transfer kinetics is characterized by the order of the temporal derivative. The latter is a unique property of the individual porous media and the diffusing agent.

Comparative study of the methane and methanol mass transfer in the mesoporous H-ZSM-5/alumina extruded pellet

Science.gov (United States)

Zhokh, Alexey A.; Strizhak, Peter E.

2018-01-01

H-ZSM-5/alumina catalyst pellet was prepared using extrusion method. The as-prepared mesoporous material was characterized using nitrogen adsorption, IR, XRD, and TEM methods. Transport of methane and methanol in the obtained H-ZSM-5/alumina extruded grain was studied. We demonstrate that the methanol transport may be described by the time-fractional diffusion equation in a fairly good manner. The measured value of the fractional order of the time-fractional derivative reveals the fast super-diffusive regime of the methanol transport in the mesoporous solid. Contrary, the methane transport has been found to follow a standard diffusion and described by the second Fick's law. These findings show that mass transfer kinetics is characterized by the order of the temporal derivative. The latter is a unique property of the individual porous media and the diffusing agent.

Direct electron crystallographic determination of zeolite zonal structures

International Nuclear Information System (INIS)

Dorset, Douglas L.; Gilmore, Christopher J.; Jorda, Jose Luis; Nicolopoulos, Stavros

2007-01-01

The prospect for improving the success of ab initio zeolite structure investigations with electron diffraction data is evaluated. First of all, the quality of intensities obtained by precession electron diffraction at small hollow cone illumination angles is evaluated for seven representative materials: ITQ-1, ITQ-7, ITQ-29, ZSM-5, ZSM-10, mordenite, and MCM-68. It is clear that, for most examples, an appreciable fraction of a secondary scattering perturbation is removed by precession at small angles. In one case, ZSM-10, it can also be argued that precession diffraction produces a dramatically improved 'kinematical' data set. There seems to no real support for application of a Lorentz correction to these data and there is no reason to expect for any of these samples that a two-beam dynamical scattering relationship between structure factor amplitude and observed intensity should be valid. Removal of secondary scattering by the precession mode appears to facilitate ab initio structure analysis. Most zeolite structures investigated could be solved by maximum entropy and likelihood phasing via error-correcting codes when precession data were used. Examples include the projected structure of mordenite that could not be determined from selected area data alone. One anomaly is the case of ZSM-5, where the best structure determination in projection is made from selected area diffraction data. In a control study, the zonal structure of SSZ-48 could be determined from selected area diffraction data by either maximum entropy and likelihood or traditional direct methods. While the maximum entropy and likelihood approach enjoys some advantages over traditional direct methods (non-dependence on predicted phase invariant sums), some effort must be made to improve the figures of merit used to identify potential structure solutions

A MAS NMR and DRIFT study of the Ga species in Ga/H-ZSM5 catalysts and their effect on propane ammoxidation

Energy Technology Data Exchange (ETDEWEB)

Pal, P. [Indian Inst. of Petroleum, Dehradun (India). Catalysis Division; Quartararo, J. [Liverpool Univ., Liverpool (United Kingdom). Leverhulme Centre for Innovative Catalysis, Dept. of Chemistry; Abd Hamid, S.B. [Malaya Univ., Postgraduate School, Bangunan (Malaysia); Derouane, E.G. [Algarve Univ., Faro (Portugal). Faculdade de Ciencias e Tecnologia; Vedrine, J.C. [Laboratoire de Physico-Chimie des Surface, Paris (France). Faculdade de Ciencias e Tecnologia; Magusin, P.C.M.M.; Anderson, B.G. [Eindhoven Univ. of Technology, Eindhoven (Netherlands). Schuit Institute of Catalysis

2005-07-01

This paper presents the results of a study that sought information about the nature and environment of the gallium (Ga) species in Ga/H-ZSM5 zeolites following H{sub 2}-O{sub 2} redox treatments applied during their activation by use of magic-angle spinning (MAS) {sup 71}Ga, {sup 27}Al, and {sup 29}Si NMR spectroscopy (Ga coordination) complemented by diffuse reflectance FT IR (DRIFT) spectroscopy (Bronsted acidity). This information was then correlated with their catalytic behavior for the ammoxidation of propane. Ga species were observed in several environments: octahedrally coordinated gallium in small Ga{sub 2}O{sub 3} particles at the external surface of the zeolite crystals; octahedrally coordinated gallium in GaO(OH) or related species; and tetrahedrally coordinated gallium in cationic-exchange positions inside the zeolite. Redox (H{sub 2}-O{sub 2}) cycles promote the migration of gallium from the GaO(OH) or Ga{sub 2}O{sub 3} species at the external surface of the zeolite crystals to cationic-exchange sites within the zeolite channels. It was concluded that the redox treatment had a beneficial effect on its catalytic performance for the ammoxidation of propane, which occurs via a bifunctional mechanism. The main product was acetonitrile at high gallium and aluminium contents. It was suggested that higher yields in acrylonitrile could be obtained through Ga-modified zeolites with a higher gallium and lower aluminium content. 22 refs., 1 tab., 6 figs.

Characterization of the Cu+ sites in MFI zeolites: combined computational and experimental study

Czech Academy of Sciences Publication Activity Database

Bludský, Ota; Nachtigall, Petr; Čičmanec, P.; Knotek, P.; Bulánek, R.

2005-01-01

Roč. 100, - (2005), 385-389 ISSN 0920-5861 R&D Projects: GA MŠk(CZ) LN00A032 Institutional research plan: CEZ:AV0Z40550506 Keywords : ZSM-5 zeolite * carbon-monoxide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.365, year: 2005

Aromatic hydrocarbon production via eucalyptus urophylla pyrolysis over several metal modified ZSM-5 catalysts – an analysis by py-GC/MS

Science.gov (United States)

Metal modified HZSM-5 catalysts were prepared by ion exchange of NH4ZSM-5 (SIO2/Al2O3 = 23) using gallium, molybdenum, nickel and zinc, and their combinations thereof. The prepared catalysts were used to evaluate catalytic pyrolysis for the conversion of Eucalyptus urophylla to fuels and chemicals, ...

Waste crab shell derived CaO impregnated Na-ZSM-5 as a solid base catalyst for the transesterification of neem oil into biodiesel

Directory of Open Access Journals (Sweden)

Vijayalakshmi Shankar

2017-11-01

Full Text Available Activated calcium oxide extracted from crab shell impregnated on Na-ZSM-5 has been investigated. Crab shells were collected, powdered and calcined at 900 °C, and CaO was impregnated on Na-ZSM-5 and calcined at 550 °C for 10 h. The CaO/Na-ZSM-5 was characterized by X-ray diffraction, scanning electron microscopy and BET surface area. The prepared catalyst was tested for its catalytic activity by transesterifing neem oil into biodiesel in the presence of methanol. The influence of various parameters including reaction time, temperature, methanol to oil ratio, catalyst concentration and dosage were also investigated. Produced biodiesel have also been tested using proton NMR spectroscopy. Biodiesel yield as 95% has been achieved with 15% CaO impregnated on Na-ZSM-5 at 75 °C. The optimum transesterification reaction conditions were identified as follows: reaction temperature, 75 °C; reaction time, 6 h; methanol-to-neem oil molar ratio, 12:1; catalyst dosage, 0.2 g; and catalyst concentration, 15%. Based on the above study, it can be concluded that the calcium oxide impregnated Na-ZSM-5 can be a potential catalyst for biodiesel production.

PREPARATION, CHARACTERIZATIONS AND MODIFICATION OF Ni-Pd/NATURAL ZEOLITE CATALYSTS

Directory of Open Access Journals (Sweden)

Wega Trisunaryanti

2010-06-01

Full Text Available Preparation, and modification of Ni-Pd/natural zeolite as well as their characterizations had been carried out. The aim of this research for the fututure is to prepare the best characters catalyst for the conversion of waste plastics fraction to gasoline fraction (C5-C12 hydrocarbons. The preparation of catalysts was performed by reacting a natural zeolite with the precursor of Ni(NO32. 9H2O and PdCl2 in an ammonia solution (25%. The modifications were performed by varying the rasio of Ni/Pd loaded to the zeolite, whereas the Pd was previously loaded and total metal content was 1 wt.% based on the zeolite. The characterization of catalysts included determination of acidity gravimetrically by adsorption of ammonia or pyridine vapour  base method, metal content by Atomic Adsorption Spectrophotometer (AAS and X-ray Fluoresence (XRF and crystallinity by X-ray Diffraction (XRD. The treatment of catalysts using Etilene Diamine Tetra Acetic acid  (EDTA was performed to study the metal distribution on the outer or inner surface of the zeolite. The characterization results showed that the loading of metals to the zeolite increased its acidity and decreased its spesific surface area, however, did not defect its crystallnity.  The metals loaded on the zeolite were distributed inside the pore and at outer surface of the zeolite. For all catalyst samples, the acidities determined using ammonia were higher than those of pyridine, and the acidities determined before the EDTA treatment was lower than those after the treatment.  Metal contents of the zeolite before the EDTA treatment were higher than those after the treatment. The EDTA treatment enhanced the crystallinity of the sampel. The relationship between the metal rasio towards the acidity of the catalyst samples were in variation. Catalyst samples produced in this research have good characters, thus promisingly can be used for conversion process of waste plastics to gasoline fraction.    Keywords

Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

Directory of Open Access Journals (Sweden)

Zeeshan Nawaz

2009-12-01

Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

Synthesis of ZSM-5 on the Surface of Foam Type Porous SiC Support

International Nuclear Information System (INIS)

Jung, Eunjin; Lee, Yoon Joo; Won, Ji Yeon; Kim, Younghee; Kim, Soo Ryong; Shin, Dong-Geun; Kwon, Woo Teck; Lee, Hyun Jae

2015-01-01

ZSM-5 crystals grew by hydrothermal synthesis method on the surface of foam type porous silicon carbide ceramics which fabricated by polymer replica method. Oxide layer was developed on the surface of the porous silicon carbide ceramics to induce growth of ZSM-5 from the surface. In this study, hydrothermal synthesis was carried out for 7 h at 150 .deg. C using TEOS, Al(NO 3 )•9H 2 O and TPAOH as raw materials in the presence of the porous silicon carbide ceramics. X-ray Powder Diffraction (XRD) and Scanning Electron Microscope (SEM) analyses were confirmed 1-3 μm sized ZSM-5 crystals have grown on the surface of porous silicon carbide ceramics. BET data shows that small pores about 10Å size drastically enhanced and surface area increased from 0.83 m 2 /g to 30.75 m 2 /g after ZSM-5 synthesis on the surface of foam type porous silicon carbide ceramics.

Methane emissions abatement by multi-ion-exchanged zeolite A prepared from both commercial-grade zeolite and coal fly ash.

Science.gov (United States)

Hui, K S; Chao, C Y H

2008-10-01

The performance of multimetal-(Cu, Cr, Zn, Ni, and Co)-ion-exchanged zeolite A prepared from both a commercial-grade sample and one produced from coal fly ash in methane emissions abatement was evaluated in this study. The ion-exchange process was used to load the metal ions in zeolite A samples. The methane conversion efficiency by the samples was studied under various parameters including the amount of metal loading (7.3-19.4 wt%), reaction temperature (25-500 degrees C), space velocity (8400-41 900 h(-1)), and methane concentration (0.5-3.2 vol %). At 500 degrees C, the original commercial-grade zeolite A catalyzed 3% of the methane only, whereas the addition of different percentages of metals in the sample enhanced the methane conversion efficiency by 40-85%. Greater methane conversion was observed by increasing the percentage of metals added to the zeolite even though the BET surface area of the zeolite consequently decreased. Higher percentage methane conversion over the multi-ion-exchanged samples was observed at lower space velocities indicating the importance of the mass diffusion of reactants and products in the zeolite. Compared to the multi-ion-exchanged zeolite A prepared from the commercial-grade zeolite, the one produced from coal fly ash demonstrated similar performances in methane emissions abatement, showing the potential use of this low cost recycled material in gaseous pollutant treatment.

Planar Zeolite Film-Based Potentiometric Gas Sensors Manufactured by a Combined Thick-Film and Electroplating Technique

Science.gov (United States)

Marr, Isabella; Reiß, Sebastian; Hagen, Gunter; Moos, Ralf

2011-01-01

Zeolites are promising materials in the field of gas sensors. In this technology-oriented paper, a planar setup for potentiometric hydrocarbon and hydrogen gas sensors using zeolites as ionic sodium conductors is presented, in which the Pt-loaded Na-ZSM-5 zeolite is applied using a thick-film technique between two interdigitated gold electrodes and one of them is selectively covered for the first time by an electroplated chromium oxide film. The influence of the sensor temperature, the type of hydrocarbons, the zeolite film thickness, and the chromium oxide film thickness is investigated. The influence of the zeolite on the sensor response is briefly discussed in the light of studies dealing with zeolites as selectivity-enhancing cover layers. PMID:22164042

Planar Zeolite Film-Based Potentiometric Gas Sensors Manufactured by a Combined Thick-Film and Electroplating Technique

Directory of Open Access Journals (Sweden)

Gunter Hagen

2011-08-01

Full Text Available Zeolites are promising materials in the field of gas sensors. In this technology-oriented paper, a planar setup for potentiometric hydrocarbon and hydrogen gas sensors using zeolites as ionic sodium conductors is presented, in which the Pt-loaded Na-ZSM-5 zeolite is applied using a thick-film technique between two interdigitated gold electrodes and one of them is selectively covered for the first time by an electroplated chromium oxide film. The influence of the sensor temperature, the type of hydrocarbons, the zeolite film thickness, and the chromium oxide film thickness is investigated. The influence of the zeolite on the sensor response is briefly discussed in the light of studies dealing with zeolites as selectivity-enhancing cover layers.

Removal of pyridine from liquid and gas phase by copper forms of natural and synthetic zeolites

Czech Academy of Sciences Publication Activity Database

Reháková, M.; Fortunová, L.; Bastl, Zdeněk; Nagyová, S.; Dolinská, S.; Jorík, V.; Jóna, E.

2011-01-01

Roč. 186, č. 1 (2011), s. 699-706 ISSN 0304-3894 R&D Projects: GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : natural zeolite * clinoptilolite * ZSM5 Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.173, year: 2011

Investigation of thermodynamic parameters of cetyl pyridinium bromide sorption onto ZSM-5 and natural clinoptilolite

International Nuclear Information System (INIS)

Ghiaci, M.; Kia, R.; Kalbasi, R.J.

2004-01-01

A study was undertaken to determine the influence of temperature and surfactant concentration on the adsorption of cetyl pyridinium bromide on two ZSM-5 zeolites, and on natural clinoptilolite. The effect of temperature on adsorption and thermodynamic properties was investigated by making measurements at (297, 303, 307, 313) K. The results show that the calculated curves from the general isotherm equation can represent the experimental data very well up to T=313 K. Based on the calculation of the thermodynamics of adsorption, it is evident that the principle contribution to the ΔG compfn hm of negative value is the large positive value of ΔS compfn hm (36 to 52 J · mol -1 ), whereas ΔH compfn hm is positive and in the range of 1 to 7 kJ · mol -1 . Therefore, similar to the micellisation in bulk solution, the second step of surfactant adsorption is an entropy-driven process

Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

Directory of Open Access Journals (Sweden)

Ting Ma

2014-04-01

Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

Aromatic Transformations Over Mesoporous ZSM-5: Advantages and Disadvantages

Czech Academy of Sciences Publication Activity Database

Musilová, Zuzana; Žilková, Naděžda; Park, S.-E.; Čejka, Jiří

2010-01-01

Roč. 53, 19-20 (2010), s. 1457-1469 ISSN 1022-5528 Institutional research plan: CEZ:AV0Z40400503 Keywords : mesoporous ZSM-5 * alkylation * disproportionation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.359, year: 2010

Direct Synthesis of Methanol by Partial Oxidation of Methane with Oxygen over Cobalt Modified Mesoporous H-ZSM-5 Catalyst

Directory of Open Access Journals (Sweden)

Yuni Krisyuningsih Krisnandi

2015-11-01

Full Text Available Partial oxidation of methane over mesoporous catalyst cobalt modified H-ZSM-5 has been carried out. Mesoporous Na-ZSM-5 (Si/Al = 35.4 was successfully synthesized using double template method which has high surface area (450 m2/g and average pore diameter distribution of 1.9 nm. The as-synthesized Na-ZSM-5 was converted to H-ZSM-5 through multi-exchange treatment with ammonium ion solution, causing decreased crystallinity and surface area, but increased porous diameter, due to dealumination during treatment process. Moreover, H-ZSM-5 was loaded with cobalt (Co = 2.5% w by the incipient impregnation method and calcined at 550 °C. Partial oxidation of methane was performed in the batch reactor with 0.75 bar methane and 2 bar of nitrogen (with impurities of 0.5% oxygen as the input at various reaction time (30, 60 and 120 min. The reaction results show that cobalt species in catalyst has an important role, because H-ZSM-5 cannot produce methanol in partial oxidation of methane. The presence of molecular oxygen increased the percentage of methanol yield. The reaction is time-dependent with the highest methanol yield (79% was acquired using Co/H-ZSM-5 catalyst for 60 min.

A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications.

Science.gov (United States)

Yuan, Zhizhang; Zhu, Xiangxue; Li, Mingrun; Lu, Wenjing; Li, Xianfeng; Zhang, Huamin

2016-02-24

Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (99 % and an energy efficiency of >81 % at 200 mA cm(-2), which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of La-ZSM-5 Coated Silicon Carbide Foam Catalyst for Toluene Methylation with Methanol

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Debarpita Ghosal

2015-07-01

Full Text Available The performance of toluene methylation reaction was studied on H-ZSM-5 catalyst modified with La, Ce and Nb at different percentage loading. It was found that 10% metal loading produced the best performance in the reaction in terms of toluene conversion. The catalyst was coated on silicon carbide foam support which showed better conversion than the pelleted catalyst. Again, among the treated and untreated H-ZSM-5, the La-ZSM-5 catalyst is chosen for the reaction for its highest selectivity towards xylene, the main product. All catalysts were characterized in terms of surface properties, SEM, XRD and NH3-TPD. Kinetic study was done on La-ZSM-5 catalyst with 10% loading. In this kineticstudy, Langmuir Hinshelwood kinetic model with surface reaction as rate controlling step was selected as the rate equation. The activation energy was found to be 47 kJ/mol. © 2015 BCREC UNDIP. All rights reserved. Received: 9th December 2014; Revised: 27th April 2015; Accepted: 29th April 2015  How to Cite: Ghosal, D., Basu, J.K., Sengupta, S. (2015. Application of La-ZSM-5 Coated Silicon Carbide Foam Catalyst for Toluene Methylation with Methanol. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 201-209. (doi:10.9767/bcrec.10.2.7872.201-209 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7872.201-209  

Nanocellulose-Zeolite Composite Films for Odor Elimination.

Science.gov (United States)

Keshavarzi, Neda; Mashayekhy Rad, Farshid; Mace, Amber; Ansari, Farhan; Akhtar, Farid; Nilsson, Ulrika; Berglund, Lars; Bergström, Lennart

2015-07-08

Free standing and strong odor-removing composite films of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite adsorbents have been colloidally processed. Thermogravimetric desorption analysis (TGA) and infrared spectroscopy combined with computational simulations showed that commercially available silicalite-1 and ZSM-5 have a high affinity and uptake of volatile odors like ethanethiol and propanethiol, also in the presence of water. The simulations showed that propanethiol has a higher affinity, up to 16%, to the two zeolites compared with ethanethiol. Highly flexible and strong free-standing zeolite-CNF films with an adsorbent loading of 89 w/w% have been produced by Ca-induced gelation and vacuum filtration. The CNF-network controls the strength of the composite films and 100 μm thick zeolite-CNF films with a CNF content of less than 10 vol % displayed a tensile strength approaching 10 MPa. Headspace solid phase microextraction (SPME) coupled to gas chromatography-mass spectroscopy (GC/MS) analysis showed that the CNF-zeolite films can eliminate the volatile thiol-based odors to concentrations below the detection ability of the human olfactory system. Odor removing zeolite-cellulose nanofibril films could enable improved transport and storage of fruits and vegetables rich in odors, for example, onion and the tasty but foul-smelling South-East Asian Durian fruit.

Metal oxide blended ZSM-5 nanocomposites as ethanol sensors

Indian Academy of Sciences (India)

Framework of ZSM-5 structure consists of intersecting ... ges quality monitoring, environmental monitoring, indoor air quality and .... metric stretching vibrations of Si–O group [22]. ..... [17] Cheng Y, Liao R H, Li J S, Sun X Y and Wang L J 2008.

A comparative study on the quality of bio-oil derived from green macroalga Enteromorpha clathrata over metal modified ZSM-5 catalysts.

Science.gov (United States)

Wang, Shuang; Cao, Bin; Liu, Xinlin; Xu, Lujiang; Hu, Yamin; Afonaa-Mensah, Stephen; Abomohra, Abd El-Fatah; He, Zhixia; Wang, Qian; Xu, Shannan

2018-05-01

The green macroalga Enteromorpha clathrata was pyrolyzed with or without catalysts at the temperature of 550 °C for producing high-quality bio-oil. The ZSM-5 and 1,2,3 mmol Mg-Ce/ZSM-5 catalysts were introduced to investigate the yields and components distribution of bio-oil. Increase of bio-oil production was obtained with the use of ZSM-5 and 1,2,3 mmol Mg-Ce/ZSM-5 catalysts. The 1 mmol Mg-Ce/ZSM-5 catalyst exhibited more promising property for promoting the relative content of C 5 -C 7 compounds, and decreasing the relative content of acids in bio-oil. The results suggested that E. clathrata had potential as pyrolysis feedstocks for producing the high-quality bio-oil with large amounts of C 5 -C 7 compounds and low relative content of acids when the 1 mmol Mg-Ce/ZSM-5 catalyst was used. Furthermore, the physicochemical properties of ZSM-5 and 1 mmol Mg-Ce/ZSM-5 catalysts were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed desorption of ammonia. Copyright © 2018 Elsevier Ltd. All rights reserved.

Local structure of Pb2 ion catalysts anchored within zeolite cavities and their photo-catalytic reactivity for the elimination of N2O

International Nuclear Information System (INIS)

Ju, Woo-Sung; Matsuoka, Masaya; Yamashita, Hiromi; Anpo, Masakazu

2001-01-01

The Pb 2+ /ZSM-5 catalyst was prepared by an ion-exchange method and its photo-catalytic activity for the decomposition of N 2 O under UV irradiation was investigated. In-situ UV-Vis absorption spectroscopy and XAFS (XANES and FT-EXAFS) investigations revealed that the Pb 2+ ions exist in a highly dispersed state within the pores of the zeolites. UV irradiation of the catalysts in the presence of N 2 O led to the photo-catalytic decomposition of N 2 O into N 2 at temperatures as low as 298κ. The effective wavelength of the irradiated UV light indicated that the excited state of the Pb 2+ ions included within the zeolite cavities plays a significant role in the photo-catalytic decomposition of N 2 O molecules. (au)

An alternative preparation method for ion exchanged catalysts: Solid state redox reaction

DEFF Research Database (Denmark)

Schneider, E.; Hagen, A.; Grunwaldt, J.-D.

2004-01-01

A new method for modifying zeolites with zinc is proposed. The solid state redox reaction between metallic zinc and ZSM-5 zeolites with different Si/Al ratios was investigated by temperature programmed hydrogen evolution (TPHE), X-ray absorption near edge structure (XANES) and diffuse reflectance...... infrared Fourier transform spectroscopy (DRIFTS). The evolution of hydrogen was detected at temperatures above 620 K. The source of hydrogen was the solid state redox reaction of the metal with protons of the support. The samples exhibit catalytic activity in ethane aromatization indicating that zinc...... should be located at the same sites as in catalysts prepared by conventional methods. Combination of XANES and catalytic activity point to zinc being mainly present in tetrahedral geometry under reaction conditions....

Preparation of Zeolite/Zinc Oxide Nanocomposites for toxic metals removal from water

Directory of Open Access Journals (Sweden)

Abdullah A. Alswata

Full Text Available This research work has proposed preparation of Zeolite/Zinc Oxide Nanocomposite (Zeolite/ZnO NCs by using a co-precipitation method. Then, the prepared Nanocomposite has been tested for adsorption of Lead Pb (II and Arsenic As (V from aqueous solution under the room pressure and temperature. After that, the prepared adsorbent has been studied by several techniques. For adsorption process; the effect of the adsorbent masses, contact time, PH and initial metals concentration as well as, the kinetics and isotherm for adsorption process have been investigated. The results revealed that; ZnO nanoparticles (NPs with average diameter 4.5 nm have successfully been loaded into Zeolite. The optimum parameters for the removal of the toxic metals 93% and 89% of Pb (II and As (V, respectively, in 100 mg/L aqua solutions were pH4, 0.15 g and 30 min. According to the obtained results; pseudo second-order kinetic and Langmuir isotherm model have higher correlation coefficients and provided a better agreement with the experimental data. The prepared sorbent showed an economical and effective way to remove the heavy toxic metals due to its ambient operation conditions, low- consumption energy and facile regeneration method. Keywords: Zeolite, ZnO, Nanocomposites, Adsorbent, Kinetic, Isotherm

Pyrolysis of soybean oil with H-ZSM5 (Proton-exchange of Zeolite Socony Mobil 5) and MCM41 (Mobil Composition of Matter No. 41) catalysts in a fixed-bed reactor

International Nuclear Information System (INIS)

Ngo, Thanh-An; Kim, Jinsoo; Kim, Sun Kuk; Kim, Seung-Soo

2010-01-01

Soybean oil was pyrolyzed with various catalysts in a fixed-bed reactor under nitrogen flow at 420 and 450 o C. The H-ZSM5 catalysts (molar ratio SiO 2 /Al 2 O 3 = 28, 40, and 180) and 2 wt% (Ga, Al or Cu) impregnated MCM41 catalysts were used in order to investigate the effect of catalysts during the pyrolysis process. The gas products in all experiments were mainly methane, ethane and propylene. The liquid products in the presence of H-ZSM5 catalysts were mainly aromatic components while those with metal/MCM41 catalysts were a mixture of alkanes, alkenes, alkadienes, aromatic and carboxylic acids. The highest coke yield of 4.4 wt% was obtained with Ga/MCM41 catalyst at the pyrolysis temperature of 420 o C. The effect of catalysts on product yield and composition was systematically investigated.

A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.

Science.gov (United States)

Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y

2018-08-01

Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.

Synthesized TiO{sub 2}/ZSM-5 composites used for the photocatalytic degradation of azo dye: Intermediates, reaction pathway, mechanism and bio-toxicity

Energy Technology Data Exchange (ETDEWEB)

Zhou, Kefu; Hu, Xin-Yan [College of the Environment and Ecology, Xiamen University, Xiamen (China); Chen, Bor-Yann; Hsueh, Chung-Chuan [Department of Chemical and Materials Engineering, National I-Lan University, I-Lan, Taiwan (China); Zhang, Qian [Department of Environmental Engineering, National Taiwan University, Taipei, Taiwan (China); Wang, Jiajie; Lin, Yu-Jung [College of the Environment and Ecology, Xiamen University, Xiamen (China); Chang, Chang-Tang, E-mail: ctchang73222@gmail.com [Department of Environmental Engineering, National I-Lan University, I-Lan, Taiwan (China)

2016-10-15

Highlights: • The major photo-catalytic degradation pathway of azo-dye was elaborated according to the identification of by-products from GC–MS and IC analysis. • Comparative assessment on characteristics of abiotic and biotic dye decolorization was analyzed. • EDTA (hole scavengers) and t-BuOH (radical scavengers) were used to determine the main active oxidative species in the system. • The toxicity effects of degradation intermediates of Reactive Black 5 (RB5) on the cellular respiratory activity were assessed. - Abstract: In this study, a one-step solid dispersion method was used to synthesize titanium dioxide (TiO{sub 2})/Zeolite Socony Mobil-5 (ZSM-5) composites with substantially reduced time and energy consumption. A degradation efficiency of more than 95% was achieved within 10 min using 50% PTZ (synthesized TiO{sub 2}/ZSM-5 composites with TiO{sub 2} contents of 50 wt% loaded on ZSM-5) at pH 7 and 25 °C. The possible degradation pathway of azo-dye Reactive Black 5 (RB5) was investigated using gas chromatography–mass spectrometry and ion chromatography (IC). The bonds between the N atoms and naphthalene groups are likely attacked first and cleaved by hydroxyl radicals, ultimately resulting in the decolorization and mineralization of the azo dye. A comparative assessment of the characteristics of abiotic and biotic dye decolorization was completed. In addition, the toxicity effects of the degradation intermediates of azo-dye RB5 on cellular respiratory activity were analyzed. The bio-toxicity results showed that the decay rate constants of CO{sub 2} production from the azo-dye RB5 samples at different degradation times increased initially and subsequently decreased, indicating that intermediates of higher toxicity could adhere to the catalyst surface and gradually destroyed by further photocatalytic oxidation. Additionally, EDTA (hole scavengers) and t-BuOH (radical scavengers) were used to detect the main active oxidative species in the system

Exceptionally stable and hierarchically porous self-standing zeolite monolith based on a solution-mediated and solid-state transformation synergistic mechanism

Energy Technology Data Exchange (ETDEWEB)

Do, Manh Huy [Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, Zhejiang (China); College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang (China); Institute of Chemical Technology, Vietnamese Academy of Science and Technology, 01 Mac Dinh Chi, District 1, Ho Chi Minh (Viet Nam); Cheng, Dang-guo, E-mail: dgcheng@zju.edu.cn [College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang (China); Chen, Fengqiu [Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, Zhejiang (China); College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang (China); Zhan, Xiaoli [College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang (China)

2015-11-15

Although many strategies exist for fabricating hierarchical zeolite monolith, it is still challenging to synthesize pure hierarchical zeolite monolith with intracrystalline meso-/macropores and stability suitable for industrial application in a general and efficient process. Here we describe a simple quasi-solid gel crystallization route to prepare hierarchical self-standing ZSM-5 zeolite monolith via the use of Na{sup +} and OH{sup −} as counterions to modify the breaking and remaking of T–O–T (T = Si or Al) bonds. X-ray diffraction (XRD), scanning electron microcopy (SEM), transmission electron microscopy (TEM), laser scan confocal microscopy (LSCM), N{sub 2} adsorption–desorption, mercury porosimetry, solid-state nuclear magnetic resonance (NMR), and compression mechanical testing were applied to elucidate the structure and mechanical stability of the obtained monolith. The self-standing monolith is composed of self-interconnected meso-/macroporous MFI crystals with tunable intracrystalline meso-/macropores and possesses an unusually mechanical stability with a crushing strength of 5.01 MPa. Combined with controllable structure of the defect-free membrane layer on the monolith top, the self-standing zeolite monolith should widen their potential applications. - Highlights: • Hierarchical self-standing MFI zeolite monoliths were synthesized via a facile method. • Na{sup +} and OH{sup −} are used as counterions for breaking and remaking of T–O–T (T = Si or Al) bonds. • Hierarchical self-standing MFI zeolite monoliths result from zeolite crystal intergrowth. • Self-standing zeolite monolith has an excellent mechanical stability with tunable intracrystalline meso-/macropores.

Deactivation of La-Fe-ZSM-5 catalyst for selective catalytic reduction of NO with NH{sup 3}. Field study results

Energy Technology Data Exchange (ETDEWEB)

Qi, Gongshin; Yang, Ralph T. [Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Chang, Ramsay; Cardoso, Sylvio [Air Pollution Control, Power Generation, Electric Power Research Institute, Palo Alto, CA 94304-1395 (United States); Smith, Randall A. [Fossil Energy Research Corporation, Laguna Hills, CA 92653 (United States)

2004-11-08

Results are summarized for a study on the effects of poisons on the La-Fe-ZSM-5 catalyst activity for the selective catalytic reduction of NO by ammonia. The deactivation of La-Fe-ZSM-5 honeycombs was studied in field tests. A honeycomb catalyst containing 25%La-Fe-ZSM-5 had an overall activity similar to that of a commercial vanadia honeycomb catalyst. Long-term activity test results show that the 25%La-Fe-ZSM-5 catalyst activity decreased to 50% after 300h and 25% after 1769h of on-stream flue gas exposure. The deactivation is correlated to the amounts of poisons deposited on the catalyst. Poisons include alkali and alkaline earth metals, As and Hg. Hg was found to be ion-exchanged from HgCl{sup 2} to form Hg-ZSM-5, and Hg was found to be among the strongest poisons. The poisoning effects of these elements appeared to be additive. Thus, from the chemical analysis of the deactivated catalyst, the deactivation of Fe-ZSM-5 can be predicted.

Decomposição do NO sobre Cu suportado em zeólitas

Directory of Open Access Journals (Sweden)

Oliveira Andréa Marins de

2004-01-01

Full Text Available Direct decomposition of NO on copper supported on zeolite catalysts such as MCM-22 and Beta was compared with that on the thoroughly studied Cu-ZSM-5. The catalysts were prepared by ion-exchange in basic media. They were characterized by atomic absorption, surface area, nitrogen adsorption at 77K, X-ray diffraction and temperature programmed reduction. The products of the reaction were analyzed by Fourier transform infrared spectroscopy using a gas cell. Catalytic activity tests indicated that zeolite catalysts, like Beta and MCM-22, lead to NO conversion values comparable to ZSM-5.

Elucidation of the mechanism of conversion of methanol and ethanol to hydrocarbons on a new type of synthetic zeolite

NARCIS (Netherlands)

Derouane, E.G.; Nagy, J.B.; Dejaifve, P.; Hooff, van J.H.C.; Spekman, B.P.A.; Védrine, J.C.; Naccache, C.

1978-01-01

13C nuclear magnetic resonance and vapor-phase chromatography have been used to investigate the conversions of methanol and ethanol to hydrocarbons on a synthetic zeolite of the type H-ZSM-5 as described by Mobil. Methanol is first dehydrated to dimethyl ether and ethylene. Then the reaction

Does Density of Cationic Sites Affect Catalytic Activity of Co Zeolites in Selective Catalytic Reduction of NO with Methane?

Czech Academy of Sciences Publication Activity Database

Dědeček, Jiří; Kaucký, Dalibor; Wichterlová, Blanka

2002-01-01

Roč. 18, 3/4 (2002), s. 283-290 ISSN 1022-5528 R&D Projects: GA AV ČR IBS4040016 Institutional research plan: CEZ:AV0Z4040901 Keywords : Co zeolites * ZSM-5 * NO reduction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.648, year: 2002

Progress on Zeolite-membrane-aided Organic Acid Esterification

Science.gov (United States)

Makertiharta, I. G. B. N.; Dharmawijaya, P. T.

2017-07-01

Esterification is a common route to produce carboxylic acid esters as important intermediates in chemical and pharmaceutical industries. However, the reaction is equilibrium limited and needs to be driven forward by selective removal one of the products. There have been some efforts to selectively remove water from reaction mixture via several separation processes (such as pervaporation and reactive distillation). Integrated pervaporation and esterification has gained increasing attention towards. Inorganic zeolite is the most popular material for pervaporation due to its high chemical resistant and separation performance towards water. Zeolite also has proven to be an effective material in removing water from organic compound. Zeolite can act not only as selective layer but also simultaneously act as a catalyst on promoting the reaction. Hence, there are many configurations in integrating zeolite membrane for esterification reaction. As a selective layer to remove water from reaction mixture, high Si/Al zeolite is preferred to enhance its hydrophilicity. However, low Si/Al zeolite is unstable in acid condition due to dealumination thus eliminate its advantages. As a catalyst, acid zeolites (e.g. H-ZSM-5) provide protons for autoprotolysis of the carboxylic acid similar to other catalyst for esterification (e.g. inorganic acid, and ion exchange resins). There are many studies related to zeolite membrane aided esterification. This paper will give brief information related to zeolite membrane role in esterification and also research trend towards it.

Direct synthesis of carbon-templating mesoporous ZSM-5 using microwave heating

Czech Academy of Sciences Publication Activity Database

Koo, J.-B.; Jiang, N.; Saravanamurugan, S.; Voláková, Martina; Musilová, Zuzana; Čejka, Jiří; Park, S.-E.

2010-01-01

Roč. 276, č. 2 (2010), s. 327-334 ISSN 0021-9517 Institutional research plan: CEZ:AV0Z40400503 Keywords : mesoporous ZSM-5 * template * microwave irradiation * carbon Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.415, year: 2010

Enhanced 29Si spin-lattice relaxation and observation of three-dimensional lattice connectivity in zeolites by two-dimensional 29Si MASS NMR

International Nuclear Information System (INIS)

Sivadinarayana, C.; Choudhary, V.R.; Ganapathy, S.

1994-01-01

It is shown that considerable sensitivity enhancement is achieved in the 29 Si magic angle sample spinning (MASS) NMR spectra of highly siliceous zeolites by pre treating the material with oxygen. The presence of adsorbed molecular oxygen in zeolite channels promotes an efficient 29 Si spin-lattice relaxation via a paramagnetic interaction between the lattice 29 Si T-site and the adsorbed oxygen on zeolite channels. This affords an efficient 2-D data collection and leads to increased sensitivity. The utility of this method is demonstrated in a two-dimensional COSY-45 NMR experiment of a high silica zeolite ZSM-5. (author). 20 refs., 3 figs., 1 tab

Experimental Determination of the Molar Absorption Coefficient of n-Hexane Adsorbed on High-Silica Zeolites.

Science.gov (United States)

Gatti, Giorgio; Olivas Olivera, Diana F; Sacchetto, Vittoria; Cossi, Maurizio; Braschi, Ilaria; Marchese, Leonardo; Bisio, Chiara

2017-09-06

Determination of the molar absorption coefficients of the CH 3 bending mode at ν˜ =1380 cm -1 (ϵ 1380 ) of n-hexane adsorbed from the gas phase on two different dealuminated zeolites is derived by a combination of IR spectroscopy and microgravimetric analysis. High-silica zeolite Y (HSZ-Y) and zeolite ZSM-5 (with SiO 2 /Al 2 O 3 ratios of 200 and 280, respectively) with different textural and surface features are selected to evaluate the effect of the pore structure and architecture on the value of ϵ 1380 of the adsorbed n-hexane. Experimental data indicate that the molecule experiences a different adsorption environment inside zeolites; thus resulting in a significant change of the dipole moment and very different ϵ 1380 values: (0.278±0.018) cm μmol -1 for HSZ-Y and (0.491±0.032) cm μmol -1 for ZSM-5. Experimental data are also supported by computational modeling, which confirms the effect of different matrices on the IR absorption intensity. This study reveals that the use of probe molecules for quantitative measurements of surface sites has to be judiciously adopted, especially if adsorption occurs in the restricted spaces of microporous materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Fast Pyrolysis of Kraft Lignin over Hierarchical HZSM-5 and Hβ Zeolites

Directory of Open Access Journals (Sweden)

Yadong Bi

2018-02-01

Full Text Available The hierarchical HZSM-5 and Hβ zeolites were prepared by alkaline post-treatment methods adopting Na2CO3, TMAOH/NaOH mixture, and NaOH as desilication sources, respectively. More mesopores are produced over two kinds of zeolites, while the micropores portion is well preserved. The mesopores formed in hierarchical Hβ zeolites were directly related to the basicity of the alkaline solution, indicating that Hβ zeolite is more sensitive to the alkaline post-treatment. The hierarchical HZSM-5 and Hβ zeolites are more active than the parent one for catalytic fast pyrolysis (CFP of Kraft lignin. Hierarchical zeolites retained the function of acid catalysis, while additionally creating larger mesopores to ensure the entry of bulkier reactant molecules. The increase of the condensable volatiles yield can be attributed to the improvement of the mass transfer performance, which correlates well with the change of mesoporous surface area. In particular, the condensable volatiles yield for the optimized hierarchical Hβ reached approximately two times that of the parent Hβ zeolites. In contrast to the parent HZSM-5, the optimized hierarchical HZSM-5 zeolite significantly reduced the selectivity of oxygenates from 27.2% to 3.3%.

CO{sub 2} capture using zeolite 13X prepared from bentonite

Energy Technology Data Exchange (ETDEWEB)

Chen, Chao [Department of Chemistry and Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of); College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang, Henan Province 464000 (China); Park, Dong-Wha [Department of Chemistry and Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of); Ahn, Wha-Seung, E-mail: whasahn@inha.ac.kr [Department of Chemistry and Chemical Engineering, Inha University, Incheon 402-751 (Korea, Republic of)

2014-02-15

Zeolite 13X was prepared using bentonite as the raw material by alkaline fusion followed by a hydrothermal treatment without adding any extra silica or alumina sources. The prepared zeolite 13X was characterized by X-ray powder diffraction, N{sub 2}-adsorption–desorption measurements, and scanning electron microscopy. The CO{sub 2} capture performance of the prepared zeolite 13X was examined under both static and flow conditions. The prepared zeolite 13X showed a high BET surface area of 688 m{sup 2}/g with a high micropore volume (0.30 cm{sup 3}/g), and exhibited high CO{sub 2} capture capacity (211 mg/g) and selectivity to N{sub 2} (CO{sub 2}/N{sub 2} = 37) at 25 °C and 1 bar. In addition, the material showed fast adsorption kinetics, and stable CO{sub 2} adsorption–desorption recycling performance at both 25 and 200 °C.

Preparation of Synthetic Zeolites from Myanmar Clay Mineral

International Nuclear Information System (INIS)

Phyu Phyu Win

2004-04-01

Faujasite type zeolite X was successfully synthesized from Myanmar clay mineral kaolinite, by treating with sodium hydroxide at 820 C followed by dissolution in water and hydrothermal treatment. It was found that the solution of fused clay powder can be crystallized at 90C under ambient pressure to synthesize faujasite type zeolite X. The effects of aging time and the amount of water on the formation of the product phase and Si/ Al ratios of the resulting products were investigated. Most of the Si and Al components in kaolinite might be dissolved into an alkaline solution and reacted to form ring-like structures. Then it was effectively transformed into zeolite materials. The maximum relative crystallinity of faujasite zeolite obtained was found to be 100%. Zeolite P was found to be a competitive phase present in some resulting products during hydrothermal treatment. The cation exchange capacity of kaolinite is very low, but increased after a proper treatment. It was found that the prepared faujasite type zeolite X, zeolite P and hydrogen zeolite (HZ) can reduce the hardness, the alkalinity, the total dissolved solid and the dissolved iron of raw water in the batch wise operation of water treatment. Therefore, it can be used as the cation exchanged resin for water treatment

Structure-activity relations for Ni-containing zeolites during NO reduction. II. Role of the chemical state of Ni

NARCIS (Netherlands)

Mosqueda Jimenez, B.I.; Jentys, A.; Seshan, Kulathuiyer; Lercher, J.A.

2003-01-01

The influence of the metal in Ni-containing zeolites used as catalysts for the reduction of NO with propane and propene was studied. In the fresh catalysts, Ni is located in ion exchange positions for Ni/MOR, Ni/ZSM-5, and Ni/MCM-22. The formation of carbonaceous deposits, the removal of Al from

High-throughput preparation and testing of ion-exchanged zeolites

International Nuclear Information System (INIS)

Janssen, K.P.F.; Paul, J.S.; Sels, B.F.; Jacobs, P.A.

2007-01-01

A high-throughput research platform was developed for the preparation and subsequent catalytic liquid-phase screening of ion-exchanged zeolites, for instance with regard to their use as heterogeneous catalysts. In this system aqueous solutions and other liquid as well as solid reagents are employed as starting materials and 24 samples are prepared on a library plate with a 4 x 6 layout. Volumetric dispensing of metal precursor solutions, weighing of zeolite and subsequent mixing/washing cycles of the starting materials and distributing reaction mixtures to the library plate are automatically performed by liquid and solid handlers controlled by a single common and easy-to-use programming software interface. The thus prepared materials are automatically contacted with reagent solutions, heated, stirred and sampled continuously using a modified liquid handling. The high-throughput platform is highly promising in enhancing synthesis of catalysts and their screening. In this paper the preparation of lanthanum-exchanged NaY zeolites (LaNaY) on the platform is reported, along with their use as catalyst for the conversion of renewables

Experimental investigation of attrition resistance of zeolite catalysts in two particle gas-solid-solid fluidization system

International Nuclear Information System (INIS)

Nawaz, Z.; Ziaoping, T.; Shu, Q.; Wei, F.; Naveed, S.

2010-01-01

In the study of mechanical degradation of 34 ZSM-5 and SAPO catalysts, using the gas jet attrition - ASTM standard fluidized bed test (D-5757), the effect of particle size and its quantitative analysis in co-fluidization environment was investigated on the air jet index (AJI) basis. In gas-solid-solid fluidized bed reactors (GSS-FBR), two different sized particles were fluidized under isothermal conditions. In case of ZSM-5 and SAPO-34, significant attrition resistance was observed, which was attributed to small pore size and specific structural strength of the mobile framework image (MFI) and chabasite (CHA) structures, respectively. The optimum AJI for SAPO-34 and ZSM-5 (of particle size 0.2 mm) in GSS-fluidization system was observed to be 0.0118 and 0.0062, respectively. In co-fluidization, deviations from Gwyn relationship were observed due to change in impact of collision. Therefore, zeolites are recommended as suitable catalysts or catalytic supports (for doping of expensive metals) and for commercial use in GSS-FBR. (author)

Characterization of the Cu+ Sites in High-Silica Zeolites Interacting with CO Molecule: Combined Computational and Experimental Study

Czech Academy of Sciences Publication Activity Database

Davidová, Markéta; Nachtigallová, Dana; Bulánek, R.; Nachtigall, Petr

2003-01-01

Roč. 107, - (2003), s. 2327-2332 ISSN 1089-5647 R&D Projects: GA MŠk LN00A032; GA ČR GA203/00/0637 Institutional research plan: CEZ:AV0Z4040901 Keywords : exchanged ZSM-5 zeolite * x-ray absorption * photoluminescence spectra Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.679, year: 2003

Recent advances of pore system construction in zeolite-catalyzed chemical industry processes.

Science.gov (United States)

Shi, Jing; Wang, Yangdong; Yang, Weimin; Tang, Yi; Xie, Zaiku

2015-12-21

The kaleidoscopic applications of zeolite catalysts (zeo-catalysts) in petrochemical processes has been considered as one of the major accomplishments in recent decades. About twenty types of zeolite have been industrially applied so far, and their versatile porous architectures have contributed their most essential features to affect the catalytic efficiency. This review depicts the evolution of pore models in zeolite catalysts accompanied by the increase in industrial and environmental demands. The indispensable roles of modulating pore models are outlined for zeo-catalysts for the enhancement of their catalytic performances in various industrial processes. The zeolites and related industrial processes discussed range from the uni-modal micropore system of zeolite Y (12-ring micropore, 12-R) in fluid catalytic cracking (FCC), zeolite ZSM-5 (10-R) in xylene isomerization and SAPO-34 (8-R) in olefin production to the multi-modal micropore system of MCM-22 (10-R and 12-R pocket) in aromatic alkylation and the hierarchical pores in FCC and catalytic cracking of C4 olefins. The rational construction of pore models, especially hierarchical features, is highlighted with a careful classification from an industrial perspective accompanied by a detailed analysis of the theoretical mechanisms.

Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

Science.gov (United States)

Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

2018-05-01

A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

Czech Academy of Sciences Publication Activity Database

Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

2017-01-01

Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol-to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

Czech Academy of Sciences Publication Activity Database

Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

2017-01-01

Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol -to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

Perturbed angular correlation study of the ion exchange of indium into silicalite zeolites

International Nuclear Information System (INIS)

Ramallo-Lopez, J.M.; Requejo, F.G.; Renteria, M.; Bibiloni, A.G.; Miro, E.E.

1999-01-01

Two indium-containing silicalite zeolites (In/H-ZSM5) catalysts prepared by wet impregnation and ionic exchange were characterized by the Perturbed Angular Correlation (PAC) technique using 111 In as probe to determine the nature of the indium species. Some of these species take part in the catalytic reaction of the selective reduction (SCR) of NO x with methane. PAC experiments were performed at 500 deg. C in air before and after reduction-reoxidation treatments on the catalysts in order to determine the origin of the different hyperfine interactions and then the degree of ionic exchange. Complementary catalytic activity characterizations were also performed.PAC experiments performed on the catalyst obtained by wet impregnation showed that all In-atoms form In 2 O 3 crystallites while almost 70% of In-atoms form In 2 O 3 in the catalyst obtained by ionic exchange. The PAC experiments of both catalysts performed after the reduction-reoxidation treatment revealed the presence of two hyperfine interactions, different from those corresponding to indium in In 2 O 3 . These hyperfine interactions should be associated to disperse In species responsible of the catalytic activity located in the ionic exchange-sites of the zeolites

Supported Zeolite Beta Layers via an Organic Template-Free Preparation Route

Directory of Open Access Journals (Sweden)

Stephanie Reuss

2018-01-01

Full Text Available Layers of high silica zeolites, synthesized with an organic structure directing agent (OSDA and grown onto porous support structures, frequently suffer from the thermal stress during the removal of OSDA via the calcination process. The different thermal expansion coefficients of the zeolite and the support material, especially when stainless steel is used as a support, causes enormous tension resulting in defect formation in the zeolite layer. However, the calcination is an easy procedure to decompose the OSDA in the pore system of the zeolite. Recently, methods to synthesize zeolite beta without the use of an organic structure directing agent have been described. In the present study, a seed-directed synthesis is used to prepare OSDA-free zeolite beta layers on stainless steel supports via an in situ preparation route. For the application as membrane, a porous stainless steel support has been chosen. The beta/stainless steel composites are characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. To prove its possible application as a membrane, the beta/stainless steel composites were also tested by single gas permeances of H2, He, CO2, N2, and CH4.

Supported Zeolite Beta Layers via an Organic Template-Free Preparation Route.

Science.gov (United States)

Reuss, Stephanie; Sanwald, Dirk; Schülein, Marion; Schwieger, Wilhelm; Al-Thabaiti, Shaeel A; Mokhtar, Mohamed; Basahel, Sulaiman N

2018-01-21

Layers of high silica zeolites, synthesized with an organic structure directing agent (OSDA) and grown onto porous support structures, frequently suffer from the thermal stress during the removal of OSDA via the calcination process. The different thermal expansion coefficients of the zeolite and the support material, especially when stainless steel is used as a support, causes enormous tension resulting in defect formation in the zeolite layer. However, the calcination is an easy procedure to decompose the OSDA in the pore system of the zeolite. Recently, methods to synthesize zeolite beta without the use of an organic structure directing agent have been described. In the present study, a seed-directed synthesis is used to prepare OSDA-free zeolite beta layers on stainless steel supports via an in situ preparation route. For the application as membrane, a porous stainless steel support has been chosen. The beta/stainless steel composites are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). To prove its possible application as a membrane, the beta/stainless steel composites were also tested by single gas permeances of H₂, He, CO₂, N₂, and CH₄.

Preparation of a zeolite-modified polymer monolith for identification of synthetic colorants in lipsticks

Energy Technology Data Exchange (ETDEWEB)

Wang, Huiqi; Li, Zheng [College of Chemistry, Jilin University, Changchun 130012 (China); Niu, Qian [Jilin Entry-Exit Inspection and Quarantine Bureau, Changchun 130062 (China); Ma, Jiutong [College of Chemistry, Jilin University, Changchun 130012 (China); Jia, Qiong, E-mail: jiaqiong@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130012 (China)

2015-10-30

Graphical abstract: Poly(methacrylic acid-ethylene dimethacrylate) monolithic column embedded with zeolites was prepared and employed for the polymer monolith microextraction of colorants combined with HPLC. - Highlights: • Zeolite, as a kind of mesoporous material, was firstly combined with PMME. • Zeolite@poly(MAA-EDMA) monolith columns were prepared for the enrichment of colorants. • Zeolite@poly(MAA-EDMA) monolith columns demonstrated relatively high extraction capacity. - Abstract: A novel zeolite-modified poly(methacrylic acid-ethylenedimethacrylate) (zeolite@poly(MAA-EDMA)) monolithic column was prepared with the in situ polymerization method and employed in polymer monolith microextraction for the separation and preconcentration of synthetic colorants combined with high performance liquid chromatography. The polymer was characterized by scanning electronmicroscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermo-gravimetric analysis. Various parameters affecting the extraction efficiency were investigated and optimized. Under the optimum experimental conditions, we obtained acceptable linearities, low limits of detection, and good intra-day/inter-day relative standard deviations. The method was applied to the determination of synthetic colorants in lipsticks with recoveries ranged from 70.7% to 109.7%. Compared with conventional methacrylic acid-based monoliths, the developed monolith exhibited high enrichment capacity because of the introduction of zeolites into the preparation process. The extraction efficiency followed the order: zeolite@poly(MAA-EDMA) > poly(MAA-EDMA) > direct HPLC analysis.

Low-Temperature Pd/Zeolite Passive NO _x Adsorbers: Structure, Performance, and Adsorption Chemistry

Energy Technology Data Exchange (ETDEWEB)

Zheng, Yang [Institute for Integrated; Kovarik, Libor [Institute for Integrated; Engelhard, Mark H. [Institute for Integrated; Wang, Yilin [Institute for Integrated; Wang, Yong [Institute for Integrated; Gao, Feng [Institute for Integrated; Szanyi, János [Institute for Integrated

2017-07-14

Pd/zeolite passive NOx adsorber (PNA) materials were prepared with solution ion-exchange between NH4/zeolites (Beta, ZSM-5 and SSZ-13) and PdCl2 solutions. The nature of Pd (dispersion, distribution and oxidation states) in these materials was characterized with Na+ ion-exchange, TEM imaging, CO titration with FTIR and in situ XPS. The NOx trapping and release properties were tested using feeds with different compositions. It is concluded that multiple Pd species coexist in these materials: atomically dispersed Pd in the cationic sites of zeolites, and PdO2 and PdO particles on the external surfaces. While Pd is largely atomically dispersed in ZSM-5, the small pore opening for SSZ-13 inhibits Pd diffusion such that the majority of Pd stays as external surface PdO2 clusters. NOx trapping and release are not simple chemisorption and desorption events, but involve rather complex chemical reactions. In the absence of CO in the feed, cationic Pd(II) sites with oxygen ligands and PdO2 clusters are reduced by NO to Pd(I) and PdO clusters. These reduced sites are the primary NO adsorption sites. In the presence of H2O, the as-formed NO2 desorb immediately. In the presence of CO in the feed, metallic Pd, “naked” Pd2+, and Pd+ sites are responsible for NO adsorption. For Pd adsorption sites with the same oxidation states but in different zeolite frameworks, NO binding energies are not expected to vary greatly. However, NO release temperatures do vary substantially with different zeolite structures. This indicates that NO transport within these materials play an important role in determining release temperatures. Finally, some rational design principles on efficient PNA materials are suggested. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a

Self-templating synthesis of hollow spheres of zeolite ZSM-5 from spray-dried aluminosilicate precursor

Czech Academy of Sciences Publication Activity Database

Pashková, Veronika; Tokarová, V.; Brabec, Libor; Dědeček, Jiří

2016-01-01

Roč. 228, JUL 2016 (2016), s. 59-63 ISSN 1387-1811 R&D Projects: GA ČR GA15-13876S; GA MŠk LM2015073 Institutional support: RVO:61388955 Keywords : MFI * zeolite shells * template free synthesis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.615, year: 2016

Computational and fourier transform infrared spectroscopic studies on carbon monoxide adsorption on the zeolites Na-ZSM-5 and K-ZSM-5: Evidence of dual-cation sites

Czech Academy of Sciences Publication Activity Database

Areán, C. O.; Delgado, M. R.; Frolich, K.; Bulánek, R.; Pulido, Maria Angeles; Bibiloni, G. F.; Nachtigall, Petr

2008-01-01

Roč. 112, č. 12 (2008), s. 4658-4666 ISSN 1932-7447 R&D Projects: GA MŠk LC512; GA ČR GA203/06/0324 Grant - others:UIB(ES) MAT2005-05350 Institutional research plan: CEZ:AV0Z40550506 Keywords : zeolit * adsorpce * FTIR Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.396, year: 2008

Preparation and performance of manganese-oxide-coated zeolite for the removal of manganese-contamination in groundwater.

Science.gov (United States)

Lyu, Cong; Yang, Xuejiao; Zhang, Shengyu; Zhang, Qihui; Su, Xiaosi

2017-12-29

A promising and easily prepared catalytic filler media, manganese-oxide-coated zeolite (MOCZ), for the removal of Mn (II) contamination in groundwater was studied. The optimal condition for MOCZ preparation was given as follows: acid activation of zeolite with 5% HCl mass percent for 12 h, then soaking of acid-activated zeolite with 7% KMnO 4 mass percent for 8 h, and finally calcination at 300°C for 5 h. Acid activation significantly enlarged the specific surface area of the zeolite (>79 m 2  g -1 ), subsequently enhancing the coating of manganese oxides onto the surface of the zeolite. This was further supported by the manganese-to-zeolite ratio (γ Mn ) and Energy dispersive analysis-mapping. The γ Mn was over 12.26 mg Mn g -1 zeolite, representing more active sites for the adsorption and catalytic-oxidation of Mn (II). As such, great performance of Mn (II) removal by MOCZ was obtained in the filter experiment. An estimated 98-100% removal efficiency of Mn (II) was achieved in a greatly short startup time (only 2 h). During the filtration process, newborn flocculent manganese oxides with a mixed-valence of manganese (Mn (II) and Mn (IV)) were generated on the MOCZ surface, further facilitating the adsorption and catalytic-oxidation of Mn (II). The filter with MOCZ as adsorbent had a great performance on the Mn (II) removal in a wide range of hydraulic retention time (HRT) (4-40 min), particularly in a short HRT. Besides, the filter prolonged the filtration period (60 days), which would significantly reduce the frequency of backwash. Thus, it could be concluded that MOCZ prepared in this study showed a good performance in terms of Mn (II) removal in waterworks, especially small waterworks in the villages/towns.

Catalytic pyrolysis of wheat bran for hydrocarbons production in the presence of zeolites and noble-metals by using TGA-FTIR method.

Science.gov (United States)

Lazdovica, K; Liepina, L; Kampars, V

2016-05-01

Pyrolysis of wheat bran with or without catalysts was investigated using TGA-FTIR method in order to determine the influence of zeolite and noble metal catalysts on the evolution profile and relative yield of the volatile compounds. The addition of all catalysts decreased the volatile matter of wheat bran from 76.3% to 75.9%, 73.9%, 73.5%, 69.7% and increased the solid residue from 18.0% to 18.4%, 20.4%, 20.8%, 24.6% under the catalyst of ZSM-5, 5% Pd/C, MCM-41, and 5% Pt/C. Noble-metal catalysts had higher activity for deoxygenation of compounds containing carbonyl, carboxyl, and hydroxyl groups than zeolites. Degradation of nitrogen containing compounds atom proceeded better in presence of zeolites. Noble-metal catalysts promoted formation of aromatics and changed the profiles of evolved compounds whereas zeolites advanced formation of aliphatics and olefins. Copyright © 2016 Elsevier Ltd. All rights reserved.

Highly Oriented Growth of Catalytically Active Zeolite ZSM‐5 Films with a Broad Range of Si/Al Ratios

OpenAIRE

Fu, Donglong; Schmidt, Joel E.; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M.

2017-01-01

Abstract Highly b‐oriented zeolite ZSM‐5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films. Herein, using structure‐directing agents with hydroxy groups, we demonstrate a new method to prepare highly b‐oriented zeolite ZSM‐5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞)...

Oxygen-containing coke species in zeolite-catalyzed conversion of methanol to hydrocarbons

KAUST Repository

Liu, Zhaohui

2016-10-06

Zeolites are the most commonly used catalysts for methanol-to-hydrocarbon (MTH) conversion. Here, we identified two oxygen-containing compounds as coke species in zeolite catalysts after MTH reactions. We investigated the possible influences of the oxygen-containing compounds on coke formation, catalyst deactivation, product selectivity, and the induction period of the MTH reaction through a series of controlled experiments in which one of the identified compounds (2,3-dimethyl-2-cyclopenten-1-one) was co-fed with methanol over a zeolite H-ZSM-5 catalyst. Our results allow us to infer that once produced, the oxygen-containing compounds block the Brønsted acid sites by strong chemisorption and their rapid conversion to aromatics expedites the formation of coke and thus the deactivation of the catalyst. A minor effect of the production of such compounds during the MTH reaction is that the aromatic-based catalytic cycle can be slightly promoted to give higher selectivity to ethylene.

Characterization of ZSM-5 modified with niobium pentoxide: the study of thiophene adsorption

Energy Technology Data Exchange (ETDEWEB)

Cavalcanti, Rodrigo M.; Barros, Ivoneide de C.L., E-mail: ibarros@ufam.edu.br [Universidade Federal do Amazonas (UFAM), Manaus, AM (Brazil). Inst. de Ciencias Exatas; Dias, Jose A.; Dias, Silvia C.L. [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica

2013-01-15

ZSM-5 adsorbents impregnated with Nb{sub 2}O{sub 5} were applied in the sulfur removal in the form of thiophene, refractory substance of difficult removal of liquid fuels. For this purpose, a model fuel containing iso-octane contaminated with thiophene in concentrations of 877.5 to 1155 ppmw was prepared. The samples were characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR) and Fourier transform-Raman (FT-Raman) spectroscopies for confirmation of the adsorbents, being prioritized the adsorption study with that containing 5 wt.% of niobium pentoxide, because it showed a greater capacity for removal of thiophene. The best results of adsorption were achieved at 353 K, a longer time to reach equilibrium was observed. Under these conditions, the best kinetic fitting was achieved using the equation of pseudo-second order, demonstrating the domain of the phenomenon of chemisorption. While under lower temperatures, the diffusion model presented a better approximation of the experimental results. Also, the increasing of temperature did enhance spontaneous processes. (author)

Long-living positron and positronium states in zeolites and microcrystalline oxides

International Nuclear Information System (INIS)

Kajcsos, Zs.; Liszkay, L.; Varga, L.; Lohonyai, L.; Lazar, K.

1995-01-01

Positron annihilation (PA) investigation were performed on zeolites (X, Y and ZSM-5) and on microcrystalline MgO, Al 2 O 3 and SiO 2 , providing long lifetime components attributed to o-Ps atoms. In addition to the positron lifetime (LT) measurements, the energy distribution (ED) of the annihilation gamma radiation spectrum was recorded in the 30 keV - 1.5 MeV range for different samples and was compared to reference distributions for Si and GaAs samples, where no long-living Ps states are formed. Apart from the strong correlation with the water content in the samples, the positron data collected testify much more pronounced positronium hosting features for powders of the mentioned oxides than for zeolites. Positron LT spectroscopy combined with recording of the ED of the annihilation radiation provides reliable information on the forming of long living 3γ states. (author) 15 refs.; 4 figs

Conversion of South African coal fly ash into high-purity ZSM-5 zeolite without additional source of silica or alumina and its application as a methanol-to-olefins catalyst

CSIR Research Space (South Africa)

Missengue, RNM

2018-03-01

Full Text Available Characteristics of ZSM-5 synthesized from H2SO4-treated coal fly ash and fused coal fly ash extracts are compared in this study. In the synthesis process, fused coal fly ash extract (without an additional silica source) was used in the synthesis...

A novel zeolite process for clean end use of hydrocarbon products

Energy Technology Data Exchange (ETDEWEB)

Keskinen, K M [Neste Oy, Porvoo (Finland). Technology Centre

1997-12-31

In recent years zeolites such as ZSM-5 have attracted considerable interest for the catalysis of a wide range of hydrocarbon transformations. A novel process developed by Neste converts light olefins to higher molecular weight hydrocarbon products. A wide range of high quality diesel, solvents and lube oils can be produced by the new NESKO process. Hydrotreated products have excellent properties; negligible sulphur or nitrogen compounds, very low aromatic content and pour point lower than -50 deg C. Proprietary technology is used in this olefin oligomerization process. (author) (7 refs.)

A novel zeolite process for clean end use of hydrocarbon products

Energy Technology Data Exchange (ETDEWEB)

Keskinen, K.M. [Neste Oy, Porvoo (Finland). Technology Centre

1996-12-31

In recent years zeolites such as ZSM-5 have attracted considerable interest for the catalysis of a wide range of hydrocarbon transformations. A novel process developed by Neste converts light olefins to higher molecular weight hydrocarbon products. A wide range of high quality diesel, solvents and lube oils can be produced by the new NESKO process. Hydrotreated products have excellent properties; negligible sulphur or nitrogen compounds, very low aromatic content and pour point lower than -50 deg C. Proprietary technology is used in this olefin oligomerization process. (author) (7 refs.)

Hydrogen/Denterium exchange during n.butane conversion on H-ZSM-5

NARCIS (Netherlands)

Narbeshuber, T.; Narbeshuber, Thomas F.; Stockenhuber, Michael; Brait, Axel; Brait, A.; Seshan, Kulathuiyer; Lercher, J.A.

1996-01-01

Steady-state isotope tracer studies and isotope transient response experiments ofn-butane conversion on H-ZSM-5 (Si/Al = 35) were carried out between 673 and 823 K. Among the three main reactions, the rate of H/D-exchange is at least one order of magnitude higher compared to the rates of cracking or

Zeolite and wollastonite synthesis from rice hull ash

International Nuclear Information System (INIS)

Fernandes, Alberto de Andrade

2006-01-01

Rice hull ash (RHA) is a industry scrap rich in amorphous silica. A simple and low-energy cost method for the extraction of this silica was researched. A low level of impurity and high reactivity material was produced, which is appropriate for the synthesis of zeolites and wollastonite (CaSiO 3 ). The synthetic zeolites has not similar structures in nature, and they have been more and more valued in the market due to their purity and efficiency in specific applications like ion exchange, molecular sieve and catalysis areas. High purity wollastonite has many applications in manufacturing and agriculture. The mineral wollastonite can be formed in nature in different ways; it is generally accepted two forming processes, both encompassing limestone metamorphism (heat and pressure). In this work, a new process for the synthesis of zeolites and wollastonite from RHA colloidal silica was developed. Moreover, the process is aimed at lower energy costs, fewer stages and fewer reactants consume. In this work, zeolite A used in detergent and zeolite ZSM-5, employed in the petrochemical industry due to its high selectivity in catalytic reactions and its high thermo and acid stability, were synthesized. The first step of the wollastonite synthesis was studied, with the purpose of obtaining calcium hydrosilicate. Eleven different hydrosilicates occur in the system Ca(OH) 2 -SiO 2 -H 2 O, in the second step it was annealed to form the wollastonite phase. (author)

Comparison of different zeolite framework types as carriers for the oral delivery of the poorly soluble drug indomethacin.

Science.gov (United States)

Karavasili, Christina; Amanatiadou, Elsa P; Kontogiannidou, Eleni; Eleftheriadis, Georgios K; Bouropoulos, Nikolaos; Pavlidou, Eleni; Kontopoulou, Ioanna; Vizirianakis, Ioannis S; Fatouros, Dimitrios G

2017-08-07

Microporous zeolites of distinct framework types, textural properties and crystal morphologies namely BEA, ZSM and NaX, have been employed as carriers to assess their effect on modulating the dissolution behavior of a BCS II model drug (indomethacin). Preparation of the loaded carriers via the incipient wetness method induced significant drug amorphization for the BEA and NaX samples, as well as high drug payloads. The stability of the amorphous drug content was retained after stressing test evaluation of the porous carriers. The dissolution profile of loaded indomethacin was evaluated in simulated gastric fluid (pH 1.2) and simulated intestinal fluids FaSSIF (fasted) and FeSSIF (fed state) conditions and was found to be dependent on the aluminosilicate ratio of the zeolites and the degree of crystalline drug content. The feasibility of the zeolitic particles as oral drug delivery systems was appraised with cytocompatibility and cellular toxicity studies in Caco-2 cultures in a time- and dose-dependent manner by means of the MTT assay and flow cytometry analysis, respectively. Intracellular accumulation of the zeolite particles was observed with no apparent cytotoxic effects at the lower concentrations tested, rendering such microporous zeolites pertinent candidates in oral drug delivery applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Selective Production of Aromatics from 2-Octanol on Zinc Ion-Exchanged MFI Zeolite Catalysts

Directory of Open Access Journals (Sweden)

Masakazu Iwamoto

2015-12-01

Full Text Available The aromatization of 2-octanol derived from castor oil as a byproduct in the formation of sebacic acid was investigated on various zeolite catalysts. Zn ion-exchanged MFI (ZSM-5 zeolites with small silica/alumina ratios and zinc contents of 0.5 to 2.0 wt. % were determined to exhibit good and stable activity for the reaction at 623 to 823 K. The yield of aromatics was 62% at 773 K and the space velocity 350 to 1400 h−1. The temperature and contact time dependences of the product distributions indicated the reaction pathways of 2-octanol→dehydration to 2-octene→decomposition to C5 and C3 compounds→further decomposition to small alkanes and alkenes→aromatization with dehydrogenation. Alcohols with carbon numbers of 5 to 8 exhibited similar distributions of products compared to 2-octanol, while corresponding carbonyl compounds demonstrated different reactivity.

Hydrothermal preparation of zeolite Li-A and ion exchange properties of Cs and Sr in salt waste

International Nuclear Information System (INIS)

Lee, S. H.; Kim, J. G.; Lee, J. H.; Kim, J. H.

2005-01-01

An advanced spent fuel management process that were based on Li reduction of the oxide spent fuel to a metallic form will generate a LiCl waste. Zeolite A has been reported as a promising immobilization medium for waste salt with CsCl and SrCl 2 . However, Sodium is accumulated as an ionic form (Na + -ion) in molten salt during ion exchange step between Na + -ion in zeolite A and Li + -ion in the molten salt. Therefore, zeolite Na-A need to be replaced by the Li-type zeolite for recycling the salt waste by removing the Cs and Sr ions. In this study, the hydrothermal preparation of zeolite Li-A was performed in 350ml pressure vessel by P. Norby method. The preparation characteristics of zeolite Li-A was investigated. And the ion exchange properties of Cs and Sr in molten LiCl salt were investigated under the condition of 923K using zeolite 4A and prepared zeolite Li-A

Biochemical evolution. I. Polymerization on internal, organophilic silica surfaces of dealuminated zeolites and feldspars

Science.gov (United States)

Smith, Joseph V.

1998-01-01

Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars. PMID:9520372

Perturbed angular correlation study of the ion exchange of indium into silicalite zeolites

Energy Technology Data Exchange (ETDEWEB)

Ramallo-Lopez, J.M., E-mail: requejo@venus.fisica.unlp.edu.ar; Requejo, F.G., E-mail: requejo@venus.fisica.unlp.edu.ar; Renteria, M., E-mail: requejo@venus.fisica.unlp.edu.ar; Bibiloni, A.G. [UNLP, Programa TENAES (CONICET) and Departamento de Fisica, Faculdad Cs Ex (Argentina)], E-mail: requejo@venus.fisica.unlp.edu.ar; Miro, E.E. [UNL, INCAPE (CONICET) and Faculdad Ing. Quimica (Argentina)

1999-09-15

Two indium-containing silicalite zeolites (In/H-ZSM5) catalysts prepared by wet impregnation and ionic exchange were characterized by the Perturbed Angular Correlation (PAC) technique using {sup 111}In as probe to determine the nature of the indium species. Some of these species take part in the catalytic reaction of the selective reduction (SCR) of NO{sub x} with methane. PAC experiments were performed at 500 deg. C in air before and after reduction-reoxidation treatments on the catalysts in order to determine the origin of the different hyperfine interactions and then the degree of ionic exchange. Complementary catalytic activity characterizations were also performed.PAC experiments performed on the catalyst obtained by wet impregnation showed that all In-atoms form In{sub 2}O{sub 3} crystallites while almost 70% of In-atoms form In{sub 2}O{sub 3} in the catalyst obtained by ionic exchange. The PAC experiments of both catalysts performed after the reduction-reoxidation treatment revealed the presence of two hyperfine interactions, different from those corresponding to indium in In{sub 2}O{sub 3}. These hyperfine interactions should be associated to disperse In species responsible of the catalytic activity located in the ionic exchange-sites of the zeolites.

Preparation of zeolite-A/chitosan hybrid composites and their bioactivities and antimicrobial activities

International Nuclear Information System (INIS)

Yu, Liang; Gong, Jie; Zeng, Changfeng; Zhang, Lixiong

2013-01-01

Zeolite-A/chitosan hybrid composites with zeolite contents of 20–55 wt.% were prepared by in situ transformation of silica/chitosan mixtures in a sodium aluminate alkaline solution through impregnation–gelation–hydrothermal synthesis. The products were characterized by X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mercury penetration porosimetry. Their in vitro bioactivities were examined using as-synthesized and Ca 2+ -exchanged hybrid composites in simulated body fluid (SBF) for hydroxyapatite (HAP) growth. Their antimicrobial activities for Escherichia coli (E. coli) in trypticase soy broth (TSB) were evaluated using Ag + -exchanged hybrid composites. The zeolite-A/chitosan hybrid composites could be prepared as various shapes, including cylinders, plates and thin films. They possessed macropores with pore sizes ranging from 100 to 300 μm and showed compressive mechanical strength as high as 3.2 MPa when the zeolite content was 35 wt.%. Fast growth on the Ca 2+ -exchanged hybrid composites was observed with the highest weight gain of 51.4% in 30 days. The 35 wt.% Ag + -exchanged hybrid composite showed the highest antimicrobial activity, which could reduce the 9 × 10 6 CFU mL −1 E. coli concentration to zero within 4 h of incubation time with the Ag + -exchanged hybrid composite amount of 0.4 g L −1 . The bioactivity and antimicrobial activity could be combined by ion-exchanging the composites first with Ca 2+ and then with Ag + . These zeolite-A/chitosan hybrid composites have potential applications on tissue engineering and antimicrobial food packaging. - Graphical abstract: Zeolite A/chitosan hybrid composites were prepared by in situ transformation of precursors in the chitosan matrix, which possess macroporous structures and exhibit superior bioactivity and antimicrobial activity and potential biomedical application. Highlights: • Zeolite A

Preparation of zeolite-A/chitosan hybrid composites and their bioactivities and antimicrobial activities

Energy Technology Data Exchange (ETDEWEB)

Yu, Liang; Gong, Jie [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009 (China); Zeng, Changfeng [College of Mechanic and Power Engineering, Nanjing University of Technology, Nanjing 210009 (China); Zhang, Lixiong, E-mail: lixiongzhang@yahoo.com [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009 (China)

2013-10-15

Zeolite-A/chitosan hybrid composites with zeolite contents of 20–55 wt.% were prepared by in situ transformation of silica/chitosan mixtures in a sodium aluminate alkaline solution through impregnation–gelation–hydrothermal synthesis. The products were characterized by X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mercury penetration porosimetry. Their in vitro bioactivities were examined using as-synthesized and Ca{sup 2+}-exchanged hybrid composites in simulated body fluid (SBF) for hydroxyapatite (HAP) growth. Their antimicrobial activities for Escherichia coli (E. coli) in trypticase soy broth (TSB) were evaluated using Ag{sup +}-exchanged hybrid composites. The zeolite-A/chitosan hybrid composites could be prepared as various shapes, including cylinders, plates and thin films. They possessed macropores with pore sizes ranging from 100 to 300 μm and showed compressive mechanical strength as high as 3.2 MPa when the zeolite content was 35 wt.%. Fast growth on the Ca{sup 2+}-exchanged hybrid composites was observed with the highest weight gain of 51.4% in 30 days. The 35 wt.% Ag{sup +}-exchanged hybrid composite showed the highest antimicrobial activity, which could reduce the 9 × 10{sup 6} CFU mL{sup −1}E. coli concentration to zero within 4 h of incubation time with the Ag{sup +}-exchanged hybrid composite amount of 0.4 g L{sup −1}. The bioactivity and antimicrobial activity could be combined by ion-exchanging the composites first with Ca{sup 2+} and then with Ag{sup +}. These zeolite-A/chitosan hybrid composites have potential applications on tissue engineering and antimicrobial food packaging. - Graphical abstract: Zeolite A/chitosan hybrid composites were prepared by in situ transformation of precursors in the chitosan matrix, which possess macroporous structures and exhibit superior bioactivity and antimicrobial activity and potential biomedical

Synthesis of 4A zeolites from kaolin for obtaining 5A zeolites through ionic exchange for adsorption of arsenic

International Nuclear Information System (INIS)

Resmini Melo, Carolina; Gracher Riella, Humberto; Cabral Kuhnen, Nivaldo; Angioletto, Elidio; Melo, Aline Resmini; Bernardin, Adriano Michael; Rocha, Marcio Roberto da; Silva, Luciano da

2012-01-01

Highlights: ► We synthesize 4A zeolite from kaolin by hydrothermal reaction with sodium hydroxide. ► The 4A zeolite synthesized underwent ion exchange with calcium ions, with different parameters, to obtain 5A zeolites. ► The best 4A zeolite obtained was used as adsorbent material for arsenic ions. ► The results showed that the 5A zeolite material obtained is a good adsorber of heavy ions. - Abstract: The synthesis of adsorbing zeolite materials requires fine control of the processing variables. There are distinct process variable settings for obtaining specific desired types of zeolites. The intent of this study was to obtain 4A zeolites from kaolin in order to obtain 5A zeolites through ionic exchange with the previously synthesized zeolite. This zeolite 5A was used as an adsorbent for arsenic ions. The results obtained were satisfactory.

Influence of zeolite pore structure on product selectivities for protolysis and hydride transfer reactions in the cracking of n-pentane.

Science.gov (United States)

Miyaji, Akimitsu; Iwase, Yasuyoshi; Nishitoba, Toshiki; Long, Nguyen Quang; Motokura, Ken; Baba, Toshihide

2015-02-21

The conversion of n-pentane was carried out to examine the effects of reaction conditions on changes in product selectivities at 823 K, using zeolites with 10- and 12-membered rings. We also investigated the influence of the pore structure of these zeolites on their catalytic activities for both protolysis and hydride transfer reactions. In the first half of this work, we examined the influence of acidic proton concentration and n-pentane pressure on the reaction rates for protolysis and hydride transfer reactions using ZSM-5 zeolites. The rates of hydride transfer reactions were more influenced by pentane pressure compared to protolysis reactions, and were proportional to the square of n-pentane pressure and the concentration of acidic protons. In the second half of this work, the influence of the zeolite pore structure on changes in product selectivities with n-pentane conversion and that on the rates of protolysis and the hydride transfer reactions were revealed using various zeolites with 10- and 12-membered rings. The catalytic activities of zeolites for the protolysis and hydride transfer reactions were influenced more by the spatial volume of the zeolite cavity than the acid strength of protons on the zeolite.

Salt-occluded zeolite waste forms: Crystal structures and transformability

International Nuclear Information System (INIS)

Richardson, J.W. Jr.

1996-01-01

Neutron diffraction studies of salt-occluded zeolite and zeolite/glass composite samples, simulating nuclear waste forms loaded with fission products, have revealed complex structures, with cations assuming the dual roles of charge compensation and occlusion (cluster formation). These clusters roughly fill the 6--8 angstrom diameter pores of the zeolites. Samples are prepared by equilibrating zeolite-A with complex molten Li, K, Cs, Sr, Ba, Y chloride salts, with compositions representative of anticipated waste systems. Samples prepared using zeolite 4A (which contains exclusively sodium cations) as starting material are observed to transform to sodalite, a denser aluminosilicate framework structure, while those prepared using zeolite 5A (sodium and calcium ions) more readily retain the zeolite-A structure. Because the sodalite framework pores are much smaller than those of zeolite-A, clusters are smaller and more rigorously confined, with a correspondingly lower capacity for waste containment. Details of the sodalite structures resulting from transformation of zeolite-A depend upon the precise composition of the original mixture. The enhanced resistance of salt-occluded zeolites prepared from zeolite 5A to sodalite transformation is thought to be related to differences in the complex chloride clusters present in these zeolite mixtures. Data relating processing conditions to resulting zeolite composition and structure can be used in the selection of processing parameters which lead to optimal waste forms

Preparation and characterization of polysulfone/zeolite mixed matrix membranes for removal of low-concentration ammonia from aquaculture wastewater.

Science.gov (United States)

Moradihamedani, Pourya; Abdullah, Abdul Halim

2018-01-01

Removal of low-concentration ammonia (1-10 ppm) from aquaculture wastewater was investigated via polysulfone (PSf)/zeolite mixed matrix membrane. PSf/zeolite mixed matrix membranes with different weight ratios (90/10, 80/20, 70/30 and 60/40 wt.%) were prepared and characterized. Results indicate that PSf/zeolite (80/20) was the most efficient membrane for removal of low-concentration ammonia. The ammonia elimination by PSf/zeolite (80/20) from aqueous solution for 10, 7, 5, 3 and 1 ppm of ammonia was 100%, 99%, 98.8%, 96% and 95% respectively. The recorded results revealed that pure water flux declined in higher loading of zeolite in the membrane matrix due to surface pore blockage caused by zeolite particles. On the other hand, ammonia elimination from water was decreased in higher contents of zeolite because of formation of cavities and macrovoids in the membrane substructure.

Preparation of Zeolite Molecular Sieve by Using Hydrogel Method

International Nuclear Information System (INIS)

Swe Zin Win; Mu Mu Htay; Mya Mya Oo

2010-12-01

Zeolite A was synthesized from hydrogel solution which prepared from silica and alumina precursors under hydrothermal condition at atmospheric pressure. Before preparing of hydrogel solution, the amount of raw materials which used in resulting hydrogel with appropriate mole ratio was calculated by material balance. In this study,totally ten experiments were carried out for zeolite A formation. The important parameters for these experiments were the kinds of precursors,their concentration (starting material composition), synthesis time and temperature. All product samples from these experiments were characterized by X-ray Diffraction (XRD), Scanning Electron Microscope (SEM) and analyzed by gravimetric method. The results show that the favourable sample for this research work which can be prepared with a molar composition of SiO2: Al2O3: 2Na2O: 70H2O by agitation at room temperature for 30 minutes, ageing at room temperature and crystallization at 95Ccentre dot centre dot for 24hrs. The percent yield of favourable result is 70%.

Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production

Energy Technology Data Exchange (ETDEWEB)

Volli, Vikranth; Purkait, M.K., E-mail: mihir@iitg.ernet.in

2015-10-30

Highlights: • Flyash was utilized for zeolites preparation for transesterification. • Single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio of 1:1.2. • Si/Al ratio of 2 resulted in the formation of zeolite X. • At 5 wt% of catalyst loading conversion was 84.6%. • The biodiesel obtained has a calorific value of 37.5 MJ/Kg. - Abstract: This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12 h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity.

Pramana – Journal of Physics | Indian Academy of Sciences

Indian Academy of Sciences (India)

Here we report the quasielastic neutron scattering and FTIR studies on the dynamics of propylene adsorbed in Na-Y and Na-ZSM5 zeolites. QENS data show that although the mechanism of translational motion of propylene is jump diffusion in both the cases of Na-Y and Na-ZSM5 zeolites, the diffusivity is affected by the ...

[Adsorption characteristics of acetone and butanone onto honeycomb ZSM-5 molecular sieve].

Science.gov (United States)

Du, Juan; Luan, Zhi-Qiang; Xie, Qiang; Ye, Ping-Wei; Li, Kai; Wang, Xi-Qin

2013-12-01

Adsorption capacity of acetone and acetone-butanone mixture onto honeycomb ZSM-5 molecular sieve was measured in this paper, and the influences of relative humidity, initial adsorbate concentration and airflow velocity on the adsorption process were investigated. Besides, adsorption performance parameters were calculated by Wheeler's equation. The results showed that relative humidity had no obvious influence on the acetone adsorption performance, which suggests that this material has good hydrophobic ability; in the low concentration range, the dynamic saturated adsorption capacity of acetone increased with the increase of initial concentration, but in the occasion of high concentration of acetone gas (more than 9 mg x L(-1)), the dynamic saturated adsorption capacity maintained at a certain level and did not vary with the increase of initial concentration; the increase of air flow velocity resulted in significant increase of acetone adsorption rate constant, at the same time the critical layer thickness of the adsorbent bed also increased significantly. In the cases of acetone-butanone mixture, the adsorption capacity of butanone onto ZSM-5 was clearly higher than that of acetone.

Enhanced propylene production in FCC by novel catalytic materials

Energy Technology Data Exchange (ETDEWEB)

Kelkar, C.P.; Harris, D.; Xu, M.; Fu, J. [BASF Catalyst LLC, Iselin, NJ (United States)

2007-07-01

Fluid catalytic cracking is expected to increasingly supply the additional incremental requirements for propylene. The most efficient route to increase propylene yield from an FCC unit is through the use of medium pore zeolites such as ZSM-5. ZSM-5 zeolite cracks near linear olefins in the gasoline range to LPG olefins such as propylene and butylenes. This paper will describe catalytic approaches to increase gasoline range olefins and the chemistry of ZSM-5 to crack those olefins. The paper will also describe novel catalytic materials designed to increase propylene. (orig.)

Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides

Czech Academy of Sciences Publication Activity Database

Hernando, H.; Moreno, I.; Fermoso, J.; Ochoa-Hernández, Cristina; Pizarro, P.; Coronado, J. M.; Čejka, Jiří; Serrano, D. P.

2017-01-01

Roč. 7, č. 3 (2017), s. 289-304 ISSN 2190-6815 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : catalytic fast pyrolysis * hierarchial zeolite * bio -oil upgrading Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides

Czech Academy of Sciences Publication Activity Database

Hernando, H.; Moreno, I.; Fermoso, J.; Ochoa-Hernández, Cristina; Pizarro, P.; Coronado, J. M.; Čejka, Jiří; Serrano, D. P.

2017-01-01

Roč. 7, č. 3 (2017), s. 289-304 ISSN 2190-6815 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : catalytic fast pyrolysis * hierarchial zeolite * bio-oil upgrading Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Hydrodeoxygenation of Methyl Laurate over Ni Catalysts Supported on Hierarchical HZSM-5 Zeolite

Directory of Open Access Journals (Sweden)

Nana Li

2017-12-01

Full Text Available The hierarchical HZSM-5 zeolite was prepared successfully by a simple NaOH treatment method. The concentration of NaOH solution was carefully tuned to optimal the zeolite acidity and pore structure. Under NaOH treatment conditions, a large number of mesopores, which interconnected with the retained micropores, were created to facilitate mass transfer performance. There are very good correlations between the decline of the relative zeolite crystallinity and the loss of micropores volume. The Ni nanoclusters were uniformly confined in the mesopores of hierarchical HZSM-5 by the excessive impregnation method. The direct deoxygenation in N2 and hydrodeoxygenation in H2 of the methyl laurate were compared respectively over the Ni/HZSM-5 catalysts. In the N2 atmosphere, the deoxygenation rate of the methyl laurate on the Ni/HZSM-5 catalyst is relatively slow. In the presence of H2, the synergistic effect between the hydrogenation function of the metal and the acid function of the zeolite supports can make the deoxygenation level more obvious. The yield of hydrocarbon products gradually reached the maximum with the appropriate treatment concentration of 1M NaOH, which could be attributed to the improved mass transfer in the hierarchical HZSM-5 supports.

PREPARATION OF ZEOLITE X COATINGS ON SODA-LIME TYPE GLASS PLATES

Directory of Open Access Journals (Sweden)

M. Tatlier

Full Text Available Abstract The dissolution of glass in highly alkaline reaction mixtures and the impact of this phenomenon on zeolite coating formation were investigated. Coating samples were prepared and characterized by X-ray diffraction (XRD, field emission gun scanning electron microscopy (FEGSEM and thermogravimetry (TG. It was demonstrated that zeolite X coatings might be prepared on soda-lime glass. Glass dissolved to some degree, up to 2% of its original mass, in the reaction mixtures for the conditions investigated. This dissolution affected the zeolite synthesis taking place on the glass surface, resulting in phases different from those obtained on inert metal surfaces in some cases, especially for the use of reaction mixtures with relatively high Si/Al ratios. The percentage of dissolution of glass plates increased with their decreasing thickness, indicating a surface phenomenon for the dissolution. The stabilities of the coatings, which varied with the synthesis conditions, benefited from the addition of extra thin layers of polyacrylic acid.

Solvent-Free Biginelli Reactions Catalyzed by Hierarchical Zeolite Utilizing a Ball Mill Technique: A Green Sustainable Process

Directory of Open Access Journals (Sweden)

Ameen Shahid

2017-03-01

Full Text Available A sustainable, green one-pot process for the synthesis of dihydropyrimidinones (DHPMs derivatives by a three-component reaction of β-ketoester derivatives, aldehyde and urea or thiourea over the alkali-treated H-ZSM-5 zeolite under ball-milling was developed. Isolation of the product with ethyl acetate shadowed by vanishing of solvent was applied. The hierachical zeolite catalyst (MFI27_6 showed high yield (86%–96% of DHPMs in a very short time (10–30 min. The recyclability of the catalyst for the subsequent reactions was examined in four subsequent runs. The catalyst was shown to be robust without a detectable reduction in catalytic activity, and high yields of products showed the efficient protocol of the Biginelli reactions.

Mesoporous carbon prepared from carbohydrate as hard template for hierarchical zeolites

DEFF Research Database (Denmark)

Egeblad, Kresten; Christensen, Claus H.

2007-01-01

treatment of a mixture of sucrose and ammonia followed by carbonization of the mixture in N-2 at high temperatures. The porous carbon produced by this method was subsequently applied as a hard template in the synthesis of mesoporous silicalite-1 and removed by combustion after synthesis. X-ray diffraction......A mesoporous carbon prepared from sucrose was successfully employed as a hard template to produce hierarchical silicalite-1, thus providing a very simple and inexpensive route to desirable zeolite catalysts from widely available raw materials. The porous carbon was prepared by hydrothermal...... the porous carbon template as well as the mesoporous zeolite single-crystal material....

Probing Zeolite Crystal Architecture and Structural Imperfections using Differently Sized Fluorescent Organic Probe Molecules.

Science.gov (United States)

Hendriks, Frank C; Schmidt, Joel E; Rombouts, Jeroen A; Lammertsma, Koop; Bruijnincx, Pieter C A; Weckhuysen, Bert M

2017-05-05

A micro-spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4-(4-diethylaminostyryl)-1-methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM-5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization-dependent measurements provide evidence for the probe molecule's alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture-dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X-ray diffraction. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

The conversion of dimethyl ether over Pt/H-ZSM5. A bifunctional catalyzed reaction

NARCIS (Netherlands)

Engelen, C.W.R.; Wolthuizen, J.P.; Hooff, van J.H.C.; Imelik, B.; Naccache, C.; Coudurier, G.

1985-01-01

At low temperatures dimethylether mixed with hydrogen reacts over a platinum loaded H-ZSM5 catalyst selectivity to methane. Two successive steps can be distinguished; first the acid-catalyzed formation of a trimethyloxoniumion, followed by a metal-catalyzed hydrogenation to methane. Experiments with

Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming

NARCIS (Netherlands)

Ristanovic, Zoran|info:eu-repo/dai/nl/328233005; Hofmann, Jan P.|info:eu-repo/dai/nl/355351110; De Cremer, Gert; Kubarev, Alexey V.; Rohnke, Marcus; Meirer, Florian; Hofkens, Johan; Roeffaers, Maarten B. J.; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

2015-01-01

Optimizing the number, distribution, and accessibility of Bronsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by

Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis.

Science.gov (United States)

van der Bij, Hendrik E; Weckhuysen, Bert M

2015-10-21

Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus-zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus-zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research.

Long-term storage of 85Kr in amorphous zeolite 5A

International Nuclear Information System (INIS)

Penzhorn, R.D.; Noppel, H.E.; Dorea, A.; Guenther, K.; Leitzig, H.; Schuster, P.

1984-01-01

Ar, Kr and Xe can be immobilized in type A zeolites as well as in mordenite and chabazite, when the original crystal structure is hydrothermally vitrified in the presence of the densified gas. Zeolites containing a high percentage of earth alcali metals yield encapsulates that are thermally very stable. Gas fixation conditions are essentially independent of the form of aggregation of the matrix. Noble gas encapsulates were characterized by their specific surface area as well as by microprobe analysis, X-ray analysis and electron diffraction. The results indicate that Kr is immobilized in units smaller than the size of a zeolite crystal. The thermal conductivity of zeolites was determined experimentally in various fluid media. With the data obtained the heat transport through a final storage vessel cooled by natural air convection was calculated. The estimated temperature profiles correlate well with those obtained in experiments simulating a storage containment. To verify the process, active samples having specific activities up to 30 mCi/g have been prepared. Leaching results demonstrate the chemical stability of the Kr/5A encapsulates. A semi-pilot facility based on the one-way autoclave concept has been constructed and demonstrated in operation

Catalytic oxidation of butyl acetate over silver-loaded zeolites

International Nuclear Information System (INIS)

Wong, Cheng Teng; Abdullah, Ahmad Zuhairi; Bhatia, Subhash

2008-01-01

The performance of silver-loaded zeolite (HY and HZSM-5) catalysts in the oxidation of butyl acetate as a model volatile organic compound (VOC) was studied. The objective was to find a catalyst with superior activity, selectivity towards deep oxidation product and stability. The catalyst activity was measured under excess oxygen condition in a packed bed reactor operated at gas hourly space velocity (GHSV) = 15,000-32,000 h -1 , reaction temperature between 150 and 500 deg. C and butyl acetate inlet concentration of 1000-4000 ppm. Both AgY and AgZSM-5 catalysts exhibited high activity in the oxidation of butyl acetate. Despite lower silver content, AgY showed better activity, attributed to better metal dispersion, surface characteristics and acidity, and its pore system. Total conversion of butyl acetate was achieved at above 400 deg. C. The oxidation of butyl acetate followed a simple power law model. The reaction orders, n and m were evaluated under differential mode by varying the VOC partial pressure between 0.004 and 0.018 atm and partial pressure of oxygen between 0.05 and 0.20 atm. The reaction rate was independent of oxygen concentration and single order with respect to VOC concentration. The activation energies were 19.78 kJ/mol for AgY and 32.26 kJ/mol for AgZSM-5, respectively

Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity.

Science.gov (United States)

Schwieger, Wilhelm; Machoke, Albert Gonche; Weissenberger, Tobias; Inayat, Amer; Selvam, Thangaraj; Klumpp, Michael; Inayat, Alexandra

2016-06-13

'Hierarchy' is a property which can be attributed to a manifold of different immaterial systems, such as ideas, items and organisations or material ones like biological systems within living organisms or artificial, man-made constructions. The property 'hierarchy' is mainly characterised by a certain ordering of individual elements relative to each other, often in combination with a certain degree of branching. Especially mass-flow related systems in the natural environment feature special hierarchically branched patterns. This review is a survey into the world of hierarchical systems with special focus on hierarchically porous zeolite materials. A classification of hierarchical porosity is proposed based on the flow distribution pattern within the respective pore systems. In addition, this review might serve as a toolbox providing several synthetic and post-synthetic strategies to prepare zeolitic or zeolite containing material with tailored hierarchical porosity. Very often, such strategies with their underlying principles were developed for improving the performance of the final materials in different technical applications like adsorptive or catalytic processes. In the present review, besides on the hierarchically porous all-zeolite material, special focus is laid on the preparation of zeolitic composite materials with hierarchical porosity capable to face the demands of industrial application.

Spatial Distribution of Zeolite ZSM-5 within Catalyst Bodies Affects Selectivity and Stability of Methanol-to-Hydrocarbons Conversion

NARCIS (Netherlands)

Castaño, P.; Ruiz-Martinez, J.; Epelde, E.; Gayubo, A.G.; Weckhuysen, B.M.

2013-01-01

Solid acids, such as zeolites, are used as catalyst materials in a wide variety of important crude oil refinery, bulk chemical synthesis, and green processes. Examples include fluid catalytic cracking (FCC),[1] methanol-to-hydrocarbons (MTH) conversion,[ 2] plastic waste valorization,[3] and biomass

Preparation of granular activated carbons from composite of powder activated carbon and modified β-zeolite and application to heavy metals removal.

Science.gov (United States)

Seyedein Ghannad, S M R; Lotfollahi, M N

2018-03-01

Heavy metals are continuously contaminating the surface and subsurface water. The adsorption process is an attractive alternative for removing the heavy metals because of its low cost, simple operation, high efficiency, and flexible design. In this study, influences of β-zeolite and Cu-modified β-zeolite on preparation of granular activated carbons (GACs) from a composite of powder activated carbon (PAC), methylcellulose as organic binder, bentonite as inorganic binder, and water were investigated. A number of granular samples were prepared by controlling the weight percentage of binder materials, PAC and zeolites as a reinforcing adsorbent. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction techniques were employed to characterize zeolite, modified zeolite and produced GAC. The produced GACs were used as the adsorbent for removal of Zn +2 , Cd 2+ and Pb 2+ ions from aqueous solutions. The results indicated that the adsorption of metals ions depended on the pH (5.5) and contact time (30 min). Maximum adsorption of 97.6% for Pb 2+ , 95.9% for Cd 2+ and 91.1% for Zn +2 occurred with a new kind of GAC made of Cu-modified β-zeolite. The Zn +2 , Cd 2+ and Pb 2+ ions sorption kinetics data were well described by a pseudo-second order model for all sorbents. The Langmuir and Freundlich isotherm models were applied to analyze the experimental equilibrium data.

Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals.

Science.gov (United States)

Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

2016-07-05

Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites.

Preparation and characterization of new zeolite membranes. Application to gaseous separation; Preparation et caracterisation de nouvelles membranes de zeolithe application a la separation gazeuse

Energy Technology Data Exchange (ETDEWEB)

Anstett, M.

1996-11-25

Zeolites are interesting for the preparation of inorganic membranes which could be used for the continuous separation of gas and liquids by gas permeation and pervaporation. Zeolites membranes are obtained by hydrothermal synthesis and are characterized by XRD, SEM, TDA, IR, chemical analysis, EPMA, NMR, MAS NMR and gas permeation. After some tests of preparation of zeolite CHA and MFI self supporting membranes, the work is turned towards the preparation of zeolite MFI membranes supported by porous disks or {alpha} alumina, glass and tubes of carbon covered with a thin layer or zirconium dioxide. It is shown that the characteristics of the support (reactivity, pores dimensions, ...) strongly influence the quality of the prepared membrane. Two originals preparation processes are finalized. For the alumina disks, a gel precursor of zeolite is firs formed at the surface of the support by immersing successively that support in two non miscible liquids before the crystallisation. The gel is then converted into the zeolite by contact with water vapor. The zeolite layer obtained is localized at the surface of the support and present not only at the outside but also at the inside of the support. The characteristics of the zeolite layer can be controlled and the method can be adapted to various porous supports. The membrane obtained is interesting for hydrocarbons separations, for example the separation of methane and isobutane. In the case of Vycor glass disks, the reactivity of the support is first enhanced by contact with saturated water vapour. The temperature of the synthesis is then chosen relatively low in order to limit the attack of the support. With that method, a basic solution can be used without degradation of the support.The basicity leads to the formation of little crystals whose assembling is compact and homogeneous. The membrane obtained is interesting for example for the separation of normal butane and isobutane. (author) 71 refs.

Solution-mediated growth of NBA-ZSM-5 crystals retarded by gel entrapment

Science.gov (United States)

Aguilar-Mamani, Wilson; Akhtar, Farid; Hedlund, Jonas; Mouzon, Johanne

2018-04-01

The synthesis of flat tablet-shaped ZSM-5 crystals from a gel using metakaolin as aluminosilicate source and n-butyl amine as structure directing agent was investigated. The evolution inside the solid phase was characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetry and mass spectrometry. A kinetic study indicated that the nucleation of the majority crystals occurred concurrently with the formation of the gel upon heating the starting liquid suspension. Microstructural evidences undeniably showed that the gel precipitated on ZSM-5 crystals and mineral impurities originating from kaolin. As a result, crystal growth was retarded by gel entrapment, as indicated by the configuration and morphology of the embedded crystals. The results presented herein are harmonized with a solution-mediated nucleation and growth mechanism. Our observations differ from the autocatalytic model that suggests that the nuclei rest inside the gel until released when the gel is consumed. Our results show instead that it is crystals that formed in an early stage before entrapment inside the gel that rest inside the gel until exposed at the gel surface. These results illustrate the limitation of the classical method used in the field to determine nucleation profiles when the crystals become trapped inside the gel.

Comprehensive Utilization of Filter Residue from the Preparation Process of Zeolite-Based Catalysts

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Shu-Qin Zheng

2016-05-01

Full Text Available A novel utilization method of filter residue from the preparation process of zeolite-based catalysts was investigated. Y zeolite and a fluid catalytic cracking (FCC catalyst were synthesized from filter residue. Compared to the Y zeolite synthesized by the conventional method, the Y zeolite synthesized from filter residue exhibited better thermal stability. The catalyst possessed wide-pore distribution. In addition, the pore volume, specific surface area, attrition resistance were superior to those of the reference catalyst. The yields of gasoline and light oil increased by 1.93 and 1.48 %, respectively. At the same time, the coke yield decreased by 0.41 %. The catalyst exhibited better gasoline and coke selectivity. The quality of the cracked gasoline had been improved.

Reduction of Nitrogen Oxides using zeolite catalysts exchanged with cobalt

International Nuclear Information System (INIS)

Garcia M, E.A.; Bustamante L, F.; Montes de C, C.

1999-01-01

The Selective Catalytic Reduction (SCR) of NOx by methane in excess oxygen was studied over several zeolite catalysts; namely cobalt loaded mordenite, ferrierite, SM-5 and the corresponding acid forms. When NO2 predominated n the NOx mixture the acid forms showed the highest N2 formation rates under dry conditions. Mordenite supported catalysts were the most active ones followed by ferrierite and ZSM-5. The most active Co-Mordenite catalyst was tested using a NOx mixture, containing mostly NO, under dry conditions and in the presence of water and SO2. The addition of 8 % water to the reaction mixture lead to a reversible deactivation, mainly at low temperatures. When the reaction mixture contained 60 ppm SO2, the N2 formation rate decreased about a half likely due to SO2 poisoning

[Preparation of HDTMA-modified Zeolite and Its Performance in Nitro-phenol Adsorption from Wastewaters].

Science.gov (United States)

Guo, Jun-yuan; Wang, Bin

2016-05-15

In this study, natural zeolite was modified by HDTMA. Effects of the modified conditions, HDTMA-modified zeolite doses, solution pH values, and reaction time on nitro-phenol removal were investigated, and the adsorption kinetics and isotherms were discussed. Compared with natural zeolite, HDTMA-modified zeolite showed better performance in nitro-phenol removal. An adsorption capacity of 2.53 mg · g⁻¹ was achieved when the concentration of HDTMA solution (pH = 10) was 1.2% in preparation of modified zeolite. This adsorption capacity was higher than that obtained by natural zeolite (0.54 mg · g⁻¹). In adsorption tests, when HDTMA- modified zeolite dose was adjusted to 8 g · L⁻¹, the removal efficiency of nitro-phenol reached 93.9% after 90 min reaction, with wastewater pH of 6. Furthermore, the nitro-phenol adsorption process could be well fitted to the pseudo-first-order kinetics model (R² > 0.90), whereas the adsorption isotherm results indicated that Langmuir model provided the best fitting for the equilibrium data at different temperatures, with R² of higher than 0.90.

Gold nanoclusters confined in a supercage of Y zeolite for aerobic oxidation of HMF under mild conditions.

Science.gov (United States)

Cai, Jiaying; Ma, Hong; Zhang, Junjie; Song, Qi; Du, Zhongtian; Huang, Yizheng; Xu, Jie

2013-10-11

Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5-furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2 , CeO2 , and Mg(OH)2 ) and channel-type zeolites (ZSM-5 and H-MOR). Detailed characterizations, such as X-ray diffraction, transmission electron microscopy, N2 -physisorption, and H2 -temperature-programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium CO{sub 2} adsorption on zeolite 13X prepared from natural clays

Energy Technology Data Exchange (ETDEWEB)

Garshasbi, Vahid [Faculty of Chemical, Petroleum and Gas Eng., Semnan University, P.O. Box 35196-45399, Semnan, Islamic Republic of Iran (Iran, Islamic Republic of); Jahangiri, Mansour, E-mail: mjahangiri@semnan.ac.ir [Faculty of Chemical, Petroleum and Gas Eng., Semnan University, P.O. Box 35196-45399, Semnan, Islamic Republic of Iran (Iran, Islamic Republic of); Anbia, Mansoor [Research Laboratory of Nanoporous Materials, Faculty of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Islamic Republic of Iran (Iran, Islamic Republic of)

2017-01-30

Highlights: • Zeolite 13X was successfully synthesized by hydrothermal treatment using natural kaolin, natural bentonite and natural feldspath. • The optimum conditions of synthesis zeolite 13X were found to be NaOH concentration = 4 M and crystallized at 65 °C for 72 h after homogenization by agitated at room temperature for 120 h. • The prepared zeolite 13X from natural kaolin (13X-K) showed a high BET surface area of 591 m{sup 2}/g and high micropore volume (0.250 cm{sup 3}/g) than other materials in this study. • The adsorption behavior of carbon dioxide and methane on zeolite 13X sample at different temperature from 298 K to 328 K was investigated. • It was found that the Langmuir–Freundlich model was more suitable than the others for description of CO{sub 2} adsorption isotherms. - Abstract: Zeolite 13X was successfully synthesized by hydrothermal treatment using natural clays extracted from Iranian resources. The preliminary natural materials and the final zeolite 13X samples were characterized by X-ray Diffraction (XRD), Fourier-Transfer Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM) and N{sub 2} adsorption–desorption isotherm. The effects of various factors such as NaOH addition amount and aging time on the crystalline products were studied during the synthesis process. The optimum conditions related to the synthesis of zeolite 13X were set. Accordingly, NaOH concentration was equal to 4 M. It was further crystallized at 65 °C for 72 h after its homogenization by agitation at room temperature for 120 h. In this study, the zeolite 13X prepared from natural kaolin (13X-K) showed a high BET surface area of 591 m{sup 2}/g with higher micropore volume (0.250 cm{sup 3}/g) than other materials. Adsorption equilibrium isotherms of CO{sub 2} were investigated using a static, volumetric method. In addition, pressures for the pure component data extended up to 20 bar. The adsorption equilibrium data of CO{sub 2} was fitted to

DFT calculations on N2O decomposition by binuclear Fe complexes in Fe/ZSM-5

NARCIS (Netherlands)

Yakovlev, A.L.; Zhidomirov, G.M.; Santen, van R.A.

2001-01-01

N2O decomposition catalyzed by oxidized Fe clusters localized in the micropores of Fe/ZSM-5 has been studied using the DFT approach and a binuclear cluster model of the active site. Three different reaction routes were found, depending on temperature and water pressure. The results show that below

DeNOx Abatement over Sonically Prepared Iron-Substituted Y, USY and MFI Zeolite Catalysts in Lean Exhaust Gas Conditions

Science.gov (United States)

Stachurska, Patrycja; Kuterasiński, Łukasz; Dziedzicka, Anna; Górecka, Sylwia; Chmielarz, Lucjan; Łojewska, Joanna; Sitarz, Maciej

2018-01-01

Iron-substituted MFI, Y and USY zeolites prepared by two preparation routes—classical ion exchange and the ultrasound modified ion-exchange method—were characterised by micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet (UV)/visible diffuse reflectance spectroscopy (UV/Vis DRS). Ultrasound irradiation, a new technique for the preparation of the metal salt suspension before incorporation to the zeolite structure, was employed. An experimental study of selective catalytic reduction (SCR) of NO with NH3 on both iron-substituted reference zeolite catalysts and those prepared through the application of ultrasound conducted during an ion-exchange process is presented. The prepared zeolite catalysts show high activity and selectivity in SCR deNOx abatement. The MFI-based iron catalysts, especially those prepared via the sonochemical method, revealed superior activity in the deNOx process, with almost 100% selectivity towards N2. The hydrothermal stability test confirmed high stability and activity of MFI-based catalysts in water-rich conditions during the deNOx reaction at 450 °C. PMID:29301370

PREPARATION AND CHARACTERIZATION OF TiO2-ZEOLITE AND ITS APPLICATION TO DEGRADE TEXTILLE WASTEWATER BY PHOTOCATALYTIC METHOD

Directory of Open Access Journals (Sweden)

Yeslia Utubira

2010-06-01

Full Text Available The preparation of titanium oxide-zeolite composite (TiO2-zeolite has been done. Preparation was initiated by dispersing oligocation of titanium solution into suspension of natural zeolite. The suspension was stirred and then filtered to separate the solid phase from the filtrate. The solid phase was heated by microwave oven to convert the oligocations into its oxide forms and the resulting material (called as TiO2-zeolite then was used to photodegrade the wastewater of PT.Jogjatex The TiO2-zeolite and unmodified zeolite were characterized using X-ray diffractometry, FT-IR spectro-photometry, X-ray fluorescence (XRF and gas sorption analysis (GSA methods to determine their physicochemical properties. Photocatalytic activity of TiO2-Zeolite was tested by exposing the suspension of TiO2-Zeolite/wastewater by the UV light of 366 nm at room temperature for 15 - 75 minutes. Characterization results exhibited that the formation of TiO2 on internal as well as external surfaces of Zeolite could not be detected  with X-ray diffractometry as well as  FT-IR spectrophotometry, however elemental analysis result with XRF indicated that titanium concentration in zeolite increased due to the inclusion, i.e from 0.26% (w/w in zeolite to 2.80% (w/w in TiO2-zeolite. Characterization result by GSA exhibited the increased of specific surface area from 19.57 m2/g in zeolite to 67.96 m2/g in TiO2-zeolite; total pore volume from 20.64 x 10-3 mL/g in zeolite to 49.561 x 10-3 mL/g in TiO2-Zeolite; pore radius average decreased from 21.10 Å in zeolite to 14.58 Å in TiO2-zeolite. Photocatalytic activity test of TiO2-zeolite on wastewater of PT. Jogjatex showed that UV radiation for 75 minutes on the mixture of TiO2-zeolite and wastewater resulted in the decreased of  COD number up to 57.85%. Meanwhile the sorption study showed that zeolite and TiO2-zeolite could decrease COD number of wastewater up to 43.95% and 57.85%, respectively.   Keywords: TiO2-zeolite

Sustained release of doxorubicin from zeolite-magnetite nanocomposites prepared by mechanical activation

International Nuclear Information System (INIS)

Arruebo, Manuel; Fernandez-Pacheco, Rodrigo; Irusta, Silvia; Arbiol, Jordi; Ibarra, M Ricardo; SantamarIa, Jesus

2006-01-01

Nanocomposites consisting of magnetite and FAU zeolite with a high surface area and adsorption capacity have been prepared by mechanical activation using high-energy milling at room temperature. FTIR results, as well as HRTEM, EFTEM, and XPS measurements, show that the resulting magnetic nanoparticles are covered by a thin aluminosilicate coating. A saturation magnetization as high as 16 emu g -1 and 94.2 Oe of coercivity were observed for the obtained composites. The main advantages of this synthesis procedure are (i) simplicity of the preparation procedure (ii) prevention of agglomeration of the magnetite nanoparticles to a large extent, and (iii) absence of free magnetite outside the zeolitic matrix. In addition, in vitro experiments revealed that the nanoparticles prepared were able to store and release substantial amounts of doxorubicin. In view of these advantages, these magnetic nanoparticles can be considered as potential candidates for drug-delivery applications

The roles of ozone and zeolite on reactive dye degradation in electrical discharge reactors.

Science.gov (United States)

Peternel, L; Kusic, H; Koprivanac, N; Locke, B R

2006-05-01

In this study high voltage pulsed corona electrical discharge advanced oxidation processes (AOPs) were applied to bleach and degrade C.I. Reactive Green 8 and C.I. Reactive Red 45 organic dyes in water solutions. Two types of hybrid gas/liquid high voltage electrical discharge (corona) reactors, known as hybrid series and hybrid parallel were studied. The difference between these reactors relates to electrode configuration, which affects the amounts of ozone, hydrogen peroxide and hydroxyl radicals produced. Experiments were conducted using dye concentrations of 20 mgl(-1) and 75 mgl(-1), with and without NH4ZSM5 zeolite addition in order to determine possible effects of added solid particles to total process efficiency. The role of ozone in combination with zeolites was assessed through comparative direct ozonation experiments with ozone supplied by an ozone generator. UV/VIS spectrophotometric measurements and measurements of total organic carbon (TOC) were used for the determination of decolorization and mineralization rates.

Catalytic Oxidation by Transition Metal Ions in Zeolites.

Science.gov (United States)

1984-09-28

exotic schemes were developed. It was previously demonstrated that MoCI5 may be reacted with a HYu (here Yu denotes a steam-stabilized or...34ultrastable" zeolite) to form a MoYu zeolite and HC1 which is removed from the system.1 In this study, MoYu zeolites have been prepared by reacting HYu with Mo

Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

Science.gov (United States)

Lee, Kyong-Hwan

2016-05-01

Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

Immobilization of krypton-85 in zeolite 5A

International Nuclear Information System (INIS)

Christensen, A.B.; Del Debbio, J.A.; Knecht, D.A.; Tanner, J.E.; Cossel, S.C.

1983-01-01

This paper describes the technical feasibility and presents a summary of a preconceptual design and cost estimate for a process to immobilize krypton-85 by sintering in zeolite 5A at 700 0 C and 100 MPa for 2 to 4 h. Krypton loading of 30 to 60 m 3 at STP per m 3 solid can be achieved. The initial water concentration in zeolite 5A has a catalytic effect on the sintering rate and must be kept at about 1 wt% by heating prior to the encapsulation run. High initial water loadings and/or encapsulation times longer than 4 h must be avoided because the sintered zeolite 5A recrystallizes to an anorthite-type feldspar and releases the trapped krypton. Data are presented to show how the process conditions affect krypton encapsulation in zeolie 5A and how to assure the quality of the product. By adding a powdered glass frit to the commercial zeolite 5A 2 mm beads, a solid mass is formed during encapsulation, which can be further compacted using standard hot isotatic pressing techniques at 33 MPa and 600 0 C to form a fused glassy matrix enclosing the amorphous zeolite. A process for encapsulating the annual krypton-85 production at a commercial 2000 metric ton of heavy metal spent fuel reprocessing plant is developed. A hot isostatic press (HIP) with an isolated work zone of 8 or 16 L capacity is required to operate for 600 or 300 cycles per year, respectively. Existing HIP technology uses work zones from 1 to 3500 L capacity at similar production rates. A combined encapsulation/compaction cycle is proposed as an option to most effectively immobilize the krypton and the zeolite. A preconceptual design and cost estimate is given for a commercial-scale Kr encapsulation facility. The facility is designed to withstand a worst case rupture of the HIP. The maximum lease is estimated to result in an off-site dose well below accident protective action guidance levels

Selective catalytic reduction of NO{sub x} to nitrogen over Co-Pt/ZSM-5: Part A. Characterization and kinetic studies

Energy Technology Data Exchange (ETDEWEB)

Maisuls, S.E.; Seshan, K.; Feast, S.; Lercher, J.A. [Laboratory for Catalytic Processes and Materials, Faculty of Chemical Technology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

2001-01-01

The selective catalytic reduction of NO by propene in the presence of excess oxygen has been studied over catalysts based on Co-Pt supported on ZSM-5. Pure Pt based catalysts are highly active, but produce large amounts of N{sub 2}O. Bimetallic Co-Pt/ZSM-5 catalysts with low Pt contents (0.1wt.%) show a synergistic effect by combining high stability and activity of Pt catalysts with the high N{sub 2} selectivity of Co catalysts. The lower selectivity to N{sub 2}O is attributed to its selective conversion over Co. The catalysts also showed high water and sulfur tolerance above 350C.

Stability of krypton fixed in zeolite-3A and -5A

International Nuclear Information System (INIS)

Matsuoka, Shingo; Nakamura, Hirone; Tamura, Takaaki; Takano, Takemi; Ito, Yasuo; Sugawara, Ichiro.

1986-01-01

The fixation operation was carried out at 450 ∼ 650 deg C, 1,000 atm for 24 h. The amount of fixed Kr was measured using thermal neutron activation analysis. For zeolite-3A the amount of Kr fixed decreased from 20 to 5 w/o as the fixation temperature rose. In the case of zeolite-5A, Kr fixation was observed at 550 deg C and above, and the amount increased to 15 w/o as the temperature rose to 650 deg C. The diffusion coefficient of Kr in the zeolite was determined from the result of heating tests. The value obtained was substituted in a diffusion equation, enabling us to predict the Kr release behavior at any temperature in a dry atmosphere. Both the samples of zeolite-3A fixed below 525 deg C and of zeolite-5A below 625 deg C showed an intensive Kr release in water that would not be expected from the release behavior under dry conditions. However, such unexpected release was not observed in either sample fixed above these respective temperatures. This could be accounted for by the fact that zeolite cations move easily when zeolite is moisturized. (author)

Catalytic Oxidation of Phenol over Zeolite Based Cu/Y-5 Catalyst: Part 1: Catalyst Preparation and Characterization

Directory of Open Access Journals (Sweden)

K. Maduna Valkaj

2015-01-01

Full Text Available The necessity to remove organic pollutants from the industrial wastewater streams has forced the development of new technologies that can produce better results in terms of pollutant removal and process efficiency in combination with low investment and operating costs. One of the new emerging processes with a potential to fulfil these demands is catalytic wet peroxide oxidation, commonly known as the CWPO process. The oxidative effect of the hydrogen peroxide is intensified by the addition of a heterogeneous catalyst that can reduce the operating conditions to atmospheric pressure and temperatures below 383 K. Zeolites, among others, are especially appealing as catalysts for selective oxidation processes due to their unique characteristics such as shape selectivity, thermal and chemical stability, and benign effect on nature and the living world. In this work, catalytic activity, selectivity and stability of Cu/Y-5 zeolite in phenol oxidation with hydrogen peroxide was examined. Catalyst samples were prepared by ion exchange method of the protonic form of commercial zeolite. The catalysts were characterized with powder X-ray diffraction (XRD, scanning electron microscopy (SEM, and AAS elemental analysis, while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and in the temperature range from 323 to 353 K. The catalyst was prepared in powdered form and the mass fraction of the active metal component on the zeolite was 3.46 %. The initial concentration of phenol solution was equal to 0.01 mol dm−3 and the concentration of hydrogen peroxide ranged from 0.01 to 0.10 mol dm−3. The obtained experimental data was tested to a proposed kinetic model for phenol oxidation r = k1 cF cVP and hydrogen peroxide decomposition rHP = k2 cHP. The kinetic parameters were estimated using the Nelder

Radioisotope tracer study of co-reactions of methanol with ethanol using 11C-labelled methanol over alumina and H-ZSM-5

International Nuclear Information System (INIS)

Sarkadi-Priboczki, E.; Kovacs, Z.; Kumar, N.; Salmi, T.; Murzin, D.Yu

2005-01-01

Complete text of publication follows. The transformation of methanol has been investigated over alumina and H-ZSM-5 in our previous experiments by 11 C-radioisotope tracing. The main product in methanol conversion over alumina was dimethyl ether due to Lewis acid sites while over H-ZSM-5 mostly hydrocarbons were formed due to both Lewis and Brrnsted acid sites. With increasing temperature first the ethanol was dehydrated to diethyl ether followed by ethene formation over alumina and H-ZSM-5. In this work, 11 C-labelled methanol as radioisotope tracer was added to non-radioactive methanol for investigation of co-reaction with non-radioactive ethanol over alumina and H- ZSM-5. The 11 C-methanol tracer was used to distinguish the methanol derivates and co-reaction derivates of methanol with ethanol against non-radioactive ethanol derivates. The yield of methyl ethyl ether as mixed ether and the influence of ethanol for the yields of C 1 -C 5 hydrocarbons were studied as a function of reaction temperature and contact time. The 11 C-methanol was formed by a radiochemical process from 11 CO 2 produced at cyclotron. The mixture of methanol and ethanol was added to 11 C-methanol and injected to the catalyst. The catalysis was carried out in a glass tube fixed-bed reactor after its pretreatment. The derivates were analyzed by radio-gas chromatography (gas chromatograph with thermal conductivity detector coupled on-line with a radioactivity detector). The comparative analysis of yields of radioactive and non-radioactive products as a function of reaction temperature gives information about the reaction pathways. Over alumina the yields of dimethyl ether and methyl ethyl ether (co-product) as radioactive and diethyl ether with ethene as non-radioactive main products were monitored as a function of reaction temperature and reaction time in the range of 513-593 K. Alongside ethanol derivates the ethene turns into main product in contrast with methyl ethyl ether and diethyl

Amine-functionalized, silver-exchanged zeolite NaY: Preparation, characterization and antibacterial activity

Energy Technology Data Exchange (ETDEWEB)

Hanim, Siti Aishah Mohd; Malek, Nik Ahmad Nizam Nik, E-mail: niknizam@fbb.utm.my; Ibrahim, Zaharah

2016-01-01

Graphical abstract: - Highlights: • Functionalization of Ag-exchanged zeolite NaY with 3-aminopropyltriethoxysilane APTES (ZSA) as antibacterial agent. • Antibacterial assay of ZSA was performed against Escherichia coli ATCC11229 and Staphylococcus aureus ATCC6538. • Functionalization of Ag-exchanged zeolite NaY with APTES significantly increased the antibacterial agent. • Different mechanisms of bacterial death were suggested for each bacteria type by the functionalized Ag-exchanged zeolite NaY. - Abstract: Amine-functionalized, silver-exchanged zeolite NaY (ZSA) were prepared with three different concentrations of 3-aminopropyltriethoxysilane (APTES) (0.01, 0.20 and 0.40 M) and four different concentrations of silver ions (25%, 50%, 100% and 200% from zeolite cation exchange capacity (CEC)). The samples were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), surface area analysis, thermogravimetric analysis (TGA) and zeta potential (ZP) analysis. The FTIR results indicated that the zeolite was functionalized by APTES and that the intensity of the peaks corresponding to APTES increased as the concentration of APTES used was increased. The antibacterial activities of the silver-exchanged zeolite NaY (ZS) and ZSA were studied against Escherichia coli ATCC11229 and Staphylococcus aureus ATCC6538 using the disc diffusion technique (DDT) and minimum inhibitory concentration (MIC). The antibacterial activity of ZSA increased with the increase in APTES on ZS, and E. coli was more susceptible towards the sample compared to S. aureus. The FESEM micrographs of the bacteria after contact with the ZSA suggested different mechanisms of bacterial death for these two bacteria due to exposure to the studied sample. The functionalization of ZS with APTES improved the antibacterial activity of the silver-zeolite, depending on the concentration of silver

Evaluation of LTA-, FAU- and MFI-type zeolites as sorbents of some toxic components of tobacco smoke

International Nuclear Information System (INIS)

Iucolano, F.; Caputo, D.; Monetta, T.; Bellucci, F.; Colella, C.

2008-01-01

Zeolites 3A, 4A, 13X, H-ZSM-5 were investigated in order to evaluate their possible use in removing toxic compounds from cigarette smoke. Ammonia and acetaldehyde were selected as representative of a wide range of possible sorbates. Adsorption equilibrium data at 313K were collected and analyzed by Langmuir and virial equations to estimate the relevant values of Henry's constant, a useful parameter to estimate the affinity sorbents-sorbates at low pressure. Unlike the Langmuir model, the virial equation provided a good fit for both ammonia and acetaldehyde equilibrium data for all sorbents in the whole range of pressures, especially at low pressure. As already assessed for nitrosamines, FAU- and MFI-type zeolites showed the highest affinity for ammonia and acetaldehyde, allowing these sorbents to be considered an effective potential resource for the removal of some of the main pollutants of tobacco smoke.

The assessment of pore connectivity in hierarchical zeolites using positron annihilation lifetime spectroscopy: instrumental and morphological aspects.

Science.gov (United States)

Zubiaga, Asier; Warringham, Robbie; Boltz, Marilyne; Cooke, David; Crivelli, Paolo; Gidley, David; Pérez-Ramírez, Javier; Mitchell, Sharon

2016-04-07

Recent studies demonstrated the power of positron annihilation lifetime spectroscopy (PALS) to characterise the connectivity and corresponding effectiveness of hierarchical pore networks in zeolites. This was based on the fractional escape of ortho-positronium (Ps), formed within the micropore framework, to vacuum. To further develop this technique, here we assess the impact of the positron implantation energy and of the zeolite crystal size and the particle morphology. Conventional measurements using fast positrons and beam measurements applying moderated positrons both readily distinguish purely microporous ZSM-5 zeolites comprised of single crystals or crystal aggregates. Unlike beam measurements, however, conventional measurements fail to discriminate model hierarchical zeolites with open or constricted mesopore architectures. Several steps are taken to rationalise these observations. The dominant contribution of Ps diffusion to the PALS response is confirmed by capping the external surface of the zeolite crystals with tetraethylorthosilicate, which greatly enhances the sensitivity to the micropore network. A one-dimensional model is constructed to predict the out-diffusion of Ps from a zeolite crystal, which is validated experimentally by comparing coffin-shaped single crystals of varying size. Calculation of the trends expected on the application of fast or moderated positrons indicates that the distinctions in the initial distribution of Ps at the crystal level cannot explain the limited sensitivity of the former to the mesopore architecture. Instead, we propose that the greater penetration of fast positrons within the sample increases the probability of Ps re-entry from intercrystalline voids into mesopores connected with the external surface of zeolite crystals, thereby reducing their fractional escape.

Ion-exchange properties of zeolite/glass hybrid materials

International Nuclear Information System (INIS)

Taira, Nobuyuki; Yoshida, Kohei; Fukushima, Takuya

2017-01-01

Hybrid materials were prepared from ground glass powder and various zeolites such as A-type, mordenite, X-type, and Y-type zeolites, and their ion removal effect was investigated. The hybrid materials of A-type, Y-type, and mordenite zeolites showed similar Sr"2"+ removal rates from aqueous solutions. The removal rate of Sr"2"+ ions increased as the amount of zeolite in the hybrid materials increased. Compared with other hybrid materials, the hybrid materials of X-type zeolite showed higher Sr"2"+ removal rates, especially for zeolite content greater than 25%. As the amount of X-type zeolite in the hybrid materials increased, the Sr"2"+ removal rate increased greatly, with a 100% removal rate when the content of X-type zeolite exceeded 62.5%. (author)

Fly ash based zeolitic pigments for application in anticorrosive paints

International Nuclear Information System (INIS)

Shaw, Ruchi; Tiwari, Sangeeta

2016-01-01

The purpose of this work is to evaluate the utilization of waste fly ash in anticorrosive paints. Zeolite NaY was synthesized from waste fly ash and subsequently modified by exchanging its nominal cation Na + with Mg 2+ and Ca 2+ ions. The metal ion exchanged zeolite was then used as anticorrosive zeolitic pigments in paints. The prepared zeolite NaY was characterized using X-Ray diffraction technique and Scanning electron microscopy. The size, shape and density of the prepared fly ash based pigments were determined by various techniques. The paints were prepared by using fly ash based zeolitic pigments in epoxy resin and the percentages of pigments used in paints were 2% and 5%. These paints were applied to the mild steel panels and the anticorrosive properties of the pigments were assessed by the electrochemical spectroscopy technique (EIS).

Immobilization of krypton-85 in zeolite 5A and porous glass

International Nuclear Information System (INIS)

Christensen, A.B.; DelDebbio, J.A.; Knecht, D.A.; Tanner, J.E.; Cossel, S.C.

1981-12-01

This report demonstrates the technical and economic feasibility for immobilizing krypton-85 by high pressure/high temperature encapsulation in zeolite 5A or thirsty Vyco porous glass. Data are presented to show how process conditions affect the encapsulation and how to compact the zeolite beads with glass frit or other additives to form a fused mass with low dispersibility potential. Krypton specific loadings of 30 and 50 m 3 STP gas per m 3 solid are readily achieved at 100 MPa in porous glass at 900 0 C and zeolite 5A at 700 0 C. Krypton is encapsulated by a sintering process where the porous glass and zeolite 5A voids are sealed. With zeolite 5A, the initial water concentration has a catalytic effect on the sintering, resulting in a transition from crystalline zeolite 5A to an amorphous aluminosilicate. Krypton leakage experiments are used to predict leakage rates from glass or zeolite of less than 0.03% and 0.3% for 10-y storage at 300 and 400 0 C, respectively. Heating the loaded zeolite at 600 to 700 0 C for 4 h removes 0.1% of the total krypton which is loosely held and reduces the subsequent leakage rates at 300 to 400 0 C. Zeolite 5A is chosen as the preferred material to immobilize krypton-85. A preconceptual design and cost estimate is given for a facility to encapsulate 110% of the krypton production of a 2000 metric ton of heavy metal per year reprocessing plant, or 230 m 3 of gas containing 19 MCi of krypton-85. A hot isostatic press (HIP) with an isolated work zone of 8 or 16 L capacity is required to operate for 600 or 300 cycles per year, respectively. Existing HIP technology uses work zones from 1 to 3500 L capacity at similar production rates. A preliminary safety evaluation shows that an incredible worst case accident could be contained and the maximum off-site dose would be well below accident protective action guidance levels

Characterisation of poly(methacrylates) formed inside zeolites by gamma irradiation

International Nuclear Information System (INIS)

Kwiatkowski, J.; Whittaker, A.K.

1996-01-01

Full text: Inclusion polymerisation was first developed in the second half of the 50's as an alternative to Ziegler-Natta co-ordination polymerisation to obtain highly stereo-regular polymers. Inclusion polymerisation was performed in organic clathrates such as thio-urea channels. However the channels are only stable when formed around the monomer. This means there is a specific concentration of monomer, namely saturation, for which the host/channel system can exist. There is also a limited number of monomers which are suitable for use with a given clathrate and the channel dimension is not usually a variable parameter for a given monomer/clathrate system. One exception is Tris(o-phenolenedioxy)cycotriphosphazene. Initiation of the monomer can be easily achieved by high energy irradiation and many of the polymers obtained show considerable chemical and steric regularity. For example poly (2,3 -dimethylbutadiene) obtained by polymerisation in a thio-urea inclusion compound has only the 1,4 trans structure and is highly crystalline. The restriction on the number of clathrate and monomer systems has lead us to investigate the use of zeolites as hosts for inclusion compounds. Zeolites exist independently of any included guest compound. They are aluminosilicate compounds whose structures form molecular-dimension channels and belong to a class of materials known as molecular sieves. Channel structures can be in 1,2 or 3 dimensions. The structural aluminium in the zeolite creates a negative charge on the lattice which is balanced by cations. In this study we have diffused methyl and ethyl methacrylate into Na-ZSM5, Beta, Y and Mordenite zeolites. The samples where irradiated under vacuum and then extracted. The structures of the exrtracted polymer have been characterized by GPC, NMR and DSC The results will be correlated as a function of the channel size of the zeolite and compared to the bulk system

Volatile organic compound adsorption in a gas-solid fluidized bed.

Science.gov (United States)

Ng, Y L; Yan, R; Tsen, L T S; Yong, L C; Liu, M; Liang, D T

2004-01-01

Fluidization finds many process applications in the areas of catalytic reactions, drying, coating, combustion, gasification and microbial culturing. This work aims to compare the dynamic adsorption characteristics and adsorption rates in a bubbling fluidized bed and a fixed bed at the same gas flow-rate, gas residence time and bed height. Adsorption with 520 ppm methanol and 489 ppm isobutane by the ZSM-5 zeolite of different particle size in the two beds enabled the differentiation of the adsorption characteristics and rates due to bed type, intraparticle mass transfer and adsorbate-adsorbent interaction. Adsorption of isobutane by the more commonly used activated carbon provided the comparison of adsorption between the two adsorbent types. With the same gas residence time of 0.79 seconds in both the bubbling bed and fixed bed of the same bed size of 40 mm diameter and 48 mm height, the experimental results showed a higher rate of adsorption in the bubbling bed as compared to the fixed bed. Intraparticle mass transfer and adsorbent-adsorbate interaction played significant roles in affecting the rate of adsorption, with intraparticle mass transfer being more dominant. The bubbling bed was observed to have a steeper decline in adsorption rate with respect to increasing outlet concentration compared to the fixed bed. The adsorption capacities of zeolite for the adsorbates studied were comparatively similar in both beds; fluidizing, and using smaller particles in the bubbling bed did not increase the adsorption capacity of the ZSM-5 zeolite. The adsorption capacity of activated carbon for isobutane was much higher than the ZSM-5 zeolite for isobutane, although at a lower adsorption rate. Fourier transform infra-red (FTIR) spectroscopy was used as an analytical tool for the quantification of gas concentration. Calibration was done using a series of standards prepared by in situ dilution with nitrogen gas, based on the ideal gas law and relating partial pressure to gas

Preparation of zeolite-A/chitosan hybrid composites and their bioactivities and antimicrobial activities.

Science.gov (United States)

Yu, Liang; Gong, Jie; Zeng, Changfeng; Zhang, Lixiong

2013-10-01

Zeolite-A/chitosan hybrid composites with zeolite contents of 20-55 wt.% were prepared by in situ transformation of silica/chitosan mixtures in a sodium aluminate alkaline solution through impregnation-gelation-hydrothermal synthesis. The products were characterized by X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mercury penetration porosimetry. Their in vitro bioactivities were examined using as-synthesized and Ca(2+)-exchanged hybrid composites in simulated body fluid (SBF) for hydroxyapatite (HAP) growth. Their antimicrobial activities for Escherichia coli (E. coli) in trypticase soy broth (TSB) were evaluated using Ag(+)-exchanged hybrid composites. The zeolite-A/chitosan hybrid composites could be prepared as various shapes, including cylinders, plates and thin films. They possessed macropores with pore sizes ranging from 100 to 300 μm and showed compressive mechanical strength as high as 3.2 MPa when the zeolite content was 35 wt.%. Fast growth on the Ca(2+)-exchanged hybrid composites was observed with the highest weight gain of 51.4% in 30 days. The 35 wt.% Ag(+)-exchanged hybrid composite showed the highest antimicrobial activity, which could reduce the 9×10(6) CFU mL(-1)E. coli concentration to zero within 4h of incubation time with the Ag(+)-exchanged hybrid composite amount of 0.4 g L(-1). The bioactivity and antimicrobial activity could be combined by ion-exchanging the composites first with Ca(2+) and then with Ag(+). These zeolite-A/chitosan hybrid composites have potential applications on tissue engineering and antimicrobial food packaging. Copyright © 2013 Elsevier B.V. All rights reserved.

Effect of Zn/ZSM-5 and FePO4 Catalysts on Cellulose Pyrolysis

Directory of Open Access Journals (Sweden)

Haian Xia

2015-01-01

Full Text Available A series of Zn/ZSM-5 catalysts with different Zn contents and FePO4 were used to pyrolyze cellulose to produce value added chemicals. The nature of these catalysts was characterized by ammonia-temperature programmed desorption (NH3-TPD, IR spectroscopy of pyridine adsorption, and X-ray diffraction (XRD techniques. Noncatalytic and catalytic pyrolytic behaviors of cellulose were studied by thermogravimetric (TG technique. The pyrolytic liquid products, that is, the biooils, were analyzed by gas chromatography-mass spectrometry (GC-MS. The major components of the biooils are anhydrosugars such as levoglucosan (LGA, 1,6-anhydro-β-D-glucofuranose (AGF, levoglucosenone (LGO, 1,6-anhydro-3,4-dideoxy-β-D-pyranosen-2-one, and 1,4:3,6-dianhydro-α-D-glucopyranose (DGP, as well as furan derivatives, alcohols, and so forth. Zn/ZSM-5 samples with Brønsted and Lewis acid sites and the FePO4 catalyst with Lewis acid sites were found to have a significant effect on the pyrolytic behaviors of cellulose and product distribution. These results show that Brønsted and Lewis acid sites modified remarkably components of the biooil, which could promote the production of furan compounds and LGO. On the basis of the findings, a model was proposed to describe the pyrolysis pathways of cellulose catalyzed by the solid acid catalysts.

Preparation by the nano-casting process of novel porous carbons from large pore zeolite templates

International Nuclear Information System (INIS)

F Gaslain; J Parmentier; V Valtchev; J Patarin; C Vix Guterl

2005-01-01

The development of new growing industrial applications such as gas storage (e.g.: methane or hydrogen) or electric double-layer capacitors has focussed the attention of many research groups. For this kind of application, porous carbons with finely tailored micro-porosity (i.e.: pore size diameter ≤ 1 nm) appear as very promising materials due to their high surface area and their specific pore size distribution. In order to meet these requirements, attention has been paid towards the feasibility of preparing microporous carbons by the nano-casting process. Since the sizes and shapes of the pores and walls respectively become the walls and pores of the resultant carbons, using templates with different framework topologies leads to various carbon replicas. The works performed with commercially available zeolites employed as templates [1-4] showed that the most promising candidate is the FAU-type zeolite, which is a large zeolite with three-dimensional channel system. The promising results obtained on FAU-type matrices encouraged us to study the microporous carbon formation on large pore zeolites synthesized in our laboratory, such as EMC-1 (International Zeolite Association framework type FAU), zeolite β (BEA) or EMC-2 (EMT). The carbon replicas were prepared following largely the nano-casting method proposed for zeolite Y by the Kyotani research group [4]: either by liquid impregnation of furfuryl alcohol (FA) followed by carbonization or by vapour deposition (CVD) of propylene, or by an association of these two processes. Heat treatment of the mixed materials (zeolite / carbon) could also follow in order to improve the structural ordering of the carbon. After removal of the inorganic template by an acidic treatment, the carbon materials obtained were characterised by several analytical techniques (XRD, N 2 and CO 2 adsorption, electron microscopy, etc...). The unique characteristics of these carbons are discussed in details in this paper and compared to those

CuY zeolite catalysts prepared by ultrasonication-assisted ion-exchange for oxidative carbonylation of methanol to dimethyl carbonate.

Science.gov (United States)

Woo, Je-Min; Seo, Jung Yoon; Kim, Hyunuk; Lee, Dong-Ho; Park, Young Cheol; Yi, Chang-Keun; Park, Yeong Seong; Moon, Jong-Ho

2018-06-01

The influence of ultrasonication treatment on the catalytic performance of CuY zeolite catalysts was investigated for the liquid-phase oxidative carbonylation of methanol to dimethyl carbonate (DMC). The deammoniation method of NH 4 Y into HY zeolites was optimized and characterized by elemental analyzer, derivative thermogravimetry, Brunauer-Emmett-Teller (BET) analyzer, and powder X-ray diffractometry, revealing that the HY zeolite deammoniated at 400 °C presented the highest surface area, complete ammonium/proton ion exchange, and no structure collapse, rendering it the best support from all the prepared zeolites. CuY zeolites were prepared via aqueous phase ion exchange with the aid of ultrasonication. Upon ultrasonication, the Cu + active centers were uniformly dispersed in the Y zeolites, penetrating the core of the zeolite particles in a very short time. In addition to enhancing the Cu dispersity, the ultrasonication treatment influenced the BET surface area, acid amount, Cu + /Cu 2+ ratio, and also had a relatively small impact on the Cu loading. Consequently, adequate exposure to ultrasonication was able to increase the conversion rate of methanol into dimethyl carbonate up to 11.4% with a comparable DMC selectivity of 23.7%. This methanol conversion is 2.65 times higher than that obtained without the ultrasonication treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization

KAUST Repository

Vollmer, Ina

2018-01-04

Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.

Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization

KAUST Repository

Vollmer, Ina; Li, Guanna; Yarulina, Irina; Kosinov, Nikolay; Hensen, Emiel J.; Houben, Klaartje; Mance, Deni; Baldus, Marc; Gascon, Jorge; Kapteijn, Freek

2018-01-01

Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.

Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

KAUST Repository

Al-Khattaf, S.; Odedairo, T.; Balasamy, R. J.

2012-01-01

Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro

Evaluation of synthetic zeolites as oral delivery vehicle for anti-inflammatory drugs

Directory of Open Access Journals (Sweden)

Elham Khodaverdi

2014-05-01

Full Text Available Objective(s: In this research, zeolite X and zeolite Y were used as vehicle to prepare intestine targeted oral delivery systems of indomethacin and ibuprofen. Materials and Methods: A soaking procedure was implemented to encapsulate indomethacin or ibuprofen within synthetic zeolites. Gravimetric methods and IR spectra of prepared formulations were used to assess drug loading efficiencies into zeolite structures. Scanning Electron Microscopy (SEM was also utilized to determine morphologies changes in synthetic zeolites after drug loading. At the next stage, dissolution studies were used to predict the in vivo performance of prepared formulations at HCl 0.1 N and PBS pH 6.5 as simulated gastric fluid (SGF and simulated intestine fluid (SIF, respectively. Results: Drug loadings of prepared formulations was determined between 24-26 % w/w. Dissolution tests at SGF were shown that zeolites could retain acidic model drugs in their porous structures and can be able to limit their release into the stomach. On the other hand, all prepared formulations completely released model drugs during 3 hr in simulated intestine fluid. Conclusion: Obtained results indicated zeolites could potentially be able to release indomethacin and ibuprofen in a sustained and controlled manner and reduced adverse effects commonly accompanying oral administrations of NSAIDs.

Cryogenic adsorption of low-concentration hydrogen on charcoal, 5A molecular sieve, sodalite, ZSM-5 and Wessalith DAY

International Nuclear Information System (INIS)

Willms, R.S.

1993-01-01

The separation of low-concentration hydrogen isotopes from helium is a processing step that is required for ceramic lithium breeding blanket processing. Cryogenic adsorption is one method of effecting this separation. In this study live adsorbents were considered for this purpose: charcoal, 5A molecular sieve, UOP S-115, ZSM-5 and Wessalith DAY. The first two adsorbents exhibit good equilibrium loadings and are shown to be quite effective at adsorbing low-concentration hydrogen isotopes. The latter three adsorbents display considerably lower equilibrium loadings. This study concludes that by using either charcoal or 5A molecular sieve, cryogenic adsorption would be an effective means of separating hydrogen isotopes from helium

Preparation of highly stable zeolite-alginate foam composite for strontium(90Sr) removal from seawater and evaluation of Sr adsorption performance.

Science.gov (United States)

Hong, Hye-Jin; Kim, Byoung-Gyu; Ryu, Jungho; Park, In-Su; Chung, Kang-Sup; Lee, Sang Moon; Lee, Jin-Bae; Jeong, Hyeon Su; Kim, Hyunchul; Ryu, Taegong

2018-01-01

Alginate bead is a promising strontium (Sr) adsorbent in seawater, but highly concentrated Na ions caused over-swelling and damaged the hydrogel bead. To improve the mechanical stability of alginate bead, flexible foam-type zeolite-alginate composite was synthesized and Sr adsorption performance was evaluated in seawater; 1-10% zeolite immobilized alginate foams were prepared by freeze-dry technique. Immobilization of zeolite into alginate foam converted macro-pores to meso-pores which lead to more compact structure. It resulted in less swollen composite in seawater medium and exhibited highly improved mechanical stability compared with alginate bead. Besides, Sr adsorption efficiency and selectivity were enhanced by immobilization of zeolite in alginate foam due to the increase of Sr binding sites (zeolite). In particular, Sr selectivity against Na was highly improved. The 10% zeolite-alginate foam exhibited a higher log K d of 3.3, while the pure alginate foam exhibited 2.7 in the presence of 0.1 M Na. Finally, in the real seawater, the 10% zeolite-alginate foam exhibited 1.5 times higher Sr adsorption efficiency than the pure alginate foam. This result reveals that zeolite-alginate foam composite is appropriate material for Sr removal in seawater due to its swelling resistance as well as improved Sr adsorption performance in complex media. Copyright © 2017 Elsevier Ltd. All rights reserved.

Upgrading of bio-oil derived from tobacco using ferrierite, ZSM-5 and Co-Mo/Al2 O3 catalysts

Directory of Open Access Journals (Sweden)

Sawitree Mulika

2015-03-01

Full Text Available This research aims to investigate bio-oil yield of tobacco leave by pyrolysis at 450-550o C. The bio-oil was upgraded by ferrierite, ZSM-5, Al2 O3 , Co-Mo/Al2 O3 and Mo2 C catalysts. Pyrolysis was carried out in a semi-batch reactor with a space velocity of 1.7 h-1 under nitrogen atmosphere. The highest liquid yield of 47.1% was observed at 500o C with the high heating value of 36.3 MJ/kg oil (organic phase. Furthermore, char and gas yields were 36.7 and 16.2%, respectively. As a result, the high heating values of the bio-oils catalyzed at 500o C by ferrierite, ZSM-5, Al2 O3 , Mo2 C and Co-Mo/Al2 O3 were 22.5, 24.7, 26.1, 35.8 and 36.8 MJ/kg oil (organic phase, respectively.

The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters.

Science.gov (United States)

Zhang, Shihong; Yang, Mingfa; Shao, Jingai; Yang, Haiping; Zeng, Kuo; Chen, Yingquan; Luo, Jun; Agblevor, Foster A; Chen, Hanping

2018-07-01

Light olefins are the key building blocks for the petrochemical industry. In this study, the effects of in-situ and ex-situ process, temperature, Fe loading, catalyst to feed ratio and gas flow rate on the olefins carbon yield and selectivity were explored. The results showed that Fe-modified ZSM-5 catalyst increased the olefins yield significantly, and the ex-situ process was much better than in-situ. With the increasing of temperature, Fe-loading amount, catalyst to feed ratio, and gas flow rate, the carbon yields of light olefins were firstly increased and further decreased. The maximum carbon yield of light olefins (6.98% C-mol) was obtained at the pyrolysis temperature of 600°C, catalyst to feed ratio of 2, gas flow rate of 100ml/min, and 3wt% Fe/ZSM-5 for cellulose. The selectivity of C 2 H 4 was more than 60% for all feedstock, and the total light olefins followed the decreasing order of cellulose, corn stalk, hemicelluloses and lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

Zeolite 5A Catalyzed Etherification of Diphenylmethanol

Science.gov (United States)

Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

2009-01-01

An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

Study on preparing the absorbent of potassium nickel hexacyanoferrate (II) loaded zeolite for removal of cesium from radioactive waste solutions and followed method for stable solidification of spent composites

International Nuclear Information System (INIS)

Pham Quynh Luong; Nguyen Hoang Lan; Nguyen Van Chinh; Nguyen Thu Trang; Vuong Huu Anh; Le Xuan Huu; Nguyen Thi Xuan; Le Van Duong

2017-01-01

The selective adsorption and stable immobilization of radioactive cesium, K-Ni-hexacyanoferrate (II) loaded zeolite (FC-zeolite) prepared by impregnation / precipitation method were studied. The uptake equilibrium of Cs + for composites FC-zeolite was attained within 8 h and estimated to be above 97% in Cs + 100 mg/l solution at pH 4-10. Maximum ion exchange capacity of Cs + ions (Q max ) for FC-zeoliteX was 112.5 and 69.7 mg/g in pure water and sea water, respectively. Those values for FC-zeolite A was 85.7 and 42.7 mg/g. Decontamination factor (DF) of FC-zeolite X for 134 Cs was 149.7 and 107.5 in pure water and sea water respectively. Study on synthesized zeolites (A and X) made of HUST was also conducted in similar manner. The values of Q max were 98.6 and 39.9 mg/g for zeolite A, and 69.5 and 20.8 mg/g for zeolite X in pure water and sea water, respectively. Decontamination factor (DF) of zeolite A and X for 134 Cs showed lower values. The spent CsFC-zeolite was solidificated in optimal experimental conditions: 5% Na 2 B 4 O 7 additives; calcination temperature at 900 o C for 2 h in air. Solid form was determined some of parameters: immobilization of Cs, compressive strength, volume reduction after calcination (%) and leaching rate of Cs + ions in deionization water. (author)

Long n-alkanes isomerization by medium pore zeolites with pore mouth and key lock mechanisms; Isomerisation des paraffines longues par des zeolithes a pores moyens selon les mecanismes ouverture de pore et cle serrure

Energy Technology Data Exchange (ETDEWEB)

Claude, M.

1999-10-01

Skeletal isomerization of long n-alkanes is practiced to improve cold flow properties of diesel and lubricant fractions. In this work, model long n-alkanes (n-C{sub 10} - n-C{sub 24}) were hydro-isomerized in a fixed bed down flow vapour phase reactor loaded with bifunctional Pt/H-ZSM-22 zeolite catalyst. The skeletal isomers were analysed and identified with GC/MS. High isomer yields were obtained. The distribution of positional mono-methyl-branched isomers obtained from n-C{sub 12} to n-C{sub 24} are typically bimodal. This is explained by adsorption and reaction of the alkanes in pore mouths and locks on the external surface of the zeolite crystals. The pore mouth mode favours branching at C{sub 2} and C{sub 3}. The 'key lock' type proceeds by penetration of the two ends of the hydrocarbon chain into a different pore opening and favours more central mono-branching of the chain. The contribution of the key lock mode increases with increasing chain length and with the reaction temperature. The preferentially formed dimethyl-branched isomers have a separation between branchings of three up to fourteen carbon atoms. The formation of the second methyl-branching occurs preferentially from a centrally branched mono-methyl-branched isomer, so that the second branching is generated always more toward the end of the chain. Owing to the differences in adsorption entropy among the locks, at higher temperatures the largest lock is preferred and the distance between the two branching along the carbon chain in the preferred isomers is biggest. Thus the work resulted in the formulation of structure-selectivity relationships. n-C{sub 18} was hydro-isomerized on other zeolites. The nature and distribution of the isomers obtained suggest that the tubular 10-ring zeolites ZSM-23, ZSM-35 and SAPO-11 also operate according to pore mouth and key lock concepts. Zeolites with 12-rings show typical product patterns for catalysis in absence of steric hindrance. (author)

Hierarchical zeolites prepared by organosilane templating : a study of the synthesis mechanism and catalytic activity

NARCIS (Netherlands)

Koekkoek, A.J.J.; Tempelman, C.H.L.; Degirmenci, V.; Guo, M.; Feng, Z.; Li, Can; Hensen, E.J.M.

2011-01-01

The crystallization of hierarchical ZSM-5 in the presence of the organosilane octadecyl-dimethyl-(3-trimethoxysilyl-propyl)-ammonium chloride as the mesoporogen was investigated as a function of time and temperature. The synthesis by this method proceeds in two steps. The rapid formation of a

On the nature of gallium species in gallium-modified mordenite and MFI zeolites. A comparative DRIFT study of carbon monoxide adsorption and hydrogen dissociation.

Science.gov (United States)

Serykh, Alexander I; Kolesnikov, Stanislav P

2011-04-21

The results of a DRIFT study of carbon monoxide molecular adsorption and hydrogen dissociative adsorption on gallium-modified mordenite and MFI (ZSM-5) zeolites are presented. It was found that in the reduced gallium-modified mordenite (Ga-MOR) both Ga(3+) and Ga(+) exchanged cations are present and can be detected by CO adsorption. Ga(3+) cations in Ga-MOR dissociatively adsorb molecular hydrogen at elevated temperatures, resulting in the formation of gallium hydride species and acidic hydroxyl groups. In the reduced Ga-MFI evacuated at 823 K under medium vacuum conditions only Ga(+) exchanged intrazeolite cations were detected. It was found, however, that Ga(3+) intrazeolite exchanged cations which form upon high-temperature disproportionation of Ga(+) cations in the reduced Ga-MFI and Ga-MOR can be stabilized by high-temperature oxidation of these zeolites.

Preliminary study of zeolite-pva composite application in removal of SR-90

International Nuclear Information System (INIS)

Las, Thamzil; Zamroni, Huzen; Sugiarto; Darsono

1998-01-01

Zeolite-PAN composite was prepared by contacting the purified Bayah and Lampung zeolites with poly-vinyl alcohol binder and cured by using Gamma-ray of Co-60 at various doses, i.e., 10, 20, 30 dan 40 kGray with dose rates 7.5 kGy/hour. Zeolite-PAN composites were treated with solution containing Sr-90 up to 5 days and the Sr sorption was measured by Liquid Scintillation Counter for determination of their sorption efficiencies. The result obtained that, zeolite-PAN composites were shown high sorption efficiencies on the composites zeolite-PVA which was formulated from 20% zeolite, irradiated by 40 kGy and obtained the sorption efficiency of 94% with the Kd values similar to the purified zeolites. (author)

Investigatons on the local structure of AG+/ZSM-5 catalysts and their photocatalytic reactivities for the decomposition of N2O at 298 κ

International Nuclear Information System (INIS)

Matsuoka, Masaya; Ju, Woo-Sung; Yamashita, Hiromi; Anpo, Masakazu

2001-01-01

Ag + /ZSM-5 catalysts were prepared by an ion-exchange method and UV-irradiation of the catalysts in the presence of N 2 O led to the photo-catalytic decomposition of N 2 O into N 2 and O 2 at 298 κ. Investigations on the effective wavelength of irradiated UV-light for the reaction as well as the in-situ characterization of the catalysts by means of XAFS, UV-Vis, photoluminescence and FT-IR spectroscopies revealed that the photoexcitation of the Ag + -N 2 O complexes formed between gaseous N 2 O and the isolated Ag + ions play a significant role in this reaction. (au)

Metal compounds in zeolites as active components of chemisorption and catalysis. Quantum chemical approach

International Nuclear Information System (INIS)

Zhidomirov, G.M.

1996-01-01

A short review of possible catalitic active sites associated with various types of metal species in zoolite is presented. The structural and electronic peculiarity of aluminum ions in zeolite lattice and their distribution in the lattice are discussed on the basis of quantum chemical calculations in connection with the formation of Broensted activity of zeolites. Various molecular models of Lewis Acid Sites associated the extra-lattice oxide-hydroxide aluminum species have been investigated by means of density functional model cluster calculations using CO molecule as a probe. Probable ways of formation of the selective oxidation center in FeZSM-5 by decomposition of dinitrogen monoxide have been studied by ab-initio quantum chemical calculations. The immediate oxidizing site is reasonably represented by the binuclear iron-hydroxide cluster with peroxo-like fragment located between iron atoms. Various probable intermediates of the selective oxidation center formation resulted from interaction of a hydroperoxide molecule with a lattice titanium ion in titanium silicalite have been investigated by quantum chemical calculations. It was concluded that this reaction requires essential structural reconstruction in the vicinity of the titanium ion. Probability of this structural reconstruction is discussed. Possible reasons of an electron-deficient and electron-enriched state of metal particles entrapped in zoolite cavities are discussed. Also, various probable molecular models of such modified metal particles in zeolite are considered

Effect of high-temperature treatment on Fe/ZSM-5 prepared by chemical vapor deposition of FeCl3. II. Nitrous oxide decomposition, selective oxidation of benzene to phenol, and selective reduction of nitric oxide by isobutane

NARCIS (Netherlands)

Zhu, Q.; Teeffelen, van R.M.; Santen, van R.A.; Hensen, E.J.M.

2004-01-01

The catalytic performance (nitrous oxide decomposition, hydroxylation of benzene to phenol with nitrous oxide, and selective reduction of nitric oxide by i-butane) was evaluated for a set of HZSM-5 and sublimed Fe/ZSM-5 catalysts, which have been extensively characterized in an earlier contribution

Optimization of catalytic glycerol steam reforming to light olefins using Cu/ZSM-5 catalyst

International Nuclear Information System (INIS)

Zakaria, Z.Y.; Amin, N.A.S.; Linnekoski, J.

2014-01-01

Highlights: • Glycerol steam reforming to light olefin using Cu/ZSM-5 process was optimized. • Response surface methodology and multi-objective genetic algorithm were employed. • Second order polynomial model produced adequately fitted experimental data. • Thermodynamic study inferred high temperature requirement for ethylene formation. • Turn-over-frequency at optimized responses is higher than the non-optimized process. - Abstract: Response surface methodology (RSM) and multi-objective genetic algorithm was employed to optimize the process parameters for catalytic conversion of glycerol, a byproduct from biodiesel production, to light olefins using Cu/ZSM-5 catalyst. The effects of operating temperature, weight hourly space velocity (WHSV) and glycerol concentration on light olefins selectivity and yield were observed. Experimental results revealed the data adequately fitted into a second-order polynomial model. The linear temperature and quadratic WHSV terms gave significant effect on both responses. Optimization of both the responses indicated that temperature favouring high light olefin formation lied beyond the experimental design range. The trend in the temperature profile concurred commensurately with the thermodynamic analysis. Multi-objective genetic algorithm was performed to attain a single set of processing parameters that could produce both the highest light olefin selectivity and yield. The turn-over-frequency (TOF) of the optimized responses demonstrated a slightly higher value than the one which was not optimized. Combination of RSM, multi-objective response and thermodynamic is useful to determine the process optimal operating conditions for industrial applications

Preparation of hierarchical micro-mesoporous aluminosilicate composites by simple Y zeolite/MCM-48 silica assembly

Energy Technology Data Exchange (ETDEWEB)

Enterría, Marina, E-mail: marina@incar.csic.es; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M.D.

2014-01-15

Highlights: • Hierarchical micro-mesoporous aluminosilicates were synthesized. • Y zeolite core/MCM-48 silica shell structures were obtained. • Y zeolite favors the formation of the mesostructure. • Porosity and structure can be varied by modifying the preparation variables. • Duration of the hydrothermal step has a great effect on the materials properties. -- Abstract: A simple procedure to obtain hierarchical micro-mesoporous aluminosilicate composites was developed by growing MCM-48 silica over commercial Y zeolite. The obtained hierarchical composites have a microporous core and a mesoporous shell. The process consists in assembling dispersed Y zeolite with a mesoporous silica phase that is formed “in situ” by “soft-templating” with cetryltrimethylammonium bromide (CTAB) as surfactant. The Y zeolite/MCM-48 silica ratio and aging time were varied to study their effects on the final porosity and structure of the hierarchical composites. The pore textural and structural characteristics of the composites did not match those of the corresponding Y zeolite/MCM-48 silica physical mixtures. This implies that the synthesized composites integrate micropores and mesopores in the same bulk. The obtained composites exhibited micropore and mesopore volumes ranging between 0.15–0.31 and 0.30–0.51 cm{sup 3}/g, respectively. X-ray diffraction and N{sub 2} adsorption results revealed that the presence of zeolite in the reaction medium favors the formation of mesopores in the obtained materials, especially for short hydrothermal treatments. TEM results showed that the obtained adsorbents are constituted by an integrated micro-mesoporous bimodal system in which Y zeolite is surrounded by a thin cover of MCM-48 silica.

Preparation of hierarchical micro-mesoporous aluminosilicate composites by simple Y zeolite/MCM-48 silica assembly

International Nuclear Information System (INIS)

Enterría, Marina; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M.D.

2014-01-01

Highlights: • Hierarchical micro-mesoporous aluminosilicates were synthesized. • Y zeolite core/MCM-48 silica shell structures were obtained. • Y zeolite favors the formation of the mesostructure. • Porosity and structure can be varied by modifying the preparation variables. • Duration of the hydrothermal step has a great effect on the materials properties. -- Abstract: A simple procedure to obtain hierarchical micro-mesoporous aluminosilicate composites was developed by growing MCM-48 silica over commercial Y zeolite. The obtained hierarchical composites have a microporous core and a mesoporous shell. The process consists in assembling dispersed Y zeolite with a mesoporous silica phase that is formed “in situ” by “soft-templating” with cetryltrimethylammonium bromide (CTAB) as surfactant. The Y zeolite/MCM-48 silica ratio and aging time were varied to study their effects on the final porosity and structure of the hierarchical composites. The pore textural and structural characteristics of the composites did not match those of the corresponding Y zeolite/MCM-48 silica physical mixtures. This implies that the synthesized composites integrate micropores and mesopores in the same bulk. The obtained composites exhibited micropore and mesopore volumes ranging between 0.15–0.31 and 0.30–0.51 cm 3 /g, respectively. X-ray diffraction and N 2 adsorption results revealed that the presence of zeolite in the reaction medium favors the formation of mesopores in the obtained materials, especially for short hydrothermal treatments. TEM results showed that the obtained adsorbents are constituted by an integrated micro-mesoporous bimodal system in which Y zeolite is surrounded by a thin cover of MCM-48 silica

Catalase-like activity studies of the manganese(II) adsorbed zeolites

Science.gov (United States)

Ćiçek, Ekrem; Dede, Bülent

2013-12-01

Preparation of manganese(II) adsorbed on zeolite 3A, 4A, 5A. AW-300, ammonium Y zeolite, organophilic, molecular sieve and catalase-like enzyme activity of manganese(II) adsorbed zeolites are reported herein. Firstly zeolites are activated at 873 K for two hours before contact manganese(II) ions. In order to observe amount of adsorption, filtration process applied for the solution. The pure zeolites and manganese(II) adsorbed zeolites were analysed by FT-IR. As a result according to the FT-IR spectra, the incorporation of manganese(II) cation into the zeolite structure causes changes in the spectra. These changes are expected particularly in the pseudolattice bands connected with the presence of alumino and silicooxygen tetrahedral rings in the zeolite structure. Furthermore, the catalytic activities of the Mn(II) adsorbed zeolites for the disproportionation of hydrogen peroxide were investigated in the presence of imidazole. The Mn(II) adsorbed zeolites display efficiency in the disproportion reactions of hydrogen peroxide, producing water and dioxygen in catalase-like activity.

Zeolite and wollastonite synthesis from rice hull ash; Sintese de zeolitas e wolastonita a partir da cinza da casca de arroz

Energy Technology Data Exchange (ETDEWEB)

Fernandes, Alberto de Andrade

2006-07-01

Rice hull ash (RHA) is a industry scrap rich in amorphous silica. A simple and low-energy cost method for the extraction of this silica was researched. A low level of impurity and high reactivity material was produced, which is appropriate for the synthesis of zeolites and wollastonite (CaSiO{sub 3}). The synthetic zeolites has not similar structures in nature, and they have been more and more valued in the market due to their purity and efficiency in specific applications like ion exchange, molecular sieve and catalysis areas. High purity wollastonite has many applications in manufacturing and agriculture. The mineral wollastonite can be formed in nature in different ways; it is generally accepted two forming processes, both encompassing limestone metamorphism (heat and pressure). In this work, a new process for the synthesis of zeolites and wollastonite from RHA colloidal silica was developed. Moreover, the process is aimed at lower energy costs, fewer stages and fewer reactants consume. In this work, zeolite A used in detergent and zeolite ZSM-5, employed in the petrochemical industry due to its high selectivity in catalytic reactions and its high thermo and acid stability, were synthesized. The first step of the wollastonite synthesis was studied, with the purpose of obtaining calcium hydrosilicate. Eleven different hydrosilicates occur in the system Ca(OH){sub 2}-SiO{sub 2}-H{sub 2}O, in the second step it was annealed to form the wollastonite phase. (author)

Bonding of Co Ions in ZSM-5, Ferrierite, and Mordenite: An X-ray Absorption, UV-Vis and IR Study