Dispersed catalysts for transforming extra heavy crude oil into transportable upgraded crude: phase identification

Energy Technology Data Exchange (ETDEWEB)

Martinez, S.; Canizales, E.; Machin, I. [Gerencia Depttal de Investigacion Estrategica en Refinacion PDVSA Intevep (Venezuela); Segovia, X.; Rivas, A.; Lopez, E.; Pena, J.P.; Rojas, J.D.; Sardella, R. [Gerencia Depttal de Infraestructura y Mejoramiento en Faja Petrolifera PDVSA Intevep (Venezuela)

2011-07-01

A new technology to convert extra heavy crude oil into transportable upgraded crude has been developed. A water/oil emulsion composed of steam and catalyst precursors is introduced in the feed which then generates unsupported dispersed catalyst in situ under thermal decomposition. The aim of this paper is to characterize the particles. The study was conducted in a laboratory and on a pilot scale on three different vacuum residues using high resolution transmission electron microscopy and a transmission electron microscope. Results showed that the particles were formed by oxides and inorganic sulphur based in transition metals and their sizes ranged between 5 and 120 nm; in addition, good dispersion was observed. This study demonstrated that the process involved in the generation of dispersed catalyst is extremely complex and showed that further work with heavy crude oils and its residua is required to understand the mechanisms involved.

Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions.

Science.gov (United States)

Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D

2018-03-01

Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

Poly(Ionic Liquid: A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP

Directory of Open Access Journals (Sweden)

Lan Yao

2018-03-01

Full Text Available Poly(ionic liquids (PILs have become the frontier domains in separation science because of the special properties of ionic liquids as well as their corresponding polymers. Considering their function in separation, we designed and synthesized a thermoregulated PIL. That is, this kind of PIL could separate with an organic phase which dissolves the monomers at ambient temperature. When heated to the reaction temperature, they become a homogeneous phase, and they separate again when the temperature falls to the ambient temperature after polymerization. Based on this, a thermoregulated phase separated catalysis (TPSC system for Cu-based atom transfer radical polymerization (ATRP was constructed. The copper catalyst (CuBr2 used here is easily separated and recycled in situ just by changing the temperature in this system. Moreover, even when the catalyst had been recycled five times, the controllability over resultant polymers is still satisfying. Finally, only 1~2 ppm metal catalyst was left in the polymer solution phase, which indicates the really high recycling efficiency.

Acrolein Production by Gas-Phase Glycerol Dehydration Using PO₄/Nb₂O5 Catalysts.

Science.gov (United States)

Lee, Kyu Am; Ryoo, HeeKyoung; Ma, Byung Chol; Kim, Youngchul

2018-02-01

In this study, modified niobium oxide were prepared to study the addictive effects on the catalytic performance for gas-phase glycerol dehydration. The catalysts were characterized by N2 adsorption/desorption, XRD, NH3-TPD, FT-IR. The amount of phosphoric acid was up to 50 wt% in niobium. As a result, the highest glycerol conversion was achieved over 20 wt% PO4/Nb2O5. It indicates that the optimal amount of phosphoric acid leads the catalyst to have appropriate acidity which is an important factor for gas-phase glycerol dehydration.

Water detritiation: better catalysts for liquid phase catalytic exchange

International Nuclear Information System (INIS)

Braet, J.

2005-01-01

Fusion reactors are our hope for a clean nuclear energy. But as they shall handle huge amounts of tritium, 1.5 10 19 Bq GWth -1 a -1 or about 50 000 times more tritium than light water fission reactors, they need detritiation. Most tritium losses can be trapped as or can easily be transformed into tritiated water. Water detritiation is preferably based on the multiplication of the large equilibrium isotope effect during the exchange reaction of tritium between hydrogen gas and liquid water in a counter current trickle bed reactor. Such LPCE (Liquid Phase Catalytic Exchange) requires an efficient hydrophobic catalyst. SCK-CEN invented and developed such a catalyst in the past. In combination with an appropriate packing, different batches of this catalyst performed very well during years of extensive testing, allowing to develop the ELEX process for water detritiation at inland reprocessing plants. The main objectives of this study were to reproduce and possibly improve the SCK-CEN catalyst for tritium exchange between hydrogen and liquid water; and to demonstrate the high overall exchange rate and thus high detritiation factors that can be realized with it in a small and simple LPCE column under typical but conservative operating conditions

The influence of phase transfer catalyst structure on reaction selectivity

International Nuclear Information System (INIS)

Demlov, Eh.V.

1995-01-01

A concise review is given of systematic studies which are concerned with the tuning of regio, frequentio-, chemo-, and diastereoselectivity by the structure or type of phase transfer catalyst. Use of MEI as an alkylating agent is described. Refs. 36, figs. 11

Characterization and parametrical study of Rh-TPPTS supported ionic liquid phase (SILP) catalysts for ethylene hydroformylation

DEFF Research Database (Denmark)

Hanh, Nguyen Thi Ha; Duc, Duc Truong; Thang, Vu Dao

2012-01-01

The supported ionic liquid phase (SILP) catalysis technology was applied to continuous, gas-phase hydroformylation of ethylene. Rh-TPPTS SILP catalysts with relatively low ionic liquid loading were shown to be stable and highly activity for ethylene hydroformylation. However, the catalytic activity......, BET surface area and pore morphology of the catalysts depended on the content of ionic liquid. Hence, catalysts with high ionic liquid loading content showed deactivation at high reaction temperatures, possibly caused by redistribution of ionic liquid out of the pores under these conditions. (C) 2012...

Designing Multifunctionality into Single Phase and Multiphase Metal-Oxide-Selective Propylene Ammoxidation Catalysts

Directory of Open Access Journals (Sweden)

James F. Brazdil

2018-03-01

Full Text Available Multifunctionality is the hallmark of most modern commercial heterogeneous catalyst systems in use today, including those used for the selective ammoxidation of propylene to acrylonitrile. It is the quintessential principle underlying commercial catalyst design efforts since petrochemical process development is invariably driven by the need to reduce manufacturing costs. This is in large part achieved through new and improved catalysts that increase selectivity and productivity. In addition, the future feedstocks for chemical processes will be invariably more refractory than those currently in use (e.g., replacing alkenes with alkanes or using CO2, thus requiring a disparate combination of chemical functions in order to effect multiple chemical transformations with the fewest separate process steps. This review summarizes the key chemical phenomena behind achieving the successful integration of multiple functions into a mixed-metal-oxide-selective ammoxidation catalyst. An experiential and functional catalyst design model is presented that consists of one or both of the following components: (1 a mixed-metal-oxide–solid solution where the individual metal components serve separate and necessary functions in the reaction mechanism through their atomic level interaction in the context of a single crystallographic structure; (2 the required elemental components and their catalytic function existing in separate phases, where these phases are able to interact for the purposes of electron and lattice oxygen transfer through the formation of a structurally coherent interface (i.e., epitaxy between the separate crystal structures. Examples are provided from the literature and explained in the context of this catalyst design model. The extension of the model concepts to the design of heterogeneous catalysts in general is also discussed.

Application of Moessbauer spectroscopy for the characterization of iron-containing catalysts

International Nuclear Information System (INIS)

Phillips, J.

1998-01-01

Work in our laboratory demonstrates the unique analytical power as well as the limits of Moessbauer Spectroscopy (MES) as a tool for characterizing the size and phase of supported iron containing catalyst particles, particularly carbon supported catalysts. The major challenge in employing MES to characterize catalytic particles is understanding the impact of the relaxation effects on the spectra. Proper methods yield particle size and phase information, whereas improper interpretation can lead to the misidentification of phases. This is illustrated by feeding ersatz 'relaxed' spectra data, generated mathematically with a program which accounts for all aspects of relaxation, to a standard fitting routine. The fitting routine misinterprets the data and provides false phase identification. Methods for recognizing relaxation phenomena and strategies for extracting correct information from relaxed spectra are reviewed. Also reviewed are the major findings of studies on carbon supported catalysts. For example, MES studies, in conjunction with other techniques, demonstrate that bulk and surface structures which are easily accessible for carbon supported bimetallics are generally not found on refractory oxides

Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

Energy Technology Data Exchange (ETDEWEB)

Sachdeva, T.O.; Pant, K.K. [Department of Chemical Engineering, Indian Institute of Technology, Delhi, New Delhi, 110016 (India)

2010-09-15

High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO{sub x}) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

International Nuclear Information System (INIS)

Sachdeva, T.O.; Pant, K.K.

2010-01-01

High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO x ) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

Propene and l-octene hydroformylation with silica-supported, ionic liquid-phase (SILP) Rh-phosphine catalysts in continuous fixed-bed mode

DEFF Research Database (Denmark)

Riisager, Anders; Eriksen, Kim Michael; Wasserscheid, Peter

2003-01-01

- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h(-1) for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.......Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium) phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM] [PF6], on a silica support. The catalysts were active in continuous gas...

Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

Science.gov (United States)

Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

2017-08-30

Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

Science.gov (United States)

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

WxC-β-SiC Nanocomposite Catalysts Used in Aqueous Phase Hydrogenation of Furfural.

Science.gov (United States)

Rogowski, Jacek; Andrzejczuk, Mariusz; Berlowska, Joanna; Binczarski, Michal; Kregiel, Dorota; Kubiak, Andrzej; Modelska, Magdalena; Szubiakiewicz, Elzbieta; Stanishevsky, Andrei; Tomaszewska, Jolanta; Witonska, Izabela Alina

2017-11-22

This study investigates the effects of the addition of tungsten on the structure, phase composition, textural properties and activities of β-SiC-based catalysts in the aqueous phase hydrogenation of furfural. Carbothermal reduction of SiO₂ in the presence of WO₃ at 1550 °C in argon resulted in the formation of W x C-β-SiC nanocomposite powders with significant variations in particle morphology and content of W x C-tipped β-SiC nano-whiskers, as revealed by TEM and SEM-EDS. The specific surface area (SSA) of the nanocomposite strongly depended on the amount of tungsten and had a notable impact on its catalytic properties for the production of furfuryl alcohol (FA) and tetrahydrofurfuryl alcohol (THFA). Nanocomposite W x C-β-SiC catalysts with 10 wt % W in the starting mixture had the highest SSA and the smallest W x C crystallites. Some 10 wt % W nanocomposite catalysts demonstrated up to 90% yield of THFA, in particular in the reduction of furfural derived from biomass, although the reproducible performance of such catalysts has yet to be achieved.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

Science.gov (United States)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan N., Pethan; Kumar Balla, Putra; Chary Komandur, V. R.

2014-08-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol-gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO3) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV-vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

International Nuclear Information System (INIS)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R.

2014-01-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO 3 ) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH 3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

Energy Technology Data Exchange (ETDEWEB)

Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R., E-mail: kvrchary@iict.res.in

2014-08-01

Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO{sub 3}) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH{sub 3} TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

Supported liquid phase catalyst coating in micro flow Mizoroki-Heck reaction

NARCIS (Netherlands)

Stouten, S.C.; Noël, T.; Wang, Q.; Hessel, V.

2015-01-01

A Supported Liquid Phase Catalyst (SLPC) coating was successfully applied for the Mizoroki–Heck reaction in micro flow. Foremost, extended on stream operation was enabled and the on stream performance stability was verified. Stable catalytic activity was achieved during two consecutive runs totaling

Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

International Nuclear Information System (INIS)

Kim, Yong Tae; Park, Eun Duck; Jung, Kwang Deog

2010-01-01

The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. γ-Al 2 O 3 , SiO 2 -Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 , AC, CeO 2 and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, N 2 -physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia (NH 3 - TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at 315 .deg. C among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/ZrO 2 and HSiW/SiO 2 -Al 2 O 3 showed the highest acrolein selectivity. In the case of HSiW/ZrO 2 , the initial catalytic activity was recovered after the removal of the accumulated carbon species at 550 .deg. C in the presence of oxygen

Synthesis of Acrolein from Glycerol Using FePO4 Catalyst in Liquid Phase Dehydration

Directory of Open Access Journals (Sweden)

Akhmad Zainal Abidin

2016-02-01

Full Text Available Acrolein is currently produced using propylene from crude oil while its price and scarcity are increasing. A renewable material such as glycerol is an attractive alternative for acrolein production. It can be obtained from crude palm oil (CPO and is a byproduct of biodiesel production. Besides being able to compete economically, glycerol is an environmentally friendly material. The purpose of this study is to synthesize acrolein from glycerol using FePO4 catalyst in liquid phase dehydration. The catalyst was prepared by three different methods: hydrothermal (catalyst A, deposition at Fe/P = 1.15 (catalyst B, and deposition at Fe/P = 1.20 (catalyst C. The experimental reaction temperature was varied at 220, 240 and 260 °C under constant atmospheric pressure. The results showed that catalyst C provided the best yield (91%, followed by catalyst A (90% and catalyst B (82%. The increasing reaction temperature showed a tendency to increase the yield of acrolein, while the presence of oxygen reduced the yield of acrolein and allowed the reaction to produce more side products such as glycerol propanal, acetaldehyde, and propionate. Catalyst reuse without any regeneration resulted in a yield profile of acrolein that continued to decline.

Stability and kinetic studies of supported ionic liquid phase catalysts for hydroformylation of propene

DEFF Research Database (Denmark)

Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

2005-01-01

Supported ionic liquid phase (SILP) catalysts have been studied with regard to their long-term stability in the continuous gas-phase hydroformylation of propene. Kinetic data have been acquired by variation of temperature, pressure, syngas composition, substrate concentration, and residence time...

Application of New Electrolyte Model to Phase Transfer Catalyst (PTC) Systems

DEFF Research Database (Denmark)

Hyung Kim, Sun; Anantpinijwatna, Amata; Kang, Jeong Won

2015-01-01

Abstract Phase transfer catalyst (PTC) is used to transfer the desirable active form of an anion from the aqueous phase to organic phase where the reaction occurs. One of major challenges for process design of the PTC system is to establish a reliable thermodynamic model capable of describing pha...... in PTC systems, thereby, extending the application range of the PTC-system model. The solubility of PTC in organic solvents, which is a key factor for strategy of PTC and solvent selection, has been calculated using the e-NRTL-SAC model....

WxC-β-SiC Nanocomposite Catalysts Used in Aqueous Phase Hydrogenation of Furfural

Directory of Open Access Journals (Sweden)

Jacek Rogowski

2017-11-01

Full Text Available This study investigates the effects of the addition of tungsten on the structure, phase composition, textural properties and activities of β-SiC-based catalysts in the aqueous phase hydrogenation of furfural. Carbothermal reduction of SiO2 in the presence of WO3 at 1550 °C in argon resulted in the formation of WxC-β-SiC nanocomposite powders with significant variations in particle morphology and content of WxC-tipped β-SiC nano-whiskers, as revealed by TEM and SEM-EDS. The specific surface area (SSA of the nanocomposite strongly depended on the amount of tungsten and had a notable impact on its catalytic properties for the production of furfuryl alcohol (FA and tetrahydrofurfuryl alcohol (THFA. Nanocomposite WxC-β-SiC catalysts with 10 wt % W in the starting mixture had the highest SSA and the smallest WxC crystallites. Some 10 wt % W nanocomposite catalysts demonstrated up to 90% yield of THFA, in particular in the reduction of furfural derived from biomass, although the reproducible performance of such catalysts has yet to be achieved.

System identification on two-phase flow stability

International Nuclear Information System (INIS)

Wu Shaorong; Zhang Youjie; Wang Dazhong; Bo Jinghai; Wang Fei

1996-01-01

The theoretical principle, experimental method and results of interrelation analysis identification for the instability of two-phase flow are described. A completely new concept of test technology and method on two-phase flow stability was developed by using he theory of information science on system stability and system identification for two-phase flow stability in thermo-physics field. Application of this method would make it possible to identify instability boundary of two-phase flow under stable operation conditions of two-phase flow system. The experiment was carried out on the thermohydraulic test system HRTL-5. Using reverse repeated pseudo-random sequences of heating power as input signal sources and flow rate as response function in the test, the two-phase flow stability and stability margin of the natural circulation system are investigated. The effectiveness and feasibility of identifying two-phase flow stability by using this system identification method were experimentally demonstrated. Basic data required for mathematics modeling of two-phase flow and analysis of two-phase flow stability were obtained, which are useful for analyzing, monitoring of the system operation condition, and forecasting of two-phase flow stability in engineering system

Synergy effects between bismuth molybdate catalyst phases (Bi/Mo from 0.57 to 2) for the selective oxidation of propylene to arcrolein

DEFF Research Database (Denmark)

Le, Minh Thang; Well, Willy van; Stoltze, Per

2005-01-01

In this work, the synergy effect between different phases of bismuth molybdate catalysts was investigated systematically. The catalysts were prepared by spray drying and had a Bi/Mo atomic between 0.57 and 2. It is found that the synergy effect is only observed in mixtures containing γ-phase. A m......-phase. A mixture with Bi/Mo ratio = 1.3 consisting of γ- and α-phase, exhibits the highest activity. Less homogeneous ‘artificial mixtures’ exhibit reduced synergy effects when compared to homogeneous ‘in situ mixtures’.......In this work, the synergy effect between different phases of bismuth molybdate catalysts was investigated systematically. The catalysts were prepared by spray drying and had a Bi/Mo atomic between 0.57 and 2. It is found that the synergy effect is only observed in mixtures containing γ...

Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

DEFF Research Database (Denmark)

Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

2009-01-01

The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

International Nuclear Information System (INIS)

Wu, Ke; Zheng, Mengjia; Han, Yuxiang; Xu, Zhaoyi; Zheng, Shourong

2016-01-01

Highlights: • Pd catalysts supported on TiO_2, CeO_2, Al_2O_3 and SiO_2 were prepared. • Deposition-precipitation method resulted in positively charged smaller Pd particle. • Complete debromination of tetrabromobisphenol A could be achieved on Pd/TiO_2. • Pd/TiO_2 prepared by the deposition-precipitation method was more active. - Abstract: Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO_2, CeO_2, Al_2O_3 and SiO_2 were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N_2 adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO_2 was much smaller than those in im-Pd/TiO_2 and pd-Pd/TiO_2. Pd particle size of the dp-Pd/TiO_2 catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO_2 catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd loading amount, the Pd catalyst supported on TiO_2 exhibited a much higher catalytic activity

Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

DEFF Research Database (Denmark)

Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie

2014-01-01

Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

Influence of the phase composition on the catalytic properties of ammonia synthesis catalysts

International Nuclear Information System (INIS)

Peev, T.M.; Bojinova, A.I.; Krylova, A.V.

1981-01-01

The phase composition of CA-1-type catalysts for ammonia synthesis was investigated by means of Moessbauer spectroscopy. A correlation was found between the catalytic activity of the samples and their wuestite content. (author)

Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

Energy Technology Data Exchange (ETDEWEB)

Berman, A D; Krylov, O V

1978-01-01

This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

Highly Selective Liquid-Phase Benzylation of Anisole with Solid-Acid Zeolite Catalysts

DEFF Research Database (Denmark)

Poreddy, Raju; Shunmugavel, Saravanamurugan; Riisager, Anders

2015-01-01

Zeolites were evaluated as solid acid catalysts for the liquid-phase benzylation of anisole with benzyl alcohol, benzyl bromide, and benzyl chloride at 80 °C. Among the examined zeolites, H-mordenite-10 (H-MOR-10) demonstrated particular high activity (>99 %) and excellent selectivity (>96...

Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

Energy Technology Data Exchange (ETDEWEB)

Wu, Ke [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Zheng, Mengjia [Kuang Yaming Honors School, Nanjing University, Nanjing 210023 (China); Han, Yuxiang [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Xu, Zhaoyi, E-mail: zhaoyixu@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Zheng, Shourong [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China)

2016-07-15

Highlights: • Pd catalysts supported on TiO{sub 2}, CeO{sub 2}, Al{sub 2}O{sub 3} and SiO{sub 2} were prepared. • Deposition-precipitation method resulted in positively charged smaller Pd particle. • Complete debromination of tetrabromobisphenol A could be achieved on Pd/TiO{sub 2}. • Pd/TiO{sub 2} prepared by the deposition-precipitation method was more active. - Abstract: Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO{sub 2}, CeO{sub 2}, Al{sub 2}O{sub 3} and SiO{sub 2} were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N{sub 2} adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO{sub 2} was much smaller than those in im-Pd/TiO{sub 2} and pd-Pd/TiO{sub 2}. Pd particle size of the dp-Pd/TiO{sub 2} catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO{sub 2} catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd

Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

International Nuclear Information System (INIS)

Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

2016-01-01

Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N 2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d 5/2 shifted to higher positions while that of Au 4f 7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity

Uniformly active phase loaded selective catalytic reduction catalysts (V_2O_5/TNTs) with superior alkaline resistance performance

International Nuclear Information System (INIS)

Wang, Haiqiang; Wang, Penglu; Chen, Xiongbo; Wu, Zhongbiao

2017-01-01

Highlights: • VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3. • Ion-exchange reaction occurs between VOSO_4 and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO_4-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH_4VO_3 and VOSO_4) were used to synthesize deNO_x catalysts. The results showed that VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V"5"+/V"4"+ redox cycles and superior oxygen mobility were achieved. Besides, VOSO_4-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V_2O_5/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

Certain aspects of the formation and identification of nanosized oxide components in heterogeneous catalysts prepared by different methods

International Nuclear Information System (INIS)

Ellert, Ol'ga G; Novotortsev, Vladimir M; Tsodikov, Mark V

2010-01-01

The results of studies into the relationship 'methods and synthesis conditions of a catalyst→catalyst structure→catalytic properties' in highly efficient crystallo-graphically amorphous copper- and iron-containing heterogeneous systems obtained by different chemical methods are generalized. Polymorphism of active phases and catalytic properties of nanostructured copper-containing zinc, zirconium, manganese and cerium oxides are discussed. Unusual transformations of nanosized Pt- and Pd-containing components on the γ-Al 2 O 3 surface in nanostructured catalysts of ethanol steam reforming into synthesis gas and reductive dehydration of ethanol to alkanes are considered. The results of comparative studies on the crystallographically amorphous mixed iron oxide catalysts synthesized by either the alkoxy method or the deposition on various supports obtained by the Moessbauer and XAFS spectroscopy and magnetic susceptibility measurements are presented. These materials are shown to be efficient catalysts of important processes such as liquid-phase oxidation of hydrocarbons, synthesis of alkenes and alkylaromatic hydrocarbons from CO and H 2 , hydrogenative transformation of brown coal organic mass to hydrocarbons.

Methods of making textured catalysts

Science.gov (United States)

Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

2010-08-17

A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

Cross-Aldol condensation of isobutyraldehyde and formaldehyde using phase transfer catalyst

Directory of Open Access Journals (Sweden)

Azhar Hashmi

2016-09-01

Full Text Available The hydroxypivaldehyde (HPA precursor intermediate for the synthesis of neopentyl glycol (NPG is prepared by novel cross Aldol condensation of isobutyraldehyde and formaldehyde at 20 °C using benzyltrimethylammonium hydroxide, a basic phase transfer catalyst. A feed mole ratio of 1.1:1.0:0.04 (isobutyraldehyde:formaldehyde:benzyltrimethylammonium hydroxide afforded hydroxypivaldehyde as white solid in almost quantitative yield with ∼100% selectivity.

Cross-Aldol condensation of isobutyraldehyde and formaldehyde using phase transfer catalyst

OpenAIRE

Azhar Hashmi

2016-01-01

The hydroxypivaldehyde (HPA) precursor intermediate for the synthesis of neopentyl glycol (NPG) is prepared by novel cross Aldol condensation of isobutyraldehyde and formaldehyde at 20 °C using benzyltrimethylammonium hydroxide, a basic phase transfer catalyst. A feed mole ratio of 1.1:1.0:0.04 (isobutyraldehyde:formaldehyde:benzyltrimethylammonium hydroxide) afforded hydroxypivaldehyde as white solid in almost quantitative yield with ∼100% selectivity.

Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

Energy Technology Data Exchange (ETDEWEB)

Zhou, Juan [School of the Environment, Donghua University, Shanghai 201620 (China); Chen, Huan, E-mail: hchen404@njust.edu.cn [Key Laboratory of Jiangsu Province for Chemical Pollution Control and Resources Reuse, School of Environmental & Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Chen, Quanyuan; Huang, Zhaolu [School of the Environment, Donghua University, Shanghai 201620 (China)

2016-11-30

Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N{sub 2} adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H{sub 2} chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d{sub 5/2} shifted to higher positions while that of Au 4f{sub 7/2} had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest

One-pot aqueous phase catalytic conversion of sorbitol to gasoline over nickel catalyst

International Nuclear Information System (INIS)

Weng, Yujing; Qiu, Songbai; Xu, Ying; Ding, Mingyue; Chen, Lungang; Zhang, Qi; Ma, Longlong; Wang, Tiejun

2015-01-01

Highlights: • Directly production gasoline (C5–C12 alkanes) from biomass-derived sugar alcohol sorbitol. • Temperature of STG (553–593 K) was lower than that of traditional methanol to gasoline (MTG) (623–773 K). • Gasoline yield of 46.9% and C7–C12 hydrocarbons reached up to 45.5% in the gasoline products. - Abstract: The carbon chain extension and hydrodeoxygenation steps play critical roles in the high-energy-density hydrocarbons production. In this paper, a systematic study had been carried out to investigate one-pot aqueous phase catalytic conversion of sorbitol to gasoline (STG) over bifunctional Ni-based catalysts. Characterization technologies of N 2 physisorption, X-ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NH 3 temperature-programmed desorption (NH 3 -TPD) were used to study the textural properties, phase compositions, acid behavior and morphologies of the catalysts. The catalytic performances were tested in a fixed bed reactor. It was found that the physically mixed Ni/HZSM-5 and Ni/silica-gel (mesoporous SG) catalyst realized the carbon chain extension and exhibited excellent performances on hydrodeoxygenation (HDO) reaction (46.9% of gasoline (C5–C12) yield and 45.5% of C7–C12 hydrocarbons in the gasoline products). Especially, the temperature of STG (553–593 K) was lower obviously than that of the traditional methanol to gasoline (MTG) process (623–773 K). It provided a novel transformation of sorbitol to long-chain alkanes by one-pot process over the bifunctional catalyst (Ni@HZSM-5/SG), wherein hydrodeoxygenation, ketonization and aldol condensation steps were integrated

Predictive Modelling of Phase-Transfer Catalyst Systems for Improved and Innovative Design

DEFF Research Database (Denmark)

Anantpinijwatna, Amata; Hyung Kim, Sun; Sales-Cruz, Mauricio

2016-01-01

Phase-transfer catalyst (PTC) systems contain two immiscible liquid phases with a heterogeneous PTC transferring active ion from one phase to the other for converting the reactant to the desired product, and in the process generating the inactive ion. This type of reacting systems is receiving...... increasing attention as a novel organic synthesis option due to its flexible and easier operation, higher production yield, and ability to eliminate expensive solvents, although, not eliminating the use of solvents. New mathematical models of the PTC system, which includes physical and chemical equilibrium......, reaction mechanism and unit operation has been developed. In the developed model, the PTC system is divided into four sub-systems of aqueous-organic solvent partition, inorganic salt in aqueous phase, PTC in aqueous phase, and PTC in aqueous phase. Each subsystem requires an appropriate thermodynamic model...

Formation of gas-phase π-allyl radicals from propylene over bismuth oxide and γ-bismuth molybdate catalysts

International Nuclear Information System (INIS)

Martir, W.; Lunsford, J.H.

1981-01-01

Gas-phase π-allyl radicals were produced when propylene reacted over Bi 2 O 3 and γ-bismuth molybdate catalysts at 723 K. The pressure in the catalyst zone was varied between 5 x 10 -3 and 1 torr. The radicals were detected by EPR spectroscopy together with a matrix isolation technique in which argon was used as the diluent. The matrix was formed on a sapphire rod at 12 K which was located 33-cm downstream from the catalyst. Bismuth oxide was more effective in the production of gas-phase allyl radicals than γ-bismuth molybdate. By contrast α-bismuth molybdate was ineffective in forming allyl radicals and MoO 3 acted as a sink for radicals which were produced elsewhere in the system. Comparison of the π-allyl radical and the stable product concentrations over Bi 2 O 3 revealed that gas-phase radical recombination reactions served as a major pathway for the formation of 1,5-hexadiene. Addition of small amounts of gas-phase oxygen increased the concentration of allyl radicals, and at greater oxygen levels allyl peroxy radicals were detected. Because of the effect of temperature on the equilibrium between allyl and allyl peroxy radicals, the latter product must be formed in the cooler part of the system

Shining X-rays on catalysts at work

Energy Technology Data Exchange (ETDEWEB)

Grunwaldt, J-D, E-mail: jdg@kt.dtu.d [Technical University of Denmark, Department of Chemical and Biochemical Engineering, Building 229, DK-2800 Kgs. Lyngby (Denmark)

2009-11-15

Structure-performance relationships gained by studying catalysts at work are considered the key to further development of catalysts underlined here by a brief overview on our research in this area. The partial oxidation of methane to hydrogen and carbon monoxide over Pt- and Rh-based catalysts and the total combustion of hydrocarbons demonstrate the importance of structural identification of catalysts in its working state and the measurement of the catalytic performance at the same time. Moreover, proper cell design is a key both here and in liquid phase reactions including preparation or high pressure reactions. In several cases structural changes during preparation, activation and reaction occur on a subminute scale or the catalyst structure varies inside a reactor as a result of temperature or concentration gradients. This, additionally, requires time and spatial resolution. Examples from time-resolved QEXAFS studies during the partial oxidation of methane over Pt- and Rh-based catalysts demonstrate some of the recent developments of the technique (use not only of Si(111) but also Si(311) crystals, angular encoder, full EXAFS spectra at subsecond recording time, and modulation excitation spectroscopy). In order to obtain spectroscopic information on the oxidation state inside a microreactor, scanning and full field X-ray microscopy with X-ray absorption spectroscopic contrast were achieved under reaction conditions. If a microbeam is applied, fast scanning techniques like QEXAFS are required. In this way, even X-ray absorption spectroscopic tomographic images of a slice of a microreactor were obtained. The studies were recently extended to spatiotemporal studies that give important insight into the dynamics of the catalyst structure in a spatial manner with subsecond time-resolution.

Functionalized Poly(propylene imine) Dendrimers as Novel Phase Transfer Catalyst in Supercritical Cabon Dioxide

NARCIS (Netherlands)

Goetheer, E.L.V.; Baars, M.W.P.L.; Broeke, van den L.J.P.; Meijer, E.W.; Keurentjes, J.T.F.

2000-01-01

Perfluoro-functionalized poly(propylene imine) dendrimers have been used as reactive extractants for anionic species and as phase transfer catalysts for two types of reactions. Different generations of dendrimers have been used for applications in carbon dioxide. First, the reactive extraction of

Magnetic catalyst bodies

NARCIS (Netherlands)

Teunissen, Wendy; Bol, A.A.; Geus, John W.

1999-01-01

After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the

Studies about the transfer phenomena of tritium from liquid to gaseous phase in a catalyst and ordered packing successive system

International Nuclear Information System (INIS)

Bornea, Anisia; Cristescu, Ion; Zamfirache, Marius; Varlam, Carmen

2002-01-01

The processes for hydrogen isotope separation are very important for nuclear technology. One of the most important processes for tritium separation, is the catalyst isotope exchange water-hydrogen. In a column of isotope exchange tritium is transferred from liquid phase (tritiated heavy water) in gaseous phase (hydrogen). In the experimental setup, which was used, the column of catalytic isotope exchange is filled with successive layers of catalyst and ordered packing. The catalyst consists of 95.5 wt.% of PTFE, 4.1 wt. % of carbon and 0.40 wt. % of platinum and was made of Raschig rings 10 x 10 x 2 mm. The ordered packing was of B7 type and consists of a phosphor bronze wire mesh of 0.18 x 0.48 mm dimension. We analysed the transfer phenomena of tritium from liquid to gaseous phase, in this system. The mathematical model presented in the paper allowed computing experimental data for testing the catalyst performances. In this way the speed constants which characterized the isotopic exchange on the catalysis bed ks, and the distillation on the ordered packing kd, were expressed as function of experimental concentrations and hydrodynamic conditions. (authors)

Technology development for iron Fischer-Tropsch catalysts

Energy Technology Data Exchange (ETDEWEB)

O`Brien, R.J.; Raje, A.; Keogh, R.A. [and others

1995-12-31

The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alpha iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

Use of solid-phase salt catalysts in furfural preparation

Energy Technology Data Exchange (ETDEWEB)

Morozov, E.F.; Shkut, V.M.; Kebich, M.S.; Kuznetsova, T.A.

1981-01-01

The manufacture of furfural (I) from tanning waste, birch sawdust, or corncobs at 220-230 degrees in the presence of 2.0-3.0% double superphosphate, ammophos, (NH/sub 4/)/sub 2/SO/sub 4/, NH/sub 4/NO/sub 3/, or NH/sub 4/Cl was evaluated. Most of I is formed within 40 minutes in the presence of NH4NO3 or NH4Cl, and within 55 minutes in the presence of double superphosphate. The highest yield of I was obtained in the presence of NH4NO3 and/or NH4Cl. The solid-phase catalyst caused a little degradation of lignocellulose.

Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst

International Nuclear Information System (INIS)

Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R.; Picasso Escobar, Gino I.

2013-01-01

The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C 12 H 15 N 3 O 2 S) was studied in order to obtain a pharmacologically active molecule known as albendazole sulfoxide. With this purpose, three heterogeneous catalysts were prepared using molybdenum (Mo) as active phase and carbon nanotubes as a multiple-layer catalyst support. The incorporation of the active phase was performed by wet impregnation, with subsequent calcination for 4 hours at 400 o C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H 2 NCONH 2 ·H 2 O 2 ) as oxidizing agent and methanol (CH 3 OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N 2 (BET) and scanning electron microscopy (SEM). The identification and quantification of the reaction products were followed by Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC), respectively. With the yield, selectivity and conversion higher than 90% after 60 minutes of reaction, albendazole sulphoxide was obtained as major product of oxidation reaction. (author)

Operando Spectroscopy of the Gas-Phase Aldol Condensation of Propanal over Solid Base Catalysts

NARCIS (Netherlands)

Hernández-giménez, Ana M.; Ruiz-martínez, Javier; Puértolas, Begoña; Pérez-ramírez, Javier; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

2017-01-01

The gas-phase aldol condensation of propanal, taken as model for the aldehyde components in bio-oils, has been studied with a combined operando set-up allowing to perform FT-IR & UV–Vis diffuse reflectance spectroscopy (DRS) with on-line mass spectrometry (MS). The selected solid base catalysts, a

TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSTS

Energy Technology Data Exchange (ETDEWEB)

Davis, B.H.

1998-07-22

The goal of the proposed work described in this Final Report was the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The work described here has optimized the catalyst composition and pretreatment operation for a low-alpha catalyst. In parallel, work has been conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies have been conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors have been studied at the laboratory scale. Catalyst performance has been determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

Influence of phase composition and structure of V-Mo mixed catalysts on the activity and selectivity in the oxidation of benzene to maleic anhydride

International Nuclear Information System (INIS)

Kripylo, P.; Ritter, D.; Hahn, H.; Spiess, H.; Kraak, P.

1981-01-01

Whereas MoO 3 and phosphate stabilize the low valence states of vanadium in the phase structure of V-Mo mixed catalysts, CoO influences the activity only, but not the selectivity. The catalysts show maxima of activity and selectivity at V/Mo ratios of 4 to 6. Ageing is caused by phase separation connected with the appearance of an MoO 3 phase and an increase of the V/Mo ratio in the phase of the active component

Uniformly active phase loaded selective catalytic reduction catalysts (V{sub 2}O{sub 5}/TNTs) with superior alkaline resistance performance

Energy Technology Data Exchange (ETDEWEB)

Wang, Haiqiang; Wang, Penglu [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China); Chen, Xiongbo [South China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou 510655 (China); Wu, Zhongbiao, E-mail: zbwu@zju.edu.cn [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China)

2017-02-15

Highlights: • VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}. • Ion-exchange reaction occurs between VOSO{sub 4} and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO{sub 4}-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH{sub 4}VO{sub 3} and VOSO{sub 4}) were used to synthesize deNO{sub x} catalysts. The results showed that VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V{sup 5+}/V{sup 4+} redox cycles and superior oxygen mobility were achieved. Besides, VOSO{sub 4}-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V{sub 2}O{sub 5}/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

International Nuclear Information System (INIS)

Blomberg, Sara; Gustafson, Johan; Lundgren, Edvin; Zhou, Jianfeng; Zetterberg, Johan

2016-01-01

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be

2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

Science.gov (United States)

Blomberg, Sara; Zhou, Jianfeng; Gustafson, Johan; Zetterberg, Johan; Lundgren, Edvin

2016-11-01

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be

Effect of phase interaction on catalytic CO oxidation over the SnO_2/Al_2O_3 model catalyst

International Nuclear Information System (INIS)

Chai, Shujing; Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang; Xian, Hui; Mi, Wenbo; Li, Xingang

2017-01-01

Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO_2 and Al_2O_3. • Interaction between SnO_2 and Al_2O_3 phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn"4"+ cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO_2/Al_2O_3 model catalysts. Our results show that interaction between the Al_2O_3 and SnO_2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO_2/Al_2O_3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO_2, which probably results from the change of electron concentration on the interface of the SnO_2 and Al_2O_3 phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn"4"+ cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO_2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

Separation and determination of polyurethane amine catalysts in polyether polyols by using UHPLC-Q-TOF-MS on a reversed-phase/cation-exchange mixed-mode column.

Science.gov (United States)

Li, Jiaxiao; Zhu, Marcel

2018-02-01

A simple, selective, and accurate ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry method was established and validated for the efficient separation and quantification of polyurethane amine catalysts in polyether polyols. Amine catalysts were primarily separated in polyether polyol-based sample by solid-phase extraction, and further baseline separated on a reversed-phase/cation-exchange mixed-mode column (SiELC Primesep™ 200) using 0.1% trifluoroacetic acid/acetonitrile as a mobile phase in gradient elution mode at a flow rate of 0.2 mL/min. High-resolution quadrupole time-of-flight mass spectrometry analysis in electrospray ionization positive mode allowed the identification as N,N'-bis[3-(dimethylamino)propyl]urea, N-[2-(2-dimethylaminoethoxy)ethyl]-N-methyl-1,3-propanediamine, and N,N,N',N'-tetramethyldipropylenetriamine. The method was validated and presented good linearity for all the analytes in blank matrices within the concentration range of 0.20-5.0 or 0.1-2.0 μg/mL with the correlation coefficients (R 2 ) ranging from 0.986 to 0.997. Method recovery ranged within 81-105% at all three levels (80, 100, and 120% of the original amount) with relative standard deviations of 1.0-6.2%. The limits of detection were in the range of 0.007-0.051 μg/mL. Good precision was obtained with relative standard deviation below 3.2 and 0.72% for peak area and retention time of three amines, respectively. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

Directory of Open Access Journals (Sweden)

Ahmed M. El-Sayed

2014-01-01

Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

exchanged Mg-Al hydrotalcite catalyst

Indian Academy of Sciences (India)

) catalysts, ... The catalyst can be easily separated by simple filtration ... surface area by the single-point N2 adsorption method ... concentration of carbonate anions (by treating the cat- .... hydrotalcite phase along with copper hydroxide and.

TECHNOLOGIES OF DOPING OF CAST IRON THROUGH THE SLAG PHASE WITH USING OF THE SPENT NICKEL- AND COPPER-CONTAINING CATALYSTS

Directory of Open Access Journals (Sweden)

I. B. Provorova

2015-01-01

Full Text Available We have defined the regularities of the doping of cast iron through the slag phase of nickel and copper due to the waste catalysts using a carbonaceous reducing agent. We have justified the need to use the cast iron chips as a seed in the composition of the slag mixture. We have defined the dependence of the degree of extraction of nickel or copper from spent catalyst on the amount of the catalyst, on the basicity of the slag mixture, on the temperature and time of melting.

Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

KAUST Repository

Song, Hyon Min

2012-01-01

The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

Microindentation as a complementary method for phase identification

Science.gov (United States)

Zupanič, Franc

2011-12-01

This work investigates the possibility of using microindentation as a complementary tool for phase identification, especially in heterogeneous microstructures. Five phases present in alloys Al64Cu23Fe13 and Al94Mn2Be2Cu2 were indented in the microindentation region. A load of 20 mN was found to be convenient for testing because it was too low to produce cracks around indents, yet high enough to avoid too large scattering of the results, occurring at smaller loads. It allowed testing of particles as small as 10 μm in the lateral direction and 3 μm in thickness. Some phases can be distinguished from others by specific characteristics of indentation curves. Otherwise, a single quantitative parameter or combinations of several indentation parameters (defined in EN ISO 14577-1) sufficed. The microindentation can considerably help by phase identification; however, a wider application will require a database, providing indentation properties for a particular phase at different loads and taking into account the indentation size effect.

Advanced Aqueous Phase Catalyst Development using Combinatorial Methods, Phase II

Data.gov (United States)

National Aeronautics and Space Administration — Combinatorial methods are proposed to develop advanced Aqueous Oxidation Catalysts (AOCs) with the capability to mineralize organic contaminants present in effluents...

Highly selective bimetallic Pt-Cu/Mg(Al)O catalysts for the aqueous-phase reforming of glycerol

NARCIS (Netherlands)

Boga, D.A.; Oord, R.; Beale, A.M.; Chung, Y.M.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

2013-01-01

Monometallic Pt and bimetallic Pt-Cu catalysts supported on Mg(Al)O mixed oxides, obtained by calcination of the corresponding layered double hydroxides (LDHs), were prepared and tested in the aqueous-phase reforming (APR) of glycerol. The effect of the Mg/Al ratio and calcination temperature of the

Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

Energy Technology Data Exchange (ETDEWEB)

Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

2014-10-17

Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

Highly Efficient Gas-Phase Oxidation of Renewable Furfural to Maleic Anhydride over Plate Vanadium Phosphorus Oxide Catalyst.

Science.gov (United States)

Li, Xiukai; Ko, Jogie; Zhang, Yugen

2018-02-09

Maleic anhydride (MAnh) and its acids are critical intermediates in chemical industry. The synthesis of maleic anhydride from renewable furfural is one of the most sought after processes in the field of sustainable chemistry. In this study, a plate vanadium phosphorus oxide (VPO) catalyst synthesized by a hydrothermal method with glucose as a green reducing agent catalyzes furfural oxidation to MAnh in the gas phase. The plate catalyst-denoted as VPO HT -has a preferentially exposed (200) crystal plane and exhibited dramatically enhanced activity, selectivity and stability as compared to conventional VPO catalysts and other state-of-the-art catalytic systems. At 360 °C reaction temperature with air as an oxidant, about 90 % yield of MAnh was obtained at 10 vol % of furfural in the feed, a furfural concentration value that is much higher than those (<2 vol %) reported for other catalytic systems. The catalyst showed good long-term stability and there was no decrease in activity or selectivity for MAnh during the time-on-stream of 25 h. The high efficiency and catalyst stability indicate the great potential of this system for the synthesis of maleic anhydride from renewable furfural. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient epoxidation of propene using molecular catalysts

DEFF Research Database (Denmark)

Markovits, Iulius I. E.; Anthofer, Michael H.; Kolding, Helene

2014-01-01

The epoxidation of propene is performed in homogeneous phase using various molecular catalysts and H2O2 or tert-butyl hydroperoxide as oxidants. A comparison between some molybdenum catalysts and methyltrioxorhenium (MTO) shows that the well known Re catalyst is the best among the examined...

Procedure for the preparation of catalysts for application in catalytic gas phase reactions

International Nuclear Information System (INIS)

1976-01-01

The invention describes the preparation of catalysts to be used in catalytic reactions in the gaseous phase. The catalytic material is disposed at the surface of a ceramic or carbon substrate (av. particle size 0.1 μ - 0.5 cm, surface area smaller than 20 m 2 /g) by bombardment of the catalytic material (Pt, Rh, Pd, Ru, Os, Ir) with energetic ions (Ne, Ar, Kr, Xe) in the vicinity of the substrate in medium vacuum

Petroleum residue upgrading with dispersed catalysts. Part 1. Catalysts activity and selectivity

Energy Technology Data Exchange (ETDEWEB)

Panariti, N.; Del Bianco, A.; Del Piero, G. [ENITECNOLOGIE S.p.A, Via Maritano 26, 20097 San Donato Mil. (Italy); Marchionna, M. [SNAMPROGETTI S.p.A, Via Maritano 26, 20097 San Donato Mil. (Italy)

2000-12-04

The results of a study aimed at the identification of the relevant chemical aspects involved in the process of upgrading heavy feedstocks in the presence of dispersed catalysts are discussed. The catalytic activity of different compounds was compared in terms of products yields and quality. Moreover, a detailed and systematic characterization of the catalysts recovered at the end of the reactions was achieved. The experimental work provided quite a large set of data, allowing to investigate the factors that may affect catalyst activity (precursor solubility, rate of activation, degree of dispersion, presence of promoters, etc.). The results of this study demonstrate that the best performances are obtained by the microcrystalline molybdenite generated in situ by oil-soluble precursors. The nature of the organic ligand does not play a very relevant role in influencing the hydrogenation activity. The presence of phosphorus, however, significantly enhances hydrodemetallation, at least in terms of vanadium removal. Bimetallic precursors show a slight synergistic effect towards the hydrodesulfurization reaction. Microsized powdered catalyst precursors have a much lower catalytic activity compared to the oil-soluble ones.

Identification of nitrogen compounds and amides from spent hydroprocessing catalyst

Energy Technology Data Exchange (ETDEWEB)

Choi, J.H.K.; Gray, M.R. (University of Alberta, Edmonton, AB (Canada). Dept. of Chemical Engineering)

1991-06-01

A spent commercial naphtha hydrotreating catalyst was analyzed to identify compounds which had accumulated on the catalyst surface during its active life. The catalyst was extracted with methylene chloride, methanol and pyridine to remove adsorbed organic material, which was rich in nitrogen and oxygen. A series of quinolones were identified in the methanol extract after enrichment with HCl-modified silica gel adsorption and subsequent silica gel chromatography. Tetra- and hexahydroquinolones with alkyl substituents up to C{sub 3} were identified. Similar amides have been identified in asphaltenes, and are very resistant to hydrogenation. Tetrahydroquinolines and piperidines were detected in the pyridine extract. 36 refs., 8 figs., 2 tabs.

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

Energy Technology Data Exchange (ETDEWEB)

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of... catalyst conversion efficiency for Phase 1 engines. The thermal stress is imposed on the test catalyst by...

Atomic scale insights into electrochemical versus gas phase oxidation of HCl over RuO2-based catalysts: A comparative review

International Nuclear Information System (INIS)

Over, Herbert

2013-01-01

In this article our current understanding of the electro-catalyzed chlorine evolution reaction (CER) in comparison with that of the heterogeneously-catalyzed gas phase oxidation of HCl (Deacon process: heterogeneous catalysis) over RuO 2 -based catalysts will be reviewed. Both types of harsh reactions are chemically similar: The main concern is catalyst stability, and in both cases the best catalyst contains RuO 2 as the catalytically active component so that a critical comparison may provide new insights into the underlying physicochemical processes. It is the primary scope of this review addresses atomic scale information on the RuO 2 -catalyzed HCl oxidation reaction either in electrochemical or in gas phase environment. In particular, the involved reaction mechanisms and the reason for the extraordinary stability of RuO 2 under such harsh reaction conditions will be discussed, emphasizing similarities and differences in the Deacon process and the CER and what can be learnt from this comparison. The distinct properties of RuO 2 , which are responsible for its extraordinary catalytic performance in both the CER and the Deacon process, are highlighted

Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

Science.gov (United States)

Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

2013-04-29

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane catalyzed by ionic type phase transfer catalyst and potassium iodide

Energy Technology Data Exchange (ETDEWEB)

Lu, Huasheng; Yin, Hengbo; Wang, Aili; Shen, Jun; Yan, Xiaobo; Liu, Yumin; Zhang, Changhua [Jiangsu University, Zhenjiang (China)

2014-01-15

Diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate was efficiently synthesized via the O-alkylation of disodium salt of diethyl 3,4-dihydroxy thiophene-2,5-dicarboxylate with 1,2-dichloroethane over ionic type phase transfer catalysts, such as tetrabutyl ammonium bromide and benzyl triethyl ammonium chloride. The ionic type phase transfer catalysts showed higher catalytic activities than the nonionic type phase transfer catalysts, such as triethylamine, pyridine, 18-crown-6, and polyethylene glycol 400/600, in the O-alkylation reaction. The conversion of the disodium salt of more than 97% and the selectivity of diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate of more than 98% were achieved when the O-alkylation reaction was synergistically catalyzed by tetrabutyl ammonium bromide and potassium iodide.

EXAFS characterization of supported metal catalysts in chemically dynamic environments

International Nuclear Information System (INIS)

Robota, H.J.

1991-01-01

Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

International Nuclear Information System (INIS)

Mahdavi, Vahid; Soleimani, Shima

2014-01-01

Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V 2 O 5 /OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V 2 O 5 /OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V 2 O 5 /K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V 2 O 5 /K-OMS-2 catalyst. • V 2 O 5 /K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V 2 O 5 /K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V 2 O 5 species. Oxidation of various alcohols was studied in the liquid phase over the V 2 O 5 /K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H 2 O 2 as the oxidant. Activity of the V 2 O 5 /K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V 2 O 5 . The kinetic of benzyl alcohol oxidation using excess TBHP over V 2 O 5 /K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated

Surface Termination of M1 Phase and Rational Design of Propane Ammoxidation Catalysts

Energy Technology Data Exchange (ETDEWEB)

Guliants, Vadim [Univ. of Cincinnati, OH (United States)

2015-02-16

This final report describes major accomplishments in this research project which has demonstrated that the M1 phase is the only crystalline phase required for propane ammoxidation to acrylonitrile and that a surface monolayer terminating the ab planes of the M1 phase is responsible for their activity and selectivity in this reaction. Fundamental studies of the topmost surface chemistry and mechanism of propane ammoxidation over the Mo-V-(Te,Sb)-(Nb,Ta)-O M1 and M2 phases resulted in the development of quantitative understanding of the surface molecular structure – reactivity relationships for this unique catalytic system. These oxides possess unique catalytic properties among mixed metal oxides, because they selectively catalyze three alkane transformation reactions, namely propane ammoxidation to acrylonitrile, propane oxidation to acrylic acid and ethane oxidative dehydrogenation, all of considerable economic significance. Therefore, the larger goal of this research was to expand this catalysis to other alkanes of commercial interest, and more broadly, demonstrate successful approaches to rational design of improved catalysts that can be applied to other selective (amm)oxidation processes.

Gas-phase Hydrogenation of Crotonaldehyde Over Nickel-on-Kieselguhr Catalyst Pellets

International Nuclear Information System (INIS)

Uraz, C.; Atalay, F.; Atalay, S.

2001-01-01

Gas phase catalytic hydrogenation of crotonaldehyde to η-butanol was investigated. A nickel based commercial catalyst produced by Harshaw was used at constant temperatures ranging from 160 to 210deg; at pressures of 1.5, 2 , and 2.5 atm and at different crotonaldehyde to hydrogen feed ratios changing from 0.134 to 0.226. The conversion of crotonaldehyde at different operating conditions were determined and the reaction rates were calculated . The experimental results were fitted to ten langmuir-Hinshelwood/ Eley Rideal type models in addition to a homogeneous kinetics modal and the best modal was identified. The effects of external and internal mass transfer resistances were found to be negligible .(authors) refs 28., 2 figs , 4 tabs

Particle Size and Crystal Phase Effects in Fischer-Tropsch Catalysts

Directory of Open Access Journals (Sweden)

Jin-Xun Liu

2017-08-01

Full Text Available Fischer-Tropsch synthesis (FTS is an increasingly important approach for producing liquid fuels and chemicals via syngas—that is, synthesis gas, a mixture of carbon monoxide and hydrogen—generated from coal, natural gas, or biomass. In FTS, dispersed transition metal nanoparticles are used to catalyze the reactions underlying the formation of carbon-carbon bonds. Catalytic activity and selectivity are strongly correlated with the electronic and geometric structure of the nanoparticles, which depend on the particle size, morphology, and crystallographic phase of the nanoparticles. In this article, we review recent works dealing with the aspects of bulk and surface sensitivity of the FTS reaction. Understanding the different catalytic behavior in more detail as a function of these parameters may guide the design of more active, selective, and stable FTS catalysts.

Synthesis of Acrolein From Glycerol Using FePO4 Catalyst in Liquid Phase Dehydration

OpenAIRE

Abidin, Akhmad Zainal; Afandi, Rani Guslianti; Graha, Hafis Pratama Rendra

2016-01-01

Acrolein is currently produced using propylene from crude oil while its price and scarcity are increasing. A renewable material such as glycerol is an attractive alternative for acrolein production. It can be obtained from crude palm oil (CPO) and is a byproduct of biodiesel production. Besides being able to compete economically, glycerol is an environmentally friendly material. The purpose of this study is to synthesize acrolein from glycerol using FePO4 catalyst in liquid phase dehydration....

Autothermal reforming catalyst having perovskite structure

Science.gov (United States)

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Wet chemical synthesis of nickel supported on alumina catalysts

International Nuclear Information System (INIS)

Freire, Ranny Rodrigues; Costa, Talita Kenya Oliveira; Morais, Ana Carla da Fonseca Ferreira; Costa, Ana Cristina Figueiredo de Melo; Freitas, Normanda Lino de

2016-01-01

Heterogenic catalysts are those found to be in a different phase on the reaction when compared to the reactants and products. Preferred when compared to homogeneous catalysts due to the easiness on which the separation is processed. The objective of this study is to obtain and characterize Alumina based catalysts impregnated with Nickel (Al_2O_3), by wet impregnation. The alumina was synthesized by combustion reaction. Before and after the impregnation the catalysts were characterized by X-ray diffraction (XRD), granulometric analysis, the textural analysis will be held by nitrogen adsorption (BET), energy-dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The results show a presence of a stable crystalline phase of Al2O3 in all the studied samples and after the impregnation the second phase formed was of NiO and NiAl_2O_4. The Al_2O_3 e Ni/Al_2O_3 catalysts resulted in clusters with a medium diameter of 18.9 and 14.2 μm, respectively. The catalysts show a medium-pore characteristic (medium pore diameter between 2 and 50 nm), the superficial area to Al_2O_3 and Ni/Al_2O_3 catalysts were 8.69 m"2/g and 5.56 m"2/g, respectively. (author)

Palladium catalyst system comprising zwitterion and/or acid-​functionalized ionic liquid

DEFF Research Database (Denmark)

2011-01-01

The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

Novel reaction engineering concepts for catalyst immobilisation in hydroformylation

Energy Technology Data Exchange (ETDEWEB)

Cole-Hamilton, D.J.; Desset, S.L.; Muldoon, M.J. [St. Andrews Univ. (United Kingdom). EaStChem, School of Chemistry; Hintermair, U. [St. Andrews Univ. (United Kingdom). EaStChem, School of Chemistry]|[CNRS, Lyon (France). Laboratoire de Chimie Organometallique de Surface; Santini, C.C. [CNRS, Lyon (France). Laboratoire de Chimie Organometallique de Surface

2006-07-01

Various methods for the separation of the aldehyde products from the catalyst and any solvent during or after hydroformylation reactions of long chain alkenes are reviewed. The catalyst can be immobilized on a soluble or insoluble support or in a phase that does not mix with the product phase under the separation conditions. Aqueous, fluorous, and ionic liquid biphasic systems as well as systems involving scCO{sub 2} sometimes in conjunction with one or other of the types of solvents listed above. Hybrid systems in which a liquid phase containing the catalyst is supported on a microporous solid support are also discussed. The advantages and disadvantages of the various systems are considered and new results concerning the addition of [1-octyl-3-methylimidazolium]Br to aqueous biphasic systems and the use of supercritical fluids to transport substrates over supported ionic liquid phases are presented. Both of these new approaches give high reaction rates, which for the supported ionic liquid phase catalysts can be maintained for at least 40 h of continuous flow operation. For the aqueous biphasic systems, leaching is low and phase separation is fast. (orig.)

Effect of Al content on the gas-phase dehydration of glycerol over silica-alumina-supported silicotungstic acid catalysts

International Nuclear Information System (INIS)

Kim, Yong Tae; You, Su Jin; Park, Eun Duck; Jung, Kwangdeog

2012-01-01

The gas-phase dehydration of glycerol to acrolein was carried out over silicotungstic acid (H 4 SiW 12 O 40 ·xH 2 O, HSiW) catalysts supported on SiO 2 , η-Al 2 O 3 , and silica-alumina with different Al contents. The HSiW catalysts supported on silica-alumina showed higher glycerol conversions and acrolein yields during the initial 2 h at 315.deg.C than did SiO 2 - and η-Al 2 O 3 -supported HSiW catalysts. Among the tested catalysts, HSiW/Si 0.9 Al 0.1Ox exhibited the highest space-time yield during the initial 2 h. The loaded HSiW species can change the acid types and suppress the formation of carbonaceous species on Al-rich silica-alumina. The deactivated HSiW supported on silica-alumina can be fully regenerated after calcination in air at 500.deg.C. As long as the molar ratio between water and glycerol was in the range of 2-11, the acrolein selectivity increased significantly with increasing water content in the feed, while the surface carbon content decreased owing to the suppression of heavy compounds

Characterization of steam-reforming catalysts

Directory of Open Access Journals (Sweden)

Santos D. C. R.M.

2004-01-01

Full Text Available The effect of the addition of Mg and Ca to Ni/ a-Al2O3 catalysts was investigatedstudied, aiming to detail the promotion mechanismaddress their role as promoters in the steam reforming reaction. Temperature- programmed reduction and H2 and CO temperature-programmed desorption experiments indicated that Mg interacts with the metallic phase. Mg-promoted catalysts showed a greater difficulty for Ni precursors reduction besides different probe molecules (H2 and CO adsorbed states. In the conversion of cyclohexane, Mg inhibited the formation of hydrogenolysis products. Nonetheless, the presence of Ca did not influence the metallic phase.

Formation of Multiple-Phase Catalysts for the Hydrogen Storage of Mg Nanoparticles by Adding Flowerlike NiS.

Science.gov (United States)

Xie, Xiubo; Ma, Xiujuan; Liu, Peng; Shang, Jiaxiang; Li, Xingguo; Liu, Tong

2017-02-22

In order to enhance the hydrogen storage properties of Mg, flowerlike NiS particles have been successfully prepared by solvothermal reaction method, and are subsequently ball milled with Mg nanoparticles (NPs) to fabricate Mg-5 wt % NiS nanocomposite. The nanocomposite displays Mg/NiS core/shell structure. The NiS shell decomposes into Ni, MgS and Mg 2 Ni multiple-phases, decorating on the surface of the Mg NPs after the first hydrogen absorption and desorption cycle at 673 K. The Mg-MgS-Mg 2 Ni-Ni nanocomposite shows enhanced hydrogenation and dehydrogenation rates: it can quickly uptake 3.5 wt % H 2 within 10 min at 423 K and release 3.1 wt % H 2 within 10 min at 573 K. The apparent hydrogen absorption and desorption activation energies are decreased to 45.45 and 64.71 kJ mol -1 . The enhanced sorption kinetics of the nanocomposite is attributed to the synergistic catalytic effects of the in situ formed MgS, Ni and Mg 2 Ni multiple-phase catalysts during the hydrogenation/dehydrogenation process, the porthole effects for the volume expansion and microstrain of the phase transformation of Mg 2 Ni and Mg 2 NiH 4 and the reduced hydrogen diffusion distance caused by nanosized Mg. This novel method of in situ producing multiple-phase catalysts gives a new horizon for designing high performance hydrogen storage material.

Oxidation catalysts on alkaline earth supports

Science.gov (United States)

Mohajeri, Nahid

2017-03-21

An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

Fischer-Tropsch synthesis in slurry-phase reactors using Co/SBA-15 catalysts

Energy Technology Data Exchange (ETDEWEB)

Rodrigues, J.J.; Lima, L.A.; Lima, W.S.; Rodrigues, M.G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], e-mail: meiry@deq.ufcg.edu.br; Fernandes, F.A.N. [Universidade Federal do Ceara (UFCE), CE (Brazil). Dept. de Engenharia Quimica

2011-07-15

The objective of this work is to describe the production of bifunctional catalysts using the incipient humidity method, producing catalysts with 15 wt.% cobalt supported in SBA-15 molecular sieve, to be applied in the Fischer-Tropsch (FT) reaction. The originality of this work is its focus on the use of a 15 wt.% Co/SBA-15 catalyst in FT synthesis in slurry reactors. The deposition of cobalt over SBA-15 support was accomplished by impregnation with a 0.1-M aqueous solution of cobalt nitrate. The Fischer-Tropsch synthesis was carried out with the catalyst at 240 deg C and 20 atm, under a COH{sub 2} atmosphere (molar ratio= 1), in a slurry reactor for 8 hours. X-ray diffraction measurements showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present under the form of Co{sub 3}O{sub 4} in the catalyst. The addition of cobalt in the SBA-15 decreased the specific superficial area of the molecular sieve. The 15 wt.% Co/SBA-15 catalyst had a 40% CO conversion rate and a high selectivity towards the production of C{sub 5}{sup +} (53.9% after 8 hours). (author)

Characterization of working iron Fischer-Tropsch catalysts using quantitative diffraction methods

Science.gov (United States)

Mansker, Linda Denise

This study presents the results of the ex-situ characterization of working iron Fischer-Tropsch synthesis (F-TS) catalysts, reacted hundreds of hours at elevated pressures, using a new quantitative x-ray diffraction analytical methodology. Compositions, iron phase structures, and phase particle morphologies were determined and correlated with the observed reaction kinetics. Conclusions were drawn about the character of each catalyst in its most and least active state. The identity of the active phase(s) in the Fe F-TS catalyst has been vigorously debated for more than 45 years. The highly-reduced catalyst, used to convert coal-derived syngas to hydrocarbon products, is thought to form a mixture of oxides, metal, and carbides upon pretreatment and reaction. Commonly, Soxhlet extraction is used to effect catalyst-product slurry separation; however, the extraction process could be producing irreversible changes in the catalyst, contributing to the conflicting results in the literature. X-ray diffraction doesn't require analyte-matrix separation before analysis, and can detect trace phases down to 300 ppm/2 nm; thus, working catalyst slurries could be characterized as-sampled. Data were quantitatively interpreted employing first principles methods, including the Rietveld polycrystalline structure method. Pretreated catalysts and pure phases were examined experimentally and modeled to explore specific behavior under x-rays. Then, the working catalyst slurries were quantitatively characterized. Empirical quantitation factors were calculated from experimental data or single crystal parameters, then validated using the Rietveld method results. In the most active form, after pretreatment in H 2 or in CO at Pambient, well-preserved working catalysts contained significant amounts of Fe7C3 with trace alpha-Fe, once reaction had commenced at elevated pressure. Amounts of Fe3O 4 were constant and small, with carbide dpavg 65 wt%, regardless of pretreatment gas and pressure, with

Highly Efficient Catalytic Synthesis of α-Amino Acids under Phase-Transfer Conditions with a Novel Catalyst/Substrate Pair

NARCIS (Netherlands)

Belokon, Yuri N.; Kochetkov, Konstantin A.; Churkina, Tatiana D.; Ikonnikov, Nikolai S.; Larionov, Oleg V.; Harutyunyan, Syuzanna R.; Vyskočil, Štepán; North, Michael; Kagan, Henri B.

2001-01-01

A facile and fast enantioselective synthesis of α-amino acids with high ee values was achieved by the asymmetric alkylation of the glycine derivative under phase-transfer conditions with (R)- or (S)-2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN). The ee value of the catalyst can be as little as 40 %

Reuse of Hydrotreating Spent Catalyst

International Nuclear Information System (INIS)

Habib, A.M.; Menoufy, M.F.; Amhed, S.H.

2004-01-01

All hydro treating catalysts used in petroleum refining processes gradually lose activity through coking, poisoning by metal, sulfur or halides or lose surface area from sintering at high process temperatures. Waste hydrotreating catalyst, which have been used in re-refining of waste lube oil at Alexandria Petroleum Company (after 5 years lifetime) compared with the same fresh catalyst were used in the present work. Studies are conducted on partial extraction of the active metals of spent catalyst (Mo and Ni) using three leaching solvents,4% oxidized oxalic acid, 10% aqueous sodium hydroxide and 10% citric acid. The leaching experiments are conducting on the de coked extrude [un crushed] spent catalyst samples. These steps are carried out in order to rejuvenate the spent catalyst to be reused in other reactions. The results indicated that 4% oxidized oxalic acid leaching solution gave total metal removal 45.6 for de coked catalyst samples while NaOH gave 35% and citric acid gave 31.9 % The oxidized leaching agent was the most efficient leaching solvent to facilitate the metal removal, and the rejuvenated catalyst was characterized by the unchanged crystalline phase The rejuvenated catalyst was applied for hydrodesulfurization (HDS) of vacuum gas oil as a feedstock, under different hydrogen pressure 20-80 bar in order to compare its HDS activity

Palladium catalyst system comprising zwitterion and/or acid-functionalized ionic liquid

DEFF Research Database (Denmark)

2011-01-01

The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3......COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

Microemulsion and Sol-Gel Synthesized ZrO₂-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural.

Science.gov (United States)

Parejas, Almudena; Montes, Vicente; Hidalgo-Carrillo, Jesús; Sánchez-López, Elena; Marinas, Alberto; Urbano, Francisco J

2017-12-18

Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively). Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water) reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO₂ (especially Zr-SG) are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

Ni Catalysts Supported on Modified Alumina for Diesel Steam Reforming

Directory of Open Access Journals (Sweden)

Antonios Tribalis

2016-01-01

Full Text Available Nickel catalysts are the most popular for steam reforming, however, they have a number of drawbacks, such as high propensity toward coke formation and intolerance to sulfur. In an effort to improve their behavior, a series of Ni-catalysts supported on pure and La-, Ba-, (La+Ba- and Ce-doped γ-alumina has been prepared. The doped supports and the catalysts have been extensively characterized. The catalysts performance was evaluated for steam reforming of n-hexadecane pure or doped with dibenzothiophene as surrogate for sulphur-free or commercial diesel, respectively. The undoped catalyst lost its activity after 1.5 h on stream. Doping of the support with La improved the initial catalyst activity. However, this catalyst was completely deactivated after 2 h on stream. Doping with Ba or La+Ba improved the stability of the catalysts. This improvement is attributed to the increase of the dispersion of the nickel phase, the decrease of the support acidity and the increase of Ni-phase reducibility. The best catalyst of the series doped with La+Ba proved to be sulphur tolerant and stable for more than 160 h on stream. Doping of the support with Ce also improved the catalytic performance of the corresponding catalyst, but more work is needed to explain this behavior.

Effect of phase interaction on catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalyst

Energy Technology Data Exchange (ETDEWEB)

Chai, Shujing [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); The Institute of Seawater Desalination and Miltipurpose Utilization, State Oceanic Administration, Tianjin 300192 (China); Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); Xian, Hui [Tianjin Polytechnic University, School of Computer Science & Software Engineering, Tianjin 300387 (China); Mi, Wenbo [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparation Technology, Faculty of Science, Tianjin University, Tianjin 300354 (China); Li, Xingang, E-mail: xingang_li@tju.edu.cn [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China)

2017-04-30

Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO{sub 2} and Al{sub 2}O{sub 3}. • Interaction between SnO{sub 2} and Al{sub 2}O{sub 3} phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn{sup 4+} cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalysts. Our results show that interaction between the Al{sub 2}O{sub 3} and SnO{sub 2} phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO{sub 2}/Al{sub 2}O{sub 3} catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO{sub 2}, which probably results from the change of electron concentration on the interface of the SnO{sub 2} and Al{sub 2}O{sub 3} phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn{sup 4+} cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO{sub 2}-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

Sulfidation of alumina-supported iron and iron-molybdenum oxide catalysts

NARCIS (Netherlands)

Ramselaar, W.L.T.M.; Crajé, M.W.J.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Kraan, van der A.M.

1990-01-01

The transition of alumina-supported iron and iron-molybdenum catalysts from the oxidic precursor to the sulfided catalysts was systematically studied by means of in-situ Mössbauer spectroscopy at room temperature. This enabled the adjudgement of various sulfidic phases in the sulfided catalysts. The

Catalyst for hydrogen-amine D exchange

International Nuclear Information System (INIS)

Holtslander, W.J.; Johnson, R.E.

1976-01-01

A process is claimed for deuterium isotopic enrichment (suitable for use in heavy water production) by amine-hydrogen exchange in which the exchange catalyst comprises a mixture of alkyl amides of two metals selected from the group consisting of the alkali metals. Catalyst mixtures comprising at least one of the alkali amides of lithium and potassium are preferred. At least one of the following benefits are obtained: decreased hydride formation, decreased thermal decomposition of alkyl amide, increased catalyst solubility in the amine phase, and increased exchange efficiency. 11 claims

Method for filling a reactor with a catalyst

DEFF Research Database (Denmark)

2013-01-01

The invention relates to a method for filling a reactor with a catalyst for the carbonylation of carbonylated compounds in the gas phase. According to said method, a SILP catalyst is covered with a filling agent which is liquid under normal conditions and is volatile under carbonylation reaction...... conditions, and a thus-treated catalyst is introduced into the reactor and the reactor is sealed....

Effective Liquid-phase Nitration of Benzene Catalyzed by a Stable Solid Acid Catalyst: Silica Supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40}

Energy Technology Data Exchange (ETDEWEB)

Gong, Shu-wen; Liu, Li-jun; Zhang, Qian; Wang, Liang-yin [Liaocheng University, Liaocheng (China)

2012-04-15

Silica supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology

Nanographene synthesized in triple-phase plasmas as a highly durable support of catalysts for polymer electrolyte fuel cells

Science.gov (United States)

Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

2018-04-01

Nanographene was synthesized in triple-phase plasmas comprising a gaseous phase, a gas-liquid boundary layer, and an in-liquid phase using a setup in which one electrode was placed in the gaseous phase while the other was immersed in the liquid phase. The triple-phase plasmas were generated using a pure alcohol, such as ethanol, 1-propanol, or 1-butanol, by applying a high voltage to a pair of electrodes made of copper or graphite. The nanographene synthesized using ethanol had high durability and thus could serve as a catalyst support in polymer electrolyte fuel cells (PEFCs). The PEFCs exhibited low degradation rates in the high-potential cycle test of a half-cell, as a result of which, a loss of only 10% was observed in the effective electrochemical surface area of Pt, even after 10,000 cycles.

Moessbauer spectroscopic investigations of Fe/Mn-Fischer-Tropsch-catalysts

International Nuclear Information System (INIS)

Deppe, P.; Papp, H.; Rosenberg, M.

1986-01-01

The phase composition of Fe/Mn oxide catalysts of different compositions after 200 h of Fischer-Tropsch synthesis have been investigated by Moessbauer spectroscopy at room temperature, 77 K and 5 K. The final composition of the bulk catalysts depends strongly on the Mn content and the temperature of reduction before the synthesis. Catalytic activity and selectivity are partly correlated to this phase composition. (Auth.)

A TECHNIQUE OF IDENTIFICATION OF THE PHASE-DISPLACEMENT GROUP OF THREE-PHASE TRANSFORMER

International Nuclear Information System (INIS)

Aburjania, A.; Begiashvili, V.; Rezan Turan

2007-01-01

It is demonstrated that the arbitrary choice of arbitrarily pisitive direction of induced currents and voltages contradicts the energy conservation law and leads to equilibrium equations and standards making no sense from the physical standpoint. Of 12 recognized standard phase-displacement groups of three-phase transformer, only three have real physical bases. The rest are based on a wrong assumption about mutual biasing of primary and secondary currents. They does not rule out the occurrence of emergency situations and, thus, must be eliminated from use. A new method of identification of the phase-displacement of three-phase transformer is proposed. The method is based on well-known physical laws with consideration for the dual character of the inertia of mutual inductance and exhausts for all possible versions of connection of transformer windings. (author)

Sodium Tetraphenylborate Catalyst Identification: Preliminary Studies Set 2

International Nuclear Information System (INIS)

Barnes, M.J.

1997-05-01

This document details the results of these tests and represents the second report of the task designed to identify soluble NaTPB decomposition catalysts. This task, performed as part of the DNFSB Recommendation 96-1 Implementation Plan, partially fulfills the request by High Level Waste Engineering and the ITP Flow Sheet Team in task Technical Request HLW-TTR-97008

Basic study of catalyst aging in the H-coal process

Energy Technology Data Exchange (ETDEWEB)

Cable, T.L.; Massoth, F.E.; Thomas, M.G.

1985-04-01

Samples of CoMo/Al/sub 2/O/sub 3/ catalysts used in an H-coal process demonstration run were studied to determine causes of catalyst deactivation. Physical and surface properties of the aged and regenerated catalysts were examined. Model compounds were used to assess four catalyst activity functions, viz., hydrodesulfurization (HDS), hydrogenation, cracking and hydrodeoxygenation (HDO). Other tests were performed to study the effects of coke and metals separately on the four catalyst activity functions. Catalyst coke content and metal deposits first increased rapidly, then more gradually with exposure time in the process run. Surface area and pore volume markedly decreased with exposure time. Catalyst activities of aged catalysts showed a rapid decline with exposure time. One-day exposure to coal resulted in significant losses in HDS and hydrogenation activities and nearly complete loss in cracking and HDO activities. Although metal deposits caused some permanent catalyst deactivation, coke had a much greater effect. Regenerated catalysts showed less recovery of catalytic activity as processing time increased. These results agreed well with product inspections from the process run. Oxygen chemisorption on aged-regenerated catalysts decreased with catalyst exposure time, indicating a significant loss of active sites. However, ESCA results showed no evidence of extensive sintering of the active MoS/sub 2/ phase. Permanent deactivation of the longer-time exposed catalysts can be ascribed, at least partly, to lateral growth of the active molybdenum sulfide phase. In addition, some loss in cobalt promotion occurred early in the process, which may account for the rapid loss in HDS and HDO activity in regenerated catalysts. 24 references.

Microemulsion and Sol-Gel Synthesized ZrO2-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural

Directory of Open Access Journals (Sweden)

Almudena Parejas

2017-12-01

Full Text Available Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively. Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO2 (especially Zr-SG are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

Science.gov (United States)

Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

2018-03-26

A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic production of fuels by the Fischer Tropsch reaction using iron catalysts

International Nuclear Information System (INIS)

Rodriguez Cepeda, Rodrigo; Pacheco Ochoa, Luis

2004-01-01

A series of iron catalysts were prepared on three different types of supports: alumina and two activated carbons from eucalyptus woods and tagua seeds. Potassium was used as promoter and palladium was deposited by the excess wetness impregnation method. The catalysts were characterized by N 2 adsorption at 77 K, XRD and TPR analysis and evaluated as Fischer-Tropsch catalysts. The carbon supported catalysts favour the production of liquid hydrocarbons and decrease the aqueous phase. Those supported with alumina form gases and aqueous phase as the main products. The α p parameters of the Schulz-Flory distribution show hydrocarbons between gasoline and diesel

Reduction of Furfural to Furfuryl Alcohol in Liquid Phase over a Biochar-Supported Platinum Catalyst

Directory of Open Access Journals (Sweden)

Ariadna Fuente-Hernández

2017-02-01

Full Text Available In this work, the liquid phase hydrogenation of furfural has been studied using a biochar-supported platinum catalyst in a batch reactor. Reactions were performed between 170 °C and 320 °C, using 3 wt % and 5 wt % of Pt supported on a maple-based biochar under hydrogen pressure varying from 500 psi to 1500 psi for reaction times between 1 h and 6 h in various solvents. Under all reactive conditions, furfural conversion was significant, whilst under specific conditions furfuryl alcohol (FA was obtained in most cases as the main product showing a selectivity around 80%. Other products as methylfuran (MF, furan, and trace of tetrahydrofuran (THF were detected. Results showed that the most efficient reaction conditions involved a 3% Pt load on biochar and operations for 2 h at 210 °C and 1500 psi using toluene as solvent. When used repetitively, the catalyst showed deactivation although only a slight variation in selectivity toward FA at the optimal experimental conditions was observed.

Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

KAUST Repository

Ladelta, Viko

2018-03-16

Poly(macrolactones) (PMLs) can be considered as biodegradable alternatives of polyethylene; however, controlling the ring-opening polymerization (ROP) of macrolactone (ML) monomers remains a challenge due to their low ring strain. To overcome this problem, phosphazene (t-BuP4), a strong superbase, has to be used as catalyst. Unfortunately, the one-pot sequential block copolymerization of MLs with small lactones (SLs) is impossible since the high basicity of t-BuP4 promotes both intra- and intermolecular transesterification reactions, thus leading to random copolymers. By using ROP and the “catalyst-switch” strategy [benzyl alcohol, t-BuP4/neutralization with diphenyl phosphate/(t-BuP2)], we were able to synthesize different well-defined PML-b-PSL block copolymers (MLs: dodecalactone, ω-pentadecalactone, and ω-hexadecalactone; SLs: δ-valerolactone and ε-caprolactone). The thermal properties and the phase behavior of these block copolymers were studied by differential scanning calorimetry and X-ray diffraction spectroscopy. This study shows that the thermal properties and phase behavior of PMLs-b-PSLs are largely influenced by the PMLs block if PMLs components constitute the majority of the block copolymers.

Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

KAUST Repository

Ladelta, Viko; Kim, Joey D.; Bilalis, Panagiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

2018-01-01

Poly(macrolactones) (PMLs) can be considered as biodegradable alternatives of polyethylene; however, controlling the ring-opening polymerization (ROP) of macrolactone (ML) monomers remains a challenge due to their low ring strain. To overcome this problem, phosphazene (t-BuP4), a strong superbase, has to be used as catalyst. Unfortunately, the one-pot sequential block copolymerization of MLs with small lactones (SLs) is impossible since the high basicity of t-BuP4 promotes both intra- and intermolecular transesterification reactions, thus leading to random copolymers. By using ROP and the “catalyst-switch” strategy [benzyl alcohol, t-BuP4/neutralization with diphenyl phosphate/(t-BuP2)], we were able to synthesize different well-defined PML-b-PSL block copolymers (MLs: dodecalactone, ω-pentadecalactone, and ω-hexadecalactone; SLs: δ-valerolactone and ε-caprolactone). The thermal properties and the phase behavior of these block copolymers were studied by differential scanning calorimetry and X-ray diffraction spectroscopy. This study shows that the thermal properties and phase behavior of PMLs-b-PSLs are largely influenced by the PMLs block if PMLs components constitute the majority of the block copolymers.

In-situ Spectroscopic Studies and Modelling of Crystallization Processes of Sulphuric Acid Catalysts

DEFF Research Database (Denmark)

Oehlers, C.; Fehrmann, Rasmus; Masters, Stephen Grenville

1996-01-01

Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe the crystall......Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe...

Sulfur deactivation of fatty ester hydrogenolysis catalysts

Energy Technology Data Exchange (ETDEWEB)

Brands, D.S.; U-A-Sai, G.; Poels, E.K.; Bliek, A. [Univ. of Amsterdam (Netherlands). Dept. of Chemical Engineering

1999-08-15

Trace organosulfur compounds present as natural impurities in oleochemical feedstocks may lead to activation of copper-containing catalysts applied for hydrogenolysis of esters toward fatty alcohols. In this paper, the sulfur deactivation of Cu/SiO{sub 2} and Cu/ZnO/SiO{sub 2} catalysts was studied in the liquid-phase hydrogenolysis of methyl palmitate. The rate of deactivation is fast and increases as a function of the sulfur-containing compound present: octadecanethiol {approx} dihexadecyl disulfide < benzyl isothiocyanate < methyl p-toluene sulfonate < dihexadecyl sulfide < dibenzothiophene. The rapid deactivation is caused by the fact that sulfur is quantitatively removed from the reaction mixture and because mainly surface sulfides are formed under hydrogenolysis conditions. The life time of a zinc-promoted catalyst is up to two times higher than that of the Cu/SiO{sub 2} catalyst, most likely due to zinc surface sulfide formation. The maximum sulfur coverage obtained after full catalyst deactivation with dibenzothiophene and dihexadecyl sulfide--the sulfur compounds that cause the fastest deactivation--may be as low as 0.07. This is due to the fact that decomposition of these compounds as well as the hydrogenolysis reaction itself proceeds on ensembles of copper atoms. Catalyst regeneration studies reveal that activity cannot be regained by reduction or combined oxidation/reduction treatments. XRD, TPR, and TPO results confirm that no distinct bulk copper or zinc sulfide or sulfate phases are present.

Calcined eggshell (CES): An efficient natural catalyst for ...

Indian Academy of Sciences (India)

hydes with active methylene compounds using calcined eggshell (CES) as an efficient ... of the important reactions to achieve carbon–carbon ... solid catalyst for biodiesel production,24 as a catalyst ... which supports for adsorption of water on CaO and ... The organic phase .... After extraction of the product with ethylac-.

Revisiting source identification, weathering models, and phase discrimination for Exxon Valdez oil

International Nuclear Information System (INIS)

Driskell, W.B.; Payne, J.R.; Shigenaka, G.

2005-01-01

A large chemistry data set for polycyclic aromatic hydrocarbon (PAH) and saturated hydrocarbon (SHC) contamination in sediment, water and tissue samples has emerged in the aftermath of the 1989 Exxon Valdez oil spill in Prince William Sound, Alaska. When the oil was fresh, source identification was a primary objective and fairly reliable. However, source identification became problematic as the oil weathered and its signatures changed. In response to concerns regarding when the impacted area will be clean again, this study focused on developing appropriate tools to confirm hydrocarbon source identifications and assess weathering in various matrices. Previous efforts that focused only on the whole or particulate-phase oil are not adequate to track dissolved-phase signal with low total PAH values. For that reason, a particulate signature index (PSI) and dissolved signature index (DSI) screening tool was developed in this study to discriminate between these 2 phases. The screening tool was used to measure the dissolved or water-soluble fraction of crude oil which occurs at much lower levels than the particulate phase, but which is more widely circulated and equally as important as the particulate oil phase. The discrimination methods can also identify normally-discarded, low total PAH samples which can increase the amount of usable data needed to model other effects of oil spills. 37 refs., 3 tabs., 10 figs

Performance characterization of hydrogen isotope exchange and recombination catalysts for tritium processing

International Nuclear Information System (INIS)

Suppiah, S.; Ryland, D.; Marcinkowska, K.; Boniface, H.; Everatt, A.

2010-01-01

AECL's hydrogen isotope exchange catalyst and recombination catalysts have been successfully applied to a wide range of industrial tritium-removal applications. The catalysts are used for Liquid Phase Catalytic Exchange (LPCE) and for gas-phase and trickle-bed recombination of hydrogen isotopes and have led to process simplification, improved safety and operational advantages. Catalyst performance design equations derived from laboratory testing of these catalysts have been validated against performance under industrial conditions. In a Combined Electrolysis and Catalytic Exchange (CECE) demonstration plant analyses of LPCE and recombiner efficiency were carried out as a function of catalyst activity over a wide range of operation. A steady-state process simulation used to model and design the hydrogen-water isotopic exchange processes, such as the CECE detritiation plant, was validated using the results of this demonstration. Catalyst development for isotope-exchange and recombination applications has continued over the last decade. As a result, significant improvements in catalyst performance have been achieved for these applications. This paper outlines the uniqueness of AECL's specialized catalysts and process designs for these applications with examples from laboratory and industrial case studies.

Deuterium exchange reaction between hydrogen and water in a trickle-bed column packed with novel catalysts

International Nuclear Information System (INIS)

Ahn, D. H.; Baek, S. W.; Lee, H. S.; Kim, K. R.; Kang, H. S.; Lee, S. H.; Jeong, H. S.

1998-01-01

The activity of a novel catalyst (Pt/SDBC) for deuterium exchange reaction between water and hydrogen streams in a trickle bed was measured. The performance of the catalyst was compared with a commercial catalyst with same metal content. The catalytic activity for the bed of wet-proofed catalyst diluted with hydrophillic packing material also measured. The Pt/SDBC catalyst shows higher activity in the liquid phase reaction than the commercial catalyst as measured in the vapor phase reaction. The performance for 50% dilution of the Pt/SDBC catalyst bed with hydrophillic packing material is better than that of the 100% bed due to more liquid holdup and better water distribution

Metal-Organic-Framework mediated supported-cobalt catalysts in multiphase hydrogenation reactions

OpenAIRE

Sun, X.

2017-01-01

The production of most industrially important chemicals involves catalysis. Depending on the difference in phases between the catalysts and reactants, one distinguishes homogenous catalysis and heterogeneous catalysis, with the latter being more attractive in real applications, due to the easy separation of products from catalysts and reusing the latter. In spite of the research and development of heterogeneous catalysts for decades, the exploration for catalysts system with outstanding activ...

Selective Production of 2-Methylfuran by Gas-Phase Hydrogenation of Furfural on Copper Incorporated by Complexation in Mesoporous Silica Catalysts.

Science.gov (United States)

Jiménez-Gómez, Carmen Pilar; Cecilia, Juan A; Moreno-Tost, Ramón; Maireles-Torres, Pedro

2017-04-10

Copper species have been incorporated in mesoporous silica (MS) through complexation with the amine groups of dodecylamine, which was used as a structure-directing agent in the synthesis. A series of Cu/SiO 2 catalysts (xCu-MS) with copper loadings (x) from 2.5 to 20 wt % was synthesized and evaluated in the gas-phase hydrogenation of furfural (FUR). The most suitable catalytic performance in terms of 2-methylfuran yield was obtained with an intermediate copper content (10 wt %). This 10Cu-MS catalyst exhibits a 2-methylfuran yield higher than 95 mol % after 5 h time-on-stream (TOS) at a reaction temperature of 210 °C with a H 2 /FUR molar ratio of 11.5 and a weight hourly space velocity (WHSV) of 1.5 h -1 . After 14 h TOS, this catalyst still showed a yield of 80 mol %. In all cases, carbonaceous deposits on the external surface were the cause of the catalyst deactivation, although sintering of the copper particles was observed for higher copper loadings. This intermediate copper loading (10 wt %) offered a suitable balance between resistance to sintering and tendency to form carbonaceous deposits. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids

Directory of Open Access Journals (Sweden)

Carmen Nájera

2004-04-01

Full Text Available Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethyleneglycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed.

Preparation of supported heterogeneous catalysts by pulse impregnation: Application to Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst

Energy Technology Data Exchange (ETDEWEB)

Haukka, M.; Pakkanen, T.A. (Univ. of Joensuu (Finland))

1994-07-01

In this paper, the authors introduce pulse impregnation, a method for preparing supported heterogeneous catalysts by successive impregnation cycles. Pulse impregnation is a method for preparing supported heterogeneous catalysts from the liquid phase. In the pulse-impregnation technique the catalyst surface is grown gradually in consecutive cycles, with each cycle consisting of separate deposition and activation steps. During the deposition step, the catalyst precursor or precursors are deposited onto the support from a suitable solvent. The actual chemically bonded catalyst phase is formed during the activation step (e.g., thermal activation). Pulse impregnation was tested in the separate deposition of 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12] onto a silica support, and in the preparation of Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, in a column-type reactor system. Macroscopically uniform deposition was achieved with both 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12]. Various solvent systems were used to control the amount of solute adsorbed during deposition. In the preparation of the Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, the ruthenium content increased nearly linearly with the number of preparation cycles. The effects of the preparation method on the catalyst activity was also tested in 1-hexane hydroformylation. 31 refs., 7 figs., 1 tab.

Studies on transfer phenomena of tritium from liquid to gaseous phase in a successive catalyst and ordered packing system

International Nuclear Information System (INIS)

Bornea, Anisia; Cristescu, Ion; Zamfirache, Marius; Varlam, Carmen

2001-01-01

The processes for hydrogen isotope separation are very important for nuclear technology. One of the most important processes in tritium separation, is the water-hydrogen catalytic isotope exchange. In a column of isotope exchange, tritium is transferred from the liquid phase (tritiated heavy water) to the gaseous phase (hydrogen). In the experimental set-up, which was used, the column of catalytic isotope exchange is filled with successive layers of catalyst Pt/C/PtFe and B7 type ordered packing of phosphor bronze. The tritium transfer from liquid phase to water vapours, is achieved on ordered packing by distillation process: (DTO)L+(D 2 O)V → (D 2 O)L+(DTO)V. On the catalytic tritium transfer from water vapours to hydrogen gas is achieved by the catalytic isotopic exchange process: (DTO)V+(D 2 )G → (D 2 O)V+(DT)G. We analyzed the transfer phenomena of tritium in this system by using the experimental data obtained. The mathematical model presented in the paper allowed computing experimental data for testing the catalyst performances. The transfer equations are solved using the Runge - Kutta method. In this way the speed constants which characterized the isotopic exchange on the catalysis bed ks, and the distillation on the ordered packing kd, were expressed as function of experimental concentrations and hydrodynamic conditions. (authors)

SILP catalysis in gas-phase hydroformylation and carbonylation

Energy Technology Data Exchange (ETDEWEB)

Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik

2006-07-01

Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

Catalyst volumetric fraction simulation in a riser of a cold flow pilot unit with aid of transmission gamma technique

International Nuclear Information System (INIS)

Santos, Kamylla A.L. dos; Lima Filho, Hilario J.B. de; Benachour, Mohand; Dantas, Carlos C.; Santos, Valdemir A. dos

2013-01-01

Was obtained the radial profile of the catalyst volume fraction in a riser of the cold flow pilot unit of the Fluid Catalytic Cracking (FCC) unit, which was used for adjustment of the entrance conditions of the catalyst in a simulation program by Computational Fluid Dynamics (CFD). The height of the riser of the Cold Flow Pilot Unity (CFPU) utilized is 6.0m and its inner diameter is 0.097 m. A radiation-γ source of Am-241 and a NaI (Tl) detector, with shielding made of lead, have been installed on a steel backing that maintains the geometry of the source-detector-riser and allows to vary the distance from the source to the detector and the radial position in a given cross section of the riser. The data associated with the simulation of volume fraction radial profile of the catalyst were: Fluent software, version 12.0; preprocessor GAMBIT, version 2.3.16; Eulerian approach; structured mesh, cell number of 60000; turbulence model used was k-ε and kinetic theory of granular flow (KTGF) was implemented to describe the solid phase. Comparison of radial profiles simulated and experimental of the catalyst volumetric fraction in the CFPU riser allowed the identification of needs adjustments in the simulation for the input of catalyst, with consequent validation for the proposed model simulation. (author)

Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

OpenAIRE

José da Silva, Márcio; Faria dos Santos, Lidiane

2013-01-01

A novel process was developed for oxidative desulfurization (ODS) in the absence of a phase transfer catalyst (PTC) using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT) as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by ace...

Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst; Oxidacion catalitica de albendazol empleando como catalizador molibdeno soportado en nanotubos de carbono

Energy Technology Data Exchange (ETDEWEB)

Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R., E-mail: msun@pucp.edu.pe [Departamento de Ciencias, Seccion Quimica. Pontificia Universidad Catolica del Peru, Avenida Universitaria 1801, Lima (Peru); Picasso Escobar, Gino I. [Laboratorio de Investigacion de Fisicoquimica, Facultad de Ciencias, Universidad Nacional de Ingenieria, Avenida Tupac Amaru 210, Lima (Peru)

2013-10-15

The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C{sub 12}H{sub 15}N{sub 3}O{sub 2}S) was studied in order to obtain a pharmacologically active molecule known as albendazole sulfoxide. With this purpose, three heterogeneous catalysts were prepared using molybdenum (Mo) as active phase and carbon nanotubes as a multiple-layer catalyst support. The incorporation of the active phase was performed by wet impregnation, with subsequent calcination for 4 hours at 400 {sup o}C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H{sub 2}NCONH{sub 2}·H{sub 2}O{sub 2}) as oxidizing agent and methanol (CH{sub 3}OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N{sub 2} (BET) and scanning electron microscopy (SEM). The identification and quantification of the reaction products were followed by Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC), respectively. With the yield, selectivity and conversion higher than 90% after 60 minutes of reaction, albendazole sulphoxide was obtained as major product of oxidation reaction. (author)

Hydrogen production from bio-fuels using precious metal catalysts

Science.gov (United States)

Pasel, Joachim; Wohlrab, Sebastian; Rotov, Mikhail; Löhken, Katrin; Peters, Ralf; Stolten, Detlef

2017-11-01

Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3) and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

Selective propene oxidation on mixed metal oxide catalysts

International Nuclear Information System (INIS)

James, David William

2002-01-01

Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Green nano-catalyst for methanolysis of non-edible Jatropha oil

International Nuclear Information System (INIS)

Teo, Siow Hwa; Rashid, Umer; Taufiq-Yap, Yun Hin

2014-01-01

Highlights: • A green nano heterogeneous base catalyst was prepared from CaO. • Transesterified Jatropha curcas oil achieved 95% of biodiesel yield at 65 °C. • Parameters affecting catalyst reaction were optimized. • Biodiesel produced was satisfied the International biodiesel standards. - Abstract: Non-edible feedstocks are regarded as a sustainable source of renewable energy. In order to find renewable, cheaper and easier methods to obtain energy, attention has been paid to develop potential green catalyst to produce renewable biodiesel. The catalyst was characterized by X-ray diffraction (XRD) results in combination with thermogravimetry–differential thermal analysis (TG–DTA), Brunauer–Emmer–Teller (BET), Fourier transfrom-infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). TEM analysis depicted that calcium methoxide (Ca(OCH 3 ) 2 ) catalysts were in size of 34.7 nm. The reaction parameters namely; reaction time, methanol/oil molar ratio, catalyst dosage were investigated for fatty acid methyl ester (FAME) yield. The highest biodiesel yield (95%) was appraised under the optimum condition (i.e. catalyst amount of 2 wt.%; methanol/oil molar ratio of 15:1, reaction time of 90 min). The Ca(OCH 3 ) 2 phase of catalyst can be regarded as an active phase to get high yield of biodiesel which was confirmed from characterization study. Furthermore, important fuel properties were also investigated and satisfied the ASTM D6751 and European 14214 biodiesel standards. Thus, Ca(OCH 3 ) 2 catalyst prepared in this study was having efficient, low toxicity, cost effective and easy to prepare for green fuels production especially biodiesel

Glycerol valorization: dehydration to acrolein over silica-supported niobia catalysts

NARCIS (Netherlands)

Shiju, N.R.; Brown, D.R.; Wilson, K.; Rothenberg, G.

2010-01-01

The catalytic dehydration of glycerol to acrolein is investigated over silica-supported niobia catalysts in a continuous fixed-bed gas-phase reactor. Various supported niobia catalysts are prepared and characterized using surface analysis and spectroscopic methods (XRD, UV-Vis, XPS, N2 adsorption),

C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

Science.gov (United States)

Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

2018-01-24

Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

Stable amorphous georgeite as a precursor to a high-activity catalyst

Science.gov (United States)

Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.; Chater, Philip A.; Carter, James H.; Morgan, David J.; Fiordaliso, Elisabetta M.; Wagner, Jakob B.; Davies, Thomas E.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.; Rosseinsky, Matthew J.; Hutchings, Graham J.

2016-03-01

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored—georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

Energy Technology Data Exchange (ETDEWEB)

Kasakov, Stanislav; Zhao, Chen; Barath, Eszter; Chase, Zizwe A.; Fulton, John L.; Camaioni, Donald M.; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A.

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanol in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.

Hydrogen production via reforming of biogas over nanostructured Ni/Y catalyst: Effect of ultrasound irradiation and Ni-content on catalyst properties and performance

Energy Technology Data Exchange (ETDEWEB)

Sharifi, Mahdi [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Abdollahifar, Mozaffar [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of)

2014-12-15

Highlights: • Synthesis of nanostructured Ni/Y catalyst by sonochemical and impregnation methods. • Enhancement of size distribution and active phase dispersion by employing sonochemical method. • Evaluation of biogas reforming over Ni/Y catalyst with different Ni-loadings. • Preparation of highly active and stable catalyst with low Ni content for biogas reforming. • Getting H{sub 2}/CO very close to equilibrium ratio by employing sonochemical method. - Abstract: The effect of ultrasound irradiation and various Ni-loadings on dispersion of active phase over zeolite Y were evaluated in biogas reforming for hydrogen production. X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray, Brunauer–Emmett–Teller, Fourier transform infrared analysis and TEM analysis were employed to observe the characteristics of nanostructured catalysts. The characterizations implied that utilization of ultrasound irradiation enhanced catalyst physicochemical properties including high dispersion of Ni on support, smallest particles size and high catalyst surface area. The reforming reactions were carried out at GHSV = 24 l/g.h, P = 1 atm, CH{sub 4}/CO{sub 2} = 1 and temperature range of 550–850 °C. Activity test displayed that ultrasound irradiated Ni(5 wt.%)/Y had the best performance and the activity remained stable during 600 min. Furthermore, the proposed reaction mechanism showed that there are three major reaction channels in biogas reforming.

Determination of concentration distribution and velocity of a catalyst in a model of a fluidized bed reactor using nuclear techniques

International Nuclear Information System (INIS)

Santos, V.A. dos.

1981-09-01

A simplified model of a cracking unit was construct. The gaseous phase consisted of air, the solid phase (zeolite catalyst cracking) and both the phases circulate at the ambiente temperature in the steady state with 500 g of catalyst and air flow of 1600 1/h. Measurements for the circulation time of the solid phase (catalyst), concentration and radial distribution of catalyst have been carried out. The reduced experimental model of the cracking reactor (FCC) was used and radioctive tracer and attenuation of γ-radiation techniques were employed. (E.G.) [pt

Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

DEFF Research Database (Denmark)

Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

2011-01-01

Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

Science.gov (United States)

Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

2015-06-22

The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High pressure flow reactor for in situ X-ray absorption spectroscopy of catalysts in gas-liquid mixtures—A case study on gas and liquid phase activation of a Co-Mo/Al2O3 hydrodesulfurization catalyst

NARCIS (Netherlands)

van Haandel, L.; Hensen, E.J.M.; Weber, Th.

2017-01-01

An in situ characterization of heterogeneous catalysts under industrial operating conditions may involve high pressure and reactants in both the gas and the liquid phase. In this paper, we describe an in situ XAS flow reactor, which is suitable to operate under such conditions (pmax 20 bar, Tmax 350

PhasePApy: A robust pure Python package for automatic identification of seismic phases

Science.gov (United States)

Chen, Chen; Holland, Austin

2016-01-01

We developed a Python phase identification package: the PhasePApy for earthquake data processing and near‐real‐time monitoring. The package takes advantage of the growing number of Python libraries including Obspy. All the data formats supported by Obspy can be supported within the PhasePApy. The PhasePApy has two subpackages: the PhasePicker and the Associator, aiming to identify phase arrival onsets and associate them to phase types, respectively. The PhasePicker and the Associator can work jointly or separately. Three autopickers are implemented in the PhasePicker subpackage: the frequency‐band picker, the Akaike information criteria function derivative picker, and the kurtosis picker. All three autopickers identify picks with the same processing methods but different characteristic functions. The PhasePicker triggers the pick with a dynamic threshold and can declare a pick with false‐pick filtering. Also, the PhasePicker identifies a pick polarity and uncertainty for further seismological analysis, such as focal mechanism determination. Two associators are included in the Associator subpackage: the 1D Associator and 3D Associator, which assign phase types to picks that can best fit potential earthquakes by minimizing root mean square (rms) residuals of the misfits in distance and time, respectively. The Associator processes multiple picks from all channels at a seismic station and aggregates them to increase computational efficiencies. Both associators use travel‐time look up tables to determine the best estimation of the earthquake location and evaluate the phase type for picks. The PhasePApy package has been used extensively for local and regional earthquakes and can work for active source experiments as well.

Hydrogen production from bio-fuels using precious metal catalysts

Directory of Open Access Journals (Sweden)

Pasel Joachim

2017-01-01

Full Text Available Fuel cell systems with integrated autothermal reforming unit require active and robust catalysts for H2 production. Thus, an experimental screening of catalysts for autothermal reforming of commercial biodiesel fuel was performed. Catalysts consisted of a monolithic cordierite substrate, an oxide support (γ-Al2O3 and Pt, Ru, Ni, PtRh and PtRu as active phase. Experiments were run by widely varying the O2/C and H2O/C molar ratios at different gas hourly space velocities. Fresh and aged catalysts were characterized by temperature programmed methods and thermogravimetry to find correlations with catalytic activity and stability.

Novel sample preparation for operando TEM of catalysts.

Science.gov (United States)

Miller, Benjamin K; Barker, Trevor M; Crozier, Peter A

2015-09-01

A new TEM sample preparation method is developed to facilitate operando TEM of gas phase catalysis. A porous Pyrex-fiber pellet TEM sample was produced, allowing a comparatively large amount of catalyst to be loaded into a standard Gatan furnace-type tantalum heating holder. The increased amount of catalyst present inside the environmental TEM allows quantitative determination of the gas phase products of a catalytic reaction performed in-situ at elevated temperatures. The product gas concentration was monitored using both electron energy loss spectroscopy (EELS) and residual gas analysis (RGA). Imaging of catalyst particles dispersed over the pellet at atomic resolution is challenging, due to charging of the insulating glass fibers. To overcome this limitation, a metal grid is placed into the holder in addition to the pellet, allowing catalyst particles dispersed over the grid to be imaged, while particles in the pellet, which are assumed to experience identical conditions, contribute to the overall catalytic conversion inside the environmental TEM cell. The gas within the cell is determined to be well-mixed, making this assumption reasonable. Copyright © 2015 Elsevier B.V. All rights reserved.

Catalyst Schools' Implementation of the Learning School Approach. Catalyst Schools Research Study Report

Science.gov (United States)

Hammer, Patricia Cahape

2016-01-01

"Catalyst schools" were 28 elementary and secondary schools selected to participate in a pilot project begun in July 2014, which explored how best to support teacher professional learning through decentralization of decision making and implementation of the Learning School approach. The pilot project was the first phase in a statewide…

Dispersed-phase catalysis in coal liquefaction

International Nuclear Information System (INIS)

Utz, B.R.; Cugini, A.V.; Frommell, E.A.

1990-01-01

This paper reports that the specific reaction (activation) conditions for the conversion of catalyst precursors to unsupported catalyst have a direct effect on the catalytic activity and dispersion. The importance of reaction intermediates in decomposition of ammonium heptamolybdate and ammonium tetrathiomolybdate, and the sensitivity of these intermediates to reaction conditions, were studied in coal liquefaction systems. Recent results indicate that optimization of activation conditions facilitates the formation of a highly dispersed and active form of molybdenum disulfide for coal liquefaction. The use of the catalyst precursors ammonium heptamolybdate, ammonium tetrathiomolybdate, and molybdenum trisulfide for the conversion of coal to soluble products will be discussed. The use of an unsupported dispersed-phase catalyst for direct coal liquefaction is not a novel concept and has been employed in may studies with varying success. Dispersed-phase catalysts soluble and oil-soluble salts, and as finely divided powders. While some methods of catalyst introduction give higher dispersion of the catalyst and greater activity for the liquefaction of coal, all of the techniques allow the formation of a finely dispersed inorganic phase

Development of Molecular Catalysts to Bridge the Gap between Heterogeneous and Homogeneous Catalysts

Science.gov (United States)

Ye, Rong

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to

Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration.

Science.gov (United States)

Wang, Wenzheng; Wang, Honglei; Zhu, Tianle; Fan, Xing

2015-07-15

Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration. Copyright © 2015. Published by Elsevier B.V.

Tri-potassium phosphate as a solid catalyst for biodiesel production from waste cooking oil

Energy Technology Data Exchange (ETDEWEB)

Guan, Guoqing; Kusakabe, Katsuki; Yamasaki, Satoko [Department of Living Environmental Science, Fukuoka Women' s University, 1-1-1 Kasumigaoka, Higashi-ku, Fukuoka 813-8529 (Japan)

2009-04-15

Transesterification of waste cooking oil with methanol, using tri-potassium phosphate as a solid catalyst, was investigated. Tri-potassium phosphate shows high catalytic properties for the transesterification reaction, compared to CaO and tri-sodium phosphate. Transesterification of waste cooking oil required approximately two times more solid catalyst than transesterification of sunflower oil. The fatty acid methyl ester (FAME) yield reached 97.3% when the transesterification was performed with a catalyst concentration of 4 wt.% at 60 C for 120 min. After regeneration of the used catalyst with aqueous KOH solution, the FAME yield recovered to 88%. Addition of a co-solvent changed the reaction state from three-phase to two-phase, but reduced the FAME yield, contrary to the results with homogeneous catalysts. The catalyst particles were easily agglomerated by the glycerol drops derived from the homogeneous liquid in the presence of co-solvents, reducing the catalytic activity. (author)

Hydrogen production by dry reforming of methane with carbon dioxide in one-dimensional nickel-based catalysts

International Nuclear Information System (INIS)

Lopez U, A. C.

2016-01-01

The main objective of this thesis is development of nickel catalysts supported over 1D matrix of cerium oxide, to be used in dry reforming methane reaction with carbon dioxide for hydrogen production. The catalysts were characterized by: Temperature Programmed Reduction (TPR), Scanning Electronic Microscopy (Sem), Surface Area (Bet method) an X Ray Diffraction (XRD). The TPR technique allowed to define reduction temperature of the active phase in the catalyst, Sem technique showed that the CeO_2 matrix had a nano rod morphology. XRD allowed to identify the crystalline phases of the catalysts. Finally, the catalysts were tested in the dry reforming methane reaction, high catalytic activity and hydrogen production were performed at 700 degrees Celsius and the catalyst with 30 wt.% of nickel. (Author)

Reduced cobalt phases of ZrO2 and Ru/ZrO2 promoted cobalt catalysts and product distributions from Fischer–Tropsch synthesis

International Nuclear Information System (INIS)

Kangvansura, Praewpilin; Schulz, Hans; Suramitr, Anwaraporn; Poo-arporn, Yingyot; Viravathana, Pinsuda; Worayingyong, Attera

2014-01-01

Highlights: • Ru/ZrO 2 , ZrO 2 promoted Co/SiO 2 for FTS were reduced by time resolved XANES. • Reduced catalysts resulted from XANES reduction showed the mixed phases of Co, CoO. • The highest percentages of CoO resulted from the high ZrO 2 promoted Co/SiO 2 . • Product distributions of 1-alkenes, iso-alkanes indicated sites for FTS and the 2° reaction. • Alkene readsorption were high corresponding to the high CoO forming branched alkanes. - Abstract: Co/SiO 2 catalysts were promoted with 4% and 8% ZrO 2 . Small amounts (0.07%) of Ru were impregnated onto 4%ZrO 2 /Co/SiO 2 . Catalysts resulting from time-resolved XANES reduction showed mixed phases of Co and CoO, with the highest percentages of Co resulting from Ru/4%ZrO 2 /Co/SiO 2 and the highest percentages of CoO resulting from 8%ZrO 2 /Co/SiO 2 . Product distributions of n-alkanes, iso-alkanes and alkenes during Fischer–Tropsch Synthesis (FTS) were used to investigate the catalyst performance of 4%ZrO 2 /Co/SiO 2 8%ZrO 2 /Co/SiO 2 and Ru/4%ZrO 2 /Co/SiO 2 . FTS steady state was studied by growth probabilities of n-alkane products. No 1-alkene was produced from Ru/4%ZrO 2 /Co/SiO 2 , indicating high availability of Fischer–Tropsch sites for long chain hydrocarbon growth, despite high methanation. Branched alkanes produced from the secondary reaction were related to the high CoO percentages on 8%ZrO 2 /Co/SiO 2 . Alkene readsorption sites were high, corresponding to the high CoO percentages, causing a high probability of forming branched alkane products

Microchannel Reactors for ISRU Applications Using Nanofabricated Catalysts, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Makel Engineering, Inc. (MEI) and USRA propose to develop microchannel reactors for In-Situ Resources Utilization (ISRU) using nanofabricated catalysts. The proposed...

Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

Energy Technology Data Exchange (ETDEWEB)

Mondal, Arijit; Mukherjee, Debkumar, E-mail: debkumarmukherjee@rediffmail.com [Ramsaday College, Department of Chemistry (India); Adhikary, Bibhutosh, E-mail: adhikarybibhu@yahoo.com [Indian Institute of Engineering, Sciences and Technology, Shibpur, Department of Chemistry (India); Ahmed, Md Azharuddin [University of Calcutta, Department of Physics (India)

2016-05-15

Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4–6 nm) can also be prepared from PdCl{sub 2} and K{sub 2}PtCl{sub 4}, respectively, using the same surfactant but require high temperature (~120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90–95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.Graphical Abstract.

The mild liquid-phase synthesis of 3-picoline from acrolein diethyl acetal and ammonia over heterogeneous catalysts

Science.gov (United States)

Luo, Cai-Wu; Chao, Zi-Sheng; Lei, Bo; Wang, Hong; Zhang, Jun; Wang, Zheng-Hao

2017-11-01

The liquid-phase synthesis of 3-picoline from the reaction of acrolein diethyl acetal and ammonia over ion-exchanged resins (D402 and D002) and HZSM-5 (Si/Al = 25) was carried out in a batch reactor. Various influencing parameters, including by the addition of water, ion-exchanged resins, reaction temperature and HZSM-5, were systematically investigated. The results showed that the reaction could be directly conducted, and organic acid wasn’t utilized. The highest yield of 3-picoline reached up to 24% using HZSM-5 as catalyst at 110 °C.

Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

Science.gov (United States)

Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Additively Manufactured Monolithic Catalyst Bed for Green Propellants, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This proposal aims to develop a low cost, high efficiency catalyst technology to address navigation and maneuver difficulties in NASA's return missions. Our approach...

Identification of emission sources of umbral flashes using phase congruency

International Nuclear Information System (INIS)

Feng Song; Yang Yun-Fei; Ji Kai-Fan; Yu Lan

2014-01-01

The emission sources of umbral flashes (UFs) are believed to be closely related to running umbral and penumbral waves, and are concluded to be associated with umbral dots in the solar photosphere. Accurate identification of emission sources of UFs is crucial for investigating these physical phenomena and their inherent relationships. A relatively novel model of shape perception, namely phase congruency (PC), uses phase information in the Fourier domain to identify the geometrical shape of the region of interest in different intensity levels, rather than intensity or gradient. Previous studies indicate that the model is suitable for identifying features with low contrast and low luminance. In the present paper, we applied the PC model to identify the emission sources of UFs and to locate their positions. For illustrating the high performance of our proposed method, two time sequences of Ca II H images derived from the Hinode/SOT on 2010 August 10 and 2013 August 20 were used. Furthermore, we also compared these results with the analysis results that are identified by the traditional/classical identification methods, including the gray-scale adjusted technique and the running difference technique. The result of our analysis demonstrates that our proposed method is more accurate and effective than the traditional identification methods when applied to identifying the emission sources of UFs and to locating their positions. (research papers)

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

Science.gov (United States)

Serna, Pedro; Gates, Bruce C

2014-08-19

-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

Catalysts for liquid phase oxidation of olefins and sulfur compounds; Catalyseurs pour l'oxydation en phase liquide d'olefines et de composes soufres

Energy Technology Data Exchange (ETDEWEB)

Palomeque Santiago, J.F.

2002-07-01

Several basic, acid and acid-base catalysts were studied for the epoxidation of olefins activated or not and dibenzo-thiophene.Hydrotalcite activation by thermic treatment and in situ re-hydration improves catalytic activity for 2-cyclohexene-1-one and isophorone. Bronsted basic sites were found to be more active than Lewis sites. Total conversion of 2-cyclohexene-1-one is reached in 1.5 h in polar solvents. W{sub 7}O{sub 24}{sup 6-} Iso-poly-anion was exchanged onto a meixnerite by a new preparation method, A meso-porous solid was obtained with good catalytic properties for cyclohexene epoxidation 100% selective to epoxide. W{sub 7}O{sub 24}{sup 6-} and WO{sub 5}{sup 2-} anions and phenyl and dodecyl-phospho-tungstates were grafted on hydrotalcites. Due to the acid-base characteristics of these solid catalysts, cyclohexene yields products of allylic reactions. Mg-La, and Mg-Al-La mixed oxides were synthesized and mixed phases were gotten. Their basic characteristics account for hydrogen peroxide decomposition which prevents DBT oxidation reaction to sulfone. On the contrary, Mg-Al re-hydrated hydrotalcites are very active for this reaction and remove 100% of sulfur compounds in 1 hour. New catalyst W-ZrO{sub 2} were synthesized with high acid properties. stable structure with temperature and high DBT conversion in less than 5 minutes of reaction. These catalytic systems can be applied for hydrocarbon desulfurization of fuels like naphtha, gas oil and kerosene. (author)

Oxidation catalyst

Science.gov (United States)

Ceyer, Sylvia T.; Lahr, David L.

2010-11-09

The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2017-10-23

Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single-turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring-opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Moessbauer investigations of the Fe-Cu-Mn catalysts for Fischer-Tropsch synthesis

International Nuclear Information System (INIS)

Spanu, V.; Filoti, G.; Ilie, I.; Zamfirescu, E.

1990-01-01

In the selective process of the syngas conversion to synthetic gasoline a bifunctional catalytic system has to be used. It was obtained by combination a Fischer-Tropsch catalyst with the HZSM-5 zeolite. The phase compositions of the precursor and the fresh catalyst were established as well as the optimum thermal treatment. The catalyst was reduced in pure H 2 or in a H 2 +CO mixture. The influence of the reduction and reaction conditions on the catalyst structure was investigated. (orig.)

Review of the Production of Biodiesel from Waste Cooking Oil using Solid Catalysts

Directory of Open Access Journals (Sweden)

N.H. Said

2015-06-01

Full Text Available The need for fossil fuels and the emissions generated from these fuels are increasing daily. Researchers are concerned with global warming as well as climate change; and energy sustainability and material usages are important issues today. Waste cooking oil (WCO can be processed into biodiesel as an alternative fuel to replace diesel. Production of biodiesel using WCO as the feedstock has been of growing interest for the last two decades. A number of research papers related to the improvements in production, raw materials and catalyst selection have been published. This paper reviews the various types of heterogeneous solid catalyst in the production of biodiesel via the transesterification of WCO. The catalysts used can be classified according to their state presence in the transesterification reaction as homogeneous or heterogeneous catalysts. Homogeneous catalysts act in the same liquid phase as the reaction mixture, whereas heterogeneous catalysts act in a solid phase with the reaction mixture. Heterogeneous catalysts are non-corrosive, a green process and environmentally friendly. They can be recycled and used several times, thus offering a more economic pathway for biodiesel production. The advantages and drawbacks of these heterogeneous catalysts are presented. Future work focuses on the application of economically and environmentally friendly solid catalysts in the production of biodiesel using WCO as the raw material.

Catalyst performance in magnetic esterification methyl soy oil

International Nuclear Information System (INIS)

Araujo, N.O.; Pereira, K R. de O.; Barros, A.B. de S.; Moura, T.F.B. de; Vilar, E.; Dantas, J.; Costa, A.C.F. de M.

2016-01-01

Growing concerns about the environment have encouraged the search for new fuels, including biodiesel, obtained from lipid sources that react with alcohol and catalyst. This aimed of this study to synthesize type catalyst (Ni-Zn)Fe_2O_4 and evaluate it in soy oil esterification. The catalyst was synthesized by combustion reaction and characterized by XRD, FTIR and BET. The esterification was carried out at high pressure reactor at 140°C for 1 hour with molar ratio of oil:alcohol 1:15 to 1 and 3% catalyst. From the XRD it was observed the formation of inverted spinel phase. FTIR revealed the presence of the vibrational bands 586, 1381, 1628, 2352, 2922, 3147 and 3457cm"-"1 and surface area 48m"2g"-"1, 10nm pore diameter and type IV isotherm, suggesting mesoporous material characteristic. The results indicate biodiesel conversion of 31.9% and 27.3% when using 1% and 3% catalyst, respectively. (author)

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

International Nuclear Information System (INIS)

Adeyinka A. Adeyiga

2001-01-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H 2 ) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H 2 /CO ratios. However, a serious problem with use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H 2 /CO=0.67 and 2.0 NL/g-cat/h with C 5 + selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron

DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

International Nuclear Information System (INIS)

Bukur, Dragomir B.; Lang, X.; Chokkaram, S.; Nowicki, L.; Wei, G.; Ding, Y.; Reddy, B.; Xiao, S.

1999-01-01

Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

Coking of residue hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Gray, M.R.; Zhao, Y.X. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical Engineering; McKnight, C.A. [Syncrude Canada Ltd., Edmonton, AB (Canada); Komar, D.A.; Carruthers, J.D. [Cytec Industries Inc., Stamford, CT (United States)

1997-11-01

One of the major causes of deactivation of Ni/Mo and Co/Mo sulfide catalysts for hydroprocessing of heavy petroleum and bitumen fractions is coke deposition. The composition and amount of coke deposited on residue hydroprocessing catalysts depends on the composition of the liquid phase of the reactor. In the Athabasca bitumen, the high molecular weight components encourage coke deposition at temperatures of 430 to 440 degrees C and at pressures of 10 to 20 MPa hydrogen pressure. A study was conducted to determine which components in the heavy residual oil fraction were responsible for coking of catalysts. Seven samples of Athabasca vacuum residue were prepared by supercritical fluid extraction with pentane before being placed in the reactor. Carbon content and hydrodesulfurization activity was measured. It was concluded that the deposition of coke depended on the presence of asphaltenes and not on other compositional variables such as content of nitrogen, aromatic carbon or vanadium.

Physico-Chemical and Catalytic Properties of Mesoporous CuO-ZrO2 Catalysts

Directory of Open Access Journals (Sweden)

Sulaiman N. Basahel

2016-04-01

Full Text Available Mesoporous CuO-ZrO2 catalysts were prepared and calcined at 500 °C. The performance of the synthesized catalysts for benzylation of benzene using benzyl chloride was studied. The bare support (macroporous ZrO2 offered 45% benzyl chloride conversion after reaction time of 10 h at 75 °C. Significant increase in benzyl chloride conversion (98% was observed after CuO loading (10 wt. % on porous ZrO2 support. The conversion was decreased to 80% with increase of CuO loading to 20 wt. %. Different characterization techniques (XRD, Raman, diffuse reflectance UV-vis, N2-physisorption, H2-TPR, XPS and acidity measurements were used to evaluate physico-chemical properties of CuO-ZrO2 catalysts; the results showed that the surface and structural characteristics of the ZrO2 phase as well as the interaction between CuO-ZrO2 species depend strongly on the CuO content. The results also indicated that ZrO2 support was comprised of monoclinic and tetragonal phases with macropores. An increase of the volume of monoclinic ZrO2 phase was observed after impregnation of 10 wt. % of CuO; however, stabilization of tetragonal ZrO2 phase was noticed after loading of 20 wt. % CuO. The presence of low-angle XRD peaks indicates that mesoscopic order is preserved in the calcined CuO-ZrO2 catalysts. XRD reflections due to CuO phase were not observed in case of 10 wt. % CuO supported ZrO2 sample; in contrast, the presence of crystalline CuO phase was observed in 20 wt. % CuO supported ZrO2 sample. The mesoporous 10 wt. % CuO supported ZrO2 catalyst showed stable catalytic activity for several reaction cycles. The observed high catalytic activity of this catalyst could be attributed to the presence of a higher number of dispersed interactive CuO (Cu2+-O-Zr4+ species, easy reducibility, and greater degree of accessible surface Lewis acid sites.

Zircon Supported Copper Catalysts for the Steam Reforming of Methanol

Science.gov (United States)

Widiastri, M.; Fendy, Marsih, I. N.

2008-03-01

Steam reforming of methanol (SRM) is known as one of the most favorable catalytic processes for producing hydrogen. Current research on zirconia, ZrO2 supported copper catalyst revealed that CuO/ZrO2 as an active catalyst for the SRM. Zircon, ZrSiO4 is available from the by-product of tin mining. In the work presented here, the catalytic properties of CuO/ZrSiO4 with various copper oxide compositions ranging from 2.70% (catalyst I), 4.12% (catalyst II), and 7.12%-mass (catalyst III), synthesized by an incipient wetness impregnation technique, were investigated to methanol conversion, selectivity towards CO formation, and effect of ZnO addition (7.83%CuO/8.01%ZnO/ZrSiO4 = catalyst V). The catalytic activity was obtained using a fixed bed reactor and the zircon supported catalyst activity was compared to those of CuO/ZnO/Al2O3 catalyst (catalyst IV) and commercial Kujang LTSC catalyst. An X-ray powder diffraction (XRD) analysis was done to identify the abundant phases of the catalysts. The catalysts topography and particle diameter were measured with scanning electron microscopy (SEM) and composition of the catalysts was measured by SEM-EDX, scanning electron microscope-energy dispersive using X-ray analysis. The results of this research provide information on the possibility of using zircon (ZrSiO4) as solid support for SRM catalysts.

Development of catalysts for chemical reactions driven by concentrated solar energy

International Nuclear Information System (INIS)

Berman, A.; Levitan, R.; Levy, M.

1992-03-01

The aim of this phase of the work is to study commercially available low priced catalysts, for the methanation and reforming processes in the closed-loop solar chemical heat pipe. This report summarized some long term tests of commercially available methanation catalysts and the measurement of their active surface before and after reaction. It was found that the 1%Ru on alumina stars catalysts (prepared by Englehard Company according to our request) is very active and stable at 350-750 C. The catalyst 'A' produced in Russia, is less active, however, did not lose the mechanical strength. The 50% Ni/SiO 2 catalyst is active as the 'A' catalyst but loses its activity after treatment at temperature > 600 C, its geometrical size shrinked. (authors). 25 refs., 25 figs., 36 tabs

Preparation of biodiesel from soybean oil by using heterogeneous catalyst

Energy Technology Data Exchange (ETDEWEB)

Ferdous, Kaniz; Rakib Uddin, M.; Islam, M.A. [Department of Chemical Engineering and Polymer Science, Shah Jalal University of Science and Technology, Sylhet 3114 (Bangladesh); Khan, Maksudur R. [Department of Chemical Engineering and Polymer Science, Shah Jalal University of Science and Technology, Sylhet 3114 (Bangladesh); Faculty of Chemical and Natural Resources Engineering, University Malaysia Pahang, 26300 Gambang, Kuantan, Pahang (Malaysia)

2013-07-01

The predicted shortage of fossil fuels and related environmental concerns has recently attracted significant attention to search alternative fuel. Biodiesel is one of the alternatives to fossil fuel. Now-a-days, most biodiesel is produced by the transesterification of oils using methanol and a homogeneous base catalyst. The use of homogeneous catalysts is normally limited to batch mode processing followed by a catalyst separation step. The immiscible glycerol phase, which accumulates during the course of the reaction, solubilizes the homogeneous base catalyst and therefore, withdraws from the reaction medium. Moreover, other difficulties of using homogeneous base catalysts relate to their sensitivity to free fatty acid (FFA) and water and resulting saponification phenomenon. High energy consumption and costly separation of the catalyst from the reaction mixture have inspired the use of heterogeneous catalyst. The use of heterogeneous catalysts does not lead to the formation of soaps through neutralization of FFA and saponification of oil. In the present paper, biodiesel was prepared from crude (soybean) oil by transesterification reaction using heterogeneous base catalyst name calcium oxide (CaO). Various reaction parameters were optimized and the biodiesel properties were evaluated.

Identification of two-phase flow regimes by time-series modeling

International Nuclear Information System (INIS)

King, C.H.; Ouyang, M.S.; Pei, B.S.

1987-01-01

The identification of two-phase flow patterns in pipes or ducts is important to the design and operation of thermal-hydraulic systems, especially in the nuclear reactor cores of boiling water reactors or in the steam generators of pressurized water reactors. Basically, two-phase flow shows some fluctuating characteristics even at steady-state conditions. These fluctuating characteristics can be analyzed by statistical methods for obtaining flow signatures. There have been a number of experimental studies conducted that are concerned with the statistical properties of void fraction or pressure pulsation in two-phase flow. In this study, the authors propose a new technique of identifying the patterns of air-water two-phase flow in a vertical pipe. This technique is based on analyzing the statistic characteristics of the pressure signals of the test loop by time-series modeling

Disproportionation phenema of wistite phase in the model iron catalysts for ammonia synthesis studied by Moessbauer spectroscopy

International Nuclear Information System (INIS)

Pattek-Janczyk, A.; Miczko, B.

1990-01-01

A model iron catalysts for ammonia synthesis containing a large amount of wustite (35 wt%) has been studied during the annealing in an inert atmosphere in the temperature range of 573-773 K. Changes in magnetite and wustite phases were followed by Muessbauer spectroscopy (MS). Before starting the thermal treatment, two kinds of wustite of different structures have been found by MS and X-ray diffraction. The behaviour of both kinds of wustite during the annealing was different. One of them, closer to the stoichiometric compound, disproportionated at once into magnetite and iron; its content decreased systematically without changes in the Muessbauer parameters. In the second wustite, only qualitatieve changes were observed at first (its nonstoichiometry decreases without changes in content and, next, this phase started to disproportionate too. (auhtor). 31 refs.; 6 figs.; 2 tabs

Synthesis of biodiesel using local natural zeolite as heterogeneous anion exchange catalyst

Science.gov (United States)

Hartono, R.; Wijanarko, A.; Hermansyah, H.

2018-04-01

Production of biodiesel using homogen catalyst: alkaline catalysts, acid catalysts, biocatalysts, and supercritical methanol are very inefficient, because these catalysts have a very high cost production of biodiesel and non-ecofriendly. The heterogeneous catalyst is then used to avoid adverse reaction of biodiesel production. The heterogeneous catalysts used is ion exchanger using natural zeolit catalists bayah banten (ZABBrht) and macroporous lewatit that can be used to produce biodiesel in the solid phase so that the separation is easier and can be used repeatedly. The results of biodiesel reach its optimum in engineering ion exchange catalyst natural zeolit bayah and macroporous lewatit which has been impregnated and calcinated at temperature 60 °C at reaction time 2 hours, are 94.8% and 95.24%, using 100 gr.KOH/100 mL Aquadest.

SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

Energy Technology Data Exchange (ETDEWEB)

James K. Neathery; Gary Jacobs; Burtron H. Davis

2004-03-31

In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.

Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

Energy Technology Data Exchange (ETDEWEB)

Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

2008-09-01

Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H₂ and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

Acid Dissolution of Depleted Uranium from Catalyst using Microwave

Energy Technology Data Exchange (ETDEWEB)

Sung, Jin Hyun; Jeong, Seong Gi; Park, Kwang Heon [Kyunghee University, Yongin (Korea, Republic of)

2011-05-15

The separation process of uranium is one of the most important fields in nuclear industry because uranium is used primary in nuclear power plants. Uranium ores are treated by either acid or alkaline reagents. Uranium can be dissolved by acid or alkaline solutions. There are two oxidation states in which the hexavalent form, the oxide of which is UO{sub 3}, and the tetravalent form, the oxide of which is UO{sub 2}. However, depleted uranium(DU) has also been used as a catalyst in specialized chemical reaction such as ammoxidation. The preferred catalyst for propylene oxidation with ammonia was a uranium oxide-antimony oxide composition. The active phase of catalyst was known as USbO{sub 5} and USb{sub 3}O{sub 10}. There is pentavalent form. Waste catalyst containing DU was generated and stored in chemical industry. In this work, we removed DU from catalyst by acid dissolution

TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

International Nuclear Information System (INIS)

Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.

2013-01-01

Highlights: ► NiW catalysts supported on TiO 2 nanotubes, titania and alumina. ► The best results are obtained with NiW/TiO 2 nanotubes in hydrodesulfurization (HDS) of thiophene. ► Active phase is Ni-WO x S y . ► Electronic promotion of W by Ti. - Abstract: High surface area TiO 2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid – Ni 3/2 PW 12 O 40 was applied as oxide precursor of the active components. The catalyst was characterized by S BET , XRD, UV–vis DRS, Raman spectroscopy, XPS, TPR and HRTEM. The results obtained were compared with those for the NiW catalysts prepared over high surface area titania and alumina supports. A polytungstate phase evidenced by Raman spectroscopy was observed indicating the destruction of the initial heteropolyanion. The catalytic experiments revealed two times higher thiophene conversion on NiW catalyst supported on Ti-NT than those of catalysts supported on alumina and titania. Increased HDS activity of the NiW catalyst supported on Ti-NT could be related to a higher amount of W oxysulfide entities interacting with Ni sulfide particles as consequence of the electronic effects of the Ti-NT observed with XPS analysis.

Esterification of oleic acid in a three-phase, fixed-bed reactor packed with a cation exchange resin catalyst.

Science.gov (United States)

Son, Sung Mo; Kimura, Hiroko; Kusakabe, Katsuki

2011-01-01

Esterification of oleic acid was performed in a three-phase fixed-bed reactor with a cation exchange resin catalyst (Amberlyst-15) at high temperature, which was varied from 80 to 120 °C. The fatty acid methyl ester (FAME) yields in the fixed-bed reactor were increased with increases in the reaction temperature, methanol flow rate and bed height. Moreover, the FAME yields were higher than those obtained using a batch reactor due to an equilibrium shift toward the product that resulted from continuous evaporation of the produced water. In addition, there was no catalyst deactivation during the esterification of oleic acid. However, addition of sunflower oil to the oleic acid reduced the FAME yield obtained from simultaneous esterification and transesterification. The FAME yield was 97.5% at a reaction temperature of 100 °C in the fixed-bed with a height of 5 cm when the methanol and oleic acid feed rates were 8.6 and 9.0 mL/h, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: Effect of calcination temperature of catalysts

International Nuclear Information System (INIS)

Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

2012-01-01

Highlights: ► Oxidative desulfurization was studied with WO x /ZrO 2 calcined at different temp. ► The importance of the phases of zirconia and tungsten oxide was suggested. ► The catalyst was analyzed thoroughly with Raman and XRD techniques. ► The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO x /ZrO 2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO x /ZrO 2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO 2 ) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO 3 and monoclinic ZrO 2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO x /ZrO 2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

Development of improved iron Fischer-Tropsch catalysts. Final technical report: Project 6464

Energy Technology Data Exchange (ETDEWEB)

Bukur, D.B.; Ledakowicz, S.; Koranne, M. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemical Engineering] [and others

1994-02-28

Despite the current worldwide oil glut, the United States will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer Tropsch (FT) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Texas A&M University (TAMU) with sponsorship from the US Department of Energy, Center for Energy and Mineral Resources at TAMU, Texas Higher Education Coordinating Board, and Air Products and Chemicals, Inc., has been working on development of improved iron FT catalysts and characterization of hydrodynamic parameters in two- and three-phase bubble columns with FT derived waxes. Our previous studies have provided an improved understanding of the role of promoters (Cu and K), binders (silica) and pretreatment procedures on catalyst activity, selectivity and longevity (deactivation). The objective of the present contract was to develop improved catalysts with enhanced slurry phase activity and higher selectivity to liquid fuels and wax. This was accomplished through systematic studies of the effects of pretreatment procedures and variations in catalyst composition (promoters and binders). The major accomplishments and results in each of these two main areas of research are summarized here.

One-step liquid phase chemical method to prepare carbon-based amorphous molybdenum sulfides: As the effective hydrogen evolution reaction catalysts

International Nuclear Information System (INIS)

Guo, Mengmeng; Wu, Qikang; Yu, Miaomiao; Wang, Yinling; Li, Maoguo

2017-01-01

Two different kinds of carbon-based amorphous molybdenum sulfide composite catalysts (activated carbon supported amorphous molybdenum sulfide and acetylene black supported amorphous molybdenum sulfide) had been prepared in a facile and scalable one-step liquid phase chemical method. The morphological and structural information of catalysts was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and it’s electro-catalytic HER activity were evaluated by linear sweep voltammetry(LSV), amperometric i-t technology and AC impedance technology. The as-prepared carbon-based amorphous molybdenum sulfides showed greatly enhanced electro-catalytic activity for HER compared with pure amorphous molybdenum sulfides. Especially, the nano-sized acetylene black supported molybdenum sulfide exhibited excellent electro-catalytic HER performances with a low onset potential of −116 mV versus reverse hydrogen electrode (RHE) and a small Tafel slope of 51 mV per decade.

Research advances in the catalysts for the selective oxidation of ethane to aldehydes

Institute of Scientific and Technical Information of China (English)

ZHANG Zhe; ZHAO Zhen; XU Chunming

2005-01-01

Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

2005-01-01

Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

SCR at bio fuels combustion - phase 2. Measures to extend catalyst life time; SCR vid biobraensleeldning - etapp 2. Aatgaerder foer att foerlaenga katalysatorns livslaengd

Energy Technology Data Exchange (ETDEWEB)

Andersson, Christer; Bodin, Henrik; Sahlqvist, Aasa [Vattenfall Utveckling AB, Aelvkarleby (Sweden); Khodayari, Raziyeh; Odenbrand, Ingemar [Lund Univ. (Sweden). Dept. of Chemical Engineering II

2000-07-01

In this project phase, the deactivation of catalysts during combustion of bio fuels, and different methods of regeneration have been investigated. The overall purpose is to improve the economic and technical possibilities to use SCR at bio fuels combustion. The two different methods for regeneration are washing with water and so called sulphation (treatment with sulphur dioxide). The results from wood fired FB-boilers show that the catalyst lose 25% (average) of the relative activity during a normal heat production season. The tendency is that a boiler with short residence time between final combustion and catalyst and/or high flame temperatures gives a faster deactivation. Such unfavourable conditions arise in FB-boilers with a large part of the combustion in freeboard/cyclone. The alkali content of the fuel (wood fuel) is of minor importance for the deactivation rate compared with the combustion conditions. The flue gas temperature within the interval 250 - 375 deg C is not an important parameter for the deactivation in the time interval 3 000 - 6 000 h. The 'new' honeycomb catalysts that were tested during phase two, BiotypA-C, evidently show different deactivation trends. The highly active BiotypC e.g. increases its activity during the first thousand hours. Calculations indicate that BiotypC at 315 deg C requires the smallest volume of catalyst over ten years of operation in order to maintain given performance. Practical consequences for downstream equipment also need to be carefully checked. Sulphation with SO{sub 2} works in the laboratory as a regeneration method for all of the tested samples. The sulphatised samples deactivation are almost comparable to a fresh sample when exposed to flue gas. About 80 % of the lost activity can be regained only by using sulphation. Plate-type catalysts gets a somewhat lower increase in activity compared to honeycomb-types, probably related to chemical rather than geometric design. High SO{sub 2}-concentration

Alumina/silica aerogel with zinc chloride as an alkylation catalyst

Directory of Open Access Journals (Sweden)

DEJAN U. SKALA

2001-10-01

Full Text Available The alumina/silica with zinc chloride aerogel alkylation catalyst was obtained using a one step sol-gel synthesis, and subsequent drying with supercritical carbon dioxide. The aerogel catalyst activity was found to be higher compared to the corresponding xerogel catalyst, as a result of the higher aerogel surface area, total pore volume and favourable pore size distribution. Mixed Al–O–Si bonds were present in both gel catalyst types. Activation by thermal treatment in air was needed prior to catalytic alkylation, due to the presence of residual organic groups on the aerogel surface. The optimal activation temperature was found to be in the range 185–225°C, while higher temperatures resulted in the removal of zinc chloride from the surface of the aerogel catalyst with a consequential decrease in the catalytic activity. On varying the zinc chloride content, the catalytic activity of the aerogel catalyst exhibited a maximum. High zinc chloride contents decreased the catalytic activity of the aerogel catalyst as the result of the pores of the catalyst being plugged with this compound, and the separation of the alumina/silica support into Al-rich and Si-rich phases. The surface area, total pore volume, pore size distribution and zinc chloride content had a similar influence on the activity of the aerogel catalyst as was the case of xerogel catalyst and supported zinc chloride catalysts.

Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanol

DEFF Research Database (Denmark)

Sharafutdinov, Irek; Elkjær, Christian Fink; de Carvalho, Hudson Wallace Pereira

2014-01-01

In this work, we present a detailed study of the formation of supported intermetallic Ni–Ga catalysts for CO2 hydrogenation to methanol. The bimetallic phase is formed during a temperature-programmed reduction of the metal nitrates. By utilizing a combination of characterization techniques......, in particular in situ and ex situ X-ray diffraction, in situ X-ray absorption spectroscopy, transmission electron microscopy combined with electron energy loss spectroscopy and X-ray fluorescence, we have studied the formation of intermetallic Ni–Ga catalysts of two compositions: NiGa and Ni5Ga3. These methods...... demonstrate that the catalysts with the desired intermetallic phase and composition are formed upon reduction in hydrogen and enable us to propose a mechanism of the Ni–Ga nanoparticles formation. By studying the effect of calcination prior to catalyst reduction, we show that the reactivity depends...

Alkylation of isobutane by butenes on zirconium sulfate catalysts

International Nuclear Information System (INIS)

Lavrenov, A.V.; Perelevskij, E.V.; Finevich, V.P.; Zajkovskij, V.I.; Paukshtis, E.A.; Duplyakiv, V.K.; Bal'zhinimaev, B.S.

2003-01-01

Preparation of applied zirconium sulfate catalysts obtained by the method of impregnation is investigated. Results of comparative study of structural, acid-base and catalytic properties of sulfated zirconium dioxide applied on silica gel and aluminium oxide are represented. Intervals of values of synthesis basic parameters and characteristics of catalysts properties providing achievement of high activity and selectivity in isobutane alkylation by butenes in liquid phase are determined [ru

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

Science.gov (United States)

Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

2006-05-25

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

Catalyst dispersion and activity under conditions of temperature-staged liquefaction

Energy Technology Data Exchange (ETDEWEB)

Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

1993-02-01

This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275[degrees]C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

Stable amorphous georgeite as a precursor to a high-activity catalyst

DEFF Research Database (Denmark)

Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.

2016-01-01

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable-and hence little known and largely ignored-georgeite. The first three of these minerals are widely used as catalyst precursors...... for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient...

In-Situ Liquid Hydrogenation of m-Chloronitrobenzene over Fe-Modified Pt/Carbon Nanotubes Catalysts

Directory of Open Access Journals (Sweden)

Feng Li

2018-02-01

Full Text Available In-situ liquid-phase hydrogenation of m-chloronitrobenzene (m-CNB based on aqueous-phase reforming (APR of ethanol and catalytic hydrogenation was carried out over Fe-modified Pt/carbon nanotubes (CNTs catalysts. The effects of Pt loading over CNTs and Fe modification on the catalytic performance of Pt/CNTs catalysts were studied. In-tube loading of Pt particles, compared with out-tube loading, considerably improved the catalytic activity. With in-tube loading, Fe-modified Pt/CNTs catalysts further improved the m-CNB in-situ hydrogenation performance. After Fe modification, Pt–Fe/CNTs catalysts formed, inside CNTs, a Pt–Fe alloy and iron oxides, which both improved catalytic hydrogenation performance and significantly enhanced ethanol APR hydrogen producing performance, thereby increasing the m-CNB in-situ hydrogenation reactivity.

ETEM Studies of Electrodes and Electro-catalysts

DEFF Research Database (Denmark)

Jooss, Christian; Mildner, Stephanie; Beleggia, Marco

2016-01-01

Environmental TEM is an excellent tool for gaining insight into the atomic and electronic structure of electro-catalysts under operating conditions. Several electrochemical reactions such as oxidation/reduction processes of electrodes, heterogeneous gas phase catalysis of water splitting...

Polyol Synthesis of Cobalt–Copper Alloy Catalysts for Higher Alcohol Synthesis from Syngas

DEFF Research Database (Denmark)

Mendes, Laiza V.P.; Snider, Jonathan L.; Fleischman, Samuel D.

2017-01-01

Novel catalysts for the selective production of higher alcohols from syngas could offer improved pathways towards synthetic fuels and chemicals. Cobalt–copper alloy catalysts have shown promising results for this reaction. To improve control over particle properties, a liquid phase nanoparticle s...

HDS, HDN and HDA activities of nickel-molybdenum catalysts supported on alumina

Energy Technology Data Exchange (ETDEWEB)

Dominguez-Crespo, M.A. [Instituto Mexicano del Petroleo, Programa de Tratamiento de Crudo Maya. Avenida Eje Central Lazaro Cardenas No.152, Col. San Bartolo Atepehuacan, 07730, Mexico D. F. (Mexico); Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada (CICATA-Altamira, IPN) Km 14.5 Carretera Tampico-puerto Industrial 89600, Altamira, Tamaulipas (Mexico); Torres-Huerta, A.M.; Ramirez-Meneses, E. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada (CICATA-Altamira, IPN) Km 14.5 Carretera Tampico-puerto Industrial 89600, Altamira, Tamaulipas (Mexico); Diaz-Garcia, L. [Instituto Mexicano del Petroleo, Programa de Tratamiento de Crudo Maya. Avenida Eje Central Lazaro Cardenas No.152, Col. San Bartolo Atepehuacan, 07730, Mexico D. F. (Mexico); Arce-Estrada, E.M. [Instituto Politecnico Nacional, Departamento de Metalurgia y Materiales. A.P. 75-876, 07300 Mexico, D. F. (Mexico)

2008-08-15

In this work, NiMo-Al{sub 2}O{sub 3} catalysts were prepared by using different alumina precursors. The supports were impregnated by means of the spray at incipient wetness technique in both basic and acid media. Both the supports and fresh catalysts were characterized by the adsorption-desorption isotherms, Temperature-Programmed Reduction (TPR), Thermal Pyridine Adsorption-Desorption (TPD) and X-Ray Diffraction analyses (XRD). After sulfidation, the NiMoS metallic particles were characterized by Transmission Electron Microscopy (TEM). The initial analyses were performed in a trickle-bed reactor by using a real feedstock (Mexican heavy gas oil) and performing hydrotreating reactions (HDS, HDN and HDA) at three different temperatures: 613, 633 and 653 K; and 54 kg cm{sup -} {sup 2}. The catalytic activities are discussed in relation to the physicochemical properties of the NiMo catalysts, alumina phase and pH of the impregnating solution. The catalytic results show an increase in the conversion profiles with temperature. The sulfur conversion was increased from 89 to 99.25%, 91-99%, 90.8-97%, 83-95% and 78-96% when the crystal size of the support varied from 3 to 20 nm, respectively. The nitrogen and aromatic conversions were also increased in the range of 23-45 wt.%. It was found that the {gamma} phase reached a higher catalytic performance than the {eta} phase. The NiMo catalysts synthesized in a basic medium showed a better catalytic performance than that obtained with those prepared in acid solutions. The significance of the kinetic data to compare the catalysts is discussed. The maximum value of the catalytic activity was reached with the catalysts with the smallest particle sizes. (author)

Development of industrial hydrogenating catalyst on rhenium base

International Nuclear Information System (INIS)

Chistyakova, G.A.; Bat', I.I.; Rebrova, V.V.

1975-01-01

Processes for forming rhenium catalysts on carbon carrier and their catalytic properties in nitrobenzene (NB) reduction were studied. Application of an ammonia preparation to the carbon surface produced impregnated carbon saturated at room temperature with a water solution of the ammonia preparation, taken in a volume equal to the volumetric capacity of the carbon. With one impregnation, 2% rhenium was taken up. Catalysts containing more than 5% rhenium were obtained by impregnating the carbon with heating and use of more concentrated solutions. Catalysts made in this way and dried at 100 0 C had the composition Re 2 OH/carbon/. The most active catalysts were those reduced at 200-250 0 C; higher temperatures, up to 300-500 0 C, decreased the activity. Study of the catalytic properties of the rhenium catalysts in a liquid phase reduction of NB showed that the specific activity of rhenium depends only slightly on the content of the active component in the catalyst and is close to the specific activity of palladium and considerably exceeds that of nickel. Study of the effect of the NB concentration and hydrogen pressure on the activity and stability of the 5% rhenium catalyst indicated that with NB concentrations from 50 to 10% the process takes place at an essentially constant rate; the order of the reaction was close to zero with an apparent activation energy of about 7000 cal/mole. At pressures of 15-200 atm the yield with the 5% catalyst was proportional to the hydrogen pressure. A big advantage of the rhenium catalysts in the reduction of NB is their high selectivity. With a higher activity than palladium and nickel catalysts, 5% rhenium catalyst produces a high operating capacity in a wide range of contact charges, which has considerable significance for industrial use in contact apparatus of the column type. Comparison of the costs of rhenium catalysts and granular carbon carrier with those of nickel, platinum, and palladium showed that 5% rhenium catalyst can

Effect of Calcination Temperatures and Mo Modification on Nanocrystalline (γ-χ-Al2O3 Catalysts for Catalytic Ethanol Dehydration

Directory of Open Access Journals (Sweden)

Tharmmanoon Inmanee

2017-01-01

Full Text Available The mixed gamma and chi crystalline phase alumina (M-Al catalysts prepared by the solvothermal method were investigated for catalytic ethanol dehydration. The effects of calcination temperatures and Mo modification were elucidated. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption, transmission electron microscopy (TEM, and NH3-temperature programmed desorption (NH3-TPD. The catalytic activity was tested for ethylene production by dehydration reaction of ethanol in gas phase at atmospheric pressure and temperature between 200°C and 400°C. It was found that the calcination temperatures and Mo modification have effects on acidity of the catalysts. The increase in calcination temperature resulted in decreased acidity, while the Mo modification on the mixed phase alumina catalyst yielded increased acidity, especially in medium to strong acids. In this study, the catalytic activity of ethanol dehydration to ethylene apparently depends on the medium to strong acid. The mixed phase alumina catalyst calcined at 600°C (M-Al-600 exhibits the complete ethanol conversion having ethylene yield of 98.8% (at 350°C and the Mo-modified catalysts promoted dehydrogenation reaction to acetaldehyde. This can be attributed to the enhancement of medium to strong acid with metal sites of catalyst.

Wet catalyst-support films for production of vertically aligned carbon nanotubes.

Science.gov (United States)

Alvarez, Noe T; Hamilton, Christopher E; Pint, Cary L; Orbaek, Alvin; Yao, Jun; Frosinini, Aldo L; Barron, Andrew R; Tour, James M; Hauge, Robert H

2010-07-01

A procedure for vertically aligned carbon nanotube (VA-CNT) production has been developed through liquid-phase deposition of alumoxanes (aluminum oxide hydroxides, boehmite) as a catalyst support. Through a simple spin-coating of alumoxane nanoparticles, uniform centimer-square thin film surfaces were coated and used as supports for subsequent deposition of metal catalyst. Uniform VA-CNTs are observed to grow from this film following deposition of both conventional evaporated Fe catalyst, as well as premade Fe nanoparticles drop-dried from the liquid phase. The quality and uniformity of the VA-CNTs are comparable to growth from conventional evaporated layers of Al(2)O(3). The combined use of alumoxane and Fe nanoparticles to coat surfaces represents an inexpensive and scalable approach to large-scale VA-CNT production that makes chemical vapor deposition significantly more competitive when compared to other CNT production techniques.

Investigation and development of heavy oil upgrading catalysts. 3

Energy Technology Data Exchange (ETDEWEB)

Lee, D.K.; Lee, I.C.; Yoon, W.L.; Lee, H.T.; Chung, H.; Hwang, Y.J.; Park, S.H. [Korea Inst. of Energy Research, Taejon (Korea, Republic of)

1995-12-01

This study aimed at the domestic development of HDS catalysts which are most fundamental and wide-used in the petroleum refinery. In this year, some experimental works were conducted for developing the effective utilization technology of the novel dispersed-catalysts in the hydro-desulfurization of heavy oils, and improving the reaction performance of alumina-supported Mo-based hydro-treating catalysts conventionally used in most of refineries. First, it was experimentally proved that the dispersed catalysts of Co-Mo could be employed for the hydro-desulfurization of a heavy atmospheric residual oil excluding the catalyst deactivation. The utilization of a carbon-expanded reactor in combination with this dispersed catalyst system exhibited an enhanced reaction performance and provided an efficient way for the separation and recovery of the dispersed catalytic component from oils. Second, the tungsten-incorporated WCoMo/{gamma}-Al{sub 2}O{sub 3} catalyst revealed the improved catalytic performance in the various hydro-treating reactions and in the initial deactivation rates for the high pressure hydro-treatment of a heavy oil as compared with the commercial CoMo/{gamma}-Al{sub 2}O{sub 3} catalyst. This new experimental finding for the promoting role of the monomeric WO{sub 3} species in CoMo/{gamma}-Al{sub 2}O{sub 3} catalyst may be generally applicable to the Mo-based alumina-sulfide phase, higher catalytic activity, and more extended service life. (author). 101 refs., 33 figs., 18 tabs.

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2007-03-31

The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of a mesoporous aluminosilicate catalyst, AlSBA-15. The Al-SBA-15 mesoporous catalyst contains strong Br{umlt o}nsted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt % Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at a temperature of 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into a psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst is being evaluated for the conversion of a heavy petroleum feedstock to naphtha and middle distillates. This phase was significantly delayed during the past six months due to a serious malfunction of the fume hoods in the Clark Atlanta University's Research Center for Science and Technology, where the project is being conducted. The fume hood system was repaired and the catalyst evaluation is now underway.

Interfacial charge distributions in carbon-supported palladium catalysts

DEFF Research Database (Denmark)

Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

2017-01-01

Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

International Nuclear Information System (INIS)

Wu, Hua-Yi; Wang, Hai-Bo; Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua; Huang, Chuan-Jing; Weng, Wei-Zheng; Wan, Hui-Lin

2015-01-01

Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N 2 -adsorption, XRD, SEM, Raman, XPS, EPR and H 2 -TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO) 2 P 2 O 7 . All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO 4 phases and the influence of Sm were also described and discussed

Tin-antimony oxide oxidation catalysts

Energy Technology Data Exchange (ETDEWEB)

Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

1998-12-15

Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

Impact of H2/CO ratios on phase and performance of Mn-modified Fe-based Fischer Tropsch synthesis catalyst

International Nuclear Information System (INIS)

Ding, Mingyue; Yang, Yong; Li, Yongwang; Wang, Tiejun; Ma, Longlong; Wu, Chuangzhi

2013-01-01

Highlights: ► Decreasing H 2 /CO ratio facilitated the conversion of Fe 3 O 4 to iron carbides on the surface layers. ► The formation of surface carbonaceous species was promoted in higher CO partial pressure. ► The formation of iron carbides on the surface of Fe 3 O 4 provided the FTS active sites. ► Decreasing H 2 /CO ratio promoted the product shifting towards heavy hydrocarbons. - Abstract: Impacts of H 2 /CO ratios on both the bulky and surface compositions of an iron–manganese based catalyst were investigated by XRD, MES, N 2 -physisorption, XPS and LRS. Fischer–Tropsch (F–T) synthesis performances were studied in a slurry-phase continuously stirred tank reactor. The characterization results showed that the fresh catalyst was comprised of the hematite, which was converted firstly to Fe 3 O 4 , and then carburized to iron carbides in both the bulk and surface regions under different H 2 /CO ratios atmosphere. Pretreatment in lower H 2 /CO ratio facilitated the formation of iron carbides on the surface of magnetite and surface carbonaceous species. During the F–T synthesis reaction, the catalyst reduced in lower H 2 /CO ratio presented higher catalytic activity, which is assigned probably to the formation of more iron carbides (especially for χ-Fe 5 C 2 ) on the surface of magnetite. The increase of CO partial pressure promoted the product distribution shifting towards heavy hydrocarbons

Electrochemically induced C-H functionalization using bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl dual redox catalysts in a two-phase electrolytic system

International Nuclear Information System (INIS)

Li, Chao; Zeng, Cheng-Chu; Hu, Li-Ming; Yang, Feng-Lin; Yoo, Seung Joon; Little, R. Daniel

2013-01-01

Highlights: •Electrocatalytic C-H bond functionalization of tetrahydroisoquinolines is reported. •The transformation is mediated by a bromide ion/TEMPO dual redox catalyst system. •The transformation is conducted in a two-phase electrolytic medium. •The mechanism is proposed to proceed via a sequence of oxidation and addition reactions involving water as a nucleophile. •The procedure features wide substrate scope, the use of mild reaction conditions. -- Abstract: The electrochemical oxidative functionalization of benzylic C-H bonds, mediated by a dual bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) redox catalyst system in a two-phase electrolytic medium, has been explored using cyclic voltammetry (CV) and preparative electrolysis techniques. The results show that electron transfer between TEMPO + and a neutral substrate occurs with an efficiency that depends upon the presence of a base. The preparative scale electrolysis led to the formation of dihydro-isoquinolinones, isochromanone and xanthenone in moderate to excellent yields. On the basis of the CV analysis and preparative electrolysis results, a reaction mechanism is proposed

Identification of phase-II metabolites of flavonoids by liquid chromatography-ion-mobility spectrometry-mass spectrometry.

Science.gov (United States)

Chalet, Clément; Hollebrands, Boudewijn; Janssen, Hans-Gerd; Augustijns, Patrick; Duchateau, Guus

2018-01-01

Flavonoids are a class of natural compounds with a broad range of potentially beneficial health properties. They are subjected to an extensive intestinal phase-II metabolism, i.e., conjugation to glucuronic acid, sulfate, and methyl groups. Flavonoids and their metabolites can interact with drug transporters and thus interfere with drug absorption, causing food-drug interactions. The site of metabolism plays a key role in the activity, but the identification of the various metabolites remains a challenge. Here, we developed an analytical method to identify the phase-II metabolites of structurally similar flavonoids. We used liquid chromatography-ion-mobility spectrometry-mass spectrometry (LC-IMS-MS) analysis to identify phase-II metabolites of flavonols, flavones, and catechins produced by HT29 cells. We showed that IMS could bring valuable structural information on the different positional isomers of the flavonols and flavones. The position of the glucuronide moiety had a strong influence on the collision cross section (CCS) of the metabolites, with only minor contribution of hydroxyl and methyl moieties. For the catechins, fragmentation data obtained from MS/MS analysis appeared more useful than IMS to determine the structure of the metabolites, mostly due to the high number of metabolites formed. Nevertheless, CCS information as a molecular fingerprint proved to be useful to identify peaks from complex mixtures. LC-IMS-MS thus appears as a valuable tool for the identification of phase-II metabolites of flavonoids. Graphical abstract Structural identification of phase-II metabolites of flavonoids using LC-IMS-MS.

Application in industry and energy production of active carbon/cobalt catalyst for nitrogen oxide neutralization

International Nuclear Information System (INIS)

Mekhandzhiev, D.; Nikolov, R.; Lyutskanov, L.; Dushanov, D.; Lakov, L.

1997-01-01

A new material for neutralization of nitrogen oxides is presented. Two or three metals containing catalysts with a good activity and selectivity towards NO x have been obtained. Preparation of carbon catalysts by deposition of the active phase precursor on the initial carbon material prior to activation is considered as the most promising method. An active carbon-based catalyst (AC/Co) has been synthesized Apricot shells preliminary impregnated with a water-alcohol solution of Co nitrate have been used as initial carbon material. after drying they have been subjected to one-phase steam pyrolysis using a fix-bed reactor. The catalyst thus obtained has a specific surface area (BET) of 53 m 2 g -1 , a favorable mesopore volume/total volume ratio (about 0.85) determined by nitrogen adsorption, a suitable mesopore distribution, about 70% of the mesopores being characterized by r p larger than 25 A and a high dispersion of the Co oxide phase. In addition the catalyst possesses the necessary mechanical resistance. The catalyst has exhibited a high activity with respect to NO x reduction with CO at low temperatures (at 150-250 o C which are the temperatures of industrial flue gases, nO conversion up to 60-95% occurs) and a high selectivity. No presence of H 2 O has been established over the whole temperature range (100-300 o C). An additional advantage of the catalyst is the fact that the amount of CO above 150 o C is lower than the stoichiometric which indicates parallel participation in the process of both the active phase and the support (active carbon) It is also important that the presented catalyst has a low price due to the use of waste products from agriculture and the elimination of special thermal treatment of the supported Co nitrate. There are possibilities of using of other organic wastes from agriculture as well as wastes obtained during flotation of coal. (author)

Study on Endurance and Performance of Impregnated Ruthenium Catalyst for Thruster System.

Science.gov (United States)

Kim, Jincheol; Kim, Taegyu

2018-02-01

Performance and endurance of the Ru catalyst were studied for nitrous oxide monopropellant thruster system. The thermal decomposition of N2O requires a considerably high temperature, which make it difficult to be utilized as a thruster propellant, while the propellant decomposition temperature can be reduced by using the catalyst through the decomposition reaction with the propellant. However, the catalyst used for the thruster was frequently exposed to high temperature and high-pressure environment. Therefore, the state change of the catalyst according to the thruster operation was analyzed. Characterization of catalyst used in the operation condition of the thruster was performed using FE-SEM and EDS. As a result, performance degradation was occurred due to the volatilization of Ru catalyst and reduction of the specific surface area according to the phase change of Al2O3.

Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

Energy Technology Data Exchange (ETDEWEB)

Jackson, N.B.; Kohler, S.; Harrington, M. [Sandia National Lab., Albuquerque, NM (United States)] [and others

1995-12-31

The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

Study on the influence of nickel and Al{sub 2}O{sub 3} support on MoS{sub 2} as hydrodenitrogenation catalysts

Energy Technology Data Exchange (ETDEWEB)

Hein, J.; Hrabar, A.; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Catalysis Research Center

2012-07-01

Alumina-supported Mo and Ni-Mo catalysts as well as an unsupported NiMo catalyst were characterized and tested in the hydrodenitrogenation (HDN) of quinoline in the presence of dibenzothiophene (DBT). The supported catalysts had a well dispersed MoS{sub 2} phase with an average stacking degree around two and slabs length below 10 nm. The unsupported NiMo sulfide catalyst exhibited long, multistacked MoS{sub 2} slabs and contained segregated Ni{sub x}S{sub y} phases. The formation of the Ni-Mo-S phase in both Ni containing catalysts was verified by X-ray absorption spectroscopy, whereas the concentration of coordinatively unsaturated sites was higher for the supported Mo and Ni-Mo catalysts than for the unsupported one. All catalysts were active in the HDN of quinoline and hydrodesulfurization of DBT. The catalytic activity increased in the order Mo/Al{sub 2}O{sub 3} < NiMo/unsupported < Ni-Mo/Al{sub 2}O{sub 3}. Thus, the influence on the catalytic activity of the promoter metal Ni is more important than the presence of a support due to the formation of the Ni-Mo-S phase (more active than MoS{sub 2}). (orig.)

Studies on recycling and utilization of spent catalysts. Preparation of active hydrodemetallization catalyst compositions from spent residue hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Marafi, Meena; Stanislaus, Antony [Petroleum Refining Department, Petroleum Research and Studies Center, Kuwait Institute for Scientific Research, P.O. Box 24885, Safat (Kuwait)

2007-02-15

Spent catalysts form a major source of solid wastes in the petroleum refining industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al{sub 2}O{sub 3} with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure fixed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst. (author)

Catalysts for Efficient Production of Carbon Nanotubes

Science.gov (United States)

Sun, Ted X.; Dong, Yi

2009-01-01

Several metal alloys have shown promise as improved catalysts for catalytic thermal decomposition of hydrocarbon gases to produce carbon nanotubes (CNTs). Heretofore almost every experiment on the production of carbon nanotubes by this method has involved the use of iron, nickel, or cobalt as the catalyst. However, the catalytic-conversion efficiencies of these metals have been observed to be limited. The identification of better catalysts is part of a continuing program to develop means of mass production of high-quality carbon nanotubes at costs lower than those achieved thus far (as much as $100/g for purified multi-wall CNTs or $1,000/g for single-wall CNTs in year 2002). The main effort thus far in this program has been the design and implementation of a process tailored specifically for high-throughput screening of alloys for catalyzing the growth of CNTs. The process includes an integral combination of (1) formulation of libraries of catalysts, (2) synthesis of CNTs from decomposition of ethylene on powders of the alloys in a pyrolytic chemical-vapor-decomposition reactor, and (3) scanning- electron-microscope screening of the CNTs thus synthesized to evaluate the catalytic efficiencies of the alloys. Information gained in this process is put into a database and analyzed to identify promising alloy compositions, which are to be subjected to further evaluation in a subsequent round of testing. Some of these alloys have been found to catalyze the formation of carbon nano tubes from ethylene at temperatures as low as 350 to 400 C. In contrast, the temperatures typically required for prior catalysts range from 550 to 750 C.

Novel sample preparation for operando TEM of catalysts

International Nuclear Information System (INIS)

Miller, Benjamin K.; Barker, Trevor M.; Crozier, Peter A.

2015-01-01

A new TEM sample preparation method is developed to facilitate operando TEM of gas phase catalysis. A porous Pyrex-fiber pellet TEM sample was produced, allowing a comparatively large amount of catalyst to be loaded into a standard Gatan furnace-type tantalum heating holder. The increased amount of catalyst present inside the environmental TEM allows quantitative determination of the gas phase products of a catalytic reaction performed in-situ at elevated temperatures. The product gas concentration was monitored using both electron energy loss spectroscopy (EELS) and residual gas analysis (RGA). Imaging of catalyst particles dispersed over the pellet at atomic resolution is challenging, due to charging of the insulating glass fibers. To overcome this limitation, a metal grid is placed into the holder in addition to the pellet, allowing catalyst particles dispersed over the grid to be imaged, while particles in the pellet, which are assumed to experience identical conditions, contribute to the overall catalytic conversion inside the environmental TEM cell. The gas within the cell is determined to be well-mixed, making this assumption reasonable. - Highlights: • High in-situ conversion of CO to CO 2 achieved by a novel TEM sample preparation method. • A 3 mm fiber pellet increases the TEM sample surface area by 50×. • Operando atomic resolution is maintained by also including a 3 mm grid in the sample. • Evidence for a well-mixed gas composition inside the ETEM cell is given

Damping characteristic identification of non-linear soil-structural system interaction by phase resonance

International Nuclear Information System (INIS)

Poterasu, V.F.

1984-01-01

It is presented a method and the phase resonance for damping characteristic identification of non-linear soil-structural interaction. The algorithm can be applied in case of any, not necessarily, damping characteristic of the system examined. For the identification, the system is harmonically excited and are considered the super-harmonic amplitudes for odd and even powers of the x. The response of shear beam system for different levels of base excitation and for different locations of the load is considered. (Author) [pt

Catalysts, methods of making catalysts, and methods of use

KAUST Repository

Renard, Laetitia; El Eter, Mohamad; Caps, Valerie; Basset, Jean-Marie

2014-01-01

Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

Catalysts, methods of making catalysts, and methods of use

KAUST Repository

Renard, Laetitia

2014-03-06

Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

Conversion of glycerol to polyglycerol over waste duck-bones as a catalyst in solvent free etherification process

Science.gov (United States)

Ayoub, Muhammad; Sufian, Suriati; Mekuria Hailegiorgis, Sintayehu; Ullah, Sami; Uemura, Yoshimitsu

2017-08-01

The alkaline catalyst derived from the duck-bones was used for conversion of glycerol to polyglycerol via solvent free etherification process. The physicochemical properties of prepared materials were duck-bones were systematically investigated as a catalyst by latest techniques of Thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface properties. TGA showed different trends of duck-bones decomposition from room temperature to 1000C. XRD pattern showed a clear and sharp peaks of a crystalline phase of CaO. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. The prepared catalyst derived from duck-bones provided high activity (99 %) for glycerol conversion and around 68 % yield for polyglycerol production. These ample wastes of duck-bones have good potential to be used as polyglycerol production catalysts due to have high quantity of Ca compare to other types of bones like cow, chicken and fish bones.

Dimethyl carbonate synthesis via transesterification of propylene carbonate with methanol by ceria-zinc catalysts: Role of catalyst support and reaction parameters

Energy Technology Data Exchange (ETDEWEB)

Kumar, Praveen; Srivastava, Vimal Chandra; Mishra, Indra Mani [Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand (India)

2015-09-15

Ceria and zinc oxide catalyst were impregnated onto various oxide supports, namely Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, individually by deposition-coprecipitation method. The synthesized catalysts (CZA, CZS and CZT having supports Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, respectively) were characterized by X-ray diffraction (XRD), NH{sub 3}- and CO{sub 2}-temperature programmed desorption (TPD) and N2 adsorption. These catalysts were used for synthesis of dimethyl carbonate (DMC) from methanol and propylene carbonate in a batch reactor. CZS was found to have larger average grain size as compared to CZA and CZT. Composite oxides (catalysts) were found to contain individual phases of ZnO, CeO{sub 2} and some spinel forms of Zn, Ce along with their supports. CZS having highest basicity and surface area showed better catalytic activity as compared to CZA and CZT. Effect of reaction temperature and methanol/PC molar ratio on DMC yield was studied and a reaction mechanism has been discussed. Maximum DMC yield of 77% was observed with CZS catalyst at 170 .deg. C with methanol/PC molar ratio of 10.

Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions

DEFF Research Database (Denmark)

Kim, Jiwhan; Roh, Chi-Woo; Sahoo, Suman Kalyan

2018-01-01

Single atomic Pt catalyst can offer efficient utilization of the expensive platinum and provide unique selectivity because it lacks ensemble sites. However, designing such a catalyst with high Pt loading and good durability is very challenging. Here, single atomic Pt catalyst supported on antimony...... functional theory calculations show that replacing Sb sites with Pt atoms in the bulk phase or at the surface of SbSn or ATO is energetically favorable. The Pt1/ATO shows superior activity and durability for formic acid oxidation reaction, compared to a commercial Pt/C catalyst. The single atomic Pt...... structure is retained even after a harsh durability test, which is performed by repeating cyclic voltammetry in the range of 0.05–1.4 V for 1800 cycles. A full cell is fabricated for direct formic acid fuel cell using the Pt1/ATO as an anode catalyst, and an order of magnitude higher cell power is obtained...

Alternative SILP-SCR Catalysts based on Guanidinium Chromates

DEFF Research Database (Denmark)

Due-Hansen, Johannes; Riisager, Anders; Ståhl, Kenny

There is an increasing global concern about human caused emissions of pollutants like sulfur and nitrogen oxides to the atmosphere leading to, e.g. smog and acid rain damaging to the human health and the environment. Selective catalytic reduction (SCR) of NOx with ammonia as reductant is the most...... duct. There is therefore a demand for alkali-resistant SCR catalysts more flexible regarding temperature of operation and position in the duct. Supported ionic liquid phase (SILP) catalysts with 1,1,3,3-Tetramethylguanidinium (TMGH+) and a chromium oxide anion supported on anatase have exhibited...

Magnetism for understanding catalyst analysis of purified carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Bellouard, Christine; Mercier, Guillaume; Cahen, Sébastien; Ghanbaja, Jaafar; Medjahdi, Ghouti [Institut Jean Lamour, CNRS-Université de Lorraine, BP 70239, 54506 Vandoeuvre-lès-Nancy (France); Gleize, Jérôme [Laboratoire de Chimie Physique-Approche Multi-échelle de Milieux Complexes-Université de Lorraine, 1 Bd Arago, 57078 Metz (France); Lamura, Gianrico [CNR-SPIN – Dipartimento di Fisica, via Dodecaneso 33, 16146 Genova (Italy); Hérold, Claire [Institut Jean Lamour, CNRS-Université de Lorraine, BP 70239, 54506 Vandoeuvre-lès-Nancy (France); Vigolo, Brigitte, E-mail: Brigitte.Vigolo@univ-lorraine.fr [Institut Jean Lamour, CNRS-Université de Lorraine, BP 70239, 54506 Vandoeuvre-lès-Nancy (France)

2016-08-01

The precise quantification of catalyst residues in purified carbon nanotubes is often a major issue in view of any fundamental and/or applicative studies. More importantly, since the best CNTs are successfully grown with magnetic catalysts, their quantification becomes strictly necessary to better understand intrinsic properties of CNT. For these reasons, we have deeply analyzed the catalyst content remained in nickel–yttrium arc-discharge single walled carbon nanotubes purified by both a chlorine-gas phase and a standard acid-based treatment. The study focuses on Ni analysis which has been investigated by transmission electron microscopy, X-ray diffraction, thermogravimetry analysis, and magnetic measurements. In the case of the acid-based treatment, all quantifications result in a decrease of the nanocrystallized Ni by a factor of two. In the case of the halogen gas treatment, analysis and quantification of Ni content is less straightforward: a huge difference appears between X-ray diffraction and thermogravimetry results. Thanks to magnetic measurements, this disagreement is explained by the presence of Ni{sup 2+} ions, belonging to NiCl{sub 2} formed during the Cl-based purification process. In particular, NiCl{sub 2} compound appears under different magnetic/crystalline phases: paramagnetic or diamagnetic, or well intercalated in between carbon sheets with an ordered magnetic phase at low temperature. - Highlights: • Cl-gas treatment of Ni catalyst of carbon nanotubes leads to NiCl{sub 2} residue. • Magnetic measurements show the transformation of Ni{sup 0} in Ni{sup 2+}through a purification process. • High temperature Cl treatment removes 75% of metallic impurities. • Cl-purification yields to an amount of metal of 1.5% in arc-discharge CNT samples.

Session 6: Liquid-phase chloro-benzene hydrogenolysis over alkali-doped zirconia supported palladium catalysts

Energy Technology Data Exchange (ETDEWEB)

Aramendia, M.A.; Borau, V.; Jimenez, C.; Marinas, A.; Marinas, J.M.; Moreno, J.M.; Ruiz, J.R.; Urbano, F.J. [University of Cordoba. Marie Curie Building, Dept. of Organic Chemistry (Spain)

2004-07-01

Chlorinated hydrocarbons constitute one of the most important kind of organic pollutants due to their environmental impact and noxious effects. Catalytic hydro-dehalogenation is now emerging as a promising non-destructive alternative technology whereby the chlorinated waste is converted to products with a commercial value. It is simple, safe, effective, and it ensures, in many instances, the regeneration of the initial raw material. One of the main problems of catalytic hydro-dehalogenation arise from the deactivating effect of the hydrogen halide released as by product. This can be surpassed by, for example, adding a base, such as NaOH, or modification of the catalyst in order to neutralize the hydrogen halide released. In conclusion, the alkali modification of the zirconia supported catalysts did not enhance the catalytic activity in comparison to the undoped Pd/ZrO{sub 2}. Moreover, the lithium doped catalyst exhibits very poor results in initial rate and final chloro-benzene conversion. This could be related to the reduction in BET surface area caused by the doping together with a lower enhancement of the surface basicity of the doped catalysts. (authors)

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

Science.gov (United States)

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

Deactivation-resistant catalyst for selective catalyst reduction of NOx

DEFF Research Database (Denmark)

2011-01-01

The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

Investigation of the promoting effect of Mn on a Pt/C catalyst for the steam and aqueous phase reforming of glycerol

Energy Technology Data Exchange (ETDEWEB)

Bossola, Filippo; Pereira-Hernández, Xavier Isidro; Evangelisti, Claudio; Wang, Yong; Dal Santo, Vladimiro

2017-05-01

The catalytic performances in steam reforming (SR) and aqueous phase reforming (APR) of glycerol of a bimetallic Pt-Mn catalyst supported on activated carbon are investigated and correlated with the surface properties of the catalyst. Under SR conditions, Mn showed a significant promoting effect over Pt/C, both in terms of hydrogen production rate and conversion, with a higher selectivity toward the glycerol dehydration products. Upon addition of Mn the amount of strong Lewis acid sites increased, promoting the dehydration of glycerol and favoring the CAO over CAC cleavage at expenses of hydrogen selectivity. Conversely, under APR conditions, a slightly higher hydrogen selectivity and only minimal enhancement in hydrogen production were found, while the products selectivity was comparable to Pt/C. Most of Mn leached into the aqueous media, but the remaining (<5% of the fresh parent sample) might be alloyed with Pt and promote the CO desorption from neighbor Pt sites.

Automatic Identification System (AIS) Transmit Testing in Louisville Phase 2

Science.gov (United States)

2014-08-01

Firewall Louisville QM 65.206.28.x NAIS Site Controller PC RS232 Serial cable TV32 Computer Cmd Center Serial splitter SAAB R40 AIS Base Station...172.17.14.6 Rack mount computer AIS Radio Interface Ethernet Switch 192.168.0.x Firewall Cable Modem 192.168.0.1 VTS Accred. Boundary serial connection...Automatic Identification System ( AIS ) Transmit Testing in Louisville Phase 2 Distribution Statement A: Approved for public release

A study on the isotopic exchange between hydrogen and water on a catalyst in the liquid phase; Etude de l'echange isotopique entre l'hydrogene et l'eau sur catalyseur en phase liquide

Energy Technology Data Exchange (ETDEWEB)

Dirian, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Montarnal, R; Balaceanu, J C [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France)

1958-07-01

It is well known that catalytic exchange in the liquid phase offers many advantages over exchange in the gaseous phase; however the rate of reaction is much smaller in the former case. The object of the following work is to study the influence of the various parameters on which the reaction rate depends (pressure, temperature, concentration, agitation), to classify catalysts according to their activity and to determine the economic possibility of liquid phase exchange. (author) [French] Il est un fait bien connu que l'echange catalytique en phase liquide presente divers avantages, compare a l'echange en phase gazeuse; la vitesse de reaction est toute fois beaucoup plus faible que dans le premier cas. L'objet du present rapport est d'etudier l'influence des differents parametres agissant sur la vitesse de reaction (pression, temperature, concentration, agitation), de classer les catalyseurs en fonction de leur activite et d'evaluer les possibilites economiques de l'echange en phase liquide. (auteur)

Bimetallic catalysts for continuous catalytic wet air oxidation of phenol.

Science.gov (United States)

Fortuny, A; Bengoa, C; Font, J; Fabregat, A

1999-01-29

Catalytic wet oxidation has proved to be effective at eliminating hazardous organic compounds, such as phenol, from waste waters. However, the lack of active long-life oxidation catalysts which can perform in aqueous phase is its main drawback. This study explores the ability of bimetallic supported catalysts to oxidize aqueous phenol solutions using air as oxidant. Combinations of 2% of CoO, Fe2O3, MnO or ZnO with 10% CuO were supported on gamma-alumina by pore filling, calcined and later tested. The oxidation was carried out in a packed bed reactor operating in trickle flow regime at 140 degrees C and 900 kPa of oxygen partial pressure. Lifetime tests were conducted for 8 days. The pH of the feed solution was also varied. The results show that all the catalysts tested undergo severe deactivation during the first 2 days of operation. Later, the catalysts present steady activity until the end of the test. The highest residual phenol conversion was obtained for the ZnO-CuO, which was significantly higher than that obtained with the 10% CuO catalyst used as reference. The catalyst deactivation is related to the dissolution of the metal oxides from the catalyst surface due to the acidic reaction conditions. Generally, the performance of the catalysts was better when the pH of the feed solution was increased.

TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

International Nuclear Information System (INIS)

Burtron H. Davis

1999-01-01

The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe(sub 3)O(sub 4). Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to(epsilon)(prime)-Fe(sub 2.2)C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to(chi)-Fe(sub 5)C(sub 2) and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe(sub 3)O(sub 4); however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94%(chi)-Fe(sub 5)C(sub 2), deactivated rapidly as the carbide was oxidized to Fe(sub 3)O(sub 4). No difference in activity, stability or deactivation rate was found for(chi)-Fe(sub 5)C(sub 2) and(epsilon)(prime)-Fe(sub 2.2)C

TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

Energy Technology Data Exchange (ETDEWEB)

Burtron H. Davis

1999-04-30

The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe{sub 3}O{sub 4}. Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to {epsilon}{prime}-Fe{sub 2.2}C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to {chi}-Fe{sub 5}C{sub 2} and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe{sub 3}O{sub 4}; however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94% {chi}-Fe{sub 5}C{sub 2}, deactivated rapidly as the carbide was oxidized to Fe{sub 3}O{sub 4}. No difference in activity, stability or deactivation rate was found for {chi}-Fe{sub 5}C{sub 2} and {epsilon}{prime}-Fe{sub 2.2}C.

Investigation of hydrodynamic behavior of a pilot-scale trickle bed reactor packed with hydrophobic catalyst using radiotracer technique

International Nuclear Information System (INIS)

Kumar, Rajesh; Mohan, Sadhana; Pant, H.J.; Sharma, V.K.; Mahajani, S.M.

2010-01-01

Exchange of isotopes of hydrogen between aqueous phase and hydrogen gas is one of the most efficient methods for separation of hydrogen isotopes and is commonly used for production of heavy water or removal of tritium from tritiated water effluents. The isotope exchange reaction can be effectively executed in a counter-current trickle bed reactor (TBR) packed with a novel metal (Pt, Pd, Ni) based hydrophobic catalyst as the conventional novel metal based hydrophilic catalysts become ineffective after they come in contact with liquid effluents. The overall exchange reaction in the TBR mainly consists of a gas-liquid mass transfer process that transfers reactants from liquid to gaseous phase followed by an isotopic exchange reaction between the reactants in gaseous phase in presence of a solid hydrophobic catalyst. However, due to water repellent nature of the catalyst, poor liquid distribution in the reactor is normally observed that deteriorates the gas-liquid mass transfer. Therefore, it was thought that if a mixture of hydrophobic catalyst and a suitable hydrophilic mass transfer packing is used to fill the TBR column then, it can improve the distribution or mixing of the liquid and gas phase and thus improve the gas-liquid mass transfer and overall performance of the reactor and needs to be confirmed

SELECTIVE HYDROGENATION OF CINNAMALDEHYDE WITH Pt AND Pt-Fe CATALYSTS: EFFECTS OF THE SUPPORT

Directory of Open Access Journals (Sweden)

A.B. da Silva

1998-06-01

Full Text Available Low-temperature reduced TiO2-supported Pt and Pt-Fe catalysts are much more active and selective for the liquid–phase hydrogenation of cinnamaldehyde to unsaturated cinnamyl alcohol than the corresponding carbon-supported catalysts. High-temperature reduced catalysts, where the SMSI effect should be present, are almost inactive for this reaction. There is at present no definitive explanation for this effect but an electronic metal-support interaction is most probably involved.

Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

Science.gov (United States)

Ghampson, Isaac Tyrone

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the

Influence of ni addition to a low-loaded palladium catalyst on the selective hydrogenation of 1-heptyne

Directory of Open Access Journals (Sweden)

Cecilia R. Lederhos

2010-01-01

Full Text Available Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%. The most active prepared catalyst, PdNi(1%, was more selective than the Lindlar catalyst.

Radiation modification of vanadium catalyst for anthracene oxidation

International Nuclear Information System (INIS)

Norek, J.; Vymetal, J.; Mucka, V.; Pospisil, M.; Cabicar, J.

1985-01-01

Vanadium pentoxide on a suitable carrier is often used as catalyst for the oxidation of anthracene in the gaseous phase to 9,10-anthraquinone. The activity and selectivity of the catalyst may be affected by irradiation. The effects were studied of gamma radiation on the properties of the catalyst where the active system was a V 2 O 5 -KOH-K 2 SO 4 mixture on a Al 2 O 3 +SiO 2 carrier. The 60 Co radiation source had an activity of 185 TBq; the carrier of the catalyst was irradiated at a dose rate of 3.05, 1.98 and 0.084 kGy/h to a total dose of 10 kGy. Irradiation increased the selectivity of the catalyst such that in the oxidation temperature optimum of 300 to 400 degC the yield of 9,10-anthraquinone increased by 4.6 to 4.8 %mol. to roughly 90 %mol.; a significant reduction of the content of acid components (phthalanhydride) in the oxidation product also occurred. This effect remained unchanged for 5 months after irradiation. A reduction of selectivity was observed at lower dose rates only in the temperature range between 400 and 480 degC. (A.K.)

Synthesis and essay of an Ionomer like catalyst of olefins epoxidation

International Nuclear Information System (INIS)

Boyaca Mendivelso, Alejandro; Tempesti, Ezio

1995-01-01

The purpose of the present work is the preparation of an ionomer with base in Molybdenum and to evaluate its activity like catalyst of olefins epoxidation like alternative of synthesis of catalysts of the Hawk process. A polymer is synthesized with available functional groups to stabilize the metal starting from sodium molybdate; the characterization is made by atomic absorption, spectroscopy to GO, and X.P.S. The characterization indicates that indeed it is possible to stabilize the Mo in the main polymeric. The evaluation in reaction in liquid phase allows similar conversions to those of a homogeneous catalyst. The selective epoxidation of olefins for alkyl hydroperoxides, it has acquired great importance inside the industrial processes obtaining of propylene oxide due to the recent use of the terbutilic alcohol (co-produced together with the epoxide), as preservative in gasoline free of lead. In the environment of these processes, and in particular in the Hawk process possibilities of technological innovation, in the concerning to the heterogenization of conventional catalysts, at the moment used in homogeneous phase. The present work collaborate to some tentative that look for to generate alternative of preparation of catalysts for the process Hawk, synthesizing and testing the activity of an ionomer like epoxidation catalyst, which tries to reproduce the chemical structure of the complexes organ-metallic pear to suppress the separation stages and necessary recovery facilitating its recurrent reutilization with eventual economic repercussions in the industrial process. It is described the procedure of synthesis of the ionomer, the characterization and the evaluation of the activity in reaction under diverse conditions. Of the made characterization it comes off that the heterogenization of catalysts for olefins epoxidation, according to the Hawk process, is possible by means of the preparation of polymers modified appropriately. Likewise the evaluation in

Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Final report

Energy Technology Data Exchange (ETDEWEB)

Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

1993-02-01

This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275{degrees}C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

Diesel Emission Control- Sulfur Effects (DECSE) Program- Phase II Summary Report: NOx Adsorber Catalysts; FINAL

International Nuclear Information System (INIS)

None

2000-01-01

The investigations performed in this project demonstrated the ability to develop a NO(sub x) regeneration strategy including both an improved lean/rich modulation cycle and rich engine calibration, which resulted in a high NO(sub x) conversion efficiency over a range of operating temperatures. A high-temperature cycle was developed to desulfurize the NO(sub x) absorber catalyst. The effectiveness of the desulfurization process was demonstrated on catalysts aged using two different sulfur level fuels. The major findings of this project are as follows: (1) The improved lean/rich engine calibration achieved as a part of this test project resulted in NO(sub x) conversion efficiencies exceeding 90% over a catalyst inlet operating temperature window of 300 C-450 C. This performance level was achieved while staying within the 4% fuel economy penalty target defined for the regeneration calibration. (2) The desulfurization procedure developed showed that six catalysts, which had been exposed to fuel sulfur levels of 3-, 16-, and 30-ppm for as long as 250 hours, could be recovered to greater than 85% NO(sub x) conversion efficiency over a catalyst inlet operating temperature window of 300 C-450 C, after a single desulfurization event. This performance level was achieved while staying within the 4% fuel economy penalty target defined for the regeneration calibration. (3) The desulfurization procedure developed has the potential to meet in-service engine operating conditions and provide acceptable driveability conditions. (4) Although aging with 78-ppm sulfur fuel reduced NO(sub x) conversion efficiency more than aging with 3-ppm sulfur fuel as a result of sulfur contamination, the desulfurization events restored the conversion efficiency to nearly the same level of performance. However, repeatedly exposing the catalyst to the desulfurization procedure developed in this program caused a continued decline in the catalyst's desulfurized performance. Additional work will be

Rutile vanadium antimonates. A new class of catalysts for selective reduction of NO with ammonia

Energy Technology Data Exchange (ETDEWEB)

Brazdil, James F.; Ebner, Ann M.; Cavalcanti, Fernando A.P. [BP Chemicals Inc., Cleveland, OH (United States)

1997-12-31

This paper describes a new class of vanadium containing oxide catalysts that are active and selective for the selective catalytic reduction of NO with ammonia. Vanadium antimony oxide based catalysts were found to be effective in the conversion of NO with little or no ammonia slippage when tested using gas mixtures containing between 300 and 700ppm NO. X-ray diffraction analyses of the catalysts show that the dominant phase present in the catalyst is vanadium antimonate having a defect rutile crystal structure. The catalysts are active and selective in the ranges of 400-460C and gas hourly space velocities of 3000-8000h{sup -1}

Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

Science.gov (United States)

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

Science.gov (United States)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

Identification of sigma and chi phases in duplex stainless steels

Energy Technology Data Exchange (ETDEWEB)

Llorca-Isern, Núria, E-mail: nullorca@ub.edu [Departament de Ciència dels Materials i Enginyeria Metallurgica, Facultat de Química, Universitat de Barcelona, Marti-Franqués 1, 08028 Barcelona (Spain); López-Luque, Héctor, E-mail: hlopezlu7@alumnes.ub.edu [Departament de Ciència dels Materials i Enginyeria Metallurgica, Facultat de Química, Universitat de Barcelona, Marti-Franqués 1, 08028 Barcelona (Spain); López-Jiménez, Isabel, E-mail: ilopezji9@alumnes.ub.edu [Departament de Ciència dels Materials i Enginyeria Metallurgica, Facultat de Química, Universitat de Barcelona, Marti-Franqués 1, 08028 Barcelona (Spain); Biezma, Maria Victoria, E-mail: maria.biezma@unican.es [Department of Earth, Materials Science and Engineering, University of Cantabria - UC, Gamazo, 1, 39004 Santander (Spain)

2016-02-15

The aim of this work is to find out the most suitable method for detecting and analyzing accurately the formation conditions of secondary phases, particularly Sigma-phase (σ-phase) and Chi-phase (χ-phase) in duplex stainless steels (UNS S32205 and UNS S32750). The microstructure was characterized after a solution annealing at 1080 °C followed by an isothermal heating at 830 °C for different time ranges, ranging from 1 min to 9 h, in order to enlighten the controversial point concerning the mechanism of χ-phase nucleation in relation with the σ-phase. Etched samples were observed using optical microscopy (MO), and scanning electron microscopy (FESEM) with a backscattered electron detector (BSE) was used on unetched samples. Compositional microanalysis (EDS) was carried out for identifying the different phases present in the steels. Sigma phase was easily observed using different etching procedures, whereas χ-phase was only clearly detected with FESEM–BSE on unetched samples. The compositional analyses showed that the molybdenum content in χ-phase almost doubles the content of this element in σ-phase, and as a result the kinetics of nucleation and growth were also found to be remarkably faster when the alloy content in the steel is higher. In addition, chromium nitrides and carbides were also observed to precipitate as a result of the heat treatments and, in the case of the chromium nitrides, they act as a favorable site for the nucleation of σ-phase and χ-phase. - Highlights: • Microscopy was used on heat treated duplex steels for microstructure identification. • FESEM–BSE observation on unetched samples provided the best contrast between phases. • Analyses of carbides, nitrides, chi and sigma phases were possible by EDS and WDS. • Chromium nitrides act as favorable site for the nucleation of chi and sigma phases. • Secondary phases nucleation kinetics are faster in superduplex than in duplex steels.

Identification of 3-phase flow patterns of heavy oil from pressure drop and flow rate data

Energy Technology Data Exchange (ETDEWEB)

Pacheco, F.; Bannwart, A.C.; Mendes, J.R.P. [Campinas State Univ., Sao Paulo (Brazil); Serapiao, A.B.S. [Sao Paulo State Univ., Sao Paulo (Brazil)

2008-07-01

Pipe flow of oil-gas-water mixtures poses a complex thermo-fluid dynamical problem. This paper examined the relationship between phase flow rates, flow pattern identification, and pressure drop in 3-phase water-assisted heavy oil in the presence of a gaseous phase. An artificial intelligence program called a support vector machine (SVM) was used to determine relevant parameters for flow pattern classification. Data from a 3-phase flow of heavy oil with gas and water in a vertical pipe was used in the study. The data were used to train the machine, which then predicted the flow pattern of the remaining data. Tests with different parameters and training data were then performed. The study showed that the proposed SVM flow pattern identification process accurately predicted flow patterns. It was concluded that the SVM took a relatively short amount of time to train. Future research is needed to apply the tool to larger flow datasets. 5 refs., 1 tab., 2 figs.

Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

Energy Technology Data Exchange (ETDEWEB)

Conrad Ingram; Mark Mitchell

2006-09-30

The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.

UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

Energy Technology Data Exchange (ETDEWEB)

Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei (China); Meng, Da Qiao [Si Chuan Institute of Materials and Technology, Jiang You (China)

2015-10-15

The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads.

UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

International Nuclear Information System (INIS)

Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi; Meng, Da Qiao

2015-01-01

The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads

Plasma and catalyst for the oxidation of NOx

Science.gov (United States)

Jõgi, Indrek; Erme, Kalev; Levoll, Erik; Raud, Jüri; Stamate, Eugen

2018-03-01

Efficient exhaust gas cleaning from NO x (NO and NO2) by absorption and adsorption based methods requires the oxidation of NO. The application of non-thermal plasma is considered as a promising oxidation method but the oxidation of NO by direct plasma remains limited due to the back-reaction of NO2 to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal-oxide catalysts in the improvement of oxidation efficiency for both direct and indirect plasma oxidation of NO x . The plasma produced active oxygen species (O, O3) were shown to play an important role in the reactions taking place on the catalyst surfaces while the exact mechanism and extent of the effect were different for direct and indirect oxidation. In the case of direct plasma oxidation, both short and long lifetime oxygen species could reach the catalyst and participate in the oxidation of NO to NO2. The back-reaction in the plasma phase remained still important factor and limited the effect of catalyst. In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst.

Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

1998-12-31

Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

Effect of preparation method on catalytic activity of Ni/ γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Miranda Morales, Barbara

2017-01-01

The performance of catalysts was shown to be strongly dependent on their methods of preparation. A study to examine the relationship between catalyst preparation procedures and the structure, dispersion, activity, and selectivity of the finished catalyst is reported. 10 wt.%Ni/γ-Al 2 O 3 catalysts were prepared by incipient wetness impregnation and by wet impregnation. The catalysts were used in the conversion of glycerol in gas phase and atmospheric pressure. The selectivity and activity of the catalysts were affected by the preparation method employed. The catalysts were characterized by thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), N 2 -physorption, H 2 -chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and temperature-programmed oxidation (TPO). The Ni particle size and dispersion of the catalysts affected the selectivity to hydrogenolysis and dehydration routes, and the formation of carbon deposits was also affected. (author) [es

An introduction to catalyst

International Nuclear Information System (INIS)

Jeon, Hak Je

1988-11-01

This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

Determination of surface coverage of catalysts : temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

NARCIS (Netherlands)

van den Broek, A.C.M.; Grondelle, van J.; Santen, van R.A.

1999-01-01

The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity

Application of the Rietveld method in structural analysis of catalysts based on CuO/CeO2

International Nuclear Information System (INIS)

Neiva, L.S.; Ribeiro, M.A.; Bispo, A.; Simoes, A.N.; Gama, L.

2011-01-01

This work has as aim to synthesize catalysts composed by CuO/CeO 2 by means two distinct methods of synthesis, they are: combustion synthesis and Pechini. The catalysts composed by CuO/CeO 2 were synthesized with CuO in condition of dopant element. The value of the CuO concentration ranged between 0 and 0.5 mol. Has been done a structural analysis related to how the kind of synthesis method used influences over physical characteristic of the catalytic material. The obtained catalysts were characterized by X-ray diffraction with refinement by Rietveld method. According to results, the synthesized catalysts showed crystalline structures formed mostly by CeO 2 phase, as expected, since this is the host matrix for the dopant element. The catalysts obtained by the Pechini method presented structures with a smaller amount of segregated phases formed by CuO, according to the results of the structural analysis. (author)

Oxidative desulfurization of benzothiophene and thiophene with WO{sub x}/ZrO{sub 2} catalysts: Effect of calcination temperature of catalysts

Energy Technology Data Exchange (ETDEWEB)

Hasan, Zubair; Jeon, Jaewoo [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Jhung, Sung Hwa, E-mail: sung@knu.ac.kr [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

2012-02-29

Highlights: Black-Right-Pointing-Pointer Oxidative desulfurization was studied with WO{sub x}/ZrO{sub 2} calcined at different temp. Black-Right-Pointing-Pointer The importance of the phases of zirconia and tungsten oxide was suggested. Black-Right-Pointing-Pointer The catalyst was analyzed thoroughly with Raman and XRD techniques. Black-Right-Pointing-Pointer The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO{sub x}/ZrO{sub 2} catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO{sub x}/ZrO{sub 2} catalyst is around 700 Degree-Sign C. The most active catalyst is composed of tetragonal zirconia (ZrO{sub 2}) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO{sub 3} and monoclinic ZrO{sub 2} for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO{sub x}/ZrO{sub 2} catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

DEFF Research Database (Denmark)

Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders

2011-01-01

Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...... be suitable for biomass fired power plant SCR applications....

Selective liquid-phase oxidation of alcohols catalyzed by a silver-based catalyst promoted by the presence of ceria

DEFF Research Database (Denmark)

Beier, Matthias Josef; Hansen, Thomas Willum; Grunwaldt, Jan-Dierk

2009-01-01

simultaneously. When a high catalytic conversion (>30% over 2 h) was found the number of catalyst components was reduced in the following tests. Thereby, a collaborative effect between a physical mixture of ceria nanoparticles and silver-impregnated silica (10 wt.% Ag–SiO2) was found. The catalytic activity...... by in situ XAS experiments. Oxygen species incorporated in the silver lattice appear to be important for the catalytic oxidation of the alcohol for which a preliminary mechanism is presented. The application of the catalyst was extended to the oxidation of a wide range of primary and secondary alcohols....... Compared to palladium and gold catalysts, the new silver catalyst performed similarly or even superior in the presence of CeO2. In addition, the presence of ceria increased the catalytic activity of all investigated catalysts....

Gaseous exchange reaction of deuterium between hydrogen and water on hydrophobic catalyst supporting platinum

International Nuclear Information System (INIS)

Izawa, Hirozumi; Isomura, Shohei; Nakane, Ryohei.

1979-01-01

The deuterium exchange reaction between hydrogen and water in the gas phase where the fed hydrogen gas is saturated with water vapor is studied experimentally by use of the proper hydrophobic catalysts supporting platinum. It is found that the activities of those catalysts for this reaction system are very high compared with the other known ones for the systems in which gas and liquid should coexist on catalyst surfaces, and that the apparent catalytic activity becomes larger as the amount of platinum supported on a catalyst particle increases. By analyses of the data the following informations are obtained. The exchange reaction can be expressed by a first order reversible reaction kinetics. The pore diffusion in the catalyst particles has significant effect on the overall reaction mechanisms. (author)

Development of nuclear methods for determining fluid-dynamic parameters in fluid catalyst cracking reactors

International Nuclear Information System (INIS)

Santos, V.A. dos; Dantas, C.C.

1986-01-01

Flow parameters of circulating fluidized bed in a simulated Fluid Catalyst Cracking reactor were determined by means of nuclear methods. The parameters were: residence time, density, inventory, circulation rate and radial distribution, for the catalyst; residence time for the gaseous phase. The nuclear methods where the gamma attenuation and the radiotracer. Two tracer techniques were developed, one for tagging of the catalyst by the 59 Fe as intrinsic tracer and another for tagging of the gaseous phase by the CH 3 82 Br as tracer. A detailed description of each measuring technique for all the investigated parameters is included. To carry out the determination for some of parameters a combination of the two methods was also applied. The results and the nuclear data are given in a table. (Author) [pt

Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

Directory of Open Access Journals (Sweden)

Arshid M. Ali

2015-01-01

Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

Identification of G-phase in aged cast CF 8 type stainless steel

International Nuclear Information System (INIS)

Bentley, J.; Miller, M.K.; Brenner, S.S.; Spitznagel, J.A.

1985-01-01

The microstructure of as-cast and aged CF 8 type stainless steel, used for the primary coolant pipes in pressurized light-water nuclear reactors, is being studied by analytical electron microscopy (AEM) and atom probe field-ion microscopy (APFIM). The phase transformations of the ferrite (approx. 19 vol % of the duplex structure) that occur after aging at 673 K for 7500 h are described by Miller et al. The present work deals with the identification of G-phase (prototype compound Ni 16 Ti 6 Si 7 ) observed in the ferrite of aged material. 2 references, 3 figures

{gamma} alumina- and HY zeolite-supported molybdenum catalysts: characterisation of the oxidic and sulfided phases; Catalyseurs a base de molybdene supporte sur alumine {gamma} et zeolithe HY: caracterisation des phases oxydes et sulfures

Energy Technology Data Exchange (ETDEWEB)

Plazenet, G

2001-10-01

Oxidic precursors of hydro-treatment catalysts (Co)Mo/alumina or zeolite were characterised by Raman spectroscopy, NMR and EXAFS at the Mo and Co K-edges. The formation of an Anderson-type alumino-molybdate compound upon impregnation of the support with an ammonium hepta-molybdate solution was confirmed for alumina, and also observed for the HY zeolitic support, with consumption of the amorphous alumina of the zeolite. In absence of the latter, ammonium hepta-molybdate precipitates. The species are conserved upon drying; upon calcination, the alumino-molybdate evolves into a surface aluminium molybdate type phase, whereas the hepta-molybdate transforms into MoO{sub 3}. The species formed upon impregnation are located in the inter-granular porosity whereas MoO{sub 3} vapor-condensation leads to formation of dimers located inside the zeolitic structure. The study of the cobalt-promoted precursors showed that the evolution of the molybdenum is the same in the case of co-impregnation preparation. Impregnation with cobalt-molybdate prevents the formation of the alumino-molybdate anion and thus enables the preservation of the Mo-Co interaction but, whatever the precursor, the leveling effect of the calcination-re-hydration steps was demonstrated. An EXAFS study at different sulfur coverages of the MoS{sub 2} platelets in the alumina-supported sulfided catalysts showed the limitations of EXAFS for size determination of MoS{sub 2} crystallites, a parameter that can be reached by AWAXS, which also conveys information about sheet-stacking. The EXAFS study of sulfided (Co)Mo/HY systems revealed incomplete sulfidation of the samples and the very high dispersion of the active phase. The absence of an observable Mo-Co interaction whatever the preparation of the promoted catalysts is consistent with the absence of promoting effect in toluene hydrogenation. (author)

Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction

Directory of Open Access Journals (Sweden)

Witold Zielinski

2016-08-01

Full Text Available A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product.

Production of Catalyst-Free Hyperpolarised Ethanol Aqueous Solution via Heterogeneous Hydrogenation with Parahydrogen

Science.gov (United States)

Salnikov, Oleg G.; Kovtunov, Kirill V.; Koptyug, Igor V.

2015-09-01

An experimental approach for the production of catalyst-free hyperpolarised ethanol solution in water via heterogeneous hydrogenation of vinyl acetate with parahydrogen and the subsequent hydrolysis of ethyl acetate was demonstrated. For an efficient hydrogenation, liquid vinyl acetate was transferred to the gas phase by parahydrogen bubbling and almost completely converted to ethyl acetate with Rh/TiO2 catalyst. Subsequent dissolution of ethyl acetate gas in water containing OH- ions led to the formation of catalyst- and organic solvent-free hyperpolarised ethanol and sodium acetate. These results represent the first demonstration of catalyst- and organic solvent-free hyperpolarised ethanol production achieved by heterogeneous hydrogenation of vinyl acetate vapour with parahydrogen and the subsequent ethyl acetate hydrolysis.

Efficient Air Desulfurization Catalysts Derived from Pig Manure Liquefaction Char

Directory of Open Access Journals (Sweden)

Rajiv Wallace

2017-11-01

Full Text Available Biochar from the liquefaction of pig manure was used as a precursor of H2S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl2 in two different ratios of char to an activation agent (1:1 and 1:2 was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 mg/g H2S. Sulfur was the predominant product of reactive adsorption. Its deposition in the pore system and blockage of the most active pores ceased the materials’ activity. The presence of the catalytic phase was necessary but not sufficient to guarantee good performance. The developed porosity, which can store oxidation products in the resulting composite, is essential for the good performance of the desulfurization process. The surface of the composite with nanographite showed the highest catalytic activity, similar to that of the commercial Midas® carbon catalyst. The results obtained indicate that a high quality reactive adsorbent/catalyst for H2S removal can be obtained from pig manure liquefaction wastes.

Electronic Identification of the Parental Phases and Mesoscopic Phase Separation of K_{x}Fe_{2-y}Se_{2} Superconductors

Directory of Open Access Journals (Sweden)

F. Chen

2011-12-01

Full Text Available The nature of the parent compound of a high-temperature superconductor (HTS often plays a pivotal role in determining its superconductivity. The parent compounds of the cuprate HTSs are antiferromagnetically ordered Mott insulators, while those of the iron-pnictide HTSs are metals with spin-density-wave order. Here we report the electronic identification of two insulating parental phases and one semiconducting parental phase of the newly discovered family of K_{x}Fe_{2-y}Se_{2} superconductors. The two insulating phases exhibit Mott-insulator-like signatures, and one of the insulating phases is even present in the superconducting and semiconducting K_{x}Fe_{2-y}Se_{2} compounds. However, it is mesoscopically phase-separated from the superconducting or semiconducting phase. Moreover, we find that both the superconducting and semiconducting phases are free of the magnetic and vacancy orders present in the insulating phases, and that the electronic structure of the superconducting phase could be developed by doping the semiconducting phase with electrons. The rich electronic properties discovered in these parental phases of the K_{x}Fe_{2-y}Se_{2} superconductors provide the foundation for studying the anomalous behavior in this new class of iron-based superconductors.

KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

Directory of Open Access Journals (Sweden)

Mohammad Sadiq

2015-08-01

Full Text Available Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68% and selectivity (100% for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

Moessbauer study on the formation process of Fe-K composition in iron-based catalyst for dehydrogenation of ethylbenzene

International Nuclear Information System (INIS)

Jiang Keyu; Zhao Zhenjie; Yang Xielong

2001-01-01

Fe-K spinel structure is the predecessor of active phase of potassium promoted iron-based catalyst for dehydrogenation of ethylbenzene. Moessbauer spectroscopy has been used to study the formation process of Fe-K spinel structure which depends on the catalyst composition and preparing condition. The results may prove useful for production of industrial catalyst

Synthesis of cerium oxide catalysts supported on MCM-41 molecular sieve

International Nuclear Information System (INIS)

Souza, E.L.S.; Barros, T.R.B.; Sousa, B.V. de

2016-01-01

Porous materials have been widely studied as catalysts and catalyst support. The MCM-41 structure is the one that has been most studied because of its application possibilities in chemical processes. This work aimed to obtain and characterize cerium oxide catalysts supported on MCM-41 molecular sieve. The molecular sieve was synthesized by the conventional method with the following molar composition: 1 SiO2: 0.30 CTABr: NH3 11: 144 H2O. Then, 25% w/w cerium was incorporated into the MCM-41 using the wet impregnation process and the material obtained was activated by calcination. From the XRD patterns was confirmed the structure of the molecular sieve, and were identified the cerium oxide phases in its structure. The textural catalysts characteristics were investigated by isotherms of N2 adsorption/desorption (BET method). (author)

Preparation and performance of Pt/PTFE/Foam SiC as a hydrophobic catalyst for LPCE

International Nuclear Information System (INIS)

He, Jianchao; Wang, Heyi; Xiao, Chengjian; Li, Jiamao; Chen, Ping; Hou, Jingwei

2016-01-01

Highlights: • A new type of foam material, Foam SiC with three-dimensional network structure, was chosen as the carrier of catalyst. • Foam SiC was hydrophobic treated by PTFE, and achieved a good hydrophobic property. • Pt/PTFE/Foam SiC was prepared by impregnation method with Pt-organic solution and gaseous phase reduction method. • The hydrophobic catalysts were packed with Dixon phosphor bronze gauze rings (about 3 mm × 3 mm) in LPCE system to test the catalytic performance. • The effect of different size of the catalyst on LPCE was been tested. - Abstract: Platinum catalysts supported on a composite of polytetrafluoroethylene (PTFE) and Foam SiC (Pt/PTFE/Foam SiC) have been proposed and prepared by an impregnation method. The as-prepared Pt/PTFE/Foam SiC was characterized by compression load testing, dynamic contact angle measurement, SEM, XRD, and TEM. The results show that the catalyst prepared by triple hydrophobic treatment had an initial contact angle of 134.2°, a good compression performance of 3.2 MPa, and platinum nanoparticles of 12.1 nm (average size). The catalytic activity of the catalyst was tested with different packing methods, reaction temperatures, and gas-liquid ratios. An excellent hydrogen isotope exchange performance was observed using a hydrophilic packing material-to-catalyst ratio of 25% and reaction temperature of 80 °C. Pt/PTFE/Foam SiC may be used as a hydrophobic catalyst for a water detritiation system (WDS) via a liquid-phase catalytic exchange process (LPCE).

Preparation and performance of Pt/PTFE/Foam SiC as a hydrophobic catalyst for LPCE

Energy Technology Data Exchange (ETDEWEB)

He, Jianchao; Wang, Heyi, E-mail: hywang@caep.cn; Xiao, Chengjian; Li, Jiamao; Chen, Ping; Hou, Jingwei

2016-12-15

Highlights: • A new type of foam material, Foam SiC with three-dimensional network structure, was chosen as the carrier of catalyst. • Foam SiC was hydrophobic treated by PTFE, and achieved a good hydrophobic property. • Pt/PTFE/Foam SiC was prepared by impregnation method with Pt-organic solution and gaseous phase reduction method. • The hydrophobic catalysts were packed with Dixon phosphor bronze gauze rings (about 3 mm × 3 mm) in LPCE system to test the catalytic performance. • The effect of different size of the catalyst on LPCE was been tested. - Abstract: Platinum catalysts supported on a composite of polytetrafluoroethylene (PTFE) and Foam SiC (Pt/PTFE/Foam SiC) have been proposed and prepared by an impregnation method. The as-prepared Pt/PTFE/Foam SiC was characterized by compression load testing, dynamic contact angle measurement, SEM, XRD, and TEM. The results show that the catalyst prepared by triple hydrophobic treatment had an initial contact angle of 134.2°, a good compression performance of 3.2 MPa, and platinum nanoparticles of 12.1 nm (average size). The catalytic activity of the catalyst was tested with different packing methods, reaction temperatures, and gas-liquid ratios. An excellent hydrogen isotope exchange performance was observed using a hydrophilic packing material-to-catalyst ratio of 25% and reaction temperature of 80 °C. Pt/PTFE/Foam SiC may be used as a hydrophobic catalyst for a water detritiation system (WDS) via a liquid-phase catalytic exchange process (LPCE).

Impeded solid state reactions and transformations in ceramic catalysts supports and catalysts

Directory of Open Access Journals (Sweden)

Ernő E. Kiss

2012-12-01

Full Text Available Impeded chemical reactions and impeded polymorphous transformation in materials are discussed, as desired effects, for stabilization of ceramic catalyst supports and ceramic based catalysts. This paper gives a short overview about the possibilities of slowing down the aging processes in ceramic catalyst supports and catalysts. Special attention is given to alumina and titania based catalysts.

Novel Reforming Catalysts

Energy Technology Data Exchange (ETDEWEB)

Pfefferle, Lisa D; Haller, Gary L

2012-10-16

Aqueous phase reforming is useful for processing oxygenated hydrocarbons to hydrogen and other more useful products. Current processing is hampered by the fact that oxide based catalysts are not stable under high temperature hydrothermal conditions. Silica in the form of structured MCM-41 is thermally a more stable support for Co and Ni than conventional high surface area amorphous silica but hydrothermal stability is not demonstrated. Carbon nanotube supports, in contrast, are highly stable under hydrothermal reaction conditions. In this project we show that carbon nanotubes are stable high activity/selectivity supports for the conversion of ethylene glycol to hydrogen.

Wet chemical synthesis of nickel supported on alumina catalysts; Sintese de catalisadores de niquel suportado em alumina por via umida

Energy Technology Data Exchange (ETDEWEB)

Freire, Ranny Rodrigues; Costa, Talita Kenya Oliveira; Morais, Ana Carla da Fonseca Ferreira; Costa, Ana Cristina Figueiredo de Melo; Freitas, Normanda Lino de, E-mail: normanda@ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil)

2016-07-01

Heterogenic catalysts are those found to be in a different phase on the reaction when compared to the reactants and products. Preferred when compared to homogeneous catalysts due to the easiness on which the separation is processed. The objective of this study is to obtain and characterize Alumina based catalysts impregnated with Nickel (Al{sub 2}O{sub 3}), by wet impregnation. The alumina was synthesized by combustion reaction. Before and after the impregnation the catalysts were characterized by X-ray diffraction (XRD), granulometric analysis, the textural analysis will be held by nitrogen adsorption (BET), energy-dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The results show a presence of a stable crystalline phase of Al2O3 in all the studied samples and after the impregnation the second phase formed was of NiO and NiAl{sub 2}O{sub 4}. The Al{sub 2}O{sub 3} e Ni/Al{sub 2}O{sub 3} catalysts resulted in clusters with a medium diameter of 18.9 and 14.2 μm, respectively. The catalysts show a medium-pore characteristic (medium pore diameter between 2 and 50 nm), the superficial area to Al{sub 2}O{sub 3} and Ni/Al{sub 2}O{sub 3} catalysts were 8.69 m{sup 2}/g and 5.56 m{sup 2}/g, respectively. (author)

Study of iron-zinc catalysts by Moessbauer spectroscopy

International Nuclear Information System (INIS)

Arriola, S.H.

1990-01-01

The Moessbauer parameters were determined on a series of catalyst mixtures of iron and zinc oxides with variable quantities of zinc. A change in the crystal structure of the iron oxide when introducing zinc into the samples was observed. The corundum structure of the α-Fe 2 O 3 phase was transformed into the spinel type of zinc ferrite when zinc oxide was present in any quantity. A strong electronic interaction between the zinc ferrite and the zinc oxide present in excess was evident. The catalysts were analyzed using x-ray fluorescence and x-ray diffraction methods. (author) 10 refs.; 4 figs.; 2 tabs

Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

Energy Technology Data Exchange (ETDEWEB)

Altman, Eric I. [Yale Univ., New Haven, CT (United States)

2015-10-06

The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO₂ relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO₂ surfaces. Building on this work on anatase, the mechanism by which TiO₂ enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO₂ substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

Phase identification of quasi-periodic flow measured by particle image velocimetry with a low sampling rate

International Nuclear Information System (INIS)

Pan, Chong; Wang, Hongping; Wang, Jinjun

2013-01-01

This work mainly deals with the proper orthogonal decomposition (POD) time coefficient method used for extracting phase information from quasi-periodic flow. The mathematical equivalence between this method and the traditional cross-correlation method is firstly proved. A two-dimensional circular cylinder wake flow measured by time-resolved particle image velocimetry within a range of Reynolds numbers is then used to evaluate the reliability of this method. The effect of both the sampling rate and Reynolds number on the identification accuracy is finally discussed. It is found that the POD time coefficient method provides a convenient alternative for phase identification, whose feasibility in low-sampling-rate measurement has additional advantages for experimentalists. (paper)

Ozone Decomposition on the Surface of Metal Oxide Catalyst

Directory of Open Access Journals (Sweden)

Batakliev Todor Todorov

2014-12-01

Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

Science.gov (United States)

Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

2017-05-09

Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

Synthesis of CaOZnO Nanoparticles Catalyst and Its Application in Transesterification of Refined Palm Oil

Directory of Open Access Journals (Sweden)

Cicik Herlina Yulianti

2014-07-01

Full Text Available The CaOZnO nanoparticle catalysts with Ca to Zn atomic ratios of 0.08 and 0.25 have been successfully synthesized by co-precipitation method. The catalyst was characterized by X-ray Diffraction (XRD analysis provided with Rietica and Maud software, Scanning Electron Microscopy (SEM and Fourier Transform Infrared spectroscopy (FT-IR, and its properties was compared with bare CaO and ZnO catalysts. The phase composition estimated by Rietica software revealed that the CaO catalyst consists of CaO and CaCO3 phases. The estimation of the particle size by Maud software, showed that the particle size of all catalysts increased by the following order: ZnO. © 2014 BCREC UNDIP. All rights reservedReceived: 1st January 2014; Revised: 10th March 2014; Accepted: 18th March 2014[How to Cite: Yulianti, C.H., Ediati, R., Hartanto, D., Purbaningtias, T.E., Chisaki, Y., Jalil, A.A., Hitam, C.K.N.L.C.K., Prasetyoko, D., (2014. Synthesis of CaOZnO Nanoparticles Catalyst and Its Application in Transesterification of Refined Palm Oil. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 100-110. (doi:10.9767/bcrec.9.2.5998.100-110][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.5998.100-110

Preparation, characterization of Mo catalysts supported on Ni- containing calcium deficient hydroxyapatite and reactivity for the thiophene HDS reaction

Directory of Open Access Journals (Sweden)

Cherif A.

2013-09-01

Full Text Available Ni-containing Calcium Hydroxyapatite (NiCaHAp; 3.31 wt.% Ni was synthesized by coprecipitation and used as catalyst support. Molybdenum was supported on NiCaHAp by impregnation using ammonium heptamolybdate. The prepared catalysts Mo(x/NiCaHAp (x: 2 to 8 wt % in Mo were characterized by elemental analysis, XRD, FT-IR, N2 adsorption-desorption and TEM-EDX. The catalysts were sulfided in-situ at 673 K under flowing H2S/H2 (15 Vol.% H2S and tested in hydrodesulfurization (HDS of thiophene at 673 K. The main XRD peaks of hydroxyapatite CaHAp phase were observed in all samples and a peak due probably to crystalline MoO3 phase was also identified from the results. However, no crystalline phase of NiO was found for the catalysts, which showed its Ni species were highly dispersed. The sulfided catalysts Mo(x/NiCaHAp presented are active in HDS of thiophene, despite the presence of some large MoO3 crystallites and incomplete sulfidation. This activity may be due to interaction of NiO and MoO3 on CaHAp resulting in the formation of Ni-Mo-S phase under flowing H2S/H2. When the molybdenum content increased the HDS activity increasead slightly, which was caused by the agglomeration of MoO3. The Mo(8/NiCaHAp catalyst is about two times less active for thiophene HDS than the commercial NiMoP/Al2O3.

An EXAFS study of the structure of Co-Mo hydrodesulfurization catalysts

International Nuclear Information System (INIS)

Clausen, B.S.; Topsoe, H.; Candia, R.; Villadsen, J.; Lengeler, B.

1981-05-01

By analysing the extended X-ray absorption fine structure (EXAFS) of the Mo absorption edge, structural information about both calcined and sulfided Mo/Al 2 O 3 and Co-Mo/Al 2 O 3 catalysts has been obtained. The calcined catalysts show only one strong backscatterer peak in the radial distribution function, which indicates that molybdenum is present in a highly disordered structure. For the Co-Mo/Al 2 O 3 catalyst the presence of cobalt seems to have some effect on the immediate surroundings of molybdenum. Upon sulfiding the catalysts, an ordering of the molybdenum-containing phase takes place as evidenced by the observation of a contribution from the second coordination shell. From a comparison with EXAFS data obtained on well-crystallized MoS 2 it is concluded that the molybdenum atoms in the catalysts are present in MoS 2 -like structures. Furthermore, from a comparison of the amplitude of the Mo-backscatterer peak it is found that these MoS 2 -like structures are ordered in very small domains. (orig.)

Catalytic biomass conversion methods, catalysts, and methods of making the same

Science.gov (United States)

Delgass, William Nicholas; Agrawal, Rakesh; Ribeiro, Fabio Henrique; Saha, Basudeb; Yohe, Sara Lynn; Abu-Omar, Mahdi M; Parsell, Trenton; Dietrich, Paul James; Klein, Ian Michael

2017-10-10

Described herein are processes for one-step delignification and hydrodeoxygenation of lignin fraction a biomass feedstock. The lignin feedstock is derived from by-products of paper production and biorefineries. Additionally described is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function. Finally, also described herein is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function.

Hydrotreating NiMo/sepiolite catalysts: influence of catalyst preparation on activity for HDS, hydrogenation and chain isomerization reactions

International Nuclear Information System (INIS)

Melo, F.V.; Sanz, E.; Corma, A.; Mifsud, A.

1987-01-01

A series of NiMo catalysts supported on a sepiolite: a) in its natural state, b) modified by acid leaching, and c) modified by cation exchange, have been prepared. The preparation variables studied were: Method of metal deposition, amount of active phase, sepiolite pretreatment, and temperature and time of sulfurization. The catalytic activity for HDS, hydrogenation, and cracking-isomerization has been studied by feeding a thiophene-cyclohexene-cyclohexane mixture and carrying out the reaction in the following conditions: 300 0 and 400 0 C reaction temperature, 20 Kg.cm -2 total pressure, and 3 to 1 molar ratio of H 2 to hydrocarbons. An optimium for HDS and hydrogenation activity was found for a 12% wt MoO 3 , and 5% wt NiO, prepared by simultaneous impregnation by the pore volume method at Ph = 5.0. The optimum conditions with these catalysts are 400 0 C and 3 hours of sulfurization. An increase in the acidity of the support produces a decrease of HDS and hydrogenation and an increase of the cracking-isomerization activities. A good correlation between HDS and the concentration of an XNiO.MoO 3 phase is found. The XNiO.MoO 3 phase is completely sulfurized to a modified MoS 2 , while NiMoO 4 and MoO 3 are only slightly sulfurized. 31 refs.; 7 figs.; 1 table

Parameter estimation and analysis of an automotive heavy-duty SCR catalyst model

DEFF Research Database (Denmark)

Åberg, Andreas; Widd, Anders; Abildskov, Jens

2017-01-01

A single channel model for a heavy-duty SCR catalyst was derived based on first principles. The model considered heat and mass transfer between the channel gas phase and the wash coat phase. The parameters of the kinetic model were estimated using bench-scale monolith isothermal data. Validation ...

Synthesis of l-threitol-based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions.

Science.gov (United States)

Rapi, Zsolt; Nemcsok, Tamás; Pálvölgyi, Ádám; Keglevich, György; Grün, Alajos; Bakó, Péter

2017-06-01

A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers. © 2017 Wiley Periodicals, Inc.

A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes

International Nuclear Information System (INIS)

Selvarani, G.; Sahu, A.K.; Choudhury, N.A.; Sridhar, P.; Pitchumani, S.; Shukla, A.K.

2007-01-01

A method, to anchor phenyl-sulfonic acid functional groups with the platinum catalyst supported onto a high surface-area carbon substrate, is reported. The use of the catalyst in the electrodes of a polymer electrolyte fuel cell (PEFC) helps enhancing its performance. Characterization of the catalyst by Fourier transform infra red (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and point-of-zero-charge (PZC) studies suggests that the improvement in performance of the PEFC is facilitated not only by enlarging the three-phase boundary in the catalyst layer but also by providing ionic-conduction paths as well as by imparting negative charge to platinum sites with concomitant oxidation of sulfur present in the carbon support. It is argued that the negatively charged platinum sites help repel water facilitating oxygen to access the catalyst sites. The PEFC with modified carbon-supported platinum catalyst electrodes exhibits 40% enhancement in its power density as compared to the one with unmodified carbon-supported platinum catalyst electrodes

Effects of impregnation methods and drying conditions on quinoline hydrodenitrogenation over Ni-W based catalysts

Energy Technology Data Exchange (ETDEWEB)

Guo, Fang; Qiu, Zegang; Zhao, Liangfu; Xiang, Hongwei [Institute of Coal Chemistry, Chinese Academy of Sciences (China); Guo, Shaoqing [Taiyuan University of Science and Technology (China)

2014-04-15

The effects of impregnation methods (co-impregnation and sequential impregnation) and drying conditions (air and vacuum) on the structure and catalytic behavior of MCM-41 supported Ni-W catalysts were investigated. The catalysts were characterized by powder X-ray diffraction (XRD) analysis, Fourier-transform infrared spectroscopy (FT-IR), diffuse reflectance UV-Vis absorbance spectroscopy (DRS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and pyridine adsorbed infrared spectroscopy (Py-IR) techniques. They were tested for hydrodenitrogenation (HDN) of quinoline at temperatures of 300-400 deg C. The HDN results showed that the catalysts prepared by co-impregnation were more active than the catalysts prepared by sequential impregnation and the catalysts prepared by drying under vacuum were more active than the catalysts dried in air. Characterization revealed that the co-impregnation method and drying under vacuum promoted the dispersion of W, the formation of the active phases, and the formation of acidic sites on the catalysts. (author)

Design of heterogeneous catalysts

DEFF Research Database (Denmark)

Frey, Anne Mette

was inspired by a computational screening, suggesting that alloys such as Ni-Fe, Co-Ni, and Co-Fe should show superior activity to the industrially used nickel catalyst. Especially the Ni-Fe system was considered to be interesting, since such alloy catalysts should be both more active and cheaper than the Ni...... catalyst. The results from the screening were experimentally verified for CO hydrogenation, CO2 hydrogenation, and simultaneous CO and CO2 hydrogenation by bimetallic Ni-Fe catalysts. These catalysts were found to be highly active and selective. The Co-Ni and Co-Fe systems were investigated for CO...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

Thermal degradation of Shredded Oil Palm Empty Fruit Bunches (SOPEFB) embedded with Cobalt catalyst by Thermogravimetric Analysis (TGA)

Science.gov (United States)

Alias, R.; Hamid, N. H.; Jaapar, J.; Musa, M.; Alwi, H.; Halim, K. H. Ku

2018-03-01

Thermal behavior and decomposition kinetics of shredded oil palm empty fruit bunches (SOPEFB) were investigated in this study by using thermogravimetric analysis (TGA). The SOPEFB were analyzed under conditions of temperature 30 °C to 900 °C with nitrogen gas flow at 50 ml/min. The SOPEFB were embedded with cobalt (II) nitrate solution with concentration 5%, 10%, 15% and 20%. The TG/DTG curves shows the degradation behavior of SOPEFB following with char production for each heating rate and each concentration of cobalt catalyst. Thermal degradation occurred in three phases, water drying phase, decomposition of hemicellulose and cellulose phase, and lignin decomposition phase. The kinetic equation with relevant parameters described the activation energy required for thermal degradation at the temperature regions of 200 °C to 350 °C. Activation energy (E) for different heating rate with SOPEFB embedded with different concentration of cobalt catalyst showing that the lowest E required was at SOPEFB with 20% concentration of cobalt catalyst..

Mercury Oxidation via Catalytic Barrier Filters Phase II

Energy Technology Data Exchange (ETDEWEB)

Wayne Seames; Michael Mann; Darrin Muggli; Jason Hrdlicka; Carol Horabik

2007-09-30

In 2004, the Department of Energy National Energy Technology Laboratory awarded the University of North Dakota a Phase II University Coal Research grant to explore the feasibility of using barrier filters coated with a catalyst to oxidize elemental mercury in coal combustion flue gas streams. Oxidized mercury is substantially easier to remove than elemental mercury. If successful, this technique has the potential to substantially reduce mercury control costs for those installations that already utilize baghouse barrier filters for particulate removal. Completed in 2004, Phase I of this project successfully met its objectives of screening and assessing the possible feasibility of using catalyst coated barrier filters for the oxidation of vapor phase elemental mercury in coal combustion generated flue gas streams. Completed in September 2007, Phase II of this project successfully met its three objectives. First, an effective coating method for a catalytic barrier filter was found. Second, the effects of a simulated flue gas on the catalysts in a bench-scale reactor were determined. Finally, the performance of the best catalyst was assessed using real flue gas generated by a 19 kW research combustor firing each of three separate coal types.

Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization

Directory of Open Access Journals (Sweden)

Jakkrit Suriboot

2016-04-01

Full Text Available Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds. It then discusses in more detail progress in dealing with these issues in ring opening metathesis polymerization chemistry. Such approaches depend on a biphasic solid/liquid or liquid separation and can use either always biphasic or sometimes biphasic systems and approaches to this problem using insoluble inorganic supports, insoluble crosslinked polymeric organic supports, soluble polymeric supports, ionic liquids and fluorous phases are discussed.

Uranium oxide catalysts: environmental applications for treatment of chlorinated organic waste from nuclear industry.

Science.gov (United States)

Lazareva, Svetlana; Ismagilov, Zinfer; Kuznetsov, Vadim; Shikina, Nadezhda; Kerzhentsev, Mikhail

2018-02-05

Huge amounts of nuclear waste, including depleted uranium, significantly contribute to the adverse environmental situation throughout the world. An approach to the effective use of uranium oxides in catalysts for the deep oxidation of chlorine-containing hydrocarbons is suggested. Investigation of the catalytic activity of the synthesized supported uranium oxide catalysts doped with Cr, Mn and Co transition metals in the chlorobenzene oxidation showed that these catalysts are comparable with conventional commercial ones. Physicochemical properties of the catalysts were studied by X-ray diffraction, temperature-programmed reduction with hydrogen (H 2 -TPR), and Fourier transform infrared spectroscopy. The higher activity of Mn- and Co-containing uranium oxide catalysts in the H 2 -TPR and oxidation of chlorobenzene in comparison with non-uranium catalysts may be related to the formation of a new disperse phase represented by uranates. The study of chlorobenzene adsorption revealed that the surface oxygen is involved in the catalytic process.

Catalysts prepared by interaction of transition metal organometallic compounds with the surface of supporters

International Nuclear Information System (INIS)

Ryndin, Yu.A.; Kuznetsov, B.N.; Moroz, Eh.M.; Tripol'skij, A.A.; Ermakov, Yu.I.

1977-01-01

The phase composition and dispersion of the catalyst (W + Pt)/SiO 2 , subjected to oxidation and reduction at an elevated temperature was investigated by roentgenographic methods (radial distribution of atoms and broadening of X-ray lines). The X-ray data are compared with the results of chemisorption measurements of platinum dispersion in the specimens and their activity in reactions of benzene hydration and ethane hydrogenolysis. It has been established that catalysts reduced at 600 deg C and not subjected to oxidation, as well as catalysts oxidized at 200 deg C and then reduced at 600 deg C are characterized by a high platinum dispersion. The dispersion catalysts are noted for their activity in the reaction of benzene hydration and ethane hydrogenolysis. On the other hand, the activity of catalysts oxidized and reduced in rigid conditions (600 deg C, air) is much lower and is close to the activity of the coarsely dispersed PtSiO 2 catalyst

BINIVOX catalyst for hydrogen production from ethanol by low ...

Indian Academy of Sciences (India)

B PATIL

2017-11-04

Nov 4, 2017 ... BINIVOX catalyst; catalytic activity; phase transition; crystal structure; thermal analysis. 1. ... and economic at the same time, are the need of the hour.5. Out of all the ... ichiometric amount of bismuth nitrate (Bi(NO3)3.5H2O).

Highly active Ni/Y-doped ZrO{sub 2} catalysts for CO{sub 2} methanation

Energy Technology Data Exchange (ETDEWEB)

Takano, H., E-mail: takano_hi@hitachizosen.co.jp [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Kirihata, Y.; Izumiya, K.; Kumagai, N. [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Habazaki, H., E-mail: habazaki@eng.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Division of Applied Chemistry & Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Hashimoto, K. [Tohoku Institute of Technology, Sendai, 277-8515 (Japan)

2016-12-01

Highlights: • The Ni/Y-doped ZrO{sub 2} catalysts show highly catalytic activity for CO{sub 2} methanation. • Bidentate carbonate is a major adsorption spice on the Ni/Y-doped ZrO{sub 2} catalysts. • The oxide support of t-ZrO{sub 2} and/or c-ZrO{sub 2} with oxygen vacancies plays a key role. - Abstract: The catalytic methanation of CO{sub 2} was carried out on Ni catalysts supported on Y-doped ZrO{sub 2} with various Y{sup 3+} concentrations and Ni/(Zr + Y) molar ratio = 1. The catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy, specific surface area, temperature-programmed desorption of CO{sub 2}, and temperature-programmed reaction. In addition, operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFT) was used to identify the adsorbed reaction intermediate. Catalysts supported on Y-doped ZrO{sub 2} show higher catalytic activity than the catalyst on Y-free ZrO{sub 2} with a monoclinic ZrO{sub 2} phase. The catalytic activity is also dependent upon the Y{sup 3+} concentration, and the highest activity was obtained for the catalyst with a Y/(Zr + Y) molar ratio of 0.333, which consists mainly of fcc Ni and cubic ZrO{sub 2} phase. Y{sup 3+} doping into ZrO{sub 2} introduces oxygen vacancies, which play an important role in enhancing the catalytic activity. The operando DRIFT study reveals that a CO adsorption intermediate is absent, and bidentate carbonate is an important intermediate for CH{sub 4} formation.

Highly dispersed metal catalyst

Science.gov (United States)

Xiao, Xin; West, William L.; Rhodes, William D.

2016-11-08

A supported catalyst having an atomic level single atom structure is provided such that substantially all the catalyst is available for catalytic function. A process of forming a single atom catalyst unto a porous catalyst support is also provided.

Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions

DEFF Research Database (Denmark)

Sádaba, Irantzu; Lopez Granados, Manuel; Riisager, Anders

2015-01-01

This review is aimed to be a brief tutorial covering the deactivation of solid catalysts in the liquid phase, with specific focus on leaching, which can be especially helpful to researchers not familiarized with catalytic processes in the liquid phase. Leaching refers to the loss of active species....... However, as a consequence of the development of new processes for biorefineries, an increasing number of reactions deal with liquid media, and thus, the stability and reusability of a solid catalyst in this situation represent a huge challenge that requires specific attention. Leaching of active phases...... is particularly problematic because of its irreversibility and it can be one of the main causes of catalyst deactivation in liquid media, threatening the sustainability of the process. This tutorial review presents a survey of the main aspects concerning the deactivation due to leaching of active species from...

[Adsorption and removal of gas-phase Hg(0) over a V2O5/AC catalyst in the presence of SO2].

Science.gov (United States)

Wang, Jun-wei; Yang, Jian-li; Liu, Zhen-yu

2009-12-01

The adsorption and removal behaviors of gas-phase Hg(0) over V2O5/AC and AC were studied under a simulated flue gas (containing N2, SO2, O2) in a fixed-bed reactor. The influences of the V2O5, loading, SO2 concentration and adsorption temperature on Hg0 adsorption were investigated. The speciation of mercury adsorbed was determined by X-ray photoelectron spectroscopy (XPS). It was found that the V2O5/AC catalyst has a much higher capability than AC for Hg(0) adsorption and removal, mainly because of the catalytic oxidation activity of V2O5. The Hg(0) adsorption capability depends on the V2O5 content of the V2O5/AC catalyst. The amounts of mercury adsorbed increase from 75.9 microg x g(-1) to 89.6 microg x g(-1) (in the absence of O2) and from 115.9 microg x g(-1) to 185.5 microg x g(-1) (in the presence of O2) as the V2O5 loading increases from 0.5% to 1.0%, which are much higher than those over AC under the same conditions (9.6 microg x g(-1) and 23.3 microg x g(-1)). SO2 in the flue gas enhances Hg(0) adsorption over the V2O5/AC catalyst, which is due to the reaction of SO2 and Hg(0) on V2O3/AC. But as the SO2 concentration increases from 500 x 10(-6) to 2000 x 10(-6), the amount of mercury adsorbed has only a slight increase. The optimal temperature for Hg(0) adsorption over the V2O5/AC catalyst is around 150 degrees C, at which the amounts of mercury adsorbed are up to 98.5 microg x g(-1) (in the absence of O2) and 187.7 microg x g(-1) (in the presence of O2). The XPS results indicate the formation of Hg(0) and HgSO4 on the surface of the V2O5/AC catalyst, which confirms the role of V2O5 and SO2.

Deuterium absorption in Mg70Al30 thin films with bilayer catalysts: A comparative neutron reflectometry study

International Nuclear Information System (INIS)

Poirier, Eric; Harrower, Chris T.; Kalisvaart, Peter; Bird, Adam; Teichert, Anke; Wallacher, Dirk; Grimm, Nico; Steitz, Roland; Mitlin, David; Fritzsche, Helmut

2011-01-01

Highlights: → Mg 70 Al 30 thin films studied for hydrogen absorption using in situ neutron reflectometry. → Films with Ta/Pd, Ti/Pd and Ni/Pd bilayer catalysts systematically compared. → Measurements reveals deuterium spillover from the catalysts to the MgAl phase. → The use of Ti-Pd bilayer offers best results in terms of amount absorbed and kinetics. → Key results cross-checked with X-ray reflectometry. - Abstract: We present a neutron reflectometry study of deuterium absorption in thin films of Al-containing Mg alloys capped with a Ta/Pd, Ni/Pd and Ti/Pd-catalyst bilayer. The measurements were performed at room temperature over the 0-1 bar pressure range under quasi-equilibrium conditions. The modeling of the measurements provided a nanoscale representation of the deuterium profile in the layers at different stages of the absorption process. The absorption mechanism observed was found to involve spillover of atomic deuterium from the catalyst layer to the Mg alloy phase, followed by the deuteration of the Mg alloy. Complete deuteration of the Mg alloy occurs in a pressure range between 100 and 500 mbar, dependent on the type of bilayer catalyst. The use of a Ti/Pd bilayer catalyst yielded the best results in terms of both storage density and kinetic properties.

Effect of coke and catalyst structure on oxidative regeneration of hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E. (CANMET, Ottawa, ON (Canada). Energy Research Laboratories)

1991-04-01

Two industrial hydroprocessing catalysts used for upgrading an atmospheric residue and a gas oil, respectively were regenerated in a fixed bed using air and 2 vol.% O{sub 2}+N{sub 2} balance mixture. The regeneration in air resulted in a significant sintering of the catalyst's material. The surface area of catalysts regenerated in 2 vol.% O{sub 2} mixture was similar to that of fresh catalysts, whereas a significant loss of surface area was observed after regeneration in air. The X-ray diffraction pattern of catalysts regenerated in 2 vol.% O{sub 2}+N{sub 2} balance mixture was also similar to that of fresh catalysts. 22 refs., 9 figs., 7 tabs.

Hydroprocessing catalyst development

Energy Technology Data Exchange (ETDEWEB)

Boorman, P.M.; Kydd, R.A.; Sorensen, T.S.; Chong, K.; Lewis, J.

1992-08-01

Co-Mo and Ni-Mo hydroprocessing catalysts were examined for their activity in removal of sulfur from thiophene in model compounds, and in the cracking and hydrocracking of cumene. Three types of support materials were examined: carbon, modified carbon, and carbon covered alumina. The objective of the study was to examine the correlation between catalyst activity in the hydrodenitrogenation of model compounds, and the resistance of the catalyst to nitrogen poisoning during use in the hydroprocessing of gas oils. The use of model compound testing provided information on the individual catalytic reactions promoted by those materials. Infrared spectroscopy was used to study surface species on the catalysts and to explain many of the trends in activity observed, revealing the role of fluoride and phosphorus as a secondary promoter. Testing of the catalysts in hydrotreating of gas oils allowed comparison of model compound results with those from a real feedstock. The gas oil was also spiked with a model nitrogen compound and the results from catalytic hydrotreating of this material were compared with those from unspiked material. A key finding was that the carbon supported catalysts were the most effective in treating high-nitrogen feeds. The very favorable deactivation properties of carbon and carbon-covered alumina supported catalysts make these promising from an industrial point of view where catalyst deactivation is a limiting factor. 171 refs., 25 figs., 43 tabs.

Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Wael Ahmed Abou Taleb Sayed

2011-01-13

This work presents the experimental results of the synthesis of unsupported and supported SiC iron oxide nanoparticles and their catalytic activity towards ethanol partial oxidation. For comparison, further unsupported iron oxide phases were investigated towards the ethanol partial oxidation. These {gamma}-Fe{sub 2}O{sub 3} and {alpha}/{gamma}-Fe{sub 2}O{sub 3} phase catalysts were prepared by the CVS method using Fe(CO){sub 5} as precursor, supplied by another author. The {alpha}-Fe{sub 2}O{sub 3} and SiC nanoparticles were prepared by the CVS method using a home made hot wall reactor technique at atmospheric pressure. Ferrocene and tetramethylsilane were used as precursor for the production process. Process parameters of precursor evaporation temperature, precursor concentration, gas mixture velocity and gas mixture dilution were investigated and optimised to produce particle sizes in a range of 10 nm. For Fe{sub 2}O{sub 3}/SiC catalyst series production, a new hot wall reactor setup was used. The particles were produced by simultaneous thermal decomposition of ferrocene and tetramethylsilane in one reactor from both sides. The production parameters of inlet tube distance inside the reactor, precursor evaporation temperature and carrier gas flow were investigated to produce a series of samples with different iron oxide content. The prepared catalysts composition, physical and chemical properties were characterized by XRD, EDX, SEM, BET surface area, FTIR, XPS and dynamic light scattering (DLS) techniques. The catalytic activity for the ethanol gas-phase oxidation was investigated in a temperature range from 260 C to 290 C. The product distributions obtained over all catalysts were analysed with mass spectrometry analysis tool. The activity of bulk Fe{sub 2}O{sub 3} and SiC nanoparticles was compared with prepared nano-iron oxide phase catalysts. The reaction parameters, such as reaction temperature and O{sub 2}/ethanol ratio were investigated. The catalysts

Alloyed Ni-Fe nanoparticles as catalysts for NH₃ decomposition

DEFF Research Database (Denmark)

Simonsen, Søren Bredmose; Chakraborty, Debasish; Chorkendorff, Ib

2012-01-01

A rational design approach was used to develop an alloyed Ni-Fe/Al2O3 catalyst for decomposition of ammonia. The dependence of the catalytic activity is tested as a function of the Ni-to-Fe ratio, the type of Ni-Fe alloy phase, the metal loading and the type of oxide support. In the tests with high...... temperatures and a low NH3-to-H2 ratio, the catalytic activity of the best Ni-Fe/Al2O3 catalyst was found to be comparable or even better to that of a more expensive Ru-based catalyst. Small Ni-Fe nanoparticle sizes are crucial for an optimal overall NH3 conversion because of a structural effect favoring...

Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

KAUST Repository

Biausque, Gregory; Laveille, Paco; Anjum, Dalaver H.; Caps, Valerie; Basset, Jean-Marie

2015-01-01

Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

KAUST Repository

Biausque, Gregory

2015-04-28

Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

Strontium cobaltite oxygen sponge catalyst and methods of use

Energy Technology Data Exchange (ETDEWEB)

Lee, Ho Nyung; Jeen, Hyoungjeen; Choi, Woo Seok; Biegalski, Michael; Folkman, Chad M.; Tung, I-Cheng; Fong, Dillon D.; Freeland, John W.; Shin, Dongwon; Ohta, Hiromichi; Chisholm, Matthew F.

2017-01-24

Rapid, reversible redox activity may be accomplished at significantly reduced temperatures, as low as about 200.degree. C., from epitaxially stabilized, oxygen vacancy ordered SrCoO.sub.2.5 and thermodynamically unfavorable perovskite SrCoO.sub.3-.delta.. The fast, low temperature redox activity in SrCoO.sub.3-.delta. may be attributed to a small Gibbs free energy difference between the two topotactic phases. Epitaxially stabilized thin films of strontium cobaltite provide a catalyst adapted to rapidly transition between oxidation states at substantially low temperatures. Methods of transitioning a strontium cobaltite catalyst from a first oxidation state to a second oxidation state are described.

Supported catalyst systems and method of making biodiesel products using such catalysts

Science.gov (United States)

Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

2015-10-20

A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

Oxygen isotope exchange on palladium catalysts

International Nuclear Information System (INIS)

Kravchuk, L.S.; Beschetvertnaya, T.I.; Novorodskij, V.G.; Novikova, M.G.; Zaretskij, M.V.; Valieva, S.V.

1983-01-01

Oxygen heteromolecular isotope exchange on unreduced palladium catalysts, distingushing by metal content is studied. Content of 18 O in gaseous phase is eoual to 46%. Calculations of heteroexchange rates are conducted with decrease of the 18 O in the gaseous phase over solid sample. Method of oxygen thermodesorption has been used to establish that palladium, deposited on γ-Al 2 O 3 during exchange process is in oxidized state; in this case strength of Pd-O bond is determined by content dispersity) of the metal. It is shown that significant increase of exchange rate on the samples with Pd >> 0.5 mass.% content can be induced as by side decomposition reaction of its oxide and corresponding dilution of gaseous mixture by ''light'' oxygen so by possibility of exchange with oxygen of PdO phase

The international symposium on 'chemical engineering of gas-liquid-solid catalyst reactions'

Energy Technology Data Exchange (ETDEWEB)

Hammer, H

1978-06-01

A report on the International Symposium on ''Chemical Engineering of Gas-Liquid-Solid Catalyst Reactions'', sponsored by the University of Liege (3/2-3/78), covers papers on the hydrodynamics, modeling and simulation, operating behavior, and chemical kinetics of trickle-bed reactors; scale-up of a trickle-bed reactor for hydrotreating Kuwait vacuum distillate; experimental results obtained in trickle-bed reactors for hydroprocessing atmospheric residua, hydrogenation of methylstyrene, hydrogenation of butanone, and hydrodemetallization of petroleum residua; advantages and disadvantages of various three-phase reactor types (e.g., for the liquid-phase hydrogenation of carbon monoxide to benzene, SNG, or methanol) and hydrodynamics, mass and heat transfer, and modeling of bubble columns with suspended catalysts (slurry reactors), and their applications (e.g., in SNG and fermentation processes).

Bimetallic Catalysts Containing Gold and Palladium for Environmentally Important Reactions

Directory of Open Access Journals (Sweden)

Ahmad Alshammari

2016-07-01

Full Text Available Supported bimetallic nanoparticles (SBN are extensively used as efficient redox catalysts. This kind of catalysis particularly using SBN has attracted immense research interest compared to their parent metals due to their unique physico-chemical properties. The primary objective of this contribution is to provide comprehensive overview about SBN and their application as promising catalysts. The present review contains four sections in total. Section 1 starts with a general introduction, recent progress, and brief summary of the application of SBN as promising catalysts for different applications. Section 2 reviews the preparation and characterization methods of SBN for a wide range of catalytic reactions. Section 3 concentrates on our own results related to the application of SBN in heterogeneous catalysis. In this section, the oxidation of cyclohexane to adipic acid (an eco-friendly and novel approach will be discussed. In addition, the application of bimetallic Pd catalysts for vapor phase toluene acetoxylation in a fixed bed reactor will also be highlighted. Acetoxylation of toluene to benzyl acetate is another green route to synthesize benzyl acetate in one step. Finally, Section 4 describes the summary of the main points and also presents an outlook on the application of SBN as promising catalysts for the production of valuable products.

Catalysts with Cu base supported in mixed oxides to generate H2: reformed of methanol in oxidant atmosphere

International Nuclear Information System (INIS)

Aguila M, M.M.; Perez H, R.; Rodriguez L, V.

2006-01-01

In this work, the characterization of Cu supported in CeO 2 -ZrO 2 , for to generate H 2 starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N 2 and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO 2 /ZrO 2 relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO 2 and added planars in the rich materials in CeO 2 . The ceria addition to the zircon favors the specific area of the mixed oxides CeO 2 -ZrO 2 and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H 2 . This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

Aqueous phase reforming of ethylene glycol - Role of intermediates in catalyst performance

NARCIS (Netherlands)

de Vlieger, Dennis; Mojet, Barbara; Lefferts, Leonardus; Seshan, Kulathuiyer

2012-01-01

Liquid product formation during the aqueous catalytic reforming of ethylene glycol (EG) was studied up to 450 °C and 250 bar pressure. Methanol, ethanol, and acetic acid were the main liquid by-products during EG reforming in the presence of alumina-supported Pt and Pt–Ni catalysts. The effect of

Effect of Surface Modification by Chelating Agents on Fischer- Tropsch Performance of Co/SiO{sub 2} Catalysts

Energy Technology Data Exchange (ETDEWEB)

Bambal, Ashish S.; Kugler, Edwin L.; Gardner, Todd H.; Dadyburjor, Dady B.

2013-11-14

The silica support of a Co-based catalyst for Fischer-Tropsch (FT) synthesis was modified by the chelating agents (CAs) nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA). After the modification, characterization of the fresh and spent catalysts show reduced crystallite sizes, a better-dispersed Co₃O₄ phase on the calcined samples, and increased metal dispersions for the reduced samples. The CA-modified catalysts display higher CO conversions, product yields, reaction rates and rate constants. The improved FT performance of CA-modified catalysts is attributed to the formation of stable complexes with Co. The superior performance of the EDTA-modified catalyst in comparison to the NTA-modified catalyst is due to the higher affinity of the former for complex formation with Co ions.

Non-destructive identification of unknown minor phases in polycrystalline bulk alloys using three-dimensional X-ray diffraction

Energy Technology Data Exchange (ETDEWEB)

Yang, Yiming, E-mail: yangyiming1988@outlook.com [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Xu, Liang [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Wang, Yudan; Du, Guohao [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Yang, Sam [Commonwealth Scientific and Industrial Research Organization, Melbourne, VIC 3168 (Australia); Xiao, Tiqiao, E-mail: tqxiao@sinap.ac.cn [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); University of Chinese Academy of Sciences, Beijing 100049 (China)

2017-02-15

Minor phases make considerable contributions to the mechanical and physical properties of metals and alloys. Unfortunately, it is difficult to identify unknown minor phases in a bulk polycrystalline material using conventional metallographic methods. Here, a non-destructive method based on three-dimensional X-ray diffraction (3DXRD) is developed to solve this problem. Simulation results demonstrate that this method is simultaneously able to identify minor phase grains and reveal their positions, orientations and sizes within bulk alloys. According to systematic simulations, the 3DXRD method is practicable for an extensive sample set, including polycrystalline alloys with hexagonal, orthorhombic and cubic minor phases. Experiments were also conducted to confirm the simulation results. The results for a bulk sample of aluminum alloy AA6061 show that the crystal grains of an unexpected γ-Fe (austenite) phase can be identified, three-dimensionally and nondestructively. Therefore, we conclude that the 3DXRD method is a powerful tool for the identification of unknown minor phases in bulk alloys belonging to a variety of crystal systems. This method also has the potential to be used for in situ observations of the effects of minor phases on the crystallographic behaviors of alloys. - Highlights: •A method based on 3DXRD is developed for identification of unknown minor phase. •Grain position, orientation and size, is simultaneously acquired. •A systematic simulation demonstrated the applicability of the proposed method. •Experimental results on a AA6061 sample confirmed the practicability of the method.

Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives

Directory of Open Access Journals (Sweden)

Jia Luo

2011-01-01

Full Text Available Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9',10'-dihydro-9',10'-anthraceno-3-pyrrolinium derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b-dihydrodibenzo[a,f]cyclopropa[cd]pentaleno}pyrrolidinium derivatives]. Whereas the covalent attachment of a benzophenone functionality to the pyrrolinium nitrogen atom did not result in an internal triplet sensitization, the introduction of a benzophenone unit as part of the counter ion enables the di-π-methane rearrangement of the dibenzobarrelene derivative in the solid-state. Preliminary experiments indicate that a cationic pyrrolidinium-annelated dibenzosemibullvalene may act as phase-transfer catalyst in alkylation reactions.

Carbon-supported iron and iron-molybdenum sulfide catalysts

International Nuclear Information System (INIS)

Ramselaar, W.L.T.M.

1988-01-01

The main objective was to describe the relations between the characteristics (composition and dispersion) of the actual sulfide phase and the catalytic activity. Attention was also paid to the influence of preparational aspects on these characteristics. The catalysts were characterized using in-situ Moessbauer spectroscopy down to 2.0 K. 254 refs.; 47 figs.; 22 tabs

Rapid experimental SAD phasing and hot-spot identification with halogenated fragments

Energy Technology Data Exchange (ETDEWEB)

Bauman, Joseph D.; Harrison, Jerry Joe E. K.; Arnold, Eddy

2016-01-01

Through X-ray crystallographic fragment screening, 4-bromopyrazole was discovered to be a `magic bullet' that is capable of binding at many of the ligand `hot spots' found in HIV-1 reverse transcriptase (RT). The binding locations can be in pockets that are `hidden' in the unliganded crystal form, allowing rapid identification of these sites forin silicoscreening. In addition to hot-spot identification, this ubiquitous yet specific binding provides an avenue for X-ray crystallographic phase determination, which can be a significant bottleneck in the determination of the structures of novel proteins. The anomalous signal from 4-bromopyrazole or 4-iodopyrazole was sufficient to determine the structures of three proteins (HIV-1 RT, influenza A endonuclease and proteinase K) by single-wavelength anomalous dispersion (SAD) from single crystals. Both compounds are inexpensive, readily available, safe and very soluble in DMSO or water, allowing efficient soaking into crystals.

Rapid experimental SAD phasing and hot-spot identification with halogenated fragments

Directory of Open Access Journals (Sweden)

Joseph D. Bauman

2016-01-01

Full Text Available Through X-ray crystallographic fragment screening, 4-bromopyrazole was discovered to be a `magic bullet' that is capable of binding at many of the ligand `hot spots' found in HIV-1 reverse transcriptase (RT. The binding locations can be in pockets that are `hidden' in the unliganded crystal form, allowing rapid identification of these sites for in silico screening. In addition to hot-spot identification, this ubiquitous yet specific binding provides an avenue for X-ray crystallographic phase determination, which can be a significant bottleneck in the determination of the structures of novel proteins. The anomalous signal from 4-bromopyrazole or 4-iodopyrazole was sufficient to determine the structures of three proteins (HIV-1 RT, influenza A endonuclease and proteinase K by single-wavelength anomalous dispersion (SAD from single crystals. Both compounds are inexpensive, readily available, safe and very soluble in DMSO or water, allowing efficient soaking into crystals.

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

Science.gov (United States)

Ahmed, Maaz S.

alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

Aromatization of n-octane over Pd/C catalysts

KAUST Repository

Yin, Mengchen; Natelson, Robert H.; Campos, Andrew A.; Kolar, Praveen; Roberts, William L.

2013-01-01

Gas-phase aromatization of n-octane was investigated using Pd/C catalyst. The objectives were to: (1) determine the effects of temperature (400-600 °C), weight hourly space velocity (WHSV) (0.8-∞), and hydrogen to hydrocarbon molar ratio (MR) (0-6) on conversion, selectivity, and yield (2) compare the activity of Pd/C with Pt/C and Pt/KL catalysts and (3) test the suitability of Pd/C for aromatization of different alkanes including n-hexane, n-heptane, and n-octane. Pd/C exhibited the best aromatization performance, including 54.4% conversion and 31.5% aromatics yield at 500 °C, WHSV = 2 h-1, and a MR of 2. The Pd/C catalyst had higher selectivity towards the preferred aromatics including ethylbenzene and xylenes, whereas Pt/KL had higher selectivity towards benzene and toluene. The results were somewhat consistent with adsorbed n-octane cyclization proceeding mainly through the six-membered ring closure mechanism. In addition, Pd/C was also capable of catalyzing aromatization of n-hexane and n-heptane. © 2012 Elsevier Ltd. All rights reserved.

Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

Energy Technology Data Exchange (ETDEWEB)

Hu, Yue [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Yang, Xiaojun, E-mail: 10100201@wit.edu.cn [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Cao, Shuo, E-mail: cao23@email.sc.edu [North America R& D Center, Clariant BU Catalysts, Louisville, 40209, KY (United States); Zhou, Jie [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Wu, Yuanxin [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Han, Jinyu [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Yan, Zhiguo [Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205 (China); Zheng, Mingming [Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Hubei Key Laboratory of Oilcrops Lipid Chemistry and Nutrition, Wuhan 430062 (China)

2017-04-01

Highlights: • Polyvinyl alcohol (PVA) inhibited the sintering and reduction of Pd nanoparticles. • Activity was improved for supported Pd catalysts with PVA modified method. • PVA modified method minimized the catalyst deactivation. • This work provides an insight of the regeneration strategies for Pd catalysts. - Abstract: A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

Hydrogen isotope separation in hydrophobic catalysts between hydrogen and liquid water

Energy Technology Data Exchange (ETDEWEB)

Ye, Linsen, E-mail: yls2005@mail.ustc.edu.cn [China Academy of Engineering Physics, Mianyang 621900 (China); Luo, Deli [Science and Technology on Surface Physics and Chemistry Laboratory, Jiangyou 621907 (China); Tang, Tao; Yang, Wan; Yang, Yong [China Academy of Engineering Physics, Mianyang 621900 (China)

2015-11-15

Hydrogen isotope catalytic exchange between hydrogen and liquid water is a very effective process for deuterium-depleted potable water production and heavy water detritiation. To improve the characteristics of hydrophobic catalysts for this type of reaction, foamed and cellular structures of hydrophobic carbon-supported platinum catalysts were successfully prepared. Separation of deuterium or tritium from liquid water was carried out by liquid-phase catalytic exchange. At a gas–liquid ratio of 1.53 and exchange temperature of 70 °C, the theoretical plate height of the hydrophobic catalyst (HETP = 34.2 cm) was slightly lower than previously reported values. Changing the concentration of the exchange column outlet water yielded nonlinear changes in the height of the packing layer. Configurations of deuterium-depleted potable water and detritiation of heavy water provide references for practical applications.

Reduction and reoxidation of cobalt Fischer-Tropsch catalysts

Energy Technology Data Exchange (ETDEWEB)

Hilmen, Anne-Mette

1996-12-31

The Fischer-Tropsch synthesis involves the hydrogenation of carbon monoxide to produce mainly hydrocarbons, water and carbon dioxide, but also alcohols, aldehydes and acids are formed. The distribution of these products is determined by the choice of catalyst and synthesis conditions. This thesis studies the reduction and reoxidation of 17%Co/Al{sub 2}O{sub 3} and 17%Co-1%Re/Al{sub 2}O{sub 3} by means of several characterization techniques. The effect of small amounts of Re on the reduction properties of Al{sub 2}O{sub 3}-supported Co catalysts has been studied by temperature-programmed reduction (TPR). An intimate mixture of CoAl{sub 2}O{sub 3} and Re/Al{sub 2}O{sub 3} catalysts showed a promoting effect of Re similar to that for co impregnated CoRe/Al{sub 2}O{sub 3}. A loose mixture of Co/Al{sub 2}O{sub 3} + Re/Al{sub 2}O{sub 3} did not show any effect of Re on the reduction of Co. But a promoting effect was observed if the mixture had been pre-treated with Ar saturated with water before the TPR. It is suggested that Re promotes the reduction of Co oxide by hydrogen spillover. It is shown that a high temperature TPK peak at 1200K assigned to Co aluminate is mainly caused by the diffusion of Co ions during the TPR and not during calcination. The Co particle size measured by x-ray diffraction on oxidized catalysts decreased compared to the particle size on the calcined catalysts, while the dispersion measured by volumetric chemisorption decreased somewhat after the oxidation-reduction treatment. The role of water in the deactivation of Co/Al{sub 2}O{sub 3} and CoRe/Al{sub 2}O{sub 3} Fischer-Tropsch catalysts has been extensively studied. There were significant differences in the reducibility of the phases formed for the two catalysts during exposure to H{sub 2}O/He. 113 refs., 76 figs., 18 tabs.

MgAl-Layered Double Hydroxide Solid Base Catalysts for Henry Reaction: A Green Protocol

Directory of Open Access Journals (Sweden)

Magda H. Abdellattif

2018-03-01

Full Text Available A series of MgAl-layered double hydroxide (MgAl-HT, the calcined form at 500 °C (MgAlOx, and the rehydrated one at 25 °C (MgAl-HT-RH were synthesized. Physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Surface area of the as-synthesized, calcined, and rehydrated catalysts was determined by N2 physisorption at −196 °C. CO2 temperature-programmed desorption (CO2-TPD was applied to determine the basic sites of catalysts. The catalytic test reaction was carried out using benzaldehyde and their derivatives with nitromethane and their derivatives. The Henry products (1–15 were obtained in a very good yield using MgAl-HT-RH catalyst either by conventional method at 90 °C in liquid phase or under microwave irradiation method. The mesoporous structure and basic nature of the rehydrated solid catalyst were responsible for its superior catalytic efficiency. The robust nature was determined by using the same catalyst five times, where the product % yield was almost unchanged significantly.

High-Activity Dealloyed Catalysts

Energy Technology Data Exchange (ETDEWEB)

Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

2014-09-30

Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

Survey on synthesis and reaction of environmentally benign water-soluble metal complex catalysts; Kankyo chowagata suiyosei sakutai shokubai no gosei hanno no chosa

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

This report describes the research trend survey results on the synthesis and reaction of water-soluble metal complexes which are regarded as environmentally benign catalysts. For the synthesis and catalysis of water-soluble complexes, synthetic methods of water-soluble phosphines, such as sulfonated TPPMS and TPPTS, are described in detail. Synthesis and reactivity of hydroxymethylphosphines are introduced, and the application of electrospray mass spectroscopy is elucidated as a tool for the analysis of them. Changes of the application of transition metal complexes with water-soluble phosphines to catalysis are described. Dual catalysts which have both functions of phase transfer catalysts and homogeneous catalysts are introduced. Concept of counter phase transfer catalysts is also introduced, and some catalytic reactions are described. In addition, this report introduces catalysis of water-soluble polymer-supported metal complexes, immobilization of metal colloids with water-soluble ligands and their analysis, and water-soluble complexes as hybrid catalysts. 144 refs., 94 figs., 10 tabs.

Cu–Co–O nano-catalysts as a burn rate modifier for composite solid propellants

Directory of Open Access Journals (Sweden)

D. Chaitanya Kumar Rao

2016-08-01

Full Text Available Nano-catalysts containing copper–cobalt oxides (Cu–Co–O have been synthesized by the citric acid (CA complexing method. Copper (II nitrate and Cobalt (II nitrate were employed in different molar ratios as the starting reactants to prepare three types of nano-catalysts. Well crystalline nano-catalysts were produced after a period of 3 hours by the calcination of CA–Cu–Co–O precursors at 550 °C. The phase morphologies and crystal composition of synthesized nano-catalysts were examined using Scanning Electron Microscope (SEM, Energy Dispersive Spectroscopy (EDS and Fourier Transform Infrared Spectroscopy (FTIR methods. The particle size of nano-catalysts was observed in the range of 90 nm–200 nm. The prepared nano-catalysts were used to formulate propellant samples of various compositions which showed high reactivity toward the combustion of HTPB/AP-based composite solid propellants. The catalytic effects on the decomposition of propellant samples were found to be significant at higher temperatures. The combustion characteristics of composite solid propellants were significantly improved by the incorporation of nano-catalysts. Out of the three catalysts studied in the present work, CuCo-I was found to be the better catalyst in regard to thermal decomposition and burning nature of composite solid propellants. The improved performance of composite solid propellant can be attributed to the high crystallinity, low agglomeration and lowering the decomposition temperature of oxidizer by the addition of CuCo-I nano-catalyst.

Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol

Directory of Open Access Journals (Sweden)

Kei Saito

2016-01-01

Full Text Available A new solid phase catalyst, poly(N-4-vinylbenzyl-1,4,7-triazacyclononane copper(I complex, grafted onto polystyrene particles, has been employed for the oxidative polymerization of 2,6-dimethylphenol using an aqueous biphasic (water/toluene solvent system. The solid catalyst was synthesized by first grafting N-(4-vinylbenzyl-1,4,7-triaza-cyclononane onto polystyrene particles using a radical mediated polymerization method and next by creating the polymer-metal complex of copper-triazacyclononane with these modified particles. Poly(2,6-dimethyl-1,4-phenylene oxide was successfully obtained from the polymerization of 2,6-dimethylphenol using this new metal-organic solid phase catalyst.

Suitability of some promising soot combustion catalysts for application in diesel exhaust treatment

Energy Technology Data Exchange (ETDEWEB)

Badini, Claudio; Saracco, Guido; Serra, Valentina; Specchia, Vito [Dipartimento di Scienza dei Materiali ed Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi, 24-10129 Torino (Italy)

1998-09-21

In this work, the effect of thermal treatment at 380C and 600C, under gaseous atmospheres containing some typical components of diesel emissions (SO{sub 2} and water), was studied on some promising catalysts for diesel particulate combustion. In particular, the ageing behaviour of two novel catalysts (based on CsVO{sub 3}+KCl and KVO{sub 3}+KCl, respectively) and of a more widely studied Cu-K-V-Cl catalyst was investigated. The catalytic activities of these novel catalysts were lower than that of the Cu-K-V-Cl one, but, contrary to this last counterpart, they almost completely maintained their activity during ageing treatments in dry or humid air at 380C and 600C, respectively. Moreover, after prolonged thermal exposure in wet air, the activity of the Cu-K-V-Cl catalyst became comparable with that of the CsVO{sub 3}+KCl one, while remaining still slightly higher than that of the KVO{sub 3}+KCl catalyst. The thermal treatments of all the catalysts under investigation in an atmosphere containing SO{sub 2} did not cause an activity decrease. X-ray diffraction analyses showed the formation of new phases (sulphates and vanadates with a K/V ratio different from that of metavanadates) which could also improve the catalytic activity, counterbalancing the loss of active components due to evaporation at high temperatures. Furthermore, the catalyst activity was evaluated after employing repeatedly these catalysts in carbon combustion. The catalytic activities were generally slightly lowered by the repeated use, even though, from this viewpoint, that of Cu-K-V-Cl was more affected than those of the other catalysts. On the basis of the obtained results the CsVO{sub 3}+KCl catalyst was found to allow the best compromise between satisfactory catalyst activity and stability

thesis of high-purity carbon nanotubes over alumina and silica supported bimetallic catalysts

Directory of Open Access Journals (Sweden)

Sanja Ratković

2009-10-01

Full Text Available Carbon nanotubes (CNTs were synthesized by a catalytic chemical vapor deposition method (CCVD of ethylene over alumina and silica supported bimetallic catalysts based on Fe, Co and Ni. The catalysts were prepared by a precipitation method, calcined at 600 °C and in situ reduced in hydrogen flow at 700 °C. The CNTs growth was carried out by a flow the mixture of C2H4 and nitrogen over the catalyst powder in a horizontal oven. The structure and morphology of as-synthesized CNTs were characterized using SEM. The as-synthesized nanotubes were purified by acid and basic treatments in order to remove impurities such as amorphous carbon, graphite nanoparticles and metal catalysts. XRD and DTA/TG analyses showed that the amounts of by-products in the purified CNTs samples were reduced significantly. According to the observed results, ethylene is an active carbon source for growing high-density CNTs with high yield but more on alumina-supported catalysts than on their silica- supported counterparts. The last might be explained by SMSI formed in the case of alumina-supported catalysts, resulting in higher active phase dispersion.

SYNTHESIS OF UNSATURATED ESTERS VIA HIGHLY EFFICIENT ESTERIFICATION CATALYZED BY POLYMER GRAFTED QUARTERNARY AMMONIUM SALTS AS TRIPHASE CATALYSTS

OpenAIRE

LIANG, ZHENG YONG; WANG, LILI; LIU, HUI; HUANG, JIN SHUO

2013-01-01

A series of unsaturated esters were prepared via condensation of sodium carboxylates and alkenyl halide under the condition of macroporous polystyrene grafted quarternary ammonium salt as recyclable phase transfer catalyst, NaI as co-catalyst, Cu powder as inhibitor and H2O as solvent. Under optimal conditions, products yields are 78.2~ 96.0%. The catalyst can be convenient recycled and reutilized for about five times without losing its activity obviously.

Nanocolloidal Ru/MgF2 Catalyst for Hydrogenation of Chloronitrobenzene and Toluene

Directory of Open Access Journals (Sweden)

Pietrowski Mariusz

2014-06-01

Full Text Available The use of magnesium fluoride support for ruthenium active phase allowed obtaining new catalysts of high activities in the hydrogenation of toluene and ortho-chloronitrobenzene. Ruthenium colloid catalysts (1 wt.% of Ru were prepared by impregnation of the support with the earlier produced polyvinylpyrrolidone (PVP-stabilized ruthenium colloids. The performances of the colloidal catalysts and those obtained by traditional impregnation were tested in the reactions of toluene hydrogenation to methylcyclohexane and selective hydrogenation of ortho-chloronitrobenzene (o-CNB to ortho-chloroaniline (o-CAN. It was shown that the use of chemical reduction method allows obtaining highly monodisperse ruthenium nanoparticles of 1.6–2.6 nm in size. After reduction in hydrogen at 400oC, the colloidal ruthenium nanoparticles were found to strongly interact with MgF2 surface (SMSI, which decreased the catalyst ability to hydrogen chemisorption, but despite this, the colloid catalysts showed higher activity in o-CNB hydrogenation and higher selectivity to o-CAN than the traditional ones. It is supposed that their higher activity can be a result of high dispersion of Ru in colloid catalysts and the higher selectivity can be a consequence of the lower availability of hydrogen on the surface.

Communicating catalysts

Science.gov (United States)

Weckhuysen, Bert M.

2018-06-01

The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

Energy Technology Data Exchange (ETDEWEB)

Leyrit, P

1999-06-28

Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

A feasible process for furfural production from the pre-hydrolysis liquor of corncob via biochar catalysts in a new biphasic system.

Science.gov (United States)

Deng, Aojie; Lin, Qixuan; Yan, Yuhuan; Li, Huiling; Ren, Junli; Liu, Chuanfu; Sun, Runcang

2016-09-01

A feasible approach was developed to produce furfural from the pre-hydrolysis liquor of corncob via biochar catalysts as the solid acid catalyst in a new biphasic system with dichloromethane (DCM) as the organic phase and the concentrated pre-hydrolysis liquor (CPHL) containing NaCl as the aqueous phase. The biochar catalyst possessing many acidity groups (SO3H, COOH and phenolic OH groups) was prepared by the carbonization and sulfonation process of the corncob hydrolyzed residue. The influence of the catalytic condition on furfural yield and selectivity was comparatively studied. It was found that 81.14% furfural yield and 83.0% furfural selectivity were obtained from CPHL containing 5wt% xylose using this biochar catalyst in the CPHL-NaCl/DCM biphasic system at 170°C for 60min. In addition, with the regeneration process, this catalyst displayed the high performance and excellent recyclability. Copyright © 2016 Elsevier Ltd. All rights reserved.

Vanadia-silica and vanadia-cesium-silica catalysts for oxidation of SO2

DEFF Research Database (Denmark)

Pârvulescu, Vasile I.; Paun, Christina; Pârvulescu, Viorica

2004-01-01

%. The samples were impregnated with Cs2SO4 resulting in a Cs:V ratio of 3:1 and then dried and calcined under the same conditions. The catalysts were characterized using several methods: sorption isotherms of N-2 at 77 K, XRD, and XPS. The results of the characterization indicated that during calcination...... catalysts were also performed. The activation of the catalysts and the catalytic behavior were monitored by in situ Raman and EPR spectroscopy. These characterization techniques indicated that the active molten phase contains vanadium oxosulfato complexes similar to the V2O5-M2S2O7 (M = alkali metal......Mesoporous vanadia-silica catalysts have been prepared by three different sol-gel procedures using tetraethylorthosilicate (TEOS), vanadyl acetylacetonate (VAA), or VOCl3 and in some cases quaternary ammonium salts ((CH3)(3)C14H29N+Br- or (C10H21)(4)N+Br-) as surfactants. According to procedure A...

Development of wet-proofed catalyst and catalytic exchange process for tritium extraction

Energy Technology Data Exchange (ETDEWEB)

Song, Myung Jae; Son, Soon Hwan; Chung, Yang Gun; Lee, Gab Bock [Korea Electric Power Corp. (KEPCO), Taejon (Korea, Republic of). Research Center

1996-12-31

To apply a liquid phase catalytic exchange(LPCE) process for the tritium extraction from tritiated heavy water, the wet proofed catalyst to allow the hydrogen isotopic exchange reaction between liquid water and hydrogen gas was developed. A styrene divinyl benzene copolymer was selected as am effective catalyst support and prepared by suspension copolymerization. After post-treatment, final catalyst supports were dipped in chloroplatinic acid solution. The catalyst support had a good physical properties at a particular preparation condition. The catalytic performance was successfully verified through hydrogen isotopic exchange reaction in the exchange column. A mathematical model for the tritium removal process consisted of LPCE front-ended process and cryogenic distillation process was established using the NTU-HTU method for LPCE column and the FUG method for cryogenic distillation column, respectively. A computer program was developed using the model and then used to investigate optimum design variables which affect the size of columns and tritium inventory (author). 84 refs., 113 figs.

Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution

Energy Technology Data Exchange (ETDEWEB)

Xu, Dongyan; Liu, Xinmin; Cao, Changqing; Guo, Qingjie [College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Dai, Ping [College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao 266061 (China)

2008-08-01

Low cost transition metal catalysts with high performance are attractive for the development of on-board hydrogen generation systems by catalytic hydrolysis of sodium borohydride (NaBH{sub 4}) in fuel cell fields. In this study, hydrogen production from alkaline NaBH{sub 4} via hydrolysis process over carbon-supported cobalt catalysts was studied. The catalytic activity of the supported cobalt catalyst was found to be highly dependent on the calcination temperatures. The hydrogen generation rate increases with calcination temperatures in the range of 200-400 C, but a high calcination temperature above 500 C led to markedly decreased activity. X-ray diffraction patterns reveal that the catalysts experience phase transition from amorphous Co-B to crystalline cobalt hydroxide with increase in calcination temperatures. The reaction performance is also dependent on the concentration of NaBH{sub 4}, and the hydrogen generation rate increases for lower NaBH{sub 4} concentrations and decreases after reaching a maximum at 10 wt.% of NaBH{sub 4}. (author)

Preparation, surface characterization and performance of a Fischer-Tropsch catalyst of cobalt supported on silica nanosprings

International Nuclear Information System (INIS)

Kengne, Blaise-Alexis Fouetio; Alayat, Abdulbaset M.; Luo, Guanqun; McDonald, Armando G.; Brown, Justin; Smotherman, Hayden; McIlroy, David N.

2015-01-01

Graphical abstract: - Highlights: • Determined that the reduction of Co nanoparticles on silica nanosprings 200 °C higher than the reduction temperature of Co in a solgel support. • The high reduction temperature of Co supported on silica nanosprings is attributed to the heat transfer properties of the nanosprings due to their high surface area. Co-silica nanospring Fischer-Tropsch catalyst can be used to produce drop in fuels such as JP-4. - Abstract: The reduction of cobalt (Co) catalyst supported on silica nanosprings for Fischer-Tropsch synthesis (FTS) has been monitored by X-ray photoelectron spectroscopy (XPS) and compared to FT catalytic activity. The cobalt is present in the starting catalyst as a Co 3 O 4 spinel phase. A two-step reduction of Co 3 O 4 to CoO and then to Co 0 is observed, which is consistent with the results of H 2 -temperature programmed reduction. During the reduction the two steps occur concurrently. The deconvolution of the Co 2p core level state for the catalyst reduced at 385 °C and 1.0 × 10 −6 Torr of H 2 revealed signatures of Co 0 , CoO, and Co 3 O 4 . The reduction saturates at a Co o concentration of approximately 41% after 20 h, which correlates with the activity and lifetime of the catalyst during FTS testing. Conversely, at 680 °C and 10 Torr of H 2 , the catalyst is completely reduced after 10 h. The evolution of the Co d-band at the Fermi level in the valence band XPS spectrum definitively verifies the metallic phase of Co. FTS evaluation of the Co/NS catalyst reduced at 609 °C showed higher production rate (3-fold) of C 6 -C 17 hydrocarbons than the catalyst reduced at 409 °C and is consistent with the XPS analysis.

Monitoring of mass flux of catalyst FCC in a Cold Pilot Unit by gamma radiation transmission

International Nuclear Information System (INIS)

Brito, Marcio Fernando Paixao de

2014-01-01

This paper proposes a model for monitoring the mass flow of catalyst FCC - Fluid Catalytic Cracking - in a CPU - Cold Pilot unit - due to the injection of air and solid by gamma radiation transmission. The CPU simplifies the process of FCC, which is represented by the catalyst cycle, and it was constructed of acrylic, so that the flow can be visualized. The CPU consists of riser separation chamber and return column, and simulates the riser reactor of the FCC process. The catalyst is injected into the column back to the base of the riser, an inclined tube, where the compressed air means that there fluidization along the riser. When the catalyst comes in the separation chamber, the solid phase is sent to the return column, and the gas phase exits the system through one of the four cyclones at the top of the separation chamber. The transmission gamma of measures will be made by means of three test sections that have source and detector shielded. Pressure drop in the riser measurements are made through three pressure gauges positioned on the riser. The source used was Am-241 gamma ray with energy of 60 keV, and detector used was a scintillator of NaI (Tl) of 2 x 2 . Measures the mass flow of catalyst are made by varying the seal of the catalyst, and density of solid in the riser because with the combination of these measures can determine the speed of the catalyst in the riser. The results show that the transmission gamma is a suitable technique for monitoring the flow of catalyst, flow model in CPU is annular, tomography third generation is more appropriate to study the CPU and the density variation in circulation in the CPU decreases linearly with increasing air flow. (author)

PET-modified red mud as catalysts for oxidative desulfurization reactions.

Science.gov (United States)

do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

2017-07-01

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

The Role of Catalyst Properties on Methanol Oxidation over V{sub 2}O{sub 5}-TiO{sub 2} Using Ozone

Energy Technology Data Exchange (ETDEWEB)

Sahle-Demessie, Endalkachew [US EPA, Office of Research and Development, NRML (United States)], E-mail: sahle-demessie.endalkachew@epa.gov; Almquist, Catherine B. [Miami University, Paper Science and Chemical Engineering Department (United States); Sehker, Sridara Chandra [US EPA, Office of Research and Development, NRML (United States)

2008-08-15

Oxidation of methanol over V{sub 2}O{sub 5} catalysts supported on anatase TiO{sub 2} that were prepared using sol-gel formation and impregnation procedures were investigated. The effects of incorporating Mg in sol-gel to influence the properties of the catalyst were also studied. The process provides an alternative low temperature reaction pathway for reducing emissions of hazardous air pollutant (HAPs) such as methanol and total reduced sulfur compounds (TRS) from pulp and paper mills. The bulk and surface composition of the catalysts were determined by XRD and SEM-EDAX, respectively. The X-ray diffraction patterns of the vanadia-titania catalysts showed mainly the anatase phase of TiO{sub 2}. Temperature programmed desorption of methanol from the different catalyst showed that the {alpha} and {beta} peaks differ significantly with V content and addition of Mg. The combination of gas phase and surface reactions on the V/TiO{sub 2} catalysts reduced the amount of ozone required for high degradation of methanol to mainly CO{sub x} with small quantities of methyl formate. In the absence of ozone the catalysts showed very low activity. It is hypothesized that the ozone is directly influencing the V{sup 4+} and V{sup 5+} redox cycle of the catalyst. Oxidation of methanol is influenced by the operation variables and catalyst properties. The results of this study revealed that the V content has significant influence on the catalyst activity, and the optimum vanadia loading of about 6 wt%. Higher turnover frequencies were observed over sol-gel catalysts than with catalysts prepared by the impregnation method.

In-situ hydrodeoxygenation of phenol by supported Ni catalyst-explanation for catalyst performance

DEFF Research Database (Denmark)

Wang, Ze; Zeng, Ying; Lin, Weigang

2017-01-01

In-situ hydrodeoxygenation of phenol with aqueous hydrogen donor over supported Ni catalyst was investigated. The supported Ni catalysts exerted very poor performance, if formic acid was used as the hydrogen donor. Catalyst modification by loading K, Na, Mg or La salt could not make the catalyst...... performance improved. If gaseous hydrogen was used as the hydrogen source the activity of Ni/Al2O3 was pretty high. CO2 was found poisonous to the catalysis, due to the competitive adoption of phenol with CO2. If formic acid was replaced by methanol, the catalyst performance improved remarkably, with major...... products of cyclohexanone and cyclohexanol. The better effect of methanol enlightened the application of the supported Ni catalyst in in-situ hydrodeoxygenation of phenol....

Isobutane alkylation over solid catalysts

Energy Technology Data Exchange (ETDEWEB)

Kozorezov, Y.I.; Lisin, V.I.

1979-05-01

Commercial alumina modified with 6Vertical Bar3< by wt boron trifluoride was active in isobutane alkylation with ethylene in a flow reactor at 5:1 isobutane-ethylene and 5-20 min reaction time. The reaction rate was first-order in ethylene and increased with increasing temperature (20/sup 0/-80/sup 0/C) and ethylene pressure (0.2-3 atm). The calculated activation energy was 8.4 kj. Kinetic data and the activity of tert.-butyl chloride, but not ethyl chloride as alkylating agents in place of ethylene suggested a carbonium-ion chain mechanism involving both surface and gas-phase reactions. The ethylene-based yield of the alkylate decreased from 132 to 41Vertical Bar3< by wt after nine hours on stream, and its bromine number increased from 0.2 to 1 g Br/sub 2//100 ml. This inhibition was attributed to adsorption on the active acidic sites of the reaction products, particularly C/sub 10//sup +/ olefins. Catalyst stabilization could probably be achieved by selecting an appropriate solvent that would continuously desorb the inhibiting products from the catalyst surface.

In-situ X-ray diffraction activation study on an Fe/TiO2 pre-catalyst.

Science.gov (United States)

Rayner, Matthew K; Billing, David G; Coville, Neil J

2014-06-01

This study focuses on the use of in situ powder X-ray diffraction (PXRD) and quantitative phase analysis using the Rietveld method to monitor the structural properties of a titania-supported iron (10% Fe/TiO2) pre-catalyst during calcination (oxidation) and activation (reduction) in the temperature range 25-900°C. The TiO2 oxidation study revealed an increase in anatase particle size before the anatase to rutile phase transformation, lending credibility to the bridging mechanism proposed by Kim et al. [(2007), Mater. Sci. Forum, 534-536, 65-68]. Pre-catalyst oxidation experiments allowed for the determination of a suitable calcination temperature (450°C) of the pre-catalyst in terms of maximum hematite concentration and appropriate particle size. These experiments also confirmed that the anatase to rutile phase transformation occurred at higher temperatures after Fe addition and that anatase was the sole donor of Ti(4+) ions, which are known to migrate into hematite (Gennari et al., 1998), during the formation of pseudobrookite (Fe2TiO5) at temperatures above 690°C. Using the results from the oxidation experiments, two pre-catalyst samples were calcined at different temperatures; one to represent the preferred case and one to represent a case where the pre-catalyst had been excessively heated. Samples of the excessively heated catalysts were exposed to different reducing gas atmospheres (5, 10 and 100% H2/N2) and heated in the in situ PXRD reactor, so that diffraction data could be collected during the activation process. The results show that reduction with gases containing low concentrations of H2 (5 and 10%) led to the formation of ilmenite (FeTiO3) and we were able to show that both anatase and rutile are consumed in the reaction. Higher concentrations of H2 led to the formation of magnetite (Fe3O4) and metallic iron (Fe(0)). We also noted a decrease in the anatase to rutile transformation temperature under reducing atmospheres when compared with the pre-catalyst

Non-PGM cell catalysts

Energy Technology Data Exchange (ETDEWEB)

Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

2017-09-27

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

Electro-catalysts for hydrogen production from ethanol for use in SOFC anodes

Energy Technology Data Exchange (ETDEWEB)

Silva, Marcos Aurelio da; Paz Fiuza, Raigenis da; Guedes, Bruna C.; Pontes, Luiz A.; Boaventura, Jaime Soares [UFBA, Salvador, Bahia (Brazil). Energy and Materials Science Group

2010-07-01

Nickel and cobalt catalysts, supported on YSZ, were prepared by wet impregnation, with and without citric acid; the metal load was 10 and 35% by weight. The catalyst composition was studied by XRF, XPS and SEM-EDS. At low metal concentration, the results of these techniques presented comparables figures; at high concentration, SEM-EDS suggested a non-uniform distribution. The analysis showed that the solids were mixed oxides and formed an alloy after reduction. The surface passivation was possible under controlled conditions. The catalytic test with the steam reforming of ethanol indicated that the metal load had almost no effect on the catalytic activity, but decreased its selectivity. Afterwards, a unitary SOFC was prepared with deposition of the cathode layer. AFM and EIS were used for the characterization of SOFC components. They showed that the electro-catalyst surface was almost all covered with the metal phase, including the large pore walls of the anode. The YSZ phase dominates the material conductance of the complete SOFC assembly (anode/electrolyte/cathode). The unitary SOFC was tested with hydrogen, gaseous ethanol or natural gas; the SOFC operating with ethanol and hydrogen fuel presented virtually no over-potential. (orig.)

Congressionally Directed Project for Passive NOx Removal Catalysts Research

Energy Technology Data Exchange (ETDEWEB)

Schneider, William [Univ. of Notre Dame, IN (United States)

2014-12-29

The Recipient proposes to produce new scientific and technical knowledge and tools to enable the discovery and deployment of highly effective materials for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) from lean combustion exhaust. A second goal is to demonstrate a closely coupled experimental and computational approach to heterogeneous catalysis research. These goals will be met through the completion of four primary technical objectives: First, an in-depth kinetic analysis will be performed on two prominent classes of NOx SCR catalysts, Fe- and Cu-exchanged beta and ZSM-5 zeolites, over a wide range of catalyst formulation and under identical, high conversion conditions as a function of gas phase composition. Second, the nanoscale structure and adsorption chemistry of these high temperature (HT) and low temperature (LT) catalysts will be determined using in situ and operando spectroscopy under the same reaction conditions. Third, first-principles molecular simulations will be used to model the metal-zeolite active sites, their adsorption chemistry, and key steps in catalytic function. Fourth, this information will be integrated into chemically detailed mechanistic and kinetic descriptions and models of the operation of these well- defined NOx SCR catalysts under practically relevant reaction conditions. The new knowledge and models that derive from this work will be published in the scientific literature.

Alloy catalyst material

DEFF Research Database (Denmark)

2014-01-01

The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...... of the novel catalyst material for synthesising hydrogen peroxide from oxygen and hydrogen, or from oxygen and water....

Nanosized spinel oxide catalysts for CO-oxidation prepared via CoMnMgAl quaternary hydrotalcite route

Energy Technology Data Exchange (ETDEWEB)

Mokhtar, M., E-mail: mmoustafa@kau.edu.s [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia); Basahel, S.N.; Al-Angary, Y.O. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia)

2010-03-18

Catalytic activity of the Co-Mn-Mg-Al mixed oxide spinel catalysts was examined in CO oxidation by O{sub 2}. The prepared catalysts were characterized by chemical analysis (ICP), infrared spectroscopy (FTIR), thermal analysis (TG, DTG), powder X-ray diffraction (XRD), surface area measurements, and scanning electron microscopy (SEM).The calcined hydrotalcite-like precursor was composed of spinel-like Co-Mn-Mg-Al mixed oxide as the only XRD crystalline phases. The nanosized spinel oxide catalysts produced by calcination of hydrotalcites showed higher S{sub BET} than CoMn-hydrotalcite samples as calcination led to dehydroxylation and carbonate decomposition of anions in interlayer spaces. All the catalysts showed 100% CO conversion at high temperature even those calcined at 800 {sup o}C. A catalyst with Co/Mn = 4 and calcined at 500 {sup o}C showed 100% CO conversion at 160 {sup o}C. Moreover, this catalyst exhibited quite good durability without deactivation in 60 h stability test.

Design of bimetal catalysts Pt-Ni/CeO_2-1D for generation of H_2 by the reforming reaction of methanol

International Nuclear Information System (INIS)

Sarmiento F, I.

2016-01-01

CeO_2 nano rods were synthesized by hydrothermal method and were used as support for preparing catalysts bimetallic Pt Ni / CeO_2-1D. The catalysts were prepared by classical impregnation by the conventional wet method. The prepared catalysts are Pt (0.5 %) - Ni (5 %) / CeO_2 and Pt (0.5 %) - Ni (15 %) / CeO_2, which were characterized by different physico-chemical techniques: Bet, Sem, TPR and XRD, that were evaluated in the Auto thermal Steam reforming of Methanol for H_2 production. The Bet surface area results, show that the surface area of the catalysts decreases as the nominal load of Ni in the catalyst, increases. Sem shows, that the catalyst support (CeO_2-1D) and the bimetallic catalysts are conformed by nano rods. By XRD were identified the crystalline phases present, in the catalytic material: cerianite distinctive phase of cerium oxide and metallic Ni; however it was not possible to observe diffraction peaks of Platinum using this technique. The temperature-programmed reduction (TPR) analysis allowed to obtain the reduction profiles, of the different species present on the catalysts. The catalytic activity tests carried out, showed that the catalysts total 100% methanol conversion is achieved at 300 degrees Celsius, making them excellent, to be used in reactions at low temperature conditions. Selectivity towards H_2, is very similar in both catalysts, and it reaches a 50% yield per mole of methanol fed stoichiometrically. (Author)

KINETICS OF PALM OIL TRANSESTERIFICATION IN METHANOL WITH POTASSIUM HYDROXIDE AS A CATALYST

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Yoeswono Yoeswono

2010-06-01

Full Text Available A study on palm oil transesterification to evaluate the effect of some parameters in the reaction on the reaction kinetics has been carried out. Transesterification was started by preparing potassium methoxide from potassium hydroxide and methanol and then mixed it with the palm oil. An aliquot was taken at certain time interval during transesterification and poured into test tube filled with distilled water to stop the reaction immediately. The oil phase that separated from the glycerol phase by centrifugation was analyzed by 1H-NMR spectrometer to determine the percentage of methyl ester conversion. Temperature and catalyst concentration were varied in order to determine the reaction rate constants, activation energies, pre-exponential factors, and effective collisions. The results showed that palm oil transesterification in methanol with 0.5 and 1 % w/w KOH/palm oil catalyst concentration appeared to follow pseudo-first order reaction. The rate constants increase with temperature. After 13 min of reaction, More methyl esters were formed using KOH 1 % than using 0.5 % w/w KOH/palm oil catalyst concentration. The activation energy (Ea and pre-exponential factor (A for reaction using 1 % w/w KOH was lower than those using 0.5 % w/w KOH.   Keywords: palm oil, transesterification, catalyst, first order kinetics, activation energy, pre-exponential factor

The combined use of EBSD and EDX analyses for the identification of complex intermetallic phases in multicomponent Al-Si piston alloys

International Nuclear Information System (INIS)

Chen, C.-L.; Thomson, R.C.

2010-01-01

Multicomponent Al-Si based casting alloys are used for a variety of engineering applications, including for example, piston alloys. Properties include good castability, high strength, light weight, good wear resistance and low thermal expansion. In order for such alloys to continue operation to increasingly higher temperatures, alloy element modifications are continually being made to further enhance the properties. Improved mechanical and physical properties are strongly dependent upon the morphologies, type and distribution of the second phases, which are in turn a function of alloy composition and cooling rate. The presence of additional elements in the Al-Si alloy system allows many complex intermetallic phases to form, which make characterisation non-trivial. These include, for example, CuAl 2 , Al 3 Ni 2 , Al 7 Cu 4 Ni, Al 9 FeNi and Al 5 Cu 2 Mg 8 Si 6 phases, all of which may have some solubility for additional elements. Identification is often non-trivial due to the fact that some of the phases have either similar crystal structures or only subtle changes in their chemistries. A combination of electron backscatter diffraction (EBSD) and energy dispersive X-ray analysis (EDX) has therefore been used for the identification of the various phases. This paper will present comparisons of phase identification methodologies using EBSD alone, and in combination with chemical information, either directly or through post processing.

Mechanistic Study of the Gas-Phase In-Source Hofmann Elimination of Doubly Quaternized Cinchona-Alkaloid Based Phase-Transfer Catalysts by (+)-Electrospray Ionization/Tandem Mass Spectrometry

Science.gov (United States)

Yang, Rong-Sheng; Sheng, Huaming; Lexa, Katrina W.; Sherer, Edward C.; Zhang, Li-Kang; Xiang, Bangping; Helmy, Roy; Mao, Bing

2017-03-01

An unusual in-source fragmentation pattern observed for 14 doubly quaternized cinchona alkaloid-based phase-transfer catalysts (PTC) was studied using (+)-ESI high resolution mass spectrometry. Loss of the substituted benzyl cation (R1 or R2) was found to be the major product ion [M2+ - R1 + or R2 +]+ in MS spectra of all PTC compounds. A Hofmann elimination product ion [M - H]+ was also observed. Only a small amount of the doubly charged M2+ ions were observed in the MS spectra, likely due to strong Columbic repulsion between the two quaternary ammonium cations in the gas phase. The positive voltage in the MS inlet but not the ESI probe was found to induce this extensive fragmentation for all PTC diboromo-salts. Compound 1 was used as an example to illustrate the proposed in-source fragmentation mechanism. The mechanism of formation of the Hofmann elimination product ion [M - H]+ was further investigated using HRMS/MS, H/D exchange, and DFT calculations. The proposed formation of 2b as the major Hofmann elimination product ion was supported both by HRMS/MS and DFT calculations. Formation of product ion 2b through a concerted unimolecular Ei elimination pathway is proposed rather than a bimolecular E2 elimination pathway for common solution Hofmann eliminations.

Deuterium absorption in Mg{sub 70}Al{sub 30} thin films with bilayer catalysts: A comparative neutron reflectometry study

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Poirier, Eric [National Research Council Canada/Canadian Neutron Beam Centre, Bldg. 459, Chalk River Laboratories, Chalk River, ON, K0J 1J0 (Canada); Harrower, Chris T.; Kalisvaart, Peter [Chemical and Materials Engineering, University of Alberta and National Research Council Canada/National Institute for Nanotechnology, Edmonton, AB, T6G 2M9 (Canada); Bird, Adam [National Research Council Canada/Canadian Neutron Beam Centre, Bldg. 459, Chalk River Laboratories, Chalk River, ON, K0J 1J0 (Canada); Teichert, Anke [Helmholtz Zentrum Berlin, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Instituut voor Kern-en Stralingsfysica and INPAC, K.U. Leuven, Celestijnenlaan 200D, B-3001 Leuven (Belgium); Laboratorium voor Vaste-Stoffysica en Magnetisme and INPAC, K.U. Leuven, Celestijnenlaan 200D, B-3001 Leuven (Belgium); Wallacher, Dirk; Grimm, Nico; Steitz, Roland [Helmholtz Zentrum Berlin, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Mitlin, David [Chemical and Materials Engineering, University of Alberta and National Research Council Canada/National Institute for Nanotechnology, Edmonton, AB, T6G 2M9 (Canada); Fritzsche, Helmut, E-mail: Helmut.Fritzsche@nrc-cnrc.gc.ca [National Research Council Canada/Canadian Neutron Beam Centre, Bldg. 459, Chalk River Laboratories, Chalk River, ON, K0J 1J0 (Canada)

2011-05-05

Highlights: > Mg{sub 70}Al{sub 30} thin films studied for hydrogen absorption using in situ neutron reflectometry. > Films with Ta/Pd, Ti/Pd and Ni/Pd bilayer catalysts systematically compared. > Measurements reveals deuterium spillover from the catalysts to the MgAl phase. > The use of Ti-Pd bilayer offers best results in terms of amount absorbed and kinetics. > Key results cross-checked with X-ray reflectometry. - Abstract: We present a neutron reflectometry study of deuterium absorption in thin films of Al-containing Mg alloys capped with a Ta/Pd, Ni/Pd and Ti/Pd-catalyst bilayer. The measurements were performed at room temperature over the 0-1 bar pressure range under quasi-equilibrium conditions. The modeling of the measurements provided a nanoscale representation of the deuterium profile in the layers at different stages of the absorption process. The absorption mechanism observed was found to involve spillover of atomic deuterium from the catalyst layer to the Mg alloy phase, followed by the deuteration of the Mg alloy. Complete deuteration of the Mg alloy occurs in a pressure range between 100 and 500 mbar, dependent on the type of bilayer catalyst. The use of a Ti/Pd bilayer catalyst yielded the best results in terms of both storage density and kinetic properties.

Vibration measurements of automobile catalyst

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Aatola, Seppo

1994-09-01

Vibration of catalyst cell, which is inside the casing of the catalyst, is difficult to measure with usual measuring instrumentation. When catalyst is in use, there is hot exhaust gas flow though the catalyst cell and temperature of the cell is approximately +900 degree(s)C. Therefore non-contact Laser- Doppler-Vibrometer was used to measure vibration velocity of the catalyst cell. The laser beam was directed towards the cell through pipe which was put through and welded to the casing of the catalyst. The outer end of the pipe was screw down with a tempered class to prevent exhaust gas flow from the pipe. The inner end of the pipe was open and few millimeters away from the measuring point. Catalyst was attached to the engine with two ways, rigidly close to the engine and flexible under the engine. The engine was running in test bench under controlled conditions. Vibration measurements were carried out during constant running speeds of the engine. Vibration signals were captured and analyzed with FFT-analyzer. Vibration of catalyst cell was strongest at running speed of 5000 rpm, from 10 to 20 g (1 g equals 9.81 ms-2), when catalyst was attached rigidly close to the engine. At running speed of 3000 rpm, vibration of catalyst cell was from 2 to 3 g in most cases, when catalyst was attached either rigidly or flexible to the engine. It is estimated that in real life, i.e. when catalyst is attached to car with same engine, vibration of catalyst cell at running speed of 5000 rpm is somewhere between 1 and 10 g. At running speed of 3000 rpm, which may be more often used when driving car (car speed approximately 100 kmh-1), vibration of catalyst cell is probably few g's.

Study of propane partial oxidation on vanadium-containing catalysts

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Komashko, G.A.; Khalamejda, S.V.; Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

1998-12-31

The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form phosphates and, according to, to create space limitations for the paraffin molecule movement out of the active group boundaries, this can be one more support in favour of the selectivity increase. With this point of view very interesting results were obtained. It has been shown that the more limited the size of the vanadium unit, the higher the selectivity is. Monoclinic phase AV{sub 2}P{sub 2}O{sub 10} which consists in clusters of four vanadium atoms is sensibly more reactive than the orthorhombic phase consists in V{sub {infinity}} infinite chains. (orig.)

Superior mercury-free catalysts for acetylene hydrochlorination to VCM. Achieving high productivities and long catalyst life-time

Energy Technology Data Exchange (ETDEWEB)

Liebens, A.T.; Piccinini, M. [Solvay S.A., Bruxelles (Belgium)

2013-11-01

New mercury-free catalytic systems based on the use of ionic liquids (IL) and noble metals (e.g. Pd, Au) have been evaluated for the hydrochlorination reaction of acetylene to produce Vinyl Chloride Monomer (VCM). Two different approaches have been investigated: gas-liquid homogeneous catalytic systems in the presence of molten IL/Metal and heterogeneous gas-solid ones using solid materials. For the latter case, very positive results have been obtained using SILP-type catalysts (SILP: Supported Ionic Liquid Phase) where IL/Metal were deposited onto a solid mesoporous support. Remarkably, both systems display very high Space Time Yield (STY) and breakthrough life-time stability. No deactivation is observed even after 500 h on stream indicating the strong advantages of these new materials compared to most investigated Au/C supported systems. The development of heterogeneous catalysts was preferred as the scale-up of gas-liquid technology implies important CAPEX investments to convert current plants from gas-solid to gas-liquid equipment. (orig.)

DWPF coupled feed flowsheet material balance with batch one sludge and copper nitrate catalyst

Energy Technology Data Exchange (ETDEWEB)

Choi, A.S.

1993-09-28

The SRTC has formally transmitted a recommendation to DWPF to replace copper formate with copper nitrate as the catalyst form during precipitate hydrolysis [1]. The SRTC was subsequently requested to formally document the technical bases for the recommendation. A memorandum was issued on August 23, 1993 detailing the activities (and responsible individuals) necessary to address the impact of this change in catalyst form on process compatibility, safety, processibility environmental impact and product glass quality [2]. One of the activities identified was the preparation of a material balance in which copper nitrate is substituted for copper formate and the identification of key comparisons between this material balance and the current Batch 1 sludge -- Late Wash material balance [3].

Catalyst for microelectromechanical systems microreactors

Science.gov (United States)

Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

2010-06-29

A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

Sulphide phases in Y zeolite for hydro-treatment reactions; Phase sulfures dans une zeolithe Y pour l'hydrotraitement

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Leyrit, P.

1999-06-28

Several types of single (Mo, Co, Pd, Pt) or binary (MoCo, PdCo, PtCo) sulphides phases supported on a HY zeolite were studied. The catalysts were first prepared and characterised in the oxide form. Their reactivity was then evaluated in toluene hydrogenation and 4.6-dimethyl-dibenzo-thiophene hydro-desulfurization reactions. Characterisation of sulphide phases supported on HY zeolite was carried out by elemental analysis, X-Ray Diffraction (XRD), Transmission Electron Microscopy and Scanning Transmission Electron Microscopy (STEM), Extended X-Ray Absorption Fine Structure (EXAFS) and Temperature Programmed Reduction coupled with HS analysis. The results show that. compared with alumina supported catalysts, zeolite used as a support enables extremely active catalysts to be obtained. It appears in particular that molybdenum sulphide phases inside the zeolite have a very high intrinsic activity at low molybdenum content. This activity is attributed to highly dispersed molybdenum sulphide phases differing from MoS{sub 2} slabs and probably present as clusters. The influence of cobalt depends of its concentration. Thus at low loadings cobalt has a strong negative effect. It has been shown, in the molybdenum case, that cobalt interaction leads to an increase in the sulphur content of the molybdenum phases. At higher cobalt loading, the formation of a mixed phase is possible but the degree of promotion remains limited. This work emphasises the advantages of using zeolite supported sulphide phases, and especially Mo and Pd phases, in the hydro-treatment reactions. It seems however that single phases present a greater interest than binary phases. (author)

Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

Science.gov (United States)

Zhang, Lei; Wen, Xin; Lei, Zhang; Gao, Long; Sha, Xiangling; Ma, Zhenhua; He, Huibin; Wang, Yusu; Jia, Yang; Li, Yonghui

2018-04-01

Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction) was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction), SEM (scanning electron microscope), BET test and transient test. The experiments show that: * The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. * The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. * The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

Study on the mechanism of a manganese-based catalyst for catalytic NOX flue gas denitration

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Lei Zhang

2018-04-01

Full Text Available Manganese-based bimetallic catalysts were prepared with self-made pyrolysis coke as carrier and its denitration performance of low-temperature SCR (selective catalyst reduction was studied. The effects of different metal species, calcination temperature, calcination time and the metal load quantity on the denitration performance of the catalyst were studied by orthogonal test. The denitration mechanism of the catalyst was analyzed by XRD (X-ray diffraction, SEM (scanning electron microscope, BET test and transient test. The experiments show that: ① The denitration efficiency of Mn-based bimetallic catalysts mainly relates to the metal type, the metal load quantity and the catalyst adjuvant type. ② The optimal catalyst preparation conditions are as follows: the load quantity of monometallic MnO2 is 10%, calcined at 300°C for 4h, and then loaded with 8% CeO2, calcined at 350°Cfor 3h. ③ The denitration mechanism of manganese-based bimetallic oxide catalysts is stated as: NH3 is firstly adsorbed by B acid center Mn-OH which nears Mn4+==O to form NH4+, NH4+ was then attacked by the gas phase NO to form N2, H2O and Mn3+-OH. Finally, Mn3+-OH was oxidized by O2 to regenerate Mn4+.

Identification of microfluidic two-phase flow patterns in lab-on-chip devices.

Science.gov (United States)

Yang, Zhaochu; Dong, Tao; Halvorsen, Einar

2014-01-01

This work describes a capacitive sensor for identification of microfluidic two-phase flow in lab-on-chip devices. With interdigital electrodes and thin insulation layer utilized, this sensor is capable of being integrated with the microsystems easily. Transducing principle and design considerations are presented with respect to the microfluidic gas/liquid flow patterns. Numerical simulation results verify the operational principle. And the factors affecting the performance of the sensor are discussed. Besides, a feasible process flow for the fabrication is also proposed.

Identification method for gas-liquid two-phase flow regime based on singular value decomposition and least square support vector machine

International Nuclear Information System (INIS)

Sun Bin; Zhou Yunlong; Zhao Peng; Guan Yuebo

2007-01-01

Aiming at the non-stationary characteristics of differential pressure fluctuation signals of gas-liquid two-phase flow, and the slow convergence of learning and liability of dropping into local minima for BP neural networks, flow regime identification method based on Singular Value Decomposition (SVD) and Least Square Support Vector Machine (LS-SVM) is presented. First of all, the Empirical Mode Decomposition (EMD) method is used to decompose the differential pressure fluctuation signals of gas-liquid two-phase flow into a number of stationary Intrinsic Mode Functions (IMFs) components from which the initial feature vector matrix is formed. By applying the singular vale decomposition technique to the initial feature vector matrixes, the singular values are obtained. Finally, the singular values serve as the flow regime characteristic vector to be LS-SVM classifier and flow regimes are identified by the output of the classifier. The identification result of four typical flow regimes of air-water two-phase flow in horizontal pipe has shown that this method achieves a higher identification rate. (authors)

A Novel Approach for Prediction of Industrial Catalyst Deactivation Using Soft Sensor Modeling

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Hamed Gharehbaghi

2016-06-01

Full Text Available Soft sensors are used for fault detection and prediction of the process variables in chemical processing units, for which the online measurement is difficult. The present study addresses soft sensor design and identification for deactivation of zeolite catalyst in an industrial-scale fixed bed reactor based on the process data. The two main reactions are disproportionation (DP and transalkylation (TA, which change toluene and C9 aromatics into xylenes and benzene. Two models are considered based on the mass conservation around the reactor. The model parameters are estimated by data-based modeling (DBM philosophy and state dependent parameter (SDP method. In the SDP method, the parameters are assumed to be a function of the system states. The results show that the catalyst activity during the period under study has approximately a monotonic trend. Identification of the system clearly shows that the xylene concentration has a determining role in the conversion of reactions. The activation energies for both DP and TA reactions are found to be 43.8 and 18 kJ/mol, respectively. The model prediction is in good agreement with the observed industrial data.

Effect of Mo-Doped Mesoporous Al-SSP Catalysts for the Catalytic Dehydration of Ethanol to Ethylene

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Titinan Chanchuey

2016-01-01

Full Text Available The catalytic dehydration of ethanol to ethylene over the mesoporous Al-SSP and Mo-doped Al-SSP catalysts was investigated. The Al-SSP catalyst was first synthesized by the modified sol-gel method and then doped with Mo by impregnation to obtain 1% Mo/Al-SSP and 5% Mo/Al-SSP catalysts (1 and 5 wt% of Mo. The final catalysts were characterized using various techniques such as XRD, N2 physisorption, SEM/EDX, TEM, and NH3-TPD. The catalytic activity for all catalysts in gas-phase ethanol dehydration reaction was determined at temperature range of 200°C to 400°C. It was found that the most crucial factor influencing the catalytic activities appears to be the acidity. The acid property of catalysts depended on the amount of Mo loading. Increased Mo loading in Al-SSP resulted in increased weak acid sites, which enhanced the catalytic activity. Besides acidity, the high concentration of Al at surface of catalyst is also essential to obtain high activity. Based on the results, the most suitable catalyst in this study is 1% Mo/Al-SSP catalyst, which can produce ethylene yield of ca. 90% at 300°C with slight amounts of diethyl ether (DEE and acetaldehyde.

CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

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Didik Prasetyoko

2010-07-01

Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

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Thuan M. Huynh

2016-11-01

Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

STUDY OF IDENTIFICATION OF TWO-PHASE FLOW PARAMETERS BY PRESSURE FLUCTUATION ANALYSIS

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Ondrej Burian

2016-12-01

Full Text Available This paper deals with identification of parameters of simple pool boiling in a vertical rectangular channel by analysis of pressure fluctuation. In this work is introduced a small experimental facility about 9 kW power, which was used for simulation of pool boiling phenomena and creation of steam-water volume. Several pressure fluctuations measurements and differential pressure fluctuations measurements at warious were carried out. Main changed parameters were power of heaters and hydraulics resistance of channel internals. Measured pressure data was statistically analysed and compared with goal to find dependencies between parameters of two-phase flow and statistical properties of pressure fluctuation. At the end of this paper are summarized final results and applicability of this method for parameters determination of two phase flow for pool boiling conditions at ambient pressure.

Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

2016-01-04

The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

A Moessbauer spectroscopic study on the action of Ce in the catalyst for dehydrogenation of etylbenzene to styrene

Energy Technology Data Exchange (ETDEWEB)

Jiang Keyu, E-mail: keyujiang@126.com [East China Normal University, Department of Physics (China); Fan Qin; Chen Tong; Miao Changxi [Shanghai Research Institute of Petrochemical Technology, SINOPEC (China); Zhao Zhenji; Yang Xielong [East China Normal University, Department of Physics (China)

2012-03-15

Two series of Fe-K catalysts for dehydrogenation of ethylbenzene to styrene were prepared with different amounts and different compounds of the additional element Ce. Moessbauer spectroscopy has been used to determine the Fe compound in the catalyst and to investigate the effect of Ce. The catalytic properties of the catalysts have also been measured. The results show that the element Ce in the catalyst is favorable to form the predecessor of the catalytic active phase, the compound KFe{sub 11}O{sub 17} and that the optimal percentage of CeO{sub 2} is 8%{approx}15% in the catalyst which is favorable to the formation of KFe{sub 11}O{sub 17} and to get better catalytic properties.

Effect of pretreatment temperature on catalytic performance of the catalysts derived from cobalt carbonyl cluster in Fischer-Tropsch Synthesis

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Byambasuren O

2017-02-01

Full Text Available The monometallic cobalt-based catalysts were prepared by pretreating the catalysts derived from carbonyl cluster precursor (CO6Co2CC(COOH2 supported on γ-Al2O3 with hydrogen at 180, 220, and 260°C respectively. The temperature effect of the pretreatments on the structure evolution of cluster precursors and the catalytic performance of the Fischer-Tropsch (F-T synthesis was investigated. The pretreated catalyst at 220°C with unique phase structure exhibited best catalytic activity and selectivity among three pretreated catalysts. Moreover, the catalysts exhibited high dispersion due to the formation of hydrogen bonds between the cluster precursor and γ-Al2O3 support.

[Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

Science.gov (United States)

Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

2013-06-01

Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

Regeneration of Hydrotreating and FCC Catalysts

Energy Technology Data Exchange (ETDEWEB)

CM Wai; JG Frye; JL Fulton; LE Bowman; LJ Silva; MA Gerber

1999-09-30

Hydrotreating, hydrocracking, and fluid catalytic cracking (FCC) catalysts are important components of petroleum refining processes. Hydrotreating and hydrocracking catalysts are used to improve the yield of high-quality light oil fractions from heavier crude oil and petroleum feedstocks containing high levels of impurities. FCC catalysts improve the yield of higher octane gasoline from crude oil. Residuum hydrotreating and cracking catalysts are susceptible to irreversible deactivation caused by adsorption of sulfur and by metals impurities, such as vanadium and nickel. The gradual buildup of these impurities in a hydrotreating catalyst eventually plugs the pores and deactivates it. Nickel and vanadium adversely affect the behavior of cracking catalysts, reducing product yield and quality. Replacing deactivated catalysts represents a significant cost in petroleum refining. Equally important are the costs and potential liabilities associated with treating and disposing spent catalysts. For example, recent US Environmental Protection Agency rulings have listed spent hydrotreating and hydrorefining catalysts as hazardous wastes. FCC catalysts, though more easily disposed of as road-base or as filler in asphalt and cement, are still an economic concern mainly because of the large volumes of spent catalysts generated. New processes are being considered to increase the useful life of catalysts or for meeting more stringent disposal requirements for spent catalysts containing metals. This report discusses a collaborative effort between Pacific Northwest National Laboratory (PNNL) and Phillips Petroleum, Inc., to identify promising chemical processes for removing metals adhered to spent hydrodesulfurization (HDS, a type of hydrotreating catalyst) and FCC catalysts. This study, conducted by PNNL, was funded by the US Department of Energy's Bartlesville Project Office. Fresh and spent catalysts were provided by Phillips Petroleum. The FCC catalyst was a rare

Naphthenic acid removal from HVGO by alkaline earth metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Ding, L.; Rahimi, P.; Hawkins, R.; Bhatt, S.; Shi, Y. [National Centre for Upgrading Technology, Devon, AB (Canada); Natural Resources Canada, Devon, AB (Canada). CanmetENERGY

2009-07-01

This poster highlighted a study that investigated naphthenic acid removal from bitumen-derived heavy vacuum gas oil (HVGO) by thermal cracking and catalytic decarboxylation over alkaline earth-metal oxides and ZnO catalysts in a batch reactor and a continuous fixed-bed reactor. X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA) temperature-programmed desorption (TPD) of carbon dioxide (CO{sub 2}-TPD), and scanning electron microscopy were used to characterize the fresh and spent catalysts. With MgO and ZnO, naphthenic acid removal proceeded via catalytic decarboxylation. No crystalline phase changes were observed after reaction. With CaO, multiple pathways such as catalytic decarboxylation, neutralization, and thermal cracking were responsible for naphthenic acid conversion. The spent catalysts contained Ca(OH){sub 2} and CaCO{sub 3}. With BaO, naphthenic acid conversion occurred through neutralization. All BaO was converted to Ba(OH){sub 2} during the reaction. tabs., figs.

Effect of Drying Temperature on Iron Fischer-Tropsch Catalysts Prepared by Solvent Deficient Precipitation

Directory of Open Access Journals (Sweden)

Michael K. Albretsen

2017-01-01

Full Text Available A novel solvent deficient precipitation (SDP method to produce nanoparticles was studied for its potential in Fischer-Tropsch synthesis (FTS catalysis. Using Fe(NO33·9H2O as the iron-containing precursor, this method produces ferrihydrite particles which are then dried, calcined, reduced, and carbidized to form the active catalytic phase for FTS. Six different drying profiles, including final drying temperatures ranging between 80 and 150°C, were used to investigate the effect of ammonium nitrate (AN, a major by-product of reaction between Fe(NO33·9H2O and NH4HCO3 in the SDP method. Since AN has two phase-transitions within this range of drying temperatures, three different AN phases can exist during the drying of the catalyst precursors. These AN phases, along with physical changes occurring during the phase transitions, may affect the pore structure and the agglomeration of ferrihydrite crystallites, suggesting possible reasons for the observed differences in catalytic performance. Catalysts dried at 130°C showed the highest FTS rate and the lowest methane selectivity. In general, better catalytic performance is related to the AN phase present during drying as follows: phase III > phase II > phase I. However, within each AN phase, lower drying temperatures led to better catalytic properties.

Partial hydrogenation of alkynes on highly selective nano-structured mesoporous silica MCM-41 composite catalyst

International Nuclear Information System (INIS)

Kojoori, R.K.

2016-01-01

In this research, we have developed a silica MCM-41/Metformin/Pd (II) nano composite catalyst for the selective hydrogenation of alkynes to the corresponding (Z)-alkenes under a mild condition of atmospheric pressure and room temperature. Firstly, functionalized Si-MCM-41 metformin catalyst with the optimum performance was prepared. Then, the synthesized catalyst was elucidated by X-ray powder diffraction, BET surface area, FT-IR spectrophotometer, Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) and applied in partial hydrogenation of different alkynes, with high selectivity and high yield. The products were characterized by 1H-NMR, 13C-NMR, FT-IR, and Mass Spectrometry (MS) that strongly approved the (Z)-double bond configuration of produced alkenes. This prepared catalyst is competitive with the best palladium catalysts known for the selective liquid phase hydrogenation of alkynes and can be easily recovered and regenerated with keeping high activity and selectivity over at least three cycles with a simple regeneration procedure. (author)

Surface chemistry and microstructural analysis of CexZr1-xO2-y model catalyst surfaces

International Nuclear Information System (INIS)

Nelson, Alan E.; Schulz, Kirk H.

2003-01-01

Cerium-zirconium mixed metal oxides are widely used as promoters in automotive emissions control catalyst systems (three-way catalysts). The addition of zirconium in the cubic lattice of ceria improves the redox properties and the thermal stability, thereby increasing the catalyst efficiency and longevity. The surface composition and availability of surface oxygen of model ceria-zirconia catalyst promoters was considered to develop a reference for future catalytic reactivity studies. The microstructure was characterized with X-ray diffraction (XRD) to determine the effect of zirconium substitution on crystalline structure and grain size. Additionally, the Ce/Zr surface atomic ratio and existence of Ce 3+ defect sites were examined with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) for samples with different zirconium concentrations. The surface composition of the model systems with respect to cerium and zirconium concentration is representative of the bulk, indicating no appreciable surface species segregation during model catalyst preparation or exposure to ultrahigh vacuum conditions and analysis techniques. Additionally, the concentration of Ce 3+ defect sites was constant and independent of composition. The quantity of surface oxygen was unaffected by electron bombardment or prolonged exposure to ultrahigh vacuum conditions. Additionally, XRD analysis did not indicate the presence of additional crystalline phases beyond the cubic structure for compositions from 100 to 25 at.% cerium, although additional phases may be present in undetectable quantities. This analysis is an important initial step for determining surface reactions and pathways for the development of efficient and sulfur-tolerant automotive emissions control catalysts

Using artificial intelligence to improve identification of nanofluid gas–liquid two-phase flow pattern in mini-channel

Directory of Open Access Journals (Sweden)

Jian Xiao

2018-01-01

Full Text Available This work combines fuzzy logic and a support vector machine (SVM with a principal component analysis (PCA to create an artificial-intelligence system that identifies nanofluid gas-liquid two-phase flow states in a vertical mini-channel. Flow-pattern recognition requires finding the operational details of the process and doing computer simulations and image processing can be used to automate the description of flow patterns in nanofluid gas-liquid two-phase flow. This work uses fuzzy logic and a SVM with PCA to improve the accuracy with which the flow pattern of a nanofluid gas-liquid two-phase flow is identified. To acquire images of nanofluid gas-liquid two-phase flow patterns of flow boiling, a high-speed digital camera was used to record four different types of flow-pattern images, namely annular flow, bubbly flow, churn flow, and slug flow. The textural features extracted by processing the images of nanofluid gas–liquid two-phase flow patterns are used as inputs to various identification schemes such as fuzzy logic, SVM, and SVM with PCA to identify the type of flow pattern. The results indicate that the SVM with reduced characteristics of PCA provides the best identification accuracy and requires less calculation time than the other two schemes. The data reported herein should be very useful for the design and operation of industrial applications.

Using artificial intelligence to improve identification of nanofluid gas-liquid two-phase flow pattern in mini-channel

Science.gov (United States)

Xiao, Jian; Luo, Xiaoping; Feng, Zhenfei; Zhang, Jinxin

2018-01-01

This work combines fuzzy logic and a support vector machine (SVM) with a principal component analysis (PCA) to create an artificial-intelligence system that identifies nanofluid gas-liquid two-phase flow states in a vertical mini-channel. Flow-pattern recognition requires finding the operational details of the process and doing computer simulations and image processing can be used to automate the description of flow patterns in nanofluid gas-liquid two-phase flow. This work uses fuzzy logic and a SVM with PCA to improve the accuracy with which the flow pattern of a nanofluid gas-liquid two-phase flow is identified. To acquire images of nanofluid gas-liquid two-phase flow patterns of flow boiling, a high-speed digital camera was used to record four different types of flow-pattern images, namely annular flow, bubbly flow, churn flow, and slug flow. The textural features extracted by processing the images of nanofluid gas-liquid two-phase flow patterns are used as inputs to various identification schemes such as fuzzy logic, SVM, and SVM with PCA to identify the type of flow pattern. The results indicate that the SVM with reduced characteristics of PCA provides the best identification accuracy and requires less calculation time than the other two schemes. The data reported herein should be very useful for the design and operation of industrial applications.

Catalysts for synthetic liquid fuels

Energy Technology Data Exchange (ETDEWEB)

Bruce, L.A.; Turney, T.W.

1987-12-01

Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

Hydrogen production by steam reforming of liquefied natural gas over a nickel catalyst supported on mesoporous alumina xerogel

Science.gov (United States)

Seo, Jeong Gil; Youn, Min Hye; Cho, Kyung Min; Park, Sunyoung; Song, In Kyu

Mesoporous alumina xerogel (A-SG) is prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

Science.gov (United States)

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas phase toluene isopropylation over high silica mordenite

Indian Academy of Sciences (India)

Mordenite (HM) catalysts with three different Si/Al ratios were compared for their activity and selectivities in gas phase toluene isopropylation with isopropanol. Catalyst with Si/Al ratio 44.9 offered better cumene selectivity, hence, it was chosen for detailed kinetic investigations. The influence of various process parameters ...

Catalytic Activity Studies of Vanadia/Silica–Titania Catalysts in SVOC Partial Oxidation to Formaldehyde: Focus on the Catalyst Composition

Directory of Open Access Journals (Sweden)

Niina Koivikko

2018-02-01

Full Text Available In this work, silica–titania supported catalysts were prepared by a sol–gel method with various compositions. Vanadia was impregnated on SiO2-TiO2 with different loadings, and materials were investigated in the partial oxidation of methanol and methyl mercaptan to formaldehyde. The materials were characterized by using N2 physisorption, X-ray diffraction (XRD, X-ray fluorescence spectroscopy (XRF, X-ray photoelectron spectroscopy (XPS, Scanning transmission electron microscope (STEM, NH3-TPD, and Raman techniques. The activity results show the high importance of an optimized SiO2-TiO2 ratio to reach a high reactant conversion and formaldehyde yield. The characteristics of mixed oxides ensure a better dispersion of the active phase on the support and in this way increase the activity of the catalysts. The addition of vanadium pentoxide on the support lowered the optimal temperature of the reaction significantly. Increasing the vanadia loading from 1.5% to 2.5% did not result in higher formaldehyde concentration. Over the 1.5%V2O5/SiO2 + 30%TiO2 catalyst, the optimal selectivity was reached at 415 °C when the maximum formaldehyde concentration was ~1000 ppm.

The Application of Moessbauer Emission Spectroscopy to Industrial Cobalt Based Fischer-Tropsch Catalysts

International Nuclear Information System (INIS)

Loosdrecht, J. van de; Berge, P. J. van; Craje, M. W. J.; Kraan, A. M. van der

2002-01-01

The application of Moessbauer emission spectroscopy to study cobalt based Fischer-Tropsch catalysts for the gas-to-liquids process was investigated. It was shown that Moessbauer emission spectroscopy could be used to study the oxidation of cobalt as a deactivation mechanism of high loading cobalt based Fischer-Tropsch catalysts. Oxidation was observed under conditions that are in contradiction with the bulk cobalt phase thermodynamics. This can be explained by oxidation of small cobalt crystallites or by surface oxidation. The formation of re-reducible Co 3+ species was observed as well as the formation of irreducible Co 3+ and Co 2+ species that interact strongly with the alumina support. The formation of the different cobalt species depends on the oxidation conditions. Iron was used as a probe nuclide to investigate the cobalt catalyst preparation procedure. A high-pressure Moessbauer emission spectroscopy cell was designed and constructed, which creates the opportunity to study cobalt based Fischer-Tropsch catalysts under realistic synthesis conditions.

Synthesis H-Zeolite catalyst by impregnation KI/KIO3 and performance test catalyst for biodiesel production

Science.gov (United States)

Widayat, W.; Rizky Wicaksono, Adit; Hakim Firdaus, Lukman; Okvitarini, Ndaru

2016-02-01

The objective of this research is to produce H-catalyst catalyst that was impregnated with KI/KIO3. The catalyst was analyzed about surface area, X-Ray Diffraction (XRD) and performance test of catalyst for biodiesel production. An H-Zeolite catalyst was synthesized from natural zeolite with chemical treatment processing, impregnation KI/KIO3 and physical treatment. The results shows that the surface area of the catalyst by 27.236 m2/g at a concentration of 5% KI. XRD analysis shows peak 2-θ at 23.627o indicating that KI was impregnated on H-zeolite catalyst. The catalyst was tested in production of biodiesel using palm oil with conventional methods for 3 hour at temperature of 70-80 oC. The result for conversion Fatty Acid Methyl Ester (FAME) reached maximum value on 87.91% under production process using catalyst 5% KIO3-H zeolite.

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

International Nuclear Information System (INIS)

Amende, Max; Kaftan, Andre; Bachmann, Philipp; Brehmer, Richard; Preuster, Patrick; Koch, Marcus

2016-01-01

Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al_2O_3 model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al_2O_3 catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al_2O_3 model catalyst and core–shell pellet were only

Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

Energy Technology Data Exchange (ETDEWEB)

Amende, Max, E-mail: max.amende@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Kaftan, Andre, E-mail: andre.kaftan@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Bachmann, Philipp, E-mail: philipp.bachmann@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Brehmer, Richard, E-mail: richard.brehmer@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Preuster, Patrick, E-mail: patrick.preuster@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Koch, Marcus, E-mail: marcus.koch@crt.cbi.uni-erlangen.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); and others

2016-01-01

Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al{sub 2}O{sub 3} model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al{sub 2}O{sub 3} catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al{sub 2}O{sub 3} model catalyst and

Ce - promoted catalyst from hydrotalcites for CO2 reforming of methane: calcination temperature effect

Directory of Open Access Journals (Sweden)

Carlos Enrique Daza

2012-01-01

Full Text Available Ce-promoted Ni-catalysts from hydrotalcites were obtained. The effect of calcination temperature on the chemical and physical properties of the catalysts was studied. Several techniques were used to determine the chemical and physical characteristics of oxides. The apparent activation energies of reduction were determined. Catalytic experiments at 48 L g-1h-1 without pre-reduction in CO2 reforming of methane were performed. The spinel-like phase in these oxides was only formed at 1000 ºC. The reduction of Ni2+ in the oxides was clearly affected by the calcination temperature which was correlated with catalytic performance. The catalyst calcined at 700 ºC showed the greatest activity.

La2O3/CaO CATALYSTS AND ITS APPLICATION IN THE OXIDATIVE COUPLING OF METHANE

OpenAIRE

Garrido-Schaeffer, A.; Dedios Yenque, G.; Ponce Alvaréz, S.

2014-01-01

La2O3/CaO catalysts were prepared at different weight percentages of La2O3.Por the coprecipitation method described porRaO, CaCO3 is prepared and then it was impregnated in a solution of La (NO) 3.6H2O thus obtaining the catalyst precursor . precursors dried at 393K and calcined at 973K, obtaining 0-15% La2O3/CaO catalysts. XRF elemental qualitative analysis was performed. By FTIR carbonates adsorbed species was observed. The presence of La2O3 and CaO phases was confirmed by XRD and BET surfa...

Post-BEMUSE Reflood Model Input Uncertainty Methods (PREMIUM) Benchmark Phase II: Identification of Influential Parameters

International Nuclear Information System (INIS)

Kovtonyuk, A.; Petruzzi, A.; D'Auria, F.

2015-01-01

The objective of the Post-BEMUSE Reflood Model Input Uncertainty Methods (PREMIUM) benchmark is to progress on the issue of the quantification of the uncertainty of the physical models in system thermal-hydraulic codes by considering a concrete case: the physical models involved in the prediction of core reflooding. The PREMIUM benchmark consists of five phases. This report presents the results of Phase II dedicated to the identification of the uncertain code parameters associated with physical models used in the simulation of reflooding conditions. This identification is made on the basis of the Test 216 of the FEBA/SEFLEX programme according to the following steps: - identification of influential phenomena; - identification of the associated physical models and parameters, depending on the used code; - quantification of the variation range of identified input parameters through a series of sensitivity calculations. A procedure for the identification of potentially influential code input parameters has been set up in the Specifications of Phase II of PREMIUM benchmark. A set of quantitative criteria has been as well proposed for the identification of influential IP and their respective variation range. Thirteen participating organisations, using 8 different codes (7 system thermal-hydraulic codes and 1 sub-channel module of a system thermal-hydraulic code) submitted Phase II results. The base case calculations show spread in predicted cladding temperatures and quench front propagation that has been characterized. All the participants, except one, predict a too fast quench front progression. Besides, the cladding temperature time trends obtained by almost all the participants show oscillatory behaviour which may have numeric origins. Adopted criteria for identification of influential input parameters differ between the participants: some organisations used the set of criteria proposed in Specifications 'as is', some modified the quantitative thresholds

Hydroconversion of Waste Cooking Oil into Green Biofuel over Hierarchical USY-Supported NiMo Catalyst: A Comparative Study of Desilication and Dealumination

Directory of Open Access Journals (Sweden)

Zongwei Zhang

2017-09-01

Full Text Available The hydroconversion of waste cooking oil into hydrocarbon fuel was investigated over the hierarchical USY zeolite-supported NiMo catalysts which were prepared by dealumination ((NH42SiF6/desilication (NaOH. The physical and acidity properties of the hierarchical catalysts were characterized by X-ray diffraction (XRD, the Brunauer-Emmett-Teller (BET infrared spectroscopy of adsorbed pyridine (Py-IR, ammonia temperature-programmed desorption (NH3-TPD, and H2 temperature-programmed reduction (H2-TPR. The Brønsted/Lewis (B/L acid distribution was little affected by dealumination and the acid density decreased significantly. However, the highly-desilicated catalysts decreased the B/L ratio obviously. Therefore, many more Mo species in the NiMoO4− and MoO3 phases were produced in the AHFS-treated catalysts, while more high-valence-state Mo species in the NiMoO4− phase were formed in the NaOH-treated catalysts. The AHFS-treated catalysts showed higher catalytic activity and better DCO2 selectivity and selective cracking for jet fuel. The 42.3% selectivity of jet fuel and 13.5% selectivity of jet-range aromatics was achieved over the 8 wt % (NH42SiF6-treated catalyst with 67% DCO2 selectivity.

Synthesis of Higher Alcohols via Syngas on Cu/Zn/Si Catalysts. Effect of Polyethylene Glycol Content

Science.gov (United States)

Cui, Rong-Ji; Yan, Xing; Fan, Jin-Chuan; Huang, Wei

2018-05-01

Cu/Zn/Si catalysts with different polyethylene glycol (PEG) content were prepared by a complete liquid-phase method, and characterized by XRD, H2-TPR, N2-adsorption, and XPS. The influence of PEG content on the higher alcohols synthesis from syngas was investigated. The results showed that addition of PEG can influence the texture and surface properties of the catalysts, and therefore affect their activity and product distribution. With an increase in PEG content, BET surface area, Cu crystallite size and surface active ingredient content of the catalysts first increased and then decreased, the CO conversion had similar variation tendency. However, the pore volume and pore diameter of the catalyst increased, and the binding energy of the active component and the content of Cu2O decreased, which resulted in higher catalyst selectivity towards higher alcohols. The highest C2+OH selectivity in total alcohols was 60.6 wt %.

Thermal conductivity of partially graphitized biocarbon obtained by carbonization of medium-density fiberboard in the presence of a Ni-based catalyst

Science.gov (United States)

Orlova, T. S.; Parfen'eva, L. S.; Smirnov, B. I.; Gutierrez-Pardo, A.; Ramirez-Rico, J.

2016-01-01

The thermal conductivity k and resistivity ρ of biocarbon matrices, prepared by carbonizing medium-density fiberboard at T carb = 850 and 1500°C in the presence of a Ni-based catalyst (samples MDF-C( Ni)) and without a catalyst (samples MDF-C), have been measured for the first time in the temperature range of 5-300 K. X-ray diffraction analysis has revealed that the bulk graphite phase arises only at T carb = 1500°C. It has been shown that the temperature dependences of the thermal conductivity of samples MDFC- 850 and MDF-C-850(Ni) in the range of 80-300 K are to each other and follow the law of k( T) ˜ T 1.65, but the use of the Ni-catalyst leads to an increase in the thermal conductivity by a factor of approximately 1.5, due to the formation of a greater fraction of the nanocrystalline phase in the presence of the Ni-catalyst at T carb = 850°C. In biocarbon MDF-C-1500 prepared without a catalyst, the dependence is k( T) ˜ T 1.65, and it is controlled by the nanocrystalline phase. In MDF-C-1500(Ni), the bulk graphite phase formed increases the thermal conductivity by a factor of 1.5-2 compared to the thermal conductivity of MDF-C-1500 in the entire temperature range of 5-300 K; k( T = 300 K) reaches the values of ˜10 W m-1 K-1, characteristic of biocarbon obtained without a catalyst only at high temperatures of T carb = 2400°C. It has been shown that MDF-C-1500(Ni) in the temperature range of 40‒300 K is characterized by the dependence, k( T) ˜ T 1.3, which can be described in terms of the model of partially graphitized biocarbon as a composite of an amorphous matrix with spherical inclusions of the graphite phase.

Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst

Energy Technology Data Exchange (ETDEWEB)

Do, Phuong T. M. [Univ. of Delaware, Newark, DE (United States); McAtee, Jesse R. [Univ. of Delaware, Newark, DE (United States); Watson, Donald A. [Univ. of Delaware, Newark, DE (United States); Lobo, Raul F. [Univ. of Delaware, Newark, DE (United States)

2012-12-12

The reaction of 2,5-dimethylfuran and ethylene to produce p-xylene represents a potentially important route for the conversion of biomass to high-value organic chemicals. Current preparation methods suffer from low selectivity and produce a number of byproducts. Using modern separation and analytical techniques, the structures of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst have been identified. From these data, a detailed reaction network is proposed, demonstrating that hydrolysis and electrophilic alkylation reactions compete with the desired Diels–Alder/dehydration sequence. This information will allow the rational identification of more selective catalysts and more selective reaction conditions.

Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

Science.gov (United States)

Akatay, Mehmed Cem

Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

Novel, high-activity hydroprocessing catalysts: Iron group phosphides

Science.gov (United States)

Wang, Xianqin

A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe2P, CoP and NO, were also prepared on a silica (SiO2) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N2 BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370°C). The reactivity studies showed that the nickel phosphide (Ni2P/SiO2) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/gamma-Al 2O3 catalyst at the same conditions, Ni2P/silica had a substantially higher HDS activity (100% vs. 76%) and HDN activity (82% vs. 38%). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni2P/SiO 2, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni2P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni2P/SiO2 sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an alpha-H activation

Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

NARCIS (Netherlands)

Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

2014-01-01

The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

Electron Tomography Reveals the Active Phase–Support Interaction in Sulfidic Hydroprocessing Catalysts

NARCIS (Netherlands)

Eijsbouts, Sonja; Li, Xuang; Juan-Alcaniz, Jana; van den Oetelaar, Leon C A; Bergwerff, Jaap; Loos, Joachim; Carlsson, Anna; Vogt, E.T.C.

2017-01-01

Conventional two-dimensional (2D) transmission electron microscopy of sulfidic hydroprocessing catalysts can be deceiving and give the impression that parts of the support are overloaded with active phase. High-angle annular dark field scanning transmission electron microscopy tomography reveals

Obtaining and characterization catalyst Ki/Al_2O_3 by physical dispersion process via wet

International Nuclear Information System (INIS)

Silva, M.C. da; Dantas, J.; Costa, A.C.F.M.; Costa, N.C.O.; Freitas, N.L. de