For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxidevanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the ...
This patent describes a catalyst composition. It consists of the catalytic oxides of iron, bismuth, molybdenum and magnesium as essential components and optionally the oxides of cobalt, nickel, phosphorus and arsenic.
A catalytic process for the oxidation of sulfur-containing gases , E.G., sulfur dioxide and simultaneous production of sulfuric acid wherein a sulfur-containing gas is reacted with an oxygencontaining gas in the presence of a catalyst comprising an iron group metal on a solid support comprising a zeolite in a silicaalumina matrix.
The authors investigate the possibility of the direct heterogeneous catalytic synthesis of ethylbenzoate from benzonitrile. The catalysts tested were oxides of aluminium, titanium, and vanadium. The main conversion product detected chromatographically was ethylbenzoate; benzaldehyde, benzamide, and benzanilide were also identified. Aluminium oxide was found to be the most effective catalyst.
Red mud is a by-product of bauxite processing through Bayer process. The amount of red mud generated depends largely on the type of ore used and the processing. Use of red mud as a catalyst can be a good alternative to the existing commercial catalysts. Its properties such as iron content in form of ferric oxide (Fe{sub 2}O{sub 3}), high surface area, sintering resistance, resistance to poisoning and low cost make it an attractive potential catalyst for many reactions. Besides red mud, ferric ion sludge from wastewater treatment plant has also been studied for its catalytic properties, mainly due to its ferric oxide constituent. This paper reviews the studies on red mud as a catalyst. The catalyst characteristics, reaction mechanisms involved and performance are examined and compared with iron oxide ...
Red mud is a waste product of the aluminium refining industry. It is composed of aluminium hydroxide and iron oxide. This study examined the feasibility of using red mud as a catalyst to eliminate volatile organic compounds in atmospheric pollutants. Volatile organic compounds can be eliminated by thermal oxidation between 600 and 1100 degrees C. However, the oxidation of volatile organic compounds can also be accomplished at lower temperatures (200 to 450 degrees C) if a catalyst is present. Currently, the low temperature destruction of volatile organic compounds is not widespread because of the difficulty in deactivating the catalyst. In this study, red mud was calcined in air at 500 degrees C. Under such conditions, the red mud converts to aluminium oxide and iron oxide. These 2 oxides are active ...
Alkali metal doped double perovskites containing manganese and at least one of cobalt, iron and nickel are useful in the oxidative coupling of alkane to higher hydrocarbons.
The oxidative dehydrodimerization of propylene to C/sub 3/-dimers (1,5-hexadiene and benzene) has been examined at 600/sup 0/C and atmospheric pressure using a (Bi/sub 2/O/sub 3/)/sub 0.85/(La/sub 2/O/sub 3/)/sub 0.15/ oxide ion-conducting catalyst in a reactor where a catalyst disk separates a feed of propylene in helium from air. The surface of the disk exposed to propylene was reoxidized not by gaseous O/sub 2/, but by the dissociative adsorption and reduction of dioxygen at the oxidant side of the disk, followed by oxide ion conduction to replace spent lattice oxygen. Selectivity to C/sub 3/-dimers when using lattice oxide migration to reoxidize the catalyst was considerably greater than when O/sub 2/ was added to the propylene feed under the same reaction conditions. This result supports the proposal that lattice ...
Experimental tests were performed in a continuous-flow hydrotreating unit at Pittsburgh Energy Technology Center to evaluate the performance of hydrous titanium-oxide supported (HTO) catalysts as hydrotreating catalysts for use in two-stage coal liquiefaction. Catalysts containing either a combination of CO, Ni, and Mo as the active metal components or Pd as the active metal componet were tested with representative hydrotreater feed stocks from the Wilsonville Advanced Coal Liquefaction Research and Development Facility. Catalyst performance evaluation was based on desulfurization and denitrogenation activity, the conversion of cyclohexane-insolbule material, and hydrogenation activity during 100-hour reactor runs. Results indicated that the HTO catalysts were comparable to a commercial Ni/Mo-alumina supported catalyst in the areas ...
The reverse micelle catalyst preparation method has been used to prepare catalysts on four supports: magnesium oxide, carbon, alumina- titania and steamed Y zeolite. These catalysts were not as active as a reference catalyst prepared during previous contracts to Union Carbide Corp. This catalyst was supported on steamed Y zerolite support and was impregnated by a pore-filling method using a nonaqueous solvent. Additional catalysts were prepared via pore- filling impregnation of steamed Y zeolites. These catalysts had levels of cobalt two to three and a half times as high as the original Union Carbide catalyst. On a catalyst volume basis they were much more active than the previous catalyst; on an atom by atom basis the cobalt was about of the same activity, ...
The oxidation of sulfur dioxide in gas diffusion electrodes (GDE) in the presence of a homogeneous catalyst, potassium iodide, is investigated. The influence of this catalyst on the voltage-current (V-I) characteristics of the electrodes and the utilization of sulfur dioxide is determined. It is shown that when using the homogeneous catalyst potassium iodide, the utilization can reach 95-100%.
The oxidative dehydrogenation (ODH) of light alkanes is an alternative way for the production of olefins. A wide variety of catalytic systems has been investigated. Vanadium oxide based catalysts were described in the literature as effective catalysts for the ODH of propane. The catalytic activity and selectivity depend on the kind of support material, the kind of dopants and the formation of complex metal oxide phases. In recent papers it was claimed that both orthovanadate and/or pyrovanadate species are selective for the ODH of propane. Niobia based materials were investigated as catalysts for acidic and selective oxidation type reactions. In the ODH of propane niobia exhibited a high selectivity to propene but the conversion of propane was low. V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} catalysts proved to be catalytically ...
The aim of this work is to test the catalytic oxidation of pyridine over zeolite-supported catalysts and to compare the difference in their activities for the oxidation of pyridine. The catalytic oxidation of pyridine pollutant on a series of copper-supported catalysts, inclusive of Cu/beta, Cu/ZSM-5, Cu/MCM-41 and Cu/{gamma}-Al{sub 2}O{sub 3}, in the presence of excess oxygen was studied. The activity of the copper-supported catalysts for the pyridine oxidation could be correlated with the binding energy of oxygen coordinated to metal copper, while the ability to control the yield of NO{sub x} appeared to be strongly dependent on the binding energy of NO bonded to metal copper. On these catalysts, two copper species, Cu(H{sub 2}O){sub 6}{sup 2+} ions and CuO were identified, in which Cu{sup 2+} ions had higher activity ...
The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg-Al mixed oxides with Mg/(Al + Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C{sub 4}-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reaction with the selective way, i.e., the oxydehydrogenation process by a redox mechanism. Infrared spectroscopy data of 1-butene adsorbed on supported vanadium ...
Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
It has been discovered that when Taiheiyo coal pulverized to 200 mesh or smaller is dispersed in naphthalene, a non-hydrogen-donor solvent, and reacted under hydrogen pressure in the presence of a red mud/sulfur catalyst, the catalyst exhibits activity in the regeneration of hydrogen donor solvents which have been hydrogen-depleted in the course of coal liquefaction. It is already known that inorganic matter contained in coal acts as a catalyst in liquefaction. This suggests that the reported effect of the red mud/sulfur catalyst is due to the iron oxide reacting with the sulfur and forming pyrrhotite. 22 refs., 6 figs., 1 tab.
Pt-based ternary catalysts have been proposed as electrode materials for low temperature fuel cells. Pt-Ru-based ternary catalysts were tested as anode materials with improved CO tolerance or enhanced activity for methanol or ethanol oxidation. Ternary catalysts based on platinum alloyed with first row transition metals were tested as cathode materials with improved activity for the oxygen reduction. This paper presents an overview of the preparation methods and structural characteristics of these ternary catalysts. (author)
The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxidecatalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much ...
The catalytic effects of copper-aluminium-magnesium oxides in the oxidative coupling of phenylethyne is described. The importance of surface properties as a redox site are discussed.
A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the ...
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 ...
This work studied the effect of the nature of the metal on the performance of Co/CeO{sub 2}, Pd/CeO{sub 2} and Pt/CeO{sub 2} catalysts in the partial oxidation of ethanol. Infrared spectroscopy of adsorbed ethanol and temperature programmed desorption of ethanol were performed in order to establish the reaction mechanism. Catalytic experiments revealed that the product distribution is strongly affected by the nature of the metal. Acetaldehyde was practically the only product formed on a Co/CeO{sub 2} catalyst while methane was also produced on Pt/CeO{sub 2} and Pd/CeO{sub 2} catalysts. These results were explained through a reaction mechanism proposed by the characterization techniques. Co/CeO{sub 2} and Pt/CeO{sub 2} catalysts show mainly ethoxy species at room temperature whereas acetate species is mainly formed on the Pd/CeO{sub 2} catalyst. The ethoxy ...
A nitrogen oxides decreasing combustion method comprising: mixing a fuel and air with each other; bringing the mixture obtained into contact with a packed catalyst; and adding a fresh supply of the fuel to the stream obtained to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion, characterized in that only a catalytic reaction or combustion occurs at the packed catalyst; the temperature of the packed catalyst is kept lower than the ignition temperature of the mixture; the adiabatic flame temperature which is reached by the non-catalytic thermal combustion of the mixed gas is lower than the temperature at which the nitrogen oxides occur. 39 figs.
The vast majority of fundamental studies of metal oxide selective oxidationcatalysts have been performed with single phase systems. These investigations established the basic tenents of the redox mechanism of selective oxidation and ammoxidation catalysis. By comparison, structural and kinetic investigations of multiphase oxidecatalysts are less numerous because of the inherent difficulties in understanding the relative contributions of separate phases to the catalytic behavior of the composite catalyst. Some attempts have been made in the past to understand the complex chemistry of multiphase catalysts and additional important insights have been realized more recently. However, a clear understanding of the most significant catalytic interactions between individual phases of a multiphase multicomponent redox ...
A new method of the synthesis of high molecular polybutylene terephthalate (PBT) is developed with the use of Irganox 1010, tris(nonylphenyl) phosphite and hypophosphite as stabilizers and boron nitride or boron oxide as a catalyst is proposed.
The authors present the results of their investigation of the effect of phosphorus compounds on the activity of tungsten-containing catalysts in the oxidation of ethane. They investigated tungsten-phosphorus catalysts with different phosphorus concentrations (calculated on the basis of P/sub 2/O/sub 5/). The catalysts were prepared by heat decomposition of the starting compounds at 750/sup 0/C for 4 h. As their starting compounds, they used two types of materials: heteropoly acids mixtures of monosubstituted ammonium phosphoric and tungstic acids. The specific surface area of the catalysts was determined using the nitrogen desorption method. The x-ray phase analysis was carried out using a DRON-1.5 diffractometer. The catalytic activity was determined using the impulse method in a reactor with a vibrofluidized catalyst layer.
In the dehydrodesulfurization of ethanethiol at 400/sup 0/C, the activities of sodium X, Y, and A zeolites decreased in the order given as did the activities of nickel, cobalt, zinc, cadmium, copper, silver, lead, manganese, barium, calcium, sodium, and iron Y zeolite catalysts. A volcano-shape order was observed between the catalytic activity and the electronegativity of the metal ions. The changes in the activity of hydrogen Y zeolite catalyst in ethanethiol dehydrodesulfurization and cumene dealkylation by calcination agreed with the decrease in the Broensted acidity but were independent of Lewis acidity. For hydrodesulfurization of thiophene, the activities of nickel, cobalt, copper, and silver Y zeolite catalysts decreased in the order given and were greater than for a commercial hydrodesulfurization catalyst; reduced and presulfided catalysts showed selective ...
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O_2. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change reversibly ...
The potential use of uranium in the field of catalysis is presented in the first part of this paper. Numerous applications of uranium binary oxides, as well as mixed oxides, are reviewed with a special emphasis on the role of U-Sb-O catalysts in selective oxidation (and ammoxidation) processes. Attempts are made to correlate the electronic structure of uranium, and especially the role that 5f electrons play in bonding, with its promising catalytic properties. In the second part, new data are given for uranium-bismuth mixed oxides in the catalytic oxidation of CO by O/sub 2/. Kinetic tests performed in a flow microreactor allow a mechanism to be proposed that involves the direct participation of lattice oxygen of the catalyst in the chemical process (redox mechanism). The high activity can be related to the ability of uranium to change ...
Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)
Formaldehyde oxidation was examined in a laboratory reactor over alumina-supported Pt, Pd, Rh, Ag, Cu-Cr, and Pd-Ag catalysts as part of a program to develop catalysts for lean-exhaust methanol-fueled vehicles. In general, the H/sub 2/CO oxidation behavior of the catalysts paralleled the CH/sub 3/OH oxidation behavior reported in Parts 1 and 2 of this series (Appl. Catal. 27(1986) 83; J. Catal. 103(1987) 419). Principal similarities were: high activity of Pt when there was no carbon monoxide (CO) in the feed, but strong inhibition by added CO; lower activity of Ag and Cu-Cr catalysts, but only weak inhibition due to added CO; enhanced activity of the Pd-Ag catalyst compared to Pd and Ag alone for feeds containing CO in addition to H/sub 2/CO; and, relatively poor activity of the Rh catalyst. The most ...
Our goal was a process to convert methane to higher hydrocarbons oxidatively, since this circumvents thermodynamic yield limits of a strictly degydrogenative process. Keller and Bhasin converted thermodynamic yield limits of a strictly dehydrogenative process. Keller and Bhasin converted methane to higher hydrocarbons by using metal oxides as oxidants, without co-fed oxygen. They stated that selectivity is necessarily poor if gaseous oxygen is present. Jones and Sofranko have also used reducible metal oxides as oxidants in a group of their parents, but later used some of those materials with continuous O{sub 2} feed without much loss of selectivity. Baerns, Lunsford and Otsuka have shown that high selectivity could be possible with co-fed O{sub 2} at least for low O{sub 2} partial pressures, over PbO-A1{sub 2}O{sub 3}, Li-MgO and rare earths. The performance of a group of ...
Despite the rapid development of literature pertaining to fundamental (1-4) studies of oxidation catalysis, a general theory of heterogeneous selective oxidation catalysis explaining the selectivity behavior of different metal oxide systems has not yet been developed. Redox mechanisms have been widely invoked in the kinetic and mechanistic descriptions of selective oxidation reactions, suggesting a dynamic behavior of hydrocarbon and oxygen interactions with the catalyst surface. Nevertheless, most of the recent theoretical approaches of this subject matter (5-7) are essentially static in nature. Correlations are made with surface structure on the basis of crystallographic considerations with selectivity being related to the nature, number, bond-strength and nearness of oxygen atoms in the neighborhood of adsorption centers. The effect of the reaction medium on the configuration of ...
Influence of residual K{sup +} on the preferential oxidation of CO in excess hydrogen (PROX) over CuO-CeO{sub 2} catalysts was investigated. CuO-CeO{sub 2} catalysts were characterized by BET, ICP, XRD, UV-Raman and TPR techniques. The results showed that the existence of residual K{sup +} made {alpha} peak in TPR of CuO-CeO{sub 2} catalysts shift to higher temperatures and depressed the PROX in the absence of CO{sub 2} and H{sub 2}O in the feed over CuO-CeO{sub 2} catalysts. However, small amount of residual K{sup +} was beneficial to the catalytic performance of CuO-CeO{sub 2} catalysts in the PROX in the presence of CO{sub 2} and H{sub 2}O in the feed. Consequently, residual K{sup +} with an appropriate content was beneficial to improve the catalytic performance of CuO-CeO{sub 2} catalysts in the presence of CO{sub 2} and H{sub 2}O. ...
The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supported catalyst after deposition onto a support and an activation stage. In this work, this method has been adapted to the preparation of alumina supported bimetallic Pd-Sn catalysts to determine its interest for the control of the properties of the bimetallic phase (size, composition and structure). In the preliminary study concerning tin oxide sols, SnO{sub 2} (size=2,3 nm) and Sn{sub 6}O{sub 4}(OH){sub 4} (size = 25 nm) nano-particles were synthesized by neutralization respectively for tin(IV) and tin(H). The control through the pH of the aggregation of the PdO and SnO{sub 2} particles revealed that increasing oxide solubility promotes integral re-dispersion of the ...
A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization (FGD) system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and -0.55 in the absence and presence of the catalyst, respectively. Apparent activation ...
Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)
This patent describes a nitrogen oxides decreasing combustion method which comprises: a first step of mixing a fuel and air with each other; a second step of bringing the mixture obtained in the first step into contact with a packed catalyst such that only catalytic combustion occurs; and a third step of adding a fresh supply of the fuel to a stream obtained from the second step to form a mixed gas and causing the mixed gas to undergo non-catalytic thermal combustion. The temperature of the packed catalyst is lower than the ignition temperature of the mixture and the adiabatic flame temperature of the mixed gas is lower than a temperature at which the nitrogen oxides occur.
Chloromethane, dichloromethane and 1,2-dichloroethane were completely decomposed in air on perovskite-type catalysts (LaMnO{sub 3}, LaCoO{sub 3}, (La{sub 0.84},Sr{sub 0.16})(Mn{sub 0.67},Co{sub 0.33})O{sub 3}) at reaction temperatures above 550C. Besides the main reaction products (carbon dioxide, water and hydrochloric acid), by-products (higher chlorinated-, C-C coupling- and cracking products) were formed in the low temperature range. Depending on the reaction temperature, residence time and kind of chlorinated hydrocarbon a reversible catalyst deactivation takes place. In the case of LaCoO{sub 3} catalysts an irreversible deactivation was observed. X-ray diffraction (XRD) and electron probe microanalysis (EPMA) measurements with the perovskite-type catalysts after interaction of chlorinated hydrocarbons indicate the formation of chlorinated species on the catalyst surface and in ...
High-throughput synthesis and screening methods have been developed for the discovery of highly active catalysts for the control of emissions from stationary and mobile sources. Low temperature CO oxidation, CO methanation, NOx abatement and the destruction of Volatile Organic Compounds (VOCs) will be discussed. The discovery libraries for primary screening consisted of both 11x11 and 16x16 catalyst arrays on 3 inch and 4 inch quartz wafers, respectively. Catalysts were prepared by robotic liquid dispensing techniques and screened for catalytic activity in Symyx's Scanning Mass Spectrometer. The screening protocols encompassed mixed metal oxides, perovskites and supported base and noble metals. Active hits were further optimized in focus libraries using shallower compositional gradients. The ScanMS is a fast serial screening tool that uses flat wafer ...
Recently there has been considerable interest in the Cu-ZSM-5 catalysts for the selective reduction of NO by light hydrocarbons for the purpose of atmospheric pollution abatement. Isobutane and n-pentane cracking were studied over Cu zeolite catalysts and these results were compared with their HY analogues at low conversions and at temperatures of 673 K and below. Three forms of the catalysts were used: those reduced in CO at 773 K; those reduced with H[sub 2] at 473 K; and those in the oxidic form (following flushing with He at 773 K). In contrast with an earlier publication, very little difference in activity was found between the two reduced forms of the catalysts did not differ significantly from each other nor from the H-form of the zeolite. They are typical of a Bronsted acid catalysis. The oxidic form of the catalyst produced excess ...
Selective catalytic reduction (SCR) of nitrogen oxides(NO{sub x}) in flue gas or engine exhaust gas with hydrocarbons as the reductant has great potential for less expense, less pollution, and easier operation than SCR with ammonia. Methane is the preferred reducing gas because of its low cost and low toxicity. Stable, low-cost catalysts for SCR with methane are required to demonstrate this technology for controlling NO{sub x} emissions. Several cobalt and nickel catalysts on synthetic clay and uranium oxide supports were investigated for their activities in reducing NO{sub x} with methane in the presence of air. The efficiency of the synthetic clay-supported nickel and cobalt catalysts for nitric oxide (NO) reduction with methane as the reducing gas was poor. The nickel oxide-uranium oxidecatalyst, ...
This patent describes a process for the preparation of acrylonitrile or methacrylonitrile by the reaction of propylene or isobutylene, molecular oxygen and ammonia at a temperature of about 200/sup 0/ to 600/sup 0/C in the presence of an oxidationcatalyst. The improvement consists of using as the oxidationcatalyst an antimony-free catalyst having the atomic ratios described by the formula: X/sub a/A/sub b/C/sub c/Fe/sub d/Bi/sub e/Mo/sub 12/O/sub x/ wherein X is Ga, In or mixtures thereof; A is alkali metal; C is Ni, Co or mixture thereof; and wherein a is 0.01 to about 4; b is 0 to about 4; c and d are 0.01 to about 12; e is 0.01 to about 6; and x is a number sufficient to satisfy the valence requirements of the other elements present. In a process for the preparation of acrylonitrile or methacryloniotrile by the reaction of propylene or isobutylene, molecular oxygen and ammonia ...
The catalytic nature of Mo(CO)/sub 6/ supported on ..gamma..-Al/sub 2/O/sub 3/, KOH-doped ..gamma..-Al/sub 2/O/sub 3/, and HY-zeolite was investigated in CO oxidation with N/sub 2/O in comparison with that of a conventional partially reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. Kinetic parameters of this reaction were obtained in the range 0 to 100/sup 0/C; the rate law r = kP/sub N/sub 2/O//sup 1/P/sub CO//sup 0/ was found on all catalysts, and the activation energy was estimated to be 9.1 kcal/mol on the Mo(CO)/sub 6/-derived catalysts and 7.1 kcal/mol on the partially reduced MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. Maximum catalytic activities were obtained by activating the Mo(CO)/sub 6/-derived catalysts at 400/sup 0/C. To obtain similar activity on the MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst, it was ...
This patent describes a catalyst comprising: (a) a non-zeolitic inorganic oxide matrix, and (b) an ultrastable Y-type crystalline zeolite, the ziolite having been pretreated by contacting the zeolite with a phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, a salt of phosphoric acid, a salt of phosphorous acid, and mixtures thereof for a time sufficient to composite an effective amount of phosphorus with the zeolite.
On handling nitric solutions in the glove box nitrous gases are formed that are sucked off via a heated activated charcoal filter and a catalyst cartridge containing e.g. the FG 590 H catalist (Degussa). By the activated charcoal the nitrous gases are reduced to N/sub 2/ and CO gas; the catalyst will oxidize CO to CO/sub 2/. The CO/sub 2/ obtained is discharged through an exhaust air filter in the glove box.
Correlations between structural aspects of solid materials and their behavior as catalysts are relatively recent. This 20-chapter book focuses on understanding of solid-state mechanisms in heterogeneous catalysis and relationship between catalytic behavior and solid state structure, emphasizing catalysis with oxides, sulfides, and zeolites.
Work continued on the correlations of catalytic activity of metals and surface structure. Work is described in the following areas: CO oxidation on a Cu/Rh(100) Bimetallic catalysts; electronic properties of bimetallic surfaces; and reflection absorption spectroscopy of bimetallic surfaces. 5 figs. (CBS)
The development of high performance electrode materials is currently one of the main activities in the field of the low temperature fuel cells, fuelled with H{sub 2}/CO or low molecular weight alcohols. A promising way to attain higher catalytic performance is to add a third element to the best binary catalysts actually used as anode and cathode materials. In Part I of this review an overview of the preparation and structural characteristics of Pt-based ternary catalysts was presented. This part of the review deals with the electrochemical properties of these catalysts regarding their CO tolerance and electrocatalytic activity for methanol and ethanol oxidation in the case of anode materials, and their activity for oxygen reduction and stability in fuel cell conditions when used as cathode materials. (author)
Discusses results of investigations into catalytic properties of various minerals during hydrogenation of Kansk-Achinsk brown coal with a view to replacing synthetic compositions based on molybdenum. Describes tests and equipment used in hydrogenation of grade B-2 Borodinsk deposit coal in tetralin (hydrogen donor). Various by-products of metallurgical processes and compounds separated from tailings containing mainly iron and sulfur and other metals were used as catalysts. States that: minerals containing iron compounds in the form of pyrites, hematites and magnetites exhibit catalytic properties when used in the hydrogenation of brown coal; pyritic catalysts enrich liquid products with hydrogen while sulfur and nitrogen content remains the same; the yield of malthenes with pyritic catalysts is no lower than with alumocobaltmolybdenum catalysts. 18 refs.
CeO{sub 2}-TiO{sub 2} catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO{sub 2}-TiO{sub 2} mixed oxides show the higher activity than pure CeO{sub 2} and TiO{sub 2}, and CeO{sub 2}-TiO{sub 2} 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO{sub 2}-TiO{sub 2} 1/1 catalyst at reaction temperature of 150 {sup o}C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO{sub 2}-TiO{sub 2} 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 {sup o}C, the air ...
In pre-experiments a tubular reactor was checked whether it is suitable for kinetic measurement on the system of the silver-catalysed partial oxidation of methanol to formaldehyde. Detrimental effects of heat-transfer and mass-transfer on the experimental results were ruled out. Investigations on the characteristics of the reaction showed that it is possible to manipulate the composition of the product mixture by changing the inlet concentration of the reactants. A modified power-law model was established to describe the reaction kinetics. It considers the preadsorption step of oxygen on the catalysts surface and fits the experimental data quite well. During the rapid oxidation the catalysts surface undergoes a drastic change. It gets coarse and has an adsorption capacity of 11 m{sup 2}/g after being exposed to the reaction mixture. (orig.)
A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).
A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).
Nowadays, the studies are focused on the search of better electrocatalysts that promote the complete oxidation of ethanol/bioethanol to CO2. To that end, amorphous bi-catalytic catalysts of composition Ni59Nb40Pt1-xYx (Y=Cu, Ru, x=0.4% at.) have been developed, obtained by mechanical alloying, resulting in higher current densities and an improvement in tolerance to adsorbed CO vs. Ni59Nb40Pt1 catalyst. By using voltammetric techniques, the appearance of three oxidation peaks can be observed. The first peak could be associated with the electrooxidative process of ethanol/bioethanol to acetaldehyde, the second peak could be the oxidation of acetaldehyde to acetic acid, and the last peak might be the final oxidation to CO2. Chrono-amperometric experiments show qualitative poisoning of catalyt...
All of the direct reaction schemes described and the corresponding process schemes are still in an exploratory state. Ethylene by oxidative coupling of methane could become competitive if process schemes are developed with significantly less expenditures for separation of the product from unconverted feed. No encouragement for formaldehyde from methane can be presently derived from the existing knowledge. Liquid-phase oxidation of methane to methanol appears to be attractive but no final judgement is possible at present. Oxidative dehydrogenation of ethylene and propane look promising although further catalyst improvement is required. Acetic acid from ethane and acrylonitrile from propane have a certain potential as an alternative to present technology. The outlook for acrolein and acrylic acid from propane is less favourable; new concepts for catalyst design are necessary. (orig.)
A process is described for the selective oxidation of ammonia to nitric oxide in about 90% or greater yield with a minimum of nitrogen or dinitrogen oxide (N/sub 2/O) as by-products, comprising: (1) contacting gaseous ammonia in an oxygen containing gas optionally with an inert gaseous diluent with a mixed metal perovskite catalyst of the general formula: ABO/sub 3/, wherein: A is selected from the alkali, alkaline earth, lanthanide, or actinide metals or a mixture of these metals having a relatively large ionic, radius, and B is selected from an element or a combination of elements selected from Groups IB, IVB, VB, VIB, VIIB, or VIII of the Periodic Table, wherein the perovskite phase of the catalyst has an equilibrium partial pressure of oxygen at 1000/sup 0/C of greater than about 10/sup -15/ bar; and (2) heating the reactants of step (1) at greater than about 500/sup 0/C under ...
A process is described for the selective oxidation of ammonia to nitric oxide in about 90% or greater yield with a minimum of nitrogen or dinitrogen oxide (N/sub 2/O) as by-products, comprising: (1) contacting gaseous ammonia in an oxygen containing gas optionally with an inert gaseous diluent with a mixed metal perovskite catalyst of the general formula: ABO/sub 3/, wherein: A is selected from the alkali, alkaline earth, lanthanide, or actinide metals or a mixture of these metals having a relatively large ionic, radius, and B is selected from an element or a combination of elements selected from Groups IB, IVB, VB, VIB, VIIB, or VIII of the Periodic Table, wherein the perovskite phase of the catalyst has an equilibrium partial pressure of oxygen at 1000"0C of greater than about 10/sup -15/ bar; and (2) heating the reactants of step (1) at greater than about 500"0C under conditions ...
This thesis is in the field of gas emission control from automobile and stationary sources. Out of the possible approaches to the elimination of pollutant gases, such as nitrogen oxides (NO{sub x}), one consists in the selective catalytic reduction (SCR) of these NO{sub x} on a suitable heterogeneous catalyst. Ammonia or hydrocarbons are employed as reducing agents. The most important catalysts active in the SCR of NO{sub x} are based on ions of transition metal either supported on several oxides or dispersed in zeolites. The catalysts have been characterized by electron magnetic resonance techniques (EPR, ENDOR, ESEEM) and the interaction of catalysts with nitrogen oxides, with reducing and poisoned agents have been followed with the same techniques. Copper dispersed on alumina and its interaction with both NO and ammonia has been ...
Ceria (CeO{sub 2})-modified PtRu/C catalysts with different compositions of Ru and CeO{sub 2}, viz. PtRu{sub 0.9}(CeO{sub 2}){sub 0.1}/C, PtRu{sub 0.7}(CeO{sub 2}){sub 0.3}/C and PtRu{sub 0.5}(CeO{sub 2}){sub 0.5}/C and unmodified PtRu/C catalyst were synthesized by the sodium borohydride reduction method. Transmission electron microscopic results indicated that the lower concentrated CeO{sub 2}-modified PtRu/C catalysts had almost a similar morphological structure (well-dispersed particles with size around 2.3-2.5nm) with that of the unmodified PtRu/C catalyst. X-ray diffraction and X-ray photoelectron spectroscopy analyses indicated the formation of PtRu alloy and presence of CeO{sub 2} in an amorphous form with a mixed oxidation states (Ce{sup 3+}-Ce{sup 4+}). Electro-catalytic activity of these catalysts for methanol oxidation was ...
The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)2] (where L = O, N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, 1H- and 13C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH2Cl2/H2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.
The isomerization of neopentane has been investigated over the 0.76 wt% Pd/SiO{sub 2} catalyst. It is found that after high temperature reduction (HTR, at 873 K) the selectivity for isomerization is much higher than that after low temperature reduction (LTR, at 573 K). A variety of experiments, including kinetic, chemisorption (O{sub 2}, H{sub 2}, and CO), temperature-programmed desorption of H{sub 2}, and X-ray diffraction, showed that this selectivity enhancement cannot be interpreted in terms of H{sub 2} retention by catalyst. Instead, the formation of Pd-Si compound(s) (most probably Pd{sub 3}Si) during HTR seems immediately responsible for the catalytic behavior of HTR Pd/SiO{sub 2} catalysts. A mechanism is proposed for the Pd-SiO{sub 2} interaction in which Pd atoms (or ions) are incorporated into the silica support (via oxygen vacancies) and a new phase of palladium silicide is formed. Regeneration by an oxygen ...
In this paper, we prepared by the sol-gel method alkaline titania catalysts, doped by gelling titanium alkoxide with aqueous solutions containing potassium, rubidium or cesium chlorides. XRD patterns showed that samples annealed at 400 and 600degreeC contained a single crystalline phase, anastase. Specific surface areas were higher in samples annealed at 400degreeC (>100m2/g) than in those annealed at 600degreeC (25m2/g). The weight density of basic sites determined by CO2-TPD drastically diminished in samples treated at 600degreeC. Catalysts were tested for the self-condensation of acetone at 300degreeC; main reaction products were isomesityl oxide, mesityl oxide and mesitylene. Samples annealed at 600degreeC showed lower acetone conversion rate and low formation of mesitylene than that o...
Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of ...
This work describes a three-step pre-treatment route for processing spent commercial Ni Mo/Al_2O_3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidizedcatalysts were leached with 9 mol L"-"1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate. (author)
The structure and catalytic properties of 2 wt.-% Pd/SiO/sub 2/ catalysts promoted with 2 wt.-% MgO and 0.2-5 wt.-% iron have been investigated. Catalysts were characterized by TPR, hydrogen chemisorption, and Moessbauer spectroscopy and their catalytic performance in methanol formation was also measured. At 16 at.-% iron a sharp maximum was observed in the activity which can be interpreted as being due to simultaneous promotion with iron and MgO. Independent mechanisms of promotion were found for the two modifiers: iron influenced the metallic component by forming bimetallic PdFe particles while MgO changed the properties of silica in a favourable way. 6 figs., 29 refs., 1 tab.
A residue in the production of alumina by the Bayer process is red mud. It contains oxides of Fe and Ti, active as hydrogenation catalyst in sulfided form, and whose catalytic activity can be improved by the activation method proposed by Pratt and Christoverson. The paper describes how the development of its activity and selectivity with reaction time was studied for the hydrogenation of a light fraction of an anthracene oil, and compared with untreated sulfided red mud. Catalyst samples were collected at different reaction times, and their texture, morphology and composition characterized by nitrogen adsorption, SEM and SEM-EDX. The loss of catalytic activity of activated sulfided red mud is slower than for untreated sulfided red mud. The main cause of this decrease in catalytic activity is the loss of surface area and superficial Fe.
Several possibilities of the use of molecular models in quantum-chemical investigations of the structure of defect centers on the surfaces of oxides on nontransition elements have been illustrated. There has been a special discussion of the assumption of the local nature of the chemical interactions in these systems, which underlies such an approach, and of the consequent laws governing the formation of their lattices in the example cases of zeolites, kaolinites, and comparable boron- and aluminum-containing oxides. A quantum-chemical interpretation of the body of experimental data from investigations of the dehydroxylation of H forms of zeolites has been given. The structure of the Lewis acid centers formed as a result, and their chemisorption properties, have been discussed.
This work reports studies of ethanol oxidation on Pt-Sn/C catalysts with nearly the same particle size and identical overall composition having different amounts of oxide and alloyed phases. Results of characterization of physical properties by transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and in situ dispersive X-ray absorption spectroscopy (DXAS) are presented. The variation in the amount of oxide and alloyed phases, promoted by heat treatments in mild temperature conditions, does not produce any significant particle growth. Cyclic voltammetry and oxidation of adsorbed CO in acid medium are used to probe the surface conditions. Data on the electrocatalytic activity towards ethanol oxidation, obtained by potential sweeps and chronoamperometry, are discussed and ...
Ni catalysts supported on {gamma}-Al{sub 2}O{sub 3}, CeO{sub 2} and CeO{sub 2}-Al{sub 2}O{sub 3} systems were tested for catalytic CO{sub 2} reforming of methane into synthesis gas. Ni/CeO{sub 2}-Al{sub 2}O{sub 3} catalysts showed much better catalytic performance than either CeO{sub 2}- or {gamma}-Al{sub 2}O{sub 3}-supported Ni catalysts. CeO{sub 2} as a support for Ni catalysts produced a strong metal-support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO{sub 2} had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/{gamma}-Al{sub 2}O{sub 3} catalysts for this reaction. A weight loading of 1-5wt% CeO{sub 2} was found to be the optimum. Ni catalysts with CeO{sub 2} promoters reduced the chemical interaction between nickel and support, resulting in an increase in ...
The selective catalytic reduction of nitric oxide by methane over copper ion-exchanged natural zeolites was investigated in a packed-bed tubular reactor. The catalytic activity of Cu-N and Cu-H-N catalysts was confirmed as NO, CH{sub 4}, and O{sub 2} displayed very little reaction in the absence of any catalyst and zeolite without ion exchange was totally inactive. A maximum NO conversion of 33% at 650 C for Cu-N-66 was achieved with 2% NO and 1% CH{sub 4} and a contact time of 0.9 g s/cm{sup 3}, but the introduction of 2% O{sub 2} reduced the NO conversion to only 12%. Ion exchange for the H-form prior to copper ion exchange was essential for oxygen to promote catalytic activity over the temperature range 250--650 C, with a maximum conversion of 30% at 450 C with O{sub 2} present. The direct reduction of NO by methane was ruled out as a possible reaction pathway.
In recent years, the influences of acid rain such as the acidification of lake water, on bio-system by the heavy metals from effluent of soils with acid rain and also on the structural materials of buildings are seriously discussed. Sulfur and nitrogen that are contained in fossil fuels are released into the atmosphere by the fuel combustion as their oxides dissolve in rain drops as sulfite and nitrous ions, where they are further oxidized into sulfate and nitrate ions These ions lower the pH of rain water resulting so-called acid rain. Therefore, it is important to accurately determine these ions in rain water for the investigation of reality of acid rain. However, it is not easy to accurately determine these ions, especially for sulfite ions in rain water, since they are quickly oxidized by the catalytic action of metallic ions such as ferric and manganous ions. And light, temperature, pH of solution and also species and ...
Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure. With the use of a disposable SOx ...
A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N2 physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH3)3 species even after calcinations and H2 reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH3)3 for the re-adsorption of ?-olefins. -- Graphical abstract: The silylation of ...
Modern combined cycle power plants with natural gas as the only fuel reach efficiencies of up to 58% for electric power generation. Nevertheless the reserves of natural gas are more limited compared to the reserves of coal. Therefore possibilities should be investigated to use coal for such plants also. One concept, that combines the use of coal in a combined cycle application with high efficiencies is examined in this paper. According to this concept the exhaust gas of the gas turbine (vitiated air) is the combustion air for the pulverised coal combustion, that takes place in the bottoming steam generator. Due to the low oxygen content of the vitiated air the burnout of the coal may be incomplete. In order to avoid the incomplete combustion of the coal and the resulting decrease of the efficiency of the plant and possible emission problems, a catalyst, that converts carbon monoxide and unburnt carbon to carbon dioxide should be installed between the heating ...
A magnetic core/shell Fe3O4/FeMnOx catalyst was prepared by a simple oxidation-precipitation method. The catalyst was characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. The characterization studies verified that Fe3O4 core was coated with a layer of Fe-Mn oxide. The Fe3O4/FeMnOx was found to be an effective and stable heterogeneous catalyst for the discoloration of methylene blue (MB) in aqueous solution by H2O2. The high catalytic activity is due to the FeMnOx shell, which not only increased the surface hydroxyl groups, but also enhanced the interfacial electron transfer. The discoloration of MB could be due to the decomposition of H2O2 into ?OH ...
The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)
A wet air oxidation (WAO) process was applied to four selected pharmaceuticals (metoprolol, naproxen, amoxicillin, and phenacetin) individually dissolved in ultra-pure water, varying the temperature and oxygen pressure. Due to the moderate (amoxicillin) or low (metoprolol, naproxen, and phenacetin) efficiency found in the oxidation of these pollutants, a catalytic wet air oxidation (CWAO) process was then tested using a platinum catalyst supported on multi-walled carbon nanotubes (CNT). In this CWAO process, the pharmaceuticals were dissolved together in ultra-pure water and in four natural water matrices-a reservoir water, a groundwater, and two waters from different municipal wastewater treatment plants. On the basis of the measurements of their removals, a discussion is given of the inf...
Pulse reactor experiments were conducted on the reactions of unlabeled or deuterium- or oxygen-18-labeled allyl alcohols over molybdenum trioxide and various bismuth molybdates in the absence or presence of oxygen and ammonia. The allyl alcohol apparently adsorbed on oxidation sites to form acrolein via allyl molybdates, and on Broensted acid sites to form diallyl ether via an allyl carbonium ion. The bismuth enhanced ..cap alpha..-hydrogen abstraction, which was the rate-determining step in the oxidation. The product distributions provided evidence that the selective oxidation of propylene to acrolein proceeds via a m-allyl molybdate which collapses to an O o-allyl molybdate prior to the second hydrogen abstraction, and that the analogous N o-complex in ammoxidation undergoes two hydrogen abstractions to form acrylonitrile. Detailed reaction schemes are developed.
The method of programmed thermodesorption has been used to study the forms of hydrogen adsorption in ZrNiHsub(x) hydride. It is shown that high concentration of the hydrogen, which extracted from hydride in the temperature range of 240-260 deg C results in appearance of ''reverse'' peak. Charge of hydride adsorption properties during its oxidation-reduction treatment is studied. Comparison with spectra of hydrogen thermodesorption from the surface of Ni/ZrO_2 deposited catalyst and zirconium oxide is carried out.
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 ...
As stated last quarter, we discovered potassium as an impurity in the mixed metal oxides. The potassium was probably incorporated into the solid during the coprecipitation using K{sub 2}CO{sub 3}. Currently NH{sub 4}OH is being used as the precipitating base. We have discovered that the precipitation agent influences the surface composition of the mixed-metal oxides. Chemical analysis of the surface and bulk compositions showed significant differences in surface compositions of the K{sub 2}CO{sub 3} and NH{sub 4}OH precipitated catalysts. In TPR experiments we have discovered that the precipitating pH markedly affects the reducibility of the ZnMnCr oxides. This shows that the choice of base as well as the pH strongly affects the surface composition of the mixed metal catalysts. Additional studies are in progress in which we are studying how the precipitating agents affect the ...
A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe{sub 2}O{sub 3} powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe{sub 2}O{sub 3} powder was used to oxidize a high carbon coal char in an inert ...
The Cu/CeO{sub 2} and Cu/Cr/CeO{sub 2} catalysts synthesized using the impregnation method were employed to investigate the selective reduction of NO{sub x} with C{sub 3}H{sub 6} at 673.15K and 1atm. The activity of CeO{sub 2} was greatly induced by loading 4wt.% of Cu onto the bare support. The presence of C{sub 3}H{sub 6} was a crucial factor for elevating the NO{sub x} conversion under lean conditions. The modification of the optimal Cu(4)/CeO{sub 2} catalyst with 3wt.% of Cr steadily improved the performance of the catalysts. Both the optimal Cu(4)/CeO{sub 2} and Cu(4)/Cr(3)/CeO{sub 2} catalysts were characterized using XRD, SEM and TPR-H{sub 2}. The co-existence of CuO, Cr{sub 2}O{sub 3} and CuCr{sub 2}O{sub 4} was believed to grant the promising performance of the Cu(4)/Cr(3)/CeO{sub 2} catalyst in SCR-HC under net oxidizing conditions.
The current work continues a project completed in 1999 by ReMaxCo Technologies in which a novel, microwave based, VLS Silicon Carbide Fibrils concept was verified. This project continues the process development of a pilot scale commercial reactor. Success will lead to sufficient quantities of fibrils to expand work by ORNL and others on heat exchanger tube development. A semicontinuous, microwave heated, vacuum reactor was designed, fabricated and tested in these experiments. Cylindrical aluminum oxide reaction boats are coated, on the inner surface, with a catalyst and placed into the reactor under a light vacuum. A series of reaction boats are then moved, one at a time, through the reactor. Each boat is first preheated with resistance heaters to 850 C to 900 C. Each reaction boat is then moved, in turn, to the microwave heated section. The catalyst is heated to the required temperature of 1200 C to 1300 C while a mixture ...
Calcined and sulfided Ni-Mo catalysts supported on ultrastable Y zeolite (USY), NaY zeolite, mordenite, and ZSM-5 were studied by high-resolution electron transmission microscopy (HRTEM) with selected-area electron diffraction (SAED) and energy-dispersive spectroscopy (EDS). Ni and Mo oxide aggregates were rarely observed in the USY-supported Ni-Mo catalyst, indicating that most of Ni and Mo may be incorporated into USY, e.g., supercavities and possibly sodalite cages. However, there were a large number of {alpha}-NiMoO{sub 4} aggregates of different particle sizes in NaY-, mordenite-, and ZSM-5-supported catalysts, and the mordenite-supported catalyst also contained MoO{sub 3} crystals. The {alpha}-NiMoO{sub 4} may be attached to the surface of substrates as individual particles or needle aggregates, it may be disseminated into mordenite particles, or it may even form an isolated ...
Nanocrystalline processing by inert gas condensation has the inherent advantages of generating: (1) high surface area nanoclusters, (2) non-stoichiometric oxides, and (3) high dispersions of dopants. This approach is exploited in the synthesis of fluorite-structured catalysts for SO{sub 2} reduction by CO. Nanocrystalline CeO{sub 2{minus}x}, La-doped CeO{sub 2{minus}x}, and Cu-doped CeO{sub 2{minus}x} were produced by magnetron sputtering from a pure or mixed metal target, followed by controlled oxidation of the metallic clusters. The as-prepared doped and undoped nanocrystalline CeO{sub 2{minus}x} materials were found to be excellent catalysts for complete SO{sub 2} conversion to elemental sulfur. Undoped nanocrystalline CeO{sub 2{minus}x} enabled light-off at 460 C, a temperature {approximately} 120 C lower than that over polycrystalline CeO{sub 2}, which is a novel effective ...
The bulk of the results from this project, besides being found in the research reports, are in the form of two theses presented for advanced degrees by two different students at two different institutions. Francis E. Porbeni is a Master`s Degree student in Chemistry at Clark Atlanta University and has prepared his Master`s Thesis entitled Simultaneous SO{sub 2} Oxidation and NO Decomposition over Copper Oxide on {gamma}-Alumina Catalysts: An Infrared Diffuse Reflectance Study. Sumit Rao, a Ph.D. student in Chemical Engineering at the Georgia Institute of Technology has defended his thesis entitled Role of Copper Ensemble Size in Silica and Zeolite Supported Catalysts for Nitric Oxide Decomposition. These two documents, which will be forwarded when final copies are available, provide the details of the bulk of the research accomplished over the duration of this project. These two ...
CO poisoning is a major issue when reformate is used as a fuel in PEM fuel cells. Normally it is necessary to reduce the CO to very low levels (#approx#5 ppm) and CO tolerant catalysts, such as Pt-Ru, are often employed. As an alternative approach, we have studied the use of pulsed oxidation for the regeneration of CO poisoned cells. Results are presented for the regeneration of Pt and Pt-Ru anodes in a PEM fuel cell fed with CO concentrations as high as 10,000 ppm. The results show periodic removal of CO from the catalyst surface by pulsed oxidation can increase the average cell potential and increase overall efficiency. A method for enhancing the performance of a fuel cell stack using a microprocessor-based Fuel Cell Health Manager (FCHM) has been developed. The results of a cost/benefit analysis for the use of a FCHM on a 4 kW residential fuel cell system are presented. (author)
Certain materials, especially Sn, passivate the rare earth-exchanged Y zeolite (REY) used in petrochemical fluid-cracking catalysts against vanadium degradation caused by V impurities in the feed oil. The mechanism of passivation was investigated here from the standpoint of high-temperature oxide acid-base reaction; i.e., where the controlling factors were considered to be Lewis acid-base reactions between V{sub 2}O{sub 5}, the RE oxides, SnO{sub 2}, etc. Molten salt tests at 680{degree}C showed SnO{sub 2}, presumably because of its acidic nature, to be essentially nonreactive with V{sub 2}O{sub 5} or Na{sub 2}O-V{sub 2}O{sub 5} compounds. A hypothesis was developed to explain how the passivation effect by Sn might result from the unique resistivity of SnO{sub 2} to reaction with V{sub 2}O{sub 5}.
In order to avoid the use of catalysts in the process of auto-thermal reforming, it is possible to adopt a running at high temperature. In this study are presented the results of simulations of an auto-thermal/recuperator hybrid reforming system; these results are obtained with the oxidation model of alkanes developed by Ranzi and Faravelli. An isothermal configuration at high temperature improves the hydrogen yield and avoids the formation of soots. The analysis of the powers to be furnished to assure such an experimental mode, and the global approach of the fuel cell system show that the management of the heat exchanges is a key parameter in this process. (O.M.)
In this paper, steady-state isotopic transient kinetic analysis (SSITKA) is used to study two model reactions, CO oxidation and CO-NO reactions, on a typical formulation of a three-way auto-catalyst. Under steady-state conditions, abrupt switches in the isotopic composition of CO ("1"2C"1"6O/"1"3C"1"8O) were carried out to produce isotopic transients in both labeled reactants and products. Along with the determination of the average surface lifetimes and concentrations of reaction intermediates, an analysis of the transient responses along the carbon reaction pathway indicated that the distribution of active sites for the formation of CO_2 was bimodal for both reactions. Furthermore, relatively few surface sites contributed to the overall reaction rate.
Natural gas is a promising alternative fuel to meet strict engine emission regulations in many countries. Natural gas engines can operate at lean burn and stoichiometric conditions with different combustion and emission characteristics. In this paper, the operating envelope, fuel economy, emissions, cycle-to-cycle variations in indicated mean effective pressure and strategies to achieve stable combustion of lean burn natural gas engines are highlighted. Stoichiometric natural gas engines are briefly reviewed. To keep the output power and torque of natural gas engines comparable to those of their gasoline or Diesel counterparts, high boost pressure should be used. High activity catalyst for methane oxidation and lean deNOx system or three way catalyst with precise air-fuel ratio control str...
Hydrotalcites with different Al/Al+Mg ratios, and prepared at different pH and different aging temperatures of the gel were used as precursors of Mg-Al mixed oxides, and their textural and physicochemical properties were determined. A complete reaction network for the isopropanol decomposition on these catalysts has been established, and it is shown that the concentration of acetone in the products cannot always be used for a direct estimation of the rate of dehydrogenation. The Al/Al+Mg ratio for which the maximum in activity is obtained depends on the base strength needed for each particular reaction. For dehydrogenation of isopropanol, this is found at Al/Al+Mg [approx] 0.25. 36 refs., 10 figs., 2 tabs.
Iron nanoparticles were produced using extracts of green tea leaves (GT-Fe NPs). The materials were characterized using TEM, SEM/EDX, XPS, XRD, and FTIR techniques and were shown to contain mainly iron oxide and iron oxohydroxide. The obtained nanoparticles were then utilized as a Fenton-like catalyst for decolorization of aqueous solutions containing methylene blue (MB) and methyl orange (MO) dyes. The related experiments investigated the removal kinetics and the effect of concentration for both MB and MO. The concentrations of dyes in aqueous solution were monitored using ultraviolet-visible (UV-vis) spectroscopy. The results indicated fast removal of the dyes with the kinetic data of MB following a second order removal rate, while those of MO were closer to a first order removal rate. T...
The ammoxidation of propane over VSb{sub y}O{sub x} catalysts (y=1, 2, 5) was investigated with respect to the role of different oxygen species in the selective and non selective reaction steps using transient experiments in the Temporal Analysis of Products (TAP) reactor. Only lattice oxygen is involved in the oxidation reactions. Using isotopic labelled oxygen it is shown that two different active sites exist on the surface. On site A, which can be reoxidized faster by gas phase oxygen compared to site B, mainly CO is formed. On site B CO{sub 2} and acrolein as well as NO and N{sub 2}O in the presence of ammonia in the feed gas are formed and reoxidation mainly occurs with bulk lattice oxygen. (orig.)
A comparative study on the thermal and catalytic degradation of polybutylene terephthalate (PBT) at atmospheric pressure was conducted. The weight loss of PBT under thermal degradation was significantly influenced by the temperature between 360degreeC and 380degreeC, but little affected by the PBT particle size. Four groups of catalysts include metal chloride, metal oxide, metal acetate, and metal copper powder were used to test PBT degradation activity. Copper (II) chloride is the most active one for increasing the percentage PBT weight loss more than 100% in comparison with the result of thermal degradation at a temperature of 360degreeC for 30min. PBT and catalyst mixtures can be prepared by impregnation and physical method, the former resulted in a better PBT degradation. The percentag...
The oxidation of carbon black, CB, in presence of CeO{sub 2} is investigated to gain a better understanding of the effect of the contact between the two solids during this reaction. Different CB/CeO{sub 2} mixtures are tested in a fixed bed reactor. The experimental data are used to propose a model for CB oxidation in presence of CeO{sub 2}. It accounts for the size distribution of CeO{sub 2} particles, the contact area between CB and CeO{sub 2}, the mass of CB in the sample and the initial ratio CB/CeO{sub 2}. Corresponding kinetic parameters are determined. 35 refs., 10 figs., 3 tabs.
Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxidecatalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond ...
The behaviour of two different catalytic precursors based on iron (FeSO{sub 4}.7H{sub 2}O) and Fe{sub 2}O{sub 3} in direct hydroconversion of two coals are studied in this paper. Coal itself was the catalytic support of the dispersed iron sulfide (from iron sulfate); when the catalyst precursor was iron oxide (from red mud), coal and catalyst were directly mixed as powders. The reaction conditions were: 10 MPa (H{sub 2}, cold) initial pressure, 30 min, and reaction temperatures of 300, 350, 400, and 425{degree}C, reaching 450 and 500{degree}C for the high-rank coal. The results from Moessbauer spectroscopy demonstrate that pyrite in all the runs, inherent to coal or added as catalyst precursor, is converted into pyrrhotite to a variable extent according to the previous iron distribution and the iron chemical state in the catalyst precursors as well as the CS{sub 2} addition. ...
To develop oxygen electrodes for rechargeable metal-air batteries, the electrochemical behaviour of gas-diffusion-type carbon electrodes loaded with Pr-Mn-Fe-based perovskite-type oxides was examined for the reduction and evolution of oxygen in 8 M KOH at 60 C. Among the oxides tested, Pr{sub 0.2}Ca{sub 0.8}Mn{sub 0.1}Fe{sub 0.9}O{sub 3} gave the highest electrode performances, e.g., current densities of 275 mA/cm{sup 2} (for oxygen reduction) and 225 mA/cm{sup 2} (for oxygen evolution) at -300 and +650 mV vs. Hg/HgO, respectively. The electrode performances were found to depend on both the catalytic activity of the oxides for H{sub 2}O{sub 2} decomposition reaction and the amounts of oxygen desorbed from the oxides. Furthermore, it was confirmed that the small zinc-air battery including the gas-diffusion-type electrode loaded with Pr{sub 0.2}Ca{sub 0.8}Mn{sub 0.1}Fe{sub 0.9}O{sub 3} showed good ...
The knowledge shown in this work of the relationships between the oxidation stage of chromium, molybdenum and tungsten and their catalytic activity in some hydrocarbon reactions was achieved by the combination of separate investigations of reduction properties and the catalytic activity of the catalysts concerned. To characterize the electronic state of the reduced surfaces, X-ray photo-electronic spectroscopy was mainly used, supplemented by electron spin resonance. The catalyst activity was measured in conventional apparatus (flow, pulse and gradient-free reactors). (orig.) [Deutsch] Die in dieser Arbeit dargestellten Erkenntnisse ueber die Zusammenhaenge zwischen der Oxidationsstufe von Chrom, Molybdaen und Wolfram und ihrer katalytischen Aktivitaet in einigen Kohlenwasserstoffreaktionen wurden durch die Kombination getrennter Untersuchungen ueber Reduktionseigenschaften und katalytische Aktivitaet der betreffenden ...
Having recently discovered that polynuclear heteroaromatic nitrogen compounds can be selectively reduced only at the nitrogen containing ring, we have now turned our attention towards the cleavage of the carbon nitrogen bonds in this reduced ring. Highlights for this reporting period are: (1) Studies with the 50% nickel oxidecatalyst clearly show that 1,2,3,4-tetrahydroquinoline(THQ) provides approximately 20% more liquid product that does quinoline. Thus a first step selective hydrogenation to 1,2,3,4-THQ would enhance the overall HDN reaction to provide a more substantial conversion to substituted benzene and aniline derivatives. (2) The dramatic effect of the nitrogen atom is to inhibit aromatic ring hydrogenation and, to some extent, carbon-carbon bond hydrogenolysis reactivity. This is shown with proplybenzene as the substrate, where only methane gas is produced in the HDN reaction with the 50% nickel oxide ...
Doped ultrafine silicon dioxide powder with a narrow particle size distribution was obtained by RF discharge-stimulated dichlorosilane (SiH2C) oxidation at a low pressure using isobutylene as the combustion inhibitor and chromium hexacarbonyl (Cr(CO)6) as the dopant. The formation and morphology of the ultrafine particles are governed by the parameters of the RF discharge and by the chemical mechanism of the combustion reaction yielding the aerosol. Submicron-sized filamentous carbon structures can be obtained by isobutylene decomposition under spark discharge conditions in the presence of a molybdenum metal catalyst.
The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher ...
Rhodium (Rh) is a critical component of current automotive three-way catalysts (TWCs), particularly with regard to NO{sub x} and CO conversion at rich and stoichiometric air-fuel ratios (A/F). Rh supported on CeO{sub 2} was active for NO{sub x} and CO conversions but could be deactivated easily by high temperature aging. The cause of the deactivation is ascribed to the sintering of CeO{sub 2}. ZrO{sub 2} incorporation into CeO{sub 2} is reported to have high thermal durability in terms of oxygen storage capacity (OSC). There has been no report showing direct experimental evidence that Rh-loaded on CeO{sub 2}-ZrO{sub 2} mixed oxides induced effects on TWC performance improvement in the actual automotive exhaust. In the present paper, the Rh-CeO{sub 2} interaction contributing to NO{sub x} reduction and the catalytic behavior of Rh-loaded CeO{sub 2}-ZrO{sub 2} mixed oxide is addressed. Incorporating CeO{sub 2}-ZrO{sub 2} into ...
An experimental and modelling study was performed for a reverse flow catalytic converter attached to a natural gas/diesel dual fuel engine. The catalytic converter had a segmented ceramic monolith honeycomb substrate and a catalytic washcoat containing a predominantly palladium catalyst. A one-dimensional single channel model was used to simulate the operation of the converter. The kinetics of the CO and methane oxidation followed first-order behaviour. The activation energy for the oxidation of methane showed a change with temperature, dropping from a value of 129 to 35 kJ/mol at a temperature of 874 K. The reverse flow converter was able to achieve high reactor temperature under conditions of low inlet gas temperature, provided that the initial reactor temperature was sufficiently high. (author)
We present a novel fabrication route yielding Raney-platinum film electrodes intended as glucose oxidation anodes for potentially implantable fuel cells. Fabrication roots on thermal alloying of an extractable metal with bulk platinum at 200^oC for 48h. In contrast to earlier works using carcinogenic nickel, we employ zinc as potentially biocompatible alloying partner. Microstructure analysis indicates that after removal of extractable zinc the porous Raney-platinum film (roughness factor ~2700) consists predominantly of the Pt3Zn phase. Release of zinc during electrode operation can be expected to have no significant effect on physiological normal levels in blood and serum, which promises good biocompatibility. In contrast to previous anodes based on hydrogel-bound catalyst particles the ...
Recently the authors showed that tetrazolium salts can be obtained during the oxidation of substituted 1,3,5-triarylformazans with potassium permanganate in a two-phase organic solvent-water system. The role of phase-transfer catalyst in this reaction is played by the tetrazolium salt, which is formed in a small amount as the result of oxidation of the formazan at the phase boundary. The method is distinguished by its extreme simplicity. However, the yield of the tetrazolium salts fluctuates within wide limits and does not exceed 62%. This is due to the fact that as the reaction proceeds the pH of the aqueous phase increases from 6 to 12. At the same time it is known that tetrazolium salts are unstable in aqueous alkaline solutions. They found that if the aqueous phase is replaced by aqueous hydrochloric acid (5 wt. %) the yields of the tetrazolium salts (Ia-g) are increased to 70-87%. For convenience of isolation the ...
Processes for the hydrogenation of carbon monoxide have had commercial importance since about 1920, when the commercial production of methanol and higher alcohols on oxidecatalysts began. Soon thereafter Fischer and Tropsch discovered that liquid hydrocarbons could be synthesized from carbon monoxide and hydrogen over Group VIII metal catalysts. Following extensive catalyst and process development efforts, this technology provided Germany with a source of liquid fuels during World War II. The period following the war saw an acceleration in research and development on the Fischer-Tropsch process, but the only commercial application that was to emerge was the SASOL process in the Union of South Africa. The oil crises of the 1970s have rekindled worldwide interest in indirect liquefaction technologies for the production of clean, high-quality motor fuels from coal. The development of more efficient coal ...
A process is described for covering methane to a higher order hydrocarbon comprising contacting a gaseous reactant consisting of methane with a phosphate-containing catalyst for a sufficient period of time and at an effective temperature to provide the phosphate-containing catalyst consisting essentially of the higher order hydrocarbon. The catalyst is represented by a formula.
A new kinetic model for a more accurate and detailed fitting of the experimental data is proposed. The model is based on the remote control mechanism (RCM). The RCM assumes that some oxides (called `donors`) are able to activate molecular oxygen transforming it to very active mobile species (spillover oxygen (O{sub OS})). O{sub OS} migrates onto the surface of the other oxide (called `acceptor`) where it creates and/or regenerates the active sites during the reaction. The model contains tow terms, one considering the creation of selective sites and the other the catalytic reaction at each site. The model has been tested in the selective oxidation of propene into acrolein (T=380, 400, 420 C; oxygen and propene partial pressures between 38 and 152 Torr). Catalysts were prepared as pure MoO{sub 3} (acceptor) and their mechanical mixtures with {alpha}-Sb{sub 2}O{sub 4} (donor) in different proportions. The ...
The investigation of various Two-Stage Liquefaction (TSL) process configurations was conducted at the Wilsonville Advanced Coal Liquefaction R D Facility between July 1982 and September 1986. The facility combines three process units. There are the liquefaction unit, either thermal (TLU) or catalytic, for the dissolution of coal, the Critical Solvent Deashing unit (CSD) for the separation of ash and undissolved coal, and a catalytic hydrogenation unit (HTR) for product upgrading and recycle process solvent replenishment. The various TSL process configurations were created by changing the process sequence of these three units and by recycling hydrotreated solvents between the units. This report presents a description of the TSL configurations investigated and an analysis of the operating and performance data from the period of study. Illinois No. 6 Burning Star Mine coal Wyodak Clovis Point Mine coal were processed. Cobalt-molybdenum and disposable iron-oxide ...
This report presents the results of Run 260 performed at the Advanced Coal Liquefaction R&D Facility in Wilsonville. The run was started on July 17, 1990 and continued until November 14, 1990, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Black Thunder mine subbituminous coal (Wyodak-Anderson seam from Wyoming Powder River Basin). Both thermal/catalytic and catalytic/thermal tests were performed to determine the methods for reducing solids buildup in a subbituminous coal operation, and to improve product yields. A new, smaller interstage separator was tested to reduce solids buildup by increasing the slurry space velocity in the separator. In order to obtain improved coal and resid conversions (compared to Run 258) full-volume thermal reactor and 3/4-volume catalytic reactor were used. Shell 324 catalyst, 1/16 in. cylindrical extrudate, at a replacement rate of 3 lb/ton of MF coal was used in the catalytic stage. Iron ...
This report presents the results of Run 260 performed at the Advanced Coal Liquefaction R D Facility in Wilsonville. The run was started on July 17, 1990 and continued until November 14, 1990, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Black Thunder mine subbituminous coal (Wyodak-Anderson seam from Wyoming Powder River Basin). Both thermal/catalytic and catalytic/thermal tests were performed to determine the methods for reducing solids buildup in a subbituminous coal operation, and to improve product yields. A new, smaller interstage separator was tested to reduce solids buildup by increasing the slurry space velocity in the separator. In order to obtain improved coal and resid conversions (compared to Run 258) full-volume thermal reactor and 3/4-volume catalytic reactor were used. Shell 324 catalyst, 1/16 in. cylindrical extrudate, at a replacement rate of 3 lb/ton of MF coal was used in the catalytic stage. Iron ...
The investigations showed that the new adsorber/catalyst composites are well suited for chemical degradation of persistent water pollutants. Compared with alternative processes, the reaction selectivity and the consumption of oxidant are more favourable as the reaction now takes place on/inside the solid. The process, which was developed originally for purification of contaminated water, can be transferred to many other systems of materials. For example, it is expected that the soot emissions of diesel engines will be reduced significantly after efficient hydrogenation of the aromatics contained in the diesel engine on molybdenum-charged mesoporous composites. [German] Mit den vorliegenden Untersuchungen konnte ein erster Nachweis gefuehrt werden, dass die neu entwickelten Adsorber/Katalysator-Komposite fuer den chemischen Abbau persistenter Wasserschadstoffe geeignet sind. Im Vergleich zu alternativen Verfahrensloesungen kann die Selektivitaet ...
In this work, wet ball milling method is used in order to improve hydrogen sorption behaviour due to its improved microstructure of solid hydrogen materials. Compared to traditional ball milling method, wet ball milling has benefits on improvement of MgH{sub 2} microstructure and further influences on its hydrogen sorption behavior. With the help of solvent tetrahydrofuran (THF), wet ball milled MgH{sub 2} powder has much smaller particle size and its specific surface area is 7 times as large as that of dry ball milled MgH{sub 2} powder. Although after ball milling the grain size is decreased a lot compared to as-received MgH{sub 2} powder, the grain size of wet ball milled MgH{sub 2} powder is larger than that of dry ball milled MgH{sub 2} powder due to the lubricant effect of solvent THF during wet ball milling. The improved particle size and specific surface area of wet ball milled MgH{sub 2} powder is found to be determining its hydrogen sorption kinetics especially at relatively ...
Mg-Al mixed oxides with Mg/Al molar ratios of 0.5--9.0 were obtained by thermal decomposition of precipitated hydrotalcite precursors. The effect of composition on structure and surface and catalytic properties was studied by combining several characterization methods with ethanol conversion reactions. The nature, density, and strength of surface basic sites depended on the Al content. The catalyst activity and selectivity of Mg-Al mixed oxides in ethanol conversion reactions depended on composition. The dehydrogenation of ethanol to acetaldehyde and the aldol condensation to n-butanol both involved the initial surface ethoxide formation on a Lewis acid-strong base pair. The dehydration of ethanol to ethylene, and the coupling and dehydration to diethyl ether increased with Al content, probably reflecting the density increase of both Al{sup 3+}-O{sup 2{minus}} pairs and low- and medium-strength basic sites. Pure Al{sub ...
Studies were conducted of the bifunctional oxygen electrode. The development of a rechargeable metal-oxygen (air) cell has been hampered to a great extent by the lack of a stable and cost effective oxygen electrode capable of use during both charge and discharge. The first type of bifunctional electrode consists of two distinct catalytifc layers. The oxygen reduction catalyst layer containing a supported gold catalyst is in contact with a hydrophilic nickel layer in which evolution of oxygen takes place. Loadings of gold from 0.5 to 1.0 mg/cm/sup 2/ were investigated; carbon, graphite, metal, and spinel oxides were evaluated as substrates. The second part of the research effort was centered on developing a reversible oxygen electrode containing only one catalytic layer for both reduction and evolution of oxygen. The work was directed specifically to the study of perovskite type of oxides with the ...
We report the fabrication and characterization of glucose-tolerant Raney-platinum cathodes for oxygen reduction in potentially implantable glucose fuel. Fabricated by extraction of aluminum from 1mm thin platinum-aluminum bi-layers annealed at 300^oC, the novel cathodes show excellent resistance against hydrolytic and oxidative attack. This renders them superior over previous cathodes fabricated from hydrogel-bound catalyst particles. Annealing times of 60, 120, and 240min result in approximately 400-550nm thin porous films (roughness factors ~100-150), which contain platinum and aluminum in a ratio of ~9:1. Aluminum release during electrode operation can be expected to have no significant effect on physiological normal levels, which promises good biocompatibility. Annealing time has a dis...
This patent describes a method of reducing the hydrogen sulfide level in streams containing hydrogen sulfide at concentrations from about 2 ppm up to about 1,000 ppm. It comprises reacting the hydrogen sulfide with an unsaturated hydrocarbon in the presence of an acidic solid catalyst selected from the group consisting of polymeric sulfonic acid resins, solid polyphosphoric acid, supported sulfuric acid, supported boric acid, silica-aluminas, clays, faujasite, mordenite, and L, omega, X or Y zeolites at mercaptan-forming concentrations, and recovering a stream having a reduced hydrogen sulfide concentration and containing no more than 5 ppm hydrogen sulfide.
The proposed active sites on the catalyst surface in heterogeneous propylene ammoxidation have been successfully modelled by structurally characterized pinacolato W(VI) tert-butylimido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium is dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Grasselli et al. (1) have been reproduced using discrete Group VI d{sup 0} organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are: (1) oxidative trapping of radicals at molybdenum imido sites, and (2) migration of the allyl group from oxygen to an imido nitrogen atom.
A rapid combustion unit (Baird and Tatlock) incorporating a combustion chamber provided with baffle plates for complete combustion of the sample without the use of a catalyst has been assembled in a glove box for the determination of carbon and hydrogen in actinide complexes. The unit has been modified employing a movable electric furnace and a proportional temperature controller, for decomposition of the sample at desired heating rates. The set-up was standardised employing various reference materials such as benzoic acid, acetanilide, sulphanilamide and 1-chloro 2:4 dinitrobenzene and the standard deviation in the measurements evaluated. It has also been used successfully for the determination of carbon in uranium carbide and carbon and hydrogen in some uranyl-#beta#-diketone-amine N-oxide complexes and in plutonium(IV) oxalate. (auth.).
A rapid combustion unit (Baird and Tatlock) incorporating a combustion chamber provided with baffle plates for complete combustion of the sample without the use of a catalyst has been assembled in a glove box for the determination of carbon and hydrogen in actinide complexes. The unit has been modified employing a movable electric furnace and a proportional temperature controller, for decomposition of the sample at desired heating rates. The set-up was standardised employing various reference materials such as benzoic acid, acetanilide, sulphanilamide and 1-chloro 2:4 dinitrobenzene and the standard deviation in the measurements evaluated. It has also been used successfully for the determination of carbon in uranium carbide and carbon and hydrogen in some uranyl-#beta#-diketone-amine N-oxide complexes and in plutonium(IV) oxalate. (auth.).
A procedure based on electrophoretic deposition (EPD) was developed to coat metal plates with powder catalysts. The method was tested on stainless-steel plates with three Ni-based catalysts for the steam reforming of ethanol. The catalysts (Ni/La2O3/g-Al2O3) contained 15% Ni and 8% La, and were prepared using three types of g-alumina with different textural properties. The powder catalysts were suspended in isopropanol, and EPD deposition was performed with a voltage of 100V and a distance between electrodes of 2cm. Deposition time was varied between 3 and 7min, which gave a thickness of the catalyst layer from around 30 to 100mm. The morphology of the catalyst layer was dependent on the textural characteristics of the g-Al2O3 used to prepare the catalyst. The activity of the catalyst plat...
Very high cobalt catalysts have been prepared on steamed and acid-washed y zeolite. These catalysts are very active. Some of them have proven to be very stable. Additionally, if provisions are made to control the temperature build up on the catalyst bed, low methane selectivities result. Additional work is indicated, for instance, perhaps even higher activity catalysts can result from higher levels of cobalt or changes in the catalyst preparation procedure. Since the issue of whether small amounts of ruthenium can promote the catalyst is not completely resolved, catalyst preparation procedure experiments should continue with ruthenium vs. ruthenium-free catalysts. For instance, different methods of impregnation and/or activation should be investigated.
A phosphorus-containing low alkali metal content zeolitic catalyst made from a clay starting material is provided. The catalyst is obtained by contacting a partially cation exchanged calcined zeolite-containing catalyst with a dihydrogen phosphate anion or a dihydrogen phosphite anion. A hydrocarbon catalytic cracking process utilizing the phosphorus-containing catalyst is also provided.
A phosphorus-containing low alkali metal content zeolitic catalyst made from a clay starting material is provided. The catalyst is obtained by contacting a partially cation exchanged calcined zeolite-containing catalyst with an anion such as a dihydrogen phosphate anion or a dihydrogen phosphite anion and additionally with an ammonium salt other than a salt of an inorganic acid of phosphorus. A hydrocarbon catalytic cracking process utilizing the phosphorus-containing catalyst is also provided.
The oxidation of CO over a Pt/{gamma}-Al{sub 2}O{sub 3} catalyst was studied by cyclic injection of CO and O{sub 2} pulses under CO and O{sub 2} pressures of 2 and 1 kPa, respectively, at temperatures of 330-650 K. A boundary reaction model yielded kinetic parameters in agreement with the results of published low-pressure studies. For CO{sub 2} formation from O{sub 2}(g) + (CO){sub ad}, CO desorption was the most important step and showed multipeak characteristics and a low activation energy (10 kJ/mol) for the boundary reaction was found. CO{sub 2} formation from O{sub 2}(g) + (CO) as well as from CO(g) + (O){sub ad} resulted from boundary reaction at oxygen island. A reaction mechanism was proposed to account for kinetics observed and interpret the varying observations noted in low-pressure studies in terms of diffusion-disguised kinetics.
There is renewed interest in the development of natural gas vehicles in response to the challenge to reduce urban air pollution and consumption of petroleum. The natural gas/diesel dual fuel engine is one way to apply natural gas to the conventional diesel engine. Dual fuel engines operating on natural gas and diesel emit less nitrogen oxides, and less carbon soot to the air compared to conventional diesel engines. The problem is that at light loads, fuel efficiency is reduced and emissions of hydrocarbons and carbon monoxide are increased. This thesis focused on control methods for emissions of hydrocarbons and carbon monoxide in the dual fuel engine at light loads. This was done by developing a reverse flow catalytic converter to complement dual fuel engine exhaust characteristics. Experimental measurements and numerical simulations of reverse flow catalytic converters were conducted. Reverse flow creates a high reactor temperature even when the engine is run at ...
Effects of the addition of precious metals (PM; Pt, Rh) on CeO{sub 2}/Al{sub 2}O{sub 3} and CeO{sub 2}/La{sub 2}O{sub 3}/Al{sub 2}O{sub 3} were confirmed to enhance the oxygen storage capacities (OSC). Increments in the OSC of the added CeO{sub 2}/La{sub 2}O{sub 3}/Al{sub 2}O{sub 3} catalysts were much greater than those in the OSC of the PM added CeO{sub 2}/Al{sub 2}O{sub 3}. The enhanced OSC is ascribed to the interaction between PM and a CeO{sub 2}-La{sub 2}O{sub 3} solid solution formed during the catalyst preparation. No enhancements in the OSC were observed on physical mixing of CeO{sub 2}/La{sub 2}O{sub 3}/Al{sub 2}O{sub 3} and Pt-Rh/Al{sub 2}O{sub 3}, although the composition ratio of PM:CeO{sub 2}:La{sub 2}O{sub 3} is the same as that in the PM added CeO{sub 2}/La{sub 2}O{sub 3}/Al{sub 2}O{sub 3}. This indicates that the intimate contacts between the precious metals and CeO{sub 2} particles dispersed on Al{sub 2}O{sub 3} are essential ...
In order to replace industrial cobalt and nickel and molybdenum catalysts, more economical catalysts, red muds, are used. Comparative data about the chemical, structural and thermal properties of different samples of red muds, which are important for catalytic hydrogenation, are cited. The different conditions for hydrogenation of coals in a reactor are examined.
A highly dispersed limonite catalyst was shown to have advantageous properties in a commercial liquefaction plant: it has high catalytic activity, low cost for catalyst production and abundant resources. 3 refs., 3 figs., 2 tabs.
The deactivation rate of a resid hydrotreating catalyst is determined by a complex set of factors involving both chemical and physical changes in the catalyst structure. The various chemical changes that are associated with resid conversion involve thermal and catalytic steps of relatively large molecular weight species with the overall rates significantly affected by mass transfer limitations. The deposition of coke and the variation in the effective promoter level by the accumulation of metals deposited from the resid are the principal factors governing deactivation. The relative importance of mass transfer restrictions on activity and catalyst deactivation can be observed in studies where the average pore diameter of the catalyst has been varied. Several models have been proposed to characterize the deactivation of resid hydroprocessing catalysts. In this paper, the authors ...
The objective of this project is the development of a new class of metalloporphyrin materials used as catalsyts for use in fuel cell applications. The metalloporphyrins are excellent candidates for use as catalysts at both the anode and cathode. The catalysts reduce oxygen in 1 M potassium hydroxide, as well as in 2 M sulfuric acid. Covalent attachment to carbon supports is being investigated. The computer-aided molecular design is an iterative process, in which experimental results feed back into the design of future catalysts.
The effect of method of sulfur addition on the hydrocracking activity of coal liquefaction catalysts was investigated using a high-pressure differential thermal analyser. The three methods of sulfur addition were: 1) physical mixing of 10 wt% elemental sulfur with red mud; 2) pre-sulfidation of red mud with hydrogen sulfide; 3) use of reagent grade pyrite. The pre-sulfided catalyst was slightly less active than the catalyst prepared by physical mixing, and both of these were changed to pyrrhotite in the course of use. Although the pyrite catalyst exhibited activity at markedly lower temperatures than those required for the other two catalysts, conversions were lower than had been expected. This is thought to be due to a different catalytic mechanism being involved. 13 references.
We present a new approach for growing Si nanowires directly from a silicon substrate, without the use of a metal catalyst, silicon vapor or CVD gasses. The growth can be performed in a furnace type configuration at moderate temperatures or in localized regions by resistive heating. Since the silicon wires grow directly from the silicon substrate, they do not need to be manipulated nor aligned for subsequent applications. Wires in the 20-50 nm diameter range with lengths over 80 ?m can be grown by this technique. We have studied the effects of various growth parameters, including temperature, substrate orientation, initial sample cleaning and carrier gasses. Results indicate that most important parameters in the growth of the nanowires are the surface cleaning, the temperature and the type of carrier gas used. A model is proposed, which involves an oxidecatalyst for the process, with the growth of the nanowires enabled by a ...
Two families of CeO{sub 2}/Al{sub 2}O{sub 3} (ACE) catalyst supports, containing 3 and 20 % wt CeO{sub 2} respectively, have been examined and compared with the pure oxides CeO{sub 2} and (transition-phase) Al{sub 2}O{sub 3}. Structural data indicate that, also in the presence of CeO{sub 2}, the Al{sub 2}O{sub 3} support undergoes all phase transitions at the usual temperatures. Electron micrographs show that particles morphology and crystals size are mainly imposed by the Al{sub 2}O{sub 3} support. The porosimetric texture indicates a more pronounced meso-porosity in the ACE systems than in pure Al{sub 2}O{sub 3}, especially in the case of low CeO{sub 2} loadings. FTIR spectra and volumetric/calorimetric data of the adsorption of CO at {approx}300 K show that the surface Lewis acidity of aluminas is severely modified by the presence of CeO{sub 2}: the overall CO uptake is increased, there is the formation of one additional family of Lewis acid ...
Samarium cobaltite ceramic perovskites, with and without platinum particles dispersion, are possible candidates as electrode for electrochemical conversion of hydrocarbon and for intermediate temperature solid oxide fuel cells (ITSOFC). In this work, samarium cobaltites were synthesized by the combustion method using cobalt, and samarium nitrates as cation precursors and urea as fuel. For containing-platinum compositions Pt (II) acetyl acetonate was also employed as precursor. The effect of Sr on the phase formation and its electrical behavior is also studied. Specific surface area (BET), SEM-EDX, TEM and XRD analysis are used to characterize the powders obtained. Powders were pressed into pellets and sintered in air in the temperature range of 1200 -1400 C. Electrical impedance spectroscopy studies (EIS) are performed on sintered samples. The as-prepared powders showed an amorphous structure and by TEM a very small particle size ({proportional_to}10 nm) was ...
Electricity generation from natural gas in gas turbine units can be made substantially more efficient by preliminary methane conversion to a synthesis gas containing hydrogen and carbon monoxide and/or by the use of some of the synthesis gas produced in industry. An alternative improvement involves the introduction of solid oxide fuel cells (SOFCs) and the use of the synthesis gas in them. In this study, a modified scheme of gas turbine cycle that includes an SOFC, a membrane reactor (instead of a traditional combustion chamber), and a catalytic reactor to perform methane conversion to produce hydrogen (synthesis gas) is proposed. Variations of the energy and exergy efficiencies of the integrated system with operating conditions are provided, showing, for example, that SOFC efficiency is enhanced if the fuel cell active area is augmented. The SOFC stack efficiency can be maximized by reducing the steam generation while increasing the stack size, although such ...
The insulating oil used in a transformer is a critical component, as its service life is typically 20 years with possibly little or no maintenance. Partial discharges (PD), thermal overloads and static discharges continually subject the oil to chemical deterioration during its operating life. To ensure equipment reliability during service, it is important that the initial quality of the new insulating oil should meet the required acceptance specifications and preferably be pre-tested before use. Accelerated aging tests have been devised to determine the life expectancy of oil in service by using forced air or oxygen flow into the oil, the presence of a copper catalyst, and at elevated temperatures. The more important standards relating to transformer application are discussed and highlights of the more important aspects of the oxidation chemistry of hydrocarbons are included. The ultimate aim of the project is the formulation of better standard ...
A liquid column was used for the experiments reported in Part 1. However, it only gives the observation of the effect of fast reaction because the liquid flow was controlled to uniform laminar flow and the contact is limited to short time of around 10 ms. In practical absorbing operation, turbulence is involved in liquid flow, and the residence time for contact is long. Hence, the absorption of trace iodine in the purified air has been experimented by using a constant interface area type stirred absorption tank. Prior to the experiment, the characteristics of the absorption tank was investigated by conducting pure carbon dioxide absorption test with purified water. It gave the conclusion that the tank was sufficiently usable for fundamental researches. In short contact time absorption, the iodine dissolved and absorbed in liquid phase is affected by reaction of hypoiodous acid and poly-iodide ion formation due to hydrolysis by basic catalyst, proceeding in the ...
This report describes results from emissions testing of a prototype diesel engine, developed by Volvo Truck Corporation of Sweden, which uses pilot injection of diesel fuel for compression ignition of alcohol fuel injection for main combustion. In addition to this dual-fuel engine, emission testing was also conducted on a heavy-duty diesel engine of similar design. Both engines were tested over the 1979 13-mode FTP, or shorter versions of this modal test, and over the 1984 Transient FTP as well as an experimental bus cycle. The dual-fuel engine was characterized with methanol, ethanol and ethanol with 30 percent water (wt %). An oxidationcatalyst was also used with methanol and ethanol. Emission characterization included regulated emissions (HC, CO, and NOX) along with total particulate, unburned alcohols, individual hydrocarbons, aldehydes, phenols, and odor. The particulate matter was characterized in terms of particle size distribution, ...
Two major modes of CO adsorption on SiO{sub 2}-supported Pd reflect different extents of back-donation, which is, at least in part, controlled by the local electron density at the adsorption site. The fraction of CO in the bridging mode (B) increases and that of the linear mode (L) decreases, with increasing size of the Pd particles, indicating high electron density at Pd atoms in terraces of close-packed crystal faces, in agreement with Smoluchowski's classical model. For samples reduced at 300{degree}C our data points and those of other authors are located on a common curve of B/L vs metal dispersion. Extensive reduction at 600{degree}C results in significantly lower B/L values, attributed to the incipient formation of a palladium silicide. Oxidation followed by reduction at 300{degree}C destroys the silicide, and the B/L value returns to the original curve.
Two major modes of CO adsorption on SiO{sub 2}-supported Pd reflect different extents of back-donation, which is, at least in part, controlled by the local electron density at the adsorption site. The fraction of CO in the bridging mode (B) increases and that of the linear mode (L) decreases, with increasing size of the Pd particles, indicating high electron density at Pd atoms in terraces of close-packed crystal faces, in agreement with Smoluchowski's classical model. For samples reduced at 300{degree}C our data points and those of other authors are located on a common curve of B/L vs metal dispersion. Extensive reduction at 600{degree}C results in significantly lower B/L values, attributed to the incipient formation of a palladium silicide. Oxidation followed by reduction at 300{degree}C destroys the silicide, and the B/L value returns to the original curve.
In our previous work, we demonstrated that biomass-generated producer gas can be converted to ethanol and acetic acid using a microbial catalyst Clostridium carboxidivorans P7{sup T}. Results showed that the producer gas (1) induced cell dormancy, (2) inhibited H{sub 2} consumption, and (3) affected the acetic acid/ethanol product distribution. Results of this work showed that tars were the likely cause of cell dormancy and product redistribution and that the addition of a 0.025{mu}m filter in the gas cleanup negated the effects of tars. C. carboxidivorans P7{sup T} can adapt to the tars (i.e. grow) only after prolonged exposure. Nitric oxide, present in the producer gas at 150ppm, is an inhibitor of the hydrogenase enzyme involved in H{sub 2} consumption. We conclude that significant conditioning of the producer gas will be required for the successful coupling of biomass-generated producer gas with fermentation to produce ethanol and acetic ...
In this study, the exhaust gas from a common-rail direct injection diesel engine was investigated both upstream and downstream warm-up catalytic converters (WCC). Three different types of ultra-low sulfur fuels (ethanol-diesel blend, ethanol-diesel blend with cetane improver and pure diesel) were tested in this study. The objective of the work was to study the engine performance and the formation of THC (total hydro carbon), CO (carbon monoxide), NO{sub x} (nitrogen oxides), smoke and PM (particulate matters) when using these fuels. THC and CO emissions of the ethanol-diesel blend fuels were slightly increased, and about 50-80% mean conversion efficiencies of THC and CO on catalysts were achieved in the ECE R49 13-mode cycle. Smoke was decreased by more than 42% in the entire ECE 13-mode cycles. From the measurement of scanning mobility particle sizer (SMPS) for the particle size range of 10-385 nm, the total number and total mass of the PM of ...
The photodegradation of two well known recalcitrant compounds was studied. At this aim, a photosystem constituted by titanium dioxide and polyaniline, both immobilised in a PVC membrane, and a sunlight simulating irradiation source was used. The optimisation of the experimental conditions, ph, ionic strength and, when operating on soils, humic acid concentration, allowed the photodegradation of Paraquat at a nearly 100% extent, while, an oxidation by hypochlorite was needed to degrade cyanuric acid. [Italian] E' stata studiata la fotodegradazione di due composti notoriamente recalcitranti a questo tipo di rimozione. Con un sistema fotocatalitico costituito da biossido di titanio e polianilina immobilizzati in una membrana di PVC ed operando con luce solare simulata e' possibile, ottimizzando le condizioni sperimentali di pH, forza ionica e - operando su terreno - concentrazione di acidi umici, ottenere la degradazione del paraquat fino a valori ...
The effect of two iron catalysts, red mud and CGS S-G, as well as Co-Mo/Al/sub 2/O/sub 3/ and Ni-Mo/Al/sub 2/O/sub 3/ commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450C under initial hydrogen pressure of 85kg/cm/sup 2/ . G with tetralin to coal weight ratio of 3. From the results obtained at 450C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.
The indirect conversion of coal to liquid hydrocarbons via steam gasification followed by synthesis gas (CO/H/sub 2/) chemistry has been the subject of intensive study for a number of decades. A key technological challenge facing researchers in this area is control over the product distribution during the hydrocarbon synthesis step. In the case of iron Fischer-Tropsch catalysts, it has been known that the addition of alkali to the metal catalyst has a significant impact on the product distribution. Iron catalysts treated with alkali produce less methane more alkenes and higher molecular weight products. In spite of numerous investigations, the details of this promotional effect are not understood on a molecular level. To explore the role of alkali in the surface chemistry of iron catalysts, the authors have carried out a combined surface science and catalytic kinetic study of a model iron ...
Co catalysts, obtained from a layered double Co?Zn?Al hydroxide, are highly active and stable towards the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) in aqueous media. The Co-673 catalyst, containing a CoO species, provided a glycerol conversion of 67.7% and a 1,2-PDO selectivity of 50.5%. The Co-873 catalyst comprising 16?nm Co nanoparticles gave a glycerol conversion of 70.6% and a 1,2-PDO selectivity of 57.8%. It was revealed that the CoO species in the Co-673 catalyst was readily converted to 50?nm Co particles under the glycerol hydrogenolysis conditions. The Co catalysts maintained a stable size and phase in recycling tests. Graphical Abstract
Objectives of the program are to understand the mechanisms of coal liquefaction, to determine the role of catalysts in the direct conversion of coal to liquids, to determine the mechanism of catalyst deactivation and to explore slurry phase catalyst systems. Specific projects include: short-contact time coal liquefaction, mineral matter effects and catalyst studies. During this period, work was performed on: (1) the stability, at reaction temperature, of a recycle solvent obtained from the Lummus Two Stage Liquefaction facility, (2) reactions of preasphaltenes and asphaltenes prepared under various reaction severities, (3) the evaluation of the catalyst level detector installed at the H-Coal facility, (4) the characterization of oil soluble metal compounds with respect to hydrogenation activity, and (5) characterization, deactivation and regeneration of ...
Industrial solid wastes (fly ash and red mud, a by-product of the aluminium industry) have been employed as supports for preparation of Ru-based catalysts. Physical and chemical treatments on red mud were conducted and these modified supports were also used for preparation of Ru-based catalysts. Those Ru catalysts were characterized by various techniques such as N2 adsorption, H{sub 2} adsorption, XRD, XPS, and temperature-programmed reduction (TPR), and were then tested for catalytic ammonia decomposition to hydrogen. It was found that red-mud-supported Ru catalyst exhibits higher ammonia conversion and hydrogen production than fly-ash-supported catalyst. Heat and chemical treatments of the red mud greatly improve the catalytic activity. Moreover, a combination of acid and heat treatments produces the highest catalytic conversion of ammonia. 35 refs., 4 figs., 4 tabs.
Y-zeolite supported catalysts were applied to the hydrocracking of coal-derived liquids. By the introduction of two-stage upgrading consisting of hydrotreating and hydrocracking, Wandoan coal-derived middle distillate was hydrocracked over Ni-Mo/Y-zeolite, producing a high gasoline fraction yield. Zeolite supported catalysts gave little hydrocracked compounds in the hydroprocessing of coal-derived heavy oils, even after hydrotreatment. The reaction inhibitors which seriously poison the active sites of zeolites were found to be small nitrogen-containing molecules. In the hydroprocessing of coal-derived heavy oils, zeolite supported catalysts were inferior to alumina supported catalysts. This is due to the high hydrocracking but low hydrogenation activity of zeolite supported catalysts. 22 refs., 5 figs., 11 tabs.
Catalyst deactivation during steam reforming of transportation fuels, primarily due to sulfur poisoning and carbon deposition, is a major hurdle in the commercialization of fuel cell technologies. In an attempt to better understand the phenomena, a previously formulated multi-component (Ni, Pd, Rh) catalyst supported on g-Al2O3 was studied under steam reforming of Jet A spiked with thiophene to achieve a total sulfur content of 1000ppm by weight. Analysis of fresh catalysts showed the presence of two groups of active metal particles, primarily distinguished by their size and composition; small particles (1-5nm) largely comprised of Rh and large particles (10-20nm) that were predominantly Ni, with or without the presence of Pd. Analysis of used catalysts showed sintering of crystallites con...
The overall objective of this research work was to prepare hydrocracking catalysts using amorphous silica-alumina (ASA) supports in combination with USY and {beta}-zeolites. Three supports: namely silica-alumina, USY and {beta}-zeolites were selected to prepare the extrudates using AP-1 as a binder, while two metal pairs: namely Ni-W and Ni-Mo were loaded on the extrudates through co-impregnation using incipient wetness technique. The catalysts were then calcined at 550C for 2h. The catalysts were tested in a fixed-bed flow reaction system for their activity, using desulfurized vacuum gas oil (DS-VGO) as a feedstock. The catalytic evaluation results of the catalysts showed that {beta}-zeolite alone and in combination with the ASA used in this study, has a potential as a support for developing heavy oil hydrocracking catalysts. A balance of weak and strong acidities of {beta}-zeolite ...
The abstracts of all the presentations (1 plenary session, 2 keynotes, 52 oral communications, 496 posters) of the thematic session 1: 'catalyst preparation and characterization' are gathered in the CD-Rom of the conference. The main application described concerns the petroleum industry. (O.M.)
A process is claimed for selectively preparing alpha-olefins having from 2 to about 22 carbon atoms by contacting a gaseous mixture containing carbon monoxide and hydrogen with an iron titanate alkali metal hydroxide catalyst at reaction conditions correlated so as to favor the formation of a substantial proportion of such alpha-olefin product.
The nano-structured Fe(III)-doped TiO{sub 2} photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe{sub x}Ti{sub 1-x}O{sub 2} (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO{sub 2} catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe{sub x}Ti{sub 1-x}O{sub 2}, and ...
We examined a catalytic effect of niobium oxide (Nb{sub 2}O{sub 5}) on the hydrogen storage properties of MgH{sub 2} prepared by mechanical ball milling method. The MgH{sub 2} composite doped with 1 mol% Nb{sub 2}O{sub 5} by ball milling for 20 h desorbed hydrogen up to {approx}6 mass% in the temperature range from 200 to 250 {sup o}C at the heating rate of 5 {sup o}C/min under a purified helium flow. After dehydrogenation at 200 {sup o}C, the product showed remarkable hydrogen absorption kinetics. A large amount of gaseous hydrogen up to {approx}4.5 mass% was absorbed even at room temperature under 1 MPa hydrogen pressure within 15 s and finally its capacity reached up to 5 mass%. Furthermore, the valence state of Nb{sub 2}O{sub 5} doped in MgH{sub 2} was examined by X-ray absorption near edge structure (XANES) measurement. The results indicated that additive Nb{sub 2}O{sub 5} was reduced by MgH{sub 2} during mechanical milling. This suggests that the Nb compound, ...
Reinforced (heterogel) silicate materials containing an amorphous and a crystalline phase are being used more and more industry. Such systems are energetically unsaturated and therefore promising for use in catalysts. The authors used two reinforced materials as supports: an aluminosilicate containing a zeolite (the cracking catalyst, tseokar) and asbestos-containing aluminosilicate. The active component was introduced by impregnation, and this was followed by heat treatment during which the chemical composition and porous structure were formed. The impregnating mixture consisted of solutions of potassium sulfate and vanadate of the required concentrations. The testing shows that reinforced heterogel systems are promising as support materials for sulfuric acid catalysts.
A method for analyzing the experimental results of coal liquefaction reactions which is applicable to a number of aspects of coal liquefaction research and process control, including rapid selectivity and performance screening for catalysts; correlation of laboratory results with process parameters; and optimization of product yield with plant process conditions is described here. Ternary diagrams of product/by-product distributions for the coal liquefaction using Co/Mo catalysts combined with a hyperbolic relationship for the conversion of various hydrocarbon fractions can be used for catalyst screening. A hydrogen consumption diagram used to provide a more significant selectivity test than the hyperbolic correlation is also included. (BLM)
The increasing environmental concern and promotion of ''green processes'' are forcing the substitution of traditional acid and base homogeneous catalysts by solid ones. Among these heterogeneous catalysts, zeolites and zeotypes can be considered as real ''green'' catalysts, due to their benign nature from an environmental point of view. The importance of these inorganic molecular sieves within the field of heterogeneous catalysis relies not only on their microporous structure and the related shape selectivity, but also on the flexibility of their chemical composition. Modification of the zeolite framework composition results in materials with acidic, basic or redox properties, whereas multifunctional catalysts can be obtained by introducing metals by ion exchange or impregnation procedures...
... analyzer section for angle resolved measurements, and a thin film evaporator with a quartz crystal microbalance to measure the mass deposition. ...
The catalytic properties of molybdena-alumina catalysts reduced in hydrogen were studied in the function of the reduction temperature, i.e. in the function of the extent of reduction. The deuterium exchange reaction of benzene was used as model catalytic reaction. It was concluded that the reaction rate constant and the multiplicity factor decreased with the extent of reduction parallel with the change in the extent of dehydroxylation of the catalysts. (orig.)
Nanosized particles are important because of their unique properties, different from the bulk, which leads to their enhanced catalytic, photocatalytic and electronic properties. This work has dealt with three different nanoparticle systems in the context of three different aspects of nanoparticle properties: (a) photocatalytis (TiO2/metal) system, (b) luminescence (CdSe) (c) alloying (Pt-Ag and Pd-Ag). The initial photocatalytic enhancement obtained by adding noble metal on semiconductor nanoparticles, degrades as fast as in 15 minutes and questions their long-term performance. XANES measurements on such irradiated systems like TiO2/Au, TiO2/Pt, TiO2/Ir indicates a positive oxidation state of these noble metals which renders them as recombination centers for photo-excited electrons and explains the decreased photocurrent. The oxidation is caused by holes. The EXAFS results also indicate a change of the interfacial structure under the effect of ...
Several kinds of catalysts for coal liquefaction were analysed by means of high pressure differential thermal analysis (DTA). The activity order is as follows: Fe(OH)/sub 3/.Ni(OH)/sub 2/ > 3665 > Fe(OH)/sub 3/.MoO/sub 3/ > Jin Chuan Mineral > concentrated pyrite > Japan red-mud approx. equal to Fe(OH)/sub 3/.CuO approx. equal to no catalyst. If the catalysts are promoted by sulphur., the activity order is 3665 + S > Fe(OH)/sub 3/.Ni(OH)/sub 2/ + S > Fe(OH)O/sub 33/ + S > Japan red mud + S > Fe(OH)O/sub 3/.CuO + S > no catalyst. The kinetic parameters of three catalysts commonly used in the liquefaction of coal were determined.
Platinum and ruthenium in carbon supported Pt and Pt-Ru catalysts were determined by direct and derivative spectrophotometric methods. Complexes of platinum and ruthenium with SnCl(3)(-) ligands (tin(II) chloride in HCl) were used to determine both metals in solutions obtained after digestion of the samples of the catalysts. Platinum in the Pt/C catalyst can be determined in solutions obtained by digestion of the samples in aqua regia. Derivative spectrophotometry was used to determine both metals in the presence of each other in solutions obtained after digestion of samples of the Pt-Ru/C catalyst in the mixture of HCl+HNO(3) (6:1). The first derivative at 377 nm (;zero-crossing' point of ruthenium) and the second-derivative values at 495 nm (;zero-crossing' point of platinum) were used to estimate the concentration of platinum and ruthenium, respectively. PMID:18967441
This quarterly report, for the period April 1-June 30, 1982, summarizes Sandia's activities in coal liquefaction process research. The overall objectives of the program are to understand the mechanisms and determine the role of catalysts in the direct conversion of coal to liquids. Primary emphasis is being given to the Integrated Two-Stage Liquefaction (ITSL) process. Specific tasks include: short-contact time coal liquefaction, mineral matter effects and catalyst studies. During this period, work was done on: the characteristics of a Liquefaction (ITSL) facility at New Brunswick, NJ; the kinetics of hydrogenation and dehydrogenation of pyrene and dihydropyrenes in batch microreactors; the impact of coal cleaning on the effectiveness of two types of slurry phase catalysts; the deactivation of aged catalyst samples obtained from the H-Coal PDU; and a catalyst deactivation ...
Rye straw was completely hydroliquefied, using red mud or CoO-MoO{sub 3} as the catalyst. Red mud catalyst exhibited a satisfactory activity only in the presence of sulphur at {approx} 673 K. Depending on reaction conditions, different amounts of gaseous and liquid products were formed. Their product distributions were comparable to those obtained in hydroliquefaction of cellulose and lignin. All results could be described by a model which assumed that: pyrolysis precedes hydrogenation of pyrolysis products; CO and CO{sub 2} are products of pyrolysis reaction; and hydrogen is consumed mainly in hydrodeoxygenation reactions. Therefore, from a practical point of view, red mud, which is known as a coal liquefaction catalyst, can also be recommended as a cheap and powerful catalyst in the hydroliquefaction of biomass. 29 refs., 6 figs., 11 tabs.
Mineral matter in coals is important in various senses for coal liquefaction. It is possible that the catalytic activity is affected by the interaction between catalyst and mineral matter. Iron-based catalyst forms pyrrhotite in the process of liquefaction, but the interaction between it and mineral matter is not known in detail. In this study, the interaction between mineral matter and catalyst and the selective reaction between them were investigated. Tanito Harum coal was used for this study. This coal contains a slight amount of siderite and jarosite besides pyrite as iron compounds. Liquefaction samples were obtained from the 1 t/d NEDOL process PSU. The solid deposits in the reactor mainly contained pyrrhotite and quartz. A slight amount of kaolinite was observed, and pyrite was little remained. It was found that the catalyst (pyrrhotite) often coexisted with quartz, clay and calcite. 8 figs., 2 ...
This invention relates with a pot-type catalyst carrier which excels as a catalyst carrier when such heavy oils as ordinary pressure distillation residue, oil sand oil, and shale oil are decomposed or treated by hydrogenation. The conventional pot-type carrier is produced by dropping a small drop of a slurry (containing a catalyst component) onto a particle bed and drying it. But the demerit is a large particle size and less catalyst activity or strength. In this invention, a mixture of such carrier components as allophane, red mud, bauxite and latellite, etc.. 60 - 80 weight parts. and a binder 20 - 40 weight parts is added with water to form a slurry of 10 - 30 weight% solid concentration. Slurry is wet-crushed to make the average particle size 0.6 - 2.0 micron, then spray-dried and burned to obtain a pot-type catalyst carrier with average particle size 30 - 200 micron and ...
10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of ...
Major advances in 'Energy and Materials Cycles' have been achieved in the removal of heavy metals from the solid residues of municipal waste incineration. It has been conclusively shown that the oxidation/reduction conditions established during the thermal treatment of filter ash have a decisive influence on the evaporation of groups of heavy metals. With respect to biomass gasification, studies have been carried out with respect to the best way of extracting pure hydrogen from the low calorific value gas that is typically obtained from a biomass gasifier. The overarching goal of the laboratory 'High Temperature Solar Technology' is the use of solar energy for the production of solar fuels, or for the reduction of CO{sub 2} emissions in large scale industrial processes that are conventionally carried out with the use of fossil fuels. In a short-term project targeted at the solar production of lime, highly encouraging results (98% ...
A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.
The production of hydrogen from the two-stage pyrolysis-gasification of polypropylene using a Ni/CeO{sub 2}/ZSM-5 catalyst has been investigated. Experiments were conducted on CeO{sub 2} loading, calcination temperature and Ni loading of the Ni/CeO{sub 2}/ZSM-5 catalyst in relation to hydrogen production. The results indicated that with increasing CeO{sub 2} loading from 5 to 30 wt.% for the 10 wt.% Ni/CeO{sub 2}/ZSM-5 catalyst calcined at 750 C, hydrogen concentration in the gas product and the theoretical potential hydrogen production were decreased from 63.0 to 49.8 vol.% and 50.4 to 21.6 wt.%, respectively. In addition, the amount of coke deposited on the catalyst was reduced from 9.5 to 6.2 wt.%. The calcination temperature had little influence on hydrogen production for the catalyst containing 5 wt.% of CeO{sub 2}. However, for the 10 wt.% Ni/CeO{sub 2}/ZSM-5 ...
Performance of various catalysts for hydrogenation of recycle solvent was evaluated for the operation of NEDOL process 1 t/d process supporting unit (PSU). Distillate between 220 and 538{degree}C derived from the liquefaction of Tanito Harum coal was used as recycle solvent. Deactivation behaviors of catalysts were compared using a prediction equation of catalyst life, by which aromatic carbon index (fa) after hydrogenation can be determined from the fa of recycle oil before hydrogenation, reaction temperature, and total hydrogenation time. Total hydrogenation time satisfying the {Delta}fa, 0.05 before and after hydrogenation were 8,000, 4,000, and 2,000 hours for NiMo-based catalysts C, A, and B, respectively. Catalyst C showed the longest life. Used catalysts were also characterized. The catalyst C showed larger mean pore size than those ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl ...
Proton exchange membrane fuel cells (PEMFCs) are attractive because of their high conversion efficiency, low pollution, lightweight, and high power density. A major area of challenges is the design and engineering of active, robust, and low-cost electrocatalysts. This report discusses recent findings of our investigations of the design and nano-engineering of platinum-vanadium-iron catalysts for use in PEMFC. The membrane electrode assembly was prepared using nano-engineered PtVFe nanoparticles with controlled composition and size supported on carbon as cathode electrocatalysts. The electrocatalytic activity and stability of the catalysts have been characterized by both rotating disk electrode and membrane electrode assembly measurements. The trimetallic catalysts have been shown to exhibit excellent electrocatalytic performance in PEMFC in comparison with commercial platinum catalysts. The results ...
The NiMo sulfide supported on Ketjen Black (KB) was more effective and yielded lighter oil products containing light fractions with their boiling point below 300{degree}C during the two stage liquefaction combining low temperature and high temperature hydrogenation the conventional NiMo/alumina catalyst and FeS2 catalyst. Although the NiMo/alumina yielded increased oil products during the two stage liquefaction, the lighter oil fractions did not increase and the heavier fractions increased mainly. This suggests that the hydrogenation of aromatic rings and successive cleavage of the rings are necessary for producing the light oil, which is derived from the sufficient hydrogenation of aromatic rings using catalysts. For the two stage reaction with NiMo/KB catalyst, it was considered that sufficient hydrogen was directly transferred to coal molecules at the first stage of the low temperature reaction, ...
Special CoMo/Al{sub 2}O{sub 3} catalysts were prepared for testing in coal liquefaction: a conventional CoMo/Al{sub 2}O{sub 3} catalyst, one containing Zn as a second promoter and one having the alumina acidified with fluorine. Their activities were compared with that of red mud. The experiments were conducted in a stirred autoclave with a subbituminous coal and solvent (tetralin, anthracene oil or creosote oil) at 425{degree}C and 17 MPa. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes with pentane, toluene and THF. The Co(Zn)Mo/Al{sub 2}O{sub 3} catalysts have far higher activities than red mud. Zn and fluorine have beneficial effects on the catalyst activity. Coal tar distillates give higher conversions and oil + gas yields than tetralin when the prepared catalysts are used. 17 refs., 7 tabs.
This semiannual report for the period October 1983-March 1984 summarizes activities in Sandia National Laboratories' continuing program of coal liquefaction research. The primary goals are to: explore novel catalytic concepts and materials for conversion of coal to liquid fuels; determine the effects of process variables on catalyst deactivation; determine the effects of coal structure and solvent properties on low temperature dissolution; study the kinetics and catalysis of hydrogen transfer reactions; develop an understanding of slurry gelling phenomena; and provide a technical assessment of coal liquefaction processes. During this period, work was performed on: the use of pyrene as a chemical probe of catalyst activity; analysis of catalysts from Wilsonville run 242 using ESCA; atmospheric pressure model compound activity testing of regenerated catalysts from Wilsonville run 242; base ...
This quarterly report for the period April through June 1984 summarizes activities in Sandia National Laboratories' continuing program of coal liquefaction research. The primary goals are to: explore novel catalytic concepts and materials for conversion of coal to liquid fuels; determine the effects of process variables on catalyst deactivation; determine the effects of coal structure and solvent properties on low temperature dissolution; study the kinetics and catalysis of hydrogen transfer reactions; develop an understanding of slurry gelling phenomena; and provide a technical assessment of coal liquefaction processes. During this period, work was performed on: analysis of catalyst samples from Wilsonville Run 246; catalyst presulfiding; catalyst activity testing using pyrene as a chemical probe; catalyst deactivation using a high-pressure model compound test reactor; ...
The purpose of this study is to prevent the deactivation of catalysts recycled in the 0.1 t/d bench scale unit (BSU). Catalysts recovered during reactions in the BSU and after reactions in the 5-liter autoclave were analyzed, to investigate the influences of the reaction condition on the property and activity of catalysts. Were used {gamma}-iron oxyhydroxide ({gamma}-FeOOH), {alpha}-iron oxyhydroxide ({alpha}-FeOOH), and natural pyrite (FeS2) as catalysts. At the S/Fe atomic ration of 1.2 under the BSU reaction condition, troilite was more easily formed from {gamma}-FeOOH compared with pyrite and {alpha}-FeOOH. As the reaction proceeded through the first, second, and third reactors, the crystal size increased, the pyrrhotite content decreased, and the troilite content increased. Deactivation due to the formation of troilite was irreversible. At the S/Fe of 3.0, however, both the formation of troilite ...
The batchwise preparation of molecular sieves for methanol conversion shows some inconsistency in catalytic stability. This is a result mainly of the change of SiO/SUB/2/Al/SUB/2O/SUB/3 in ion exchange to an H-type sieve. The dealumination during ion exchange depends upon crystal size and structural factors, which can be characterised by the cyclohexane adsorption of the raw molecular sieve. A high SiO/SUB/2/Al/SUB/2O/SUB/3 H-molecular sieve can be prepared from a molecular sieve of high adsorption capacity, this leading to a catalyst of higher stability. (4 refs.)
Palladium silicide was formed on the sol-gel derived SiO2 supported Pd catalysts prepared by ion-exchange method (Pd/SiO2-SG-ion). However, the catalysts exhibited superior performances than commercial SiO2 supported ones in liquid-phase semihydrogenation of phenylacetylene. It was probably due to an inhibition of a product of styrene, which is adsorbed on the surface of Pd, more strongly on Pd/SiO2-SG in which Pd is electron-deficient as shown by larger binding energy from XPS results.
Catalytic testing of inorganic catalysts was continued with the highly active sulfate-modified zirconia catalyst prepared here. Using isobutanol as the only reactant over this catalyst, it was demonstrated that high conversion and selectivity to isobutene was achieved at 175[degrees]C. In addition, the high selectivity to isobutene, i.e. 79--86 mol%, was maintained at higher space velocities and higher temperatures. A high productivity of 11.35 mol isobutene was achieved at 225[degrees]C. Utilizing a methanol/isobutanol = 2/1 molar ratio reactant mixture over the ZrO[sub 2]/SO[sub 4][sup 2[minus
One-pot multi-component condensation of benzyl, aldehydes, ammonium acetate and primary amines were used for synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted-1H-imidazole derivatives under MW radiation using amberlyst A-15 as a catalysts. This catalyst has several advantages (simple work-up, low cost and reusability).
The present paper is a comparative study of the cerium-containing nickel catalysts supported on x- and y-zeolites. In general, the addition of cerium ions caused an increase in the catalytic activity for CO hydrogenation and shifted the product selectivity to high molecular weight hydrocarbons. The degree of the effect of cerium additive depends on the ratio of cerium to nickel contents, the reduction temperature, and the nature of the supporting materials. Catalyst characterization, including volumetric hydrogen chemisorption, temperature programmed reduction/desorption, x-ray diffraction, surface area measurements, in-situ infrared spectroscopy and x-ray photoelectron spectroscopy, was performed in order to interpret the phenomena due to the effects of cerium additives and the support effect on Ni/zeolite catalysts.
It was demonstrated that R 2?R 4 saturated monohydric alcohols can be synthesized from CO and H2 in the presence of Fe catalysts containing a carbon support of the Sibunit type with granule sizes of 3?5, 1?2, and 0.05?0.1 mm in a fixed-bed reactor at 3 MPa and 240?300?C. It was found that the activity of Fe/Sibunit catalysts and their selectivity for the formation of liquid synthetic products increased with the size of granules and the amount of iron. The catalysts make it possible to obtain fatty alcohols, in which the fraction of R 2?R 4 alcohols is as high as 75%, in yields to 56 g/m3.
Graphical abstract: - Abstract: Low loading platinum-cobalt (Pt-Co) cathode catalyst on a Nafion(Na+)-bonded carbon layer is fabricated by using galvanostatic pulse technique to show the advantage of electrodeposition for high utilization of catalyst in proton exchange membrane fuel cell (PEMFC). We observed that Pt-Co catalysts evenly exist on the surface of carbon electrode and its thickness is about 5.8 ?m, which is four times thinner than conventional Pt/C. Improved single cell power performance of Pt-Co cathode catalysts with a ratio of 3.2:1 compared with Pt/C is clearly presented.
The photocatalyzed degradation of pyridine in the gas phase was investigated using titanium dioxide semiconductor supported on mordenite. The complete mineralization was found to occur over a catalyst containing 75 wt% TiO{sub 2} and 25 wt% mordenite in about 180 min in the presence of saturated water vapor at O{degrees}C (4.6 Torr). Low water vapor pressure of 0.096 Torr was found to be sufficient to achieve a reasonably high percentage and rate of degradation. Diffusion of pyridine within the catalyst adversely affects the activity when the thickness of the catalyst coating exceeds the penetration depth of illumination. The activity of the zeolite-supported catalysts was higher than that of TiO{sub 2}. The photonic efficiency for the complete mineralization of pyridine to CO{sub 2} was determined to be 0.48. 29 refs., 6 refs., 1 tab.
The performance of Ag-promoted Pd/Al2O3 catalysts, which were prepared by the selective deposition of Ag onto Pd using a surface redox (SR) method, during acetylene hydrogenation was compared with that of catalysts prepared by impregnation. The Pd surface was more effectively modified with Ag added by SR, even when small amounts of Ag were added. The catalyst prepared by SR showed a higher ethylene selectivity than the one prepared by impregnation, because SR allowed both the preferential deposition of Ag on the low-coordination sites of Pd and a greater electronic modification of Pd by Ag.
As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.
Acrylonitrile is a versatile intermediate and is produced by the Sohio ammoxidation process world-wide at a level of 8 billion pounds per year. In the catalytic process, propylene, ammonia and air are converted to acrylonitrile directly. The most widely used catalysts are mixed metal molybdates or antimonates. The current investigation deals with metal tellurates as possible low temperature ammoxidation catalysts. Of the catalysts investigated, iron-selenium-tellurates are of particular interest since they exhibit good ammoxidation activity already at 320/sup 0/C which is about 100/sup 0/C lower than the temperature required for molybdate or antimonate systems. Mechanistically, the tellurates behave more similarly to the antimonates than the molybdates. 3 tabs., 4 figs., 13 refs.
Isopropyl chloroacetate has been synthesized by esterification of chloroacetic acid and isopropanol, using lanthanum dodecyl sulfate (LDDS) as the catalyst. Various factors that affected the esterification have been investigated, such as reaction time, different water-carrying agent and the amount of catalyst. Under the condition of 1.2/1 molar ratio of isopropanol to chloroacetic acid, 1.0% catalyst (molar percent of chloroacetic acid), 2.5 h reaction time, 5 mL cyclohexane as water-carrying agent and reflux temperature, the esterification conversion of isopropyl chloroacetate reaches 98.3%. The catalytic activity of LDDS is almost equal to that of a Bronsted acid. LDDS, as one kind of water-tolerant Lewis acid, is an excellent catalyst compared to the traditional Lewis acid. (author)
Proton exchange membrane (PEM) fuel cells are energy sources that have the ... for H2 /02 PEM fuel cells because their catalysts have properties suitable for 0 ...
The fixed bed pilot plant, the catalyst testing procedure, and the calculations for conversion and selectivities were previously described in the technical progress report covering the period of 3/16/88 to 6/16/88 for Contract DE-AC22-87PC79812. Conversions and hydrocarbon selectivities were calculated using data from an on-line gas chromatography (GC) analyzer. Alcohol selectivities were calculated using data from an on-line boiling point GC analyzer which analyzed the liquid product. The catalysts were prepared via the steps of impregnation, calcination, and reduction on a special Y-zeolite-derived support. The impregnation step consisted of evaporation of metal salts on to the support from an aqueous solution. For one catalyst (No. 6531-188) the metal salts were evaporated on to the support from a reverse micelle solution containing the metal salts. All the catalysts were calcined for four hours at ...
Platinum(II) complexes have been investigated in the hydration of alkynes. These catalysts offer improved regioselectivity over Hg(II) counterparts. 1 fig., 2 tabs.
The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis-Menten kinetics. A large value of KM (KM=5.01+-0.16 M) is obtained, which indicates that the Rh-solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate-catalyst complexes, which are undetectable by experimental means, suggest that the major substrate-catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism...
A hydrous oxide film for the application as dielectric film is synthesized by immersion of pure aluminum in hot water. From a Rutherford backscattering analysis, the ratio of aluminum to oxygen atoms was found to be 3:2 in the anodized aluminum oxide film, and 2:1 in the hydrous oxide layer. Anodization of the hydrous oxide layer was more effective for the transition of amorphous anodic oxides to the crystalline aluminum oxides.
The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solid state carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.
In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supported catalysts were prepared. Catalytic activities of them were investigated for the hydrogenation of 1-methylnaphthalene, to discuss the influences of metals and carbon species on the catalytic activity. Various water soluble and oil soluble Mo and Ni salts were used for NiMo supported catalysts. Among various carbon supports, Ketjen Black (KB) was effective for preparing the catalyst showing the most excellent hydrogenation activity. The KB and Black Pearl 2000 (BP2000) showing high hydrogenation activity were fine particles having high specific surface area more than 1000 m{sup 2}/g and primary particle diameter around 30 nm. This was inferred to contribute to the high dispersion support of active metals. Since such fine particles ...
Standard SCR catalysts possess high activity for the hydrolysis of HNCO and thus explain the suitability of urea as a selective reducing agent for NO{sub x}. At high space velocities HNCO-slip can get perceptible over the entire temperature range. This can be attributed to the fact that the temperature dependence is strong for the SCR reaction, but weak for the hydrolysis reaction. (author) 3 figs., 5 refs.
Co-processing of Battle River coal and Cold Lake oil sand bitumen from Canada was carried out in the presence of Ni-Mo, Co-Mo and red-mud/sulfur catalysts under reaction conditions of 400-450{degree}C, 10-120 min and 22-23 MPa of reaction hydrogen pressure by using a 500 ml shaking-type autoclave. The conversion of Battle River coal during the reprocessing was 97.1 wt% (daf) at 450{degree}C for 121 min with Ni-Mo catalyst, higher than 95.7 wt% (daf) at 450{degree}C for 120 min with red-mud/sulfur catalyst and anthracite oil. Cold lake oil sand bitumen was excellent solvent to liquefy Battle River coal comparing with anthracite on. In the presence of Ni-Mo catalyst during the coprocessing, the hydrogen consumption was nearly the same as that with red-mud/sulfur catalyst. Ni-Mo catalyst gave higher conversion of Battle River coal in the initial stage of the ...
The author discusses the accelerated aging tests performed using Hondo and Maya as aging resids with a commercial large pore hydrotreating catalyst. The results from these tests were compared with those obtained under a normal full life test. The test resid was a sample of a typical refinery charge and the activities for sulfur and vanadium removal were determined at 720"0F after successive brief periods of exposure to the heavier oils.
Process solvent was hydrogenated in the brown coal liquefaction, to investigate the influence of it on the prethermal treatment and liquefaction. Consequently, it was found that the n-hexane soluble (HS) yield was improved. In this study, capacity of hydrogen transfer from solvent during prethermal treatment and effects of catalyst were investigated. Since prethermal treatment in oil was effective for improving the oil yield in the presence of hydrogen/catalyst or high hydrogen-donor solvent, influence of hydrogen-donor performance of solvent or addition of catalyst on the hydrogenation behavior of coal and the characteristics of products during prethermal treatment were investigated in relation to successive liquefaction results. As a result, it was found that the increase of HS yield was due to the acceleration of conversion of THF-insoluble using high hydrogen-donor solvent and/or by adding catalyst. ...
A study has been made of the reactor blockages occurring in the course of direct hydroliquefaction of Miike coal, Taiheiyo coal and Yallourn coal briquets in a tubular reactor. The liquefaction tests were carried out at 450 C under 24.6 MPa hydrogen pressure, with red mud and sulfur catalyst. From the observed balances for catalyst and coal ash, it was inferred that reactor blockages are due to sedimentation of catalyst and ash. The conditions for catalyst and coal ash run-off were determined after solvent and slurry flow rates had been altered to suit the type of coal being tested. It was found that ash run-off occurred more readily as the difference between the slurry flow velocity and the natural sedimentation velocity of red mud in the coal liquids increased. Even when ash run-off was occurring, however, the ash concentration of the slurry in the reactor was higher than the concentration in the feed ...
Because hydrogenation of coal to liquid products (oils) is accompanied by distributions of complex by-product mixtures (IOM, preasphaltenes, asphaltenes and gases) which change as a function of reaction variables (time, temperature and pressure) and reactor configuration, the determination of selectivity relationships for coal liquefaction catalysts has been a difficult and time-consuming task involving numerous experiments to adequately describe catalyst performance over a range of conditions. This paper describes a method for analyzing the experimental results of coal liquefaction reactions which may be applied to a number of aspects of coal liquefaction research and process control, including: rapid selectivity and performance screening for catalysts; correlation of laboratory results with process parameters; and optimization of product yield for plant process conditions. Catalyst selectivity and ...
Pd-Si metallic glasses have been utilized as catalysts in the Fischer-Tropsch reaction. The glasses are selective of ethane, whereas the in-situ crystallized glasses select a range of hydrocarbons characteristic of conventional Pd catalysts. This shift in selectivity has been observed in other hydrogenation reactions. Surface crystallization caused by the reaction conditions causes variable selectivity. Crystallization in reaction conditions has been monitored by DSC. During the course of the grant we developed the use of (+)- apopinene (6,6-dimethyl-1R,5R-bicyclo(3.1.1)hept-2-ene) as a molecular probe for determining the number and kinds of active sites on metallic glass catalysts. To accomplish this we conducted many experiments for comparison on other types of catalysts. These were foils, powders, and highly dispersed metals on several different supports. The glassy surfaces appear to be three ...
It is thought that iron-based catalysts for coal liquefaction exercise their catalytic activity by forming pyrrhotite (Fe(1-x)S). However, there are still a lot of unknown problems remained concerning the formation and agglomeration behaviors of pyrrhotite. These make a difficulty for improving the activity of iron-based catalysts. In this study, sulfiding behaviors of {alpha}-iron oxyhydroxide ({alpha}-FeOOH) and {gamma}-iron oxyhydroxide ({gamma}-FeOOH) were investigated to reveal the formation and agglomeration behaviors of pyrrhotite. It was found that pyrrhotite was easily converted from ferric oxyhydroxide catalysts having large specific surface areas at the sulfiding temperature below 250{degree}C, and fine crystallites of pyrrhotite were formed at the initial stage of sulfiding. Crystal growth of pyrrhotite at the sulfiding temperature over 350{degree}C depended on the catalyst forms. It was ...
For developing coal liquefaction processes, it is an important problem to improve the light oil yield with increased oil yield. It was previously reported that distillate mainly containing lighter fraction can be produced with high oil yield by reducing the iron/sulfur catalyst addition in slurry, by recycling gas in the process operation, by utilizing these effects, and by using heavy oil as recycling solvent. In this study, the maximum distillate yield of Victorian brown coal was investigated through continuous liquefaction using a bench scale unit. In addition, operation conditions for obtaining sufficient oil yield were investigated under the reduced catalyst addition into one-third. Consequently, it was confirmed that the maximum content of lighter fraction in distillate product was obtained with reduced catalyst addition by using heavy oil as recycling solvent, by adopting new catalyst, and by ...
Abstract in english Higher olefins are produced as a by product in a number of refinery processes and are one of the potential raw materials to produce propylene. In the present study, FCC model feed compound was considered to explore the olefin cracking features and options to enhance propylene using 30% SAPO-34 zeolite as catalyst in a micro-reactor. The superior selectivity of propylene (73 wt%) and higher total olefin selectivity was obtained over 30% SAPO-34 catalyst than over Y or ZSM- (more) 5 zeolite catalysts. The thermodynamical constraints were found to be relatively less serious in the case of 1-hexene conversion. Most of the 1-hexene follows a direct cracking pathway to give two propylene molecules, due to weak acid sites and better diffusion opportunities. The higher temperature and short residence time could also suppress the hydrogen transfer reactions. From OPE (olefins performance envelop) the products ...
Palladium/magnetite nanoparticulate catalysts were developed for efficient elimination of halogenated organic pollutants from contaminated wastewater. Particle recovery from treated water can be ensured via magnetic separation. However, in worst-case scenarios, this catalyst removal step might fail, leading to particle release into the environment. Therefore, a toxicological study was conducted to investigate the impact of both pure magnetite and palladium/magnetite nanoparticle exposure upon human skin (HaCaT) and human colon (CaCo-2) cell lines and a cell line from rainbow trout gills (RTgill-W1). To quantify cell viability after particle exposure, three endpoints were examined for all tested cell lines. Additionally, the formation of reactive oxygen species was studied for the human cells. The results showed only minor effects of the particles on the tested cell systems and support the assumption that palladium/magnetite ...
A patent is claimed for a direct coal liquefication process which is carried out by interaction with a paste, consisting of small-fragment coal, oil and catalysts, with H/sub 2/ at increased temperatures and pressures. The catalyst is a mixture of 1 part per weight of Fe-ore that's been activated by aqueous treatment, and 0.1-1.0 powder-form S. The Fe-ore can be magnetite, limonite, hematite, pyrite, ferrous sand or ''red mud'' (byproduct of the Bayer process), with the ''red mud'' and limonite, having a particle size of about 100 mesh is preferable. Activation of Fe-ore includes aqueous treatment in boiling water for 30-120 min with subsequent drying; annealing at a temp. of 300-700/sup 0/C for 10-120 min; submerging into cold water and final drying. The catalyst is added to the paste in the amount of 0.03-0.3 parts per weight to one part of ...
In October 1980, Air Products and Chemicals, Inc. began a three year contract with the DOE: Catalyst and Reactor Development for a Liquid Phase Fischer-Tropsch Process. The program contains four major tasks: (1) Project Work Plan, (2) Slurry Catalyst Development, (3) Slurry Reactor Design Studies, and (4) Pilot Facility Design. This report describes work on Tasks 2 and 3 carried out in the third quarter of the contract. In Task 2, the computerized search of the Fischer-Tropsch literature was continued, and improvements were made in data processing programs. Shakedown tests were completed on the first 300 ml slurry reactor, and construction of the second and third reactors began. Five modified conventional slurry catalysts were prepared, and two batches were tested in the gas phase giving information on selectivity as a function of composition and activation. Four supported cluster catalyst were ...
A laser pyrolysis technique has been used to produce ultrafine particles of iron carbide with diameters ranging from 2 to 20 nm. Catalysis using iron carbide was investigated in the liquefaction of Wyodak subbituminous coal; yields were determined. A study was carried out to examine the possibility of using an ultrasonic extraction technique as a rapid method of product work-up of samples following pretreatment or liquefaction experiments. A similar study had shown that extraction of coal-derived products by an ultrasonic method was rapid and gave yields and product distributions comparable to those obtained by Soxhlet extraction. On another project, three different types of supported catalysts were used to test activity for the combined water-gas shift hydrogenation of a synthetic donor solvent. The three catalysts tested were: (1) Alumina supported NiMo catalyst-Shell 324m; (2) Bulk hydrous TiO NiMo ...
This report presents the results of Run 261 performed at the Advanced Coal Liquefaction R & D Facility in Wilsonville, Alabama. The run started on January 12, 1991 and continued until May 31, 1991, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Illinois No. 6 seam bituminous coal (from Burning star No. 2 mine). In the first part of Run 261, a new bimodal catalyst, EXP-AO-60, was tested for its performance and attrition characteristics in the catalytic/catalytic mode of the CC-ITSL process. The main objective of this part of the run was to obtain good process performance in the low/high temperature mode of operation along with well-defined distillation product end boiling points. In the second part of Run 261, Criterion (Shell) 324 catalyst was tested. The objective of this test was to evaluate the operational stability and catalyst and process performance while processing the high ash ...
This thesis deals with the analysis of dominant loss mechanisms in direct methanol fuel cells (DMFC) and hydrogen fed polymer electrolyte membrane fuel cells (PEFC) by means of experimental characterization and modeling work. Due to different fuels used in these two fuel cell types, the dominant loss mechanisms are different in their nature. All in-situ characterization techniques that are used in this work are based on a novel test fuel cell with embedded reference electrodes. The first part of this work presents a new concept for realizing a reference electrode configuration in a polymer electrolyte membrane fuel cell by means of laser ablation. The laser beam is used to evaporate a small gap into the electrode surface of a catalyst coated membrane (CCM) to isolate the reference electrode from the working/counter electrode (WE/CE). This method enables the simultaneous ablation of the electrodes on both sides of the CCM because the membrane is transparent for the ...
The oxidative stress theory of aging predicts that manipulations that alter oxidative stress/damage will alter aging. The gold standard for determining whether aging is altered is lifespan,...Full Text Available
Bi-U mixed oxides were synthesized by two methods and characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The samples were tested for the catalytic oxidation of carbon monoxide by oxygen. A stepwise redox mechanism consistent with the kinetic results is proposed. (orig.).
The effect of thermal pretreatment in N[sub 2] up to 723 K and the activation treatments in H[sub 2] and an inert atmosphere on the properties of Ni and Co activated-charcoal-supported catalysts were studied. Catalysts were characterized by means of N[sub 2] adsorption at 77 K, H[sub 2] chemisorption at room temperature, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The catalysts' activity and selectivity for acetone hydrogenation to 2-propanol under unusual and severe conditions (473 K and high overall acetone conversion) were also measured. TGA and XRD evidence was found for the charcoal-support-promoted NiO and CoO reduction to the metallic states when the catalysts were subjected to an inert atmosphere above 723 K caused a loss of acetone hydrogenation activity (calculated on a metal load basis) for both the Ni and Co ...
Chemical oxidation is a treatment technology that uses powertul chemical oxidizers to destroy organic contaminants. Typical oxidizers used in chemical oxidation processes include ozone, hydrogen peroxide, chlorine, and potassium permanganate. The chemical reaction products are usually simple organic compounds, such as carboxylic acids, and/or inorganic compounds, such as carbon dioxide, water, and simple inorganic complexes (e.g., chloride salts, in the case of chemical oxidation treatment of chlorinated solvents).
Porcine pancreatic lipase immobilized on celite particles has been employed as a catalyst for the esterification of dodecanol and decanoic acid in a predominantly organic system. Solvent influence on the equilibrium position and on the catalyst activity has been studied using 20 solvents, including aliphatic and aromatic hydrocarbons, ethers, ketones, nitro- and halogenated hydrocarbons, and esters. The equilibrium constant for esterification correlates well with the solubility of water in the organic solvent, which in turn shows a good relationship with a function of Guttman's donor number and the electron pair acceptance index number of the solvent. This may be rationalized in terms of the requirements for solvation of water and of the reactants. The catalyst activity, measured as the initial rate of the esterification reaction, is best correlated as a function of both n-octanol-water partition coefficient (log P) and ...
Abstract in english Ru(1%)/SiO2 and Cu(1%)Ru(1%)/SiO2 catalysts were prepared by cogelation. The effect of pH and the amount of water on the physical-chemical properties and the catalytic properties of them were analyzed. The acid medium increased the formation of microporosity and the formation of small size of metallic ruthenium particle. The variation of the water quantity used in the gelation not modify considerably the texture neither the dispersion of the noble metal. The reduction lev (more) el of all prepared catalyst was similar, showing displacement in some of reduction peaks. The toluene hydrogenation indicated that the conversion and the quantity of hydrogenate product varied with the pH and the quantity of water used in the gelation. The addition of copper to Ru/SiO2 catalysts diminished the reactive conversion and their hydrogenant activity
In the course of designing a catalytic porous membrane reactor for experimental studies, both inside and outside of the non-reaction zones as well as the two ends of the membrane need to be completely sealed to ensure that there is no flow across the membrane in the non-reaction zone. Experiments show that up to 50% of the total flow across the membrane may be contributed by the axial flow along the wall of the non-reaction zones if only one side of the membrane is sealed. Another problem that cannot be solved by sealing is the capillary flow of the catalyst along the tube wall into the non-reaction zones when the catalyst is doped on the membrane. One of the best ways to avoid this axial flow of catalyst would be to use non-porous tubes in the non-reaction zones and join them with the porous membrane tube. In doing so, the cost of the membrane reactor could be reduced simply because shorter membrane tube is needed.
A dense Pd-Ag membrane reactor (MR) with 100% hydrogen selectivity packed with either Rh/La2O3 or Rh/La2O3-SiO2 as catalysts was used to carry out the dry reforming of methane. The membrane reactor simulation was performed using a well-known reactor model. For this purpose, we employed the equations derived from complete kinetic studies of the dry reforming of methane reaction in connection with both catalysts. In addition, we developed the kinetic equation for the reverse water gas shift reaction (RWGS). The combination of detailed kinetic studies with the measured permeation flux for the Pd-Ag membrane allowed a complete comparison between experimental and simulated operation variables. The variables studied for both catalysts were methane conversion and hydrogen permeation as a function...
Atmospheric pressure tests were performed in which a palladium catalyst ignites and stabilizes the homogeneous combustion of methane. Palladium exhibited a reversible deactivation at temperatures above 750 C, which acted to ``self-regulate`` its operating temperature. A properly treated palladium catalyst could be employed to preheat a methane/air mixture to temperatures required for ignition of gaseous combustion (ca. 800 C) without itself being exposed to the mixture adiabatic flame temperature. The operating temperature of the palladium was found to be relatively insensitive to the methane fuel concentration or catalyst inlet temperature over a wide range of conditions. Thus, palladium is well suited for application in the ignition and stabilization of methane combustion.
In Polymer Electrolyte Fuel Cell (PEFC) technology the reducing of volume and mass of the fuel cell stack and the improvement of catalyst utilization are of great interest. These parameters affect applicability and system cost. In this work we present an alternative way for reducing the stack volume by combining gas distribution and catalytic active area in one plate. Micro machined glassy carbon electrodes serve as support material for the platinum catalyst, as well as gas distributor at the same time. A comparison of these electrodes with conventional platinum-black gas diffusion electrodes under fuel cell conditions shows that the new system is a promising electrode type for enhanced power density and catalyst utilization. (author) 3 figs., 5 refs.
Hydrogenation of napthalene to tetralin using activated red mud as catalyst was studied as a typical hydrogen-donor system. Under the chosen reaction conditions, unprocessed red mud resulted in a conversion of napthalene of 3.55%. The most active catalyst, prepared by adding 20 wt% of TiO/SUB/2 to the red mud, followed by acid digestion and re-precipitation, resulted in a 58% conversion of naphthalene. This technology may have an important bearing on processes such as coal hydrogenation or crude-oil-residue processing, where the rate of reaction and product quality may depend upon the rate at which a hydrogen-donor solvent can be re-hydrogenated. (7 refs.)
Asphaltenes precipitated from an Arabian Mix vacuum residue were hydrocracked in a batch autoclave at 435 and 460{degree}C for 5-90 min. Experiments without catalyst, with modified red mud and with an industrial Co Mo/Al{sub 2}O{sub 3} catalyst were compared. The products were fractionated into gas, naphtha, oil, asphaltenes and coke. Feed asphaltenes and several product fractions were characterised by elemental analysis, by average molecular mass and by {sup 1}H n.m.r. Due to the hydrogenation activity, both catalysts caused - with similar efficiency - the decrease of coke formation and the increase of quantity and quality of oil. 21 refs., 9 figs., 5 tabs.
Abstract Dynamic testing of a phosphoric acid-based high temperature PEM fuel cell shows a peculiar phenomenon. A certain current loss is observed after temperature cycling at constant voltage. This loss is incidentally recovered by applying a cell voltage spike to open circuit voltage. Experimental investigations into temperature, cell voltage, and ageing effects show that this phenomenon might occur due to the orientation of the adsorbed phosphate species on the platinum catalyst surface. Along with some supporting literature and experimental results, a hypothesis is presented in order to explain this occurrence. Phosphoric acid adsorption hysteresis on platinum catalyst due to temperature cycling could cause the temporary cell current loss. Electrode potential-dependent molecule symmetr...
Red mud has been activated by dissolution in hydrochloric acid and reprecipitation with ammonia. The activated material has been evaluated as a catalyst for the hydrogenation of naphthalene, phenanthrene and pyrene and in the hydroliquefaction of both a high and low rank coal utilizing solvents of high and low hydrogen donating ability. Activation led to a substantial increase in the ability to hydrogenate the model compounds and a significant increase in oil yield was obtained in the hydroliquefaction of a low rank coal in the presence of a poor donor solvent. However, activation did not lead to significant increases in overall yields of liquids in other cases and the activated red mud was significantly less active than a commercial nickel-molybdenum-sulphur catalyst. 27 refs., 1 fig., 5 tabs.
A new heterogeneous catalyst for the esterification of free fatty acids and the transesterification of vegetable oils is reported. The layered compound zinc hydroxide nitrate (Zn5(OH)8(NO3)22H2O) was very effective in the alcoholysis of palm oil and the esterification of lauric acid with m(ethanol), even when hydrated ethanol was used. Over the range of 100-140degreeC, the ester yield was the highest at 140degreeC, while the catalyst concentration had a much greater effect on ester yields than the molar ratio of alcohol to acid did. Total ester contents above 95wt% were obtained in both reactions and 93.2wt% glycerin streams were recovered as a result of methanolysis.
The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence ...
Enzymes are versatile catalysts in laboratories and on an industrial scale; improving their immobilization would be beneficial to broadening their applicability and ensuring their (re)use. Lipid-coated...Full Text Available
The effect of neutralizing cations on the secondary reactions of the primary products from CO hydrogenation over ion-exchanged zeolite-supported Ru catalysts was investigated using zeolites with different alkali cations (Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/). The transformation of olefins (propylene and butene) on the zeolites without the metal, under conditions similar to those used for CO hydrogenation, was also studied in order to understand the effect of the various constituents of the support, i.e., the Broensted acid sites generated during catalyst preparation and the alkali cations, on possible secondary reactions of the primary olefinic products. It was established that secondary acid-catalyzed reactions of these primary products can play a major role in shaping product selectivity during CO hydrogenation over zeolite-supported catalysts. Depending on the concentration and the strength of the acid ...
Propylene polymerizations were carried out with {phi}{sub 2}C(Flu)(Cp)ZrCl{sub 2} and SiMe{sub 2}(Ind)2ZrCl{sub 2} catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f{sub 2}C(Flu)(Cp)ZrCl{sub 2}, SiO{sub 2} and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)
Propylene polymerizations were carried out with #phi#_2C(Flu)(Cp)ZrCl_2 and SiMe_2(Ind)2ZrCl_2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f_2C(Flu)(Cp)ZrCl_2, SiO_2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)
...wood smoke, emissions, pollution, heaters, environment, Earthbeat - 25/5/2002: Woodsmoke, Health & the Environment Love that Planet All in the Mind The Buzz Health Report In Conversation Ockhams Razor Science Show The Lab Health Matters Catalyst Quantum ...
Research programs on coal liquefaction are presented. Major topics include: coprocessing, two-stage liquefaction, low severity liquefaction, coal/catalyst and liquefaction chemistry. Individual projects are processed separately for the data bases. (CBS)
In the course of observing by means of Auger spectroscopy graphite gasification reactions catalyzed by metals, it has been found that in the presence of hydrogen, nickel appears to diffuse from the surface into the bulk of the graphite. When potassium is deposited on graphite, it is volatilized above 400/sup 0/C. Surprisingly the production of methane and carbon dioxide from the reaction of graphite and steam was catalyzed by potassium at as low a temperature as 250/sup 0/C. It has been shown that literature on the alkylation of benzene with synthesis gas is erroneous and that the products reported are due to Lewis acid catalyzed cracking of benzene. A novel cobalt mediated, reversible cleavage of a vinyl-hydrogen bond has been discovered. All products from the thermal decomposition of tetralin have been identified. The stereochemistry of cis-1, 2 dihydrotetralin was determined. In the utilization of the water gas shift reaction as a reducing agent for model coal compounds it has been ...
Oxidation of propylene with oxygen, air and a mixture of nitrogen?oxygen in a barrier discharge is investigated. The selectivity towards formation of propylene oxide in pure oxygen is shown to be as high as 45 wt% and the propylene conversion ratio is found to be 12.9 wt%. In the oxidation with air, the propylene oxide selectivity is 23 wt%, while the conversion is 7.5 wt%. The values of propylene conversion and selectivity towards formation of propylene oxide in a barrier discharge are consistent with those obtained by the thermocatalytic methods for production of propylene oxide.
An investigation of the effect of blending of two different coals in various ratios on the hydrogenation reaction was carried out using a red mud-sulphur catalyst. Three Japanese coals and an Australian brown coal were used in the study. The conversion of the blended coals was compared with that obtained with each of the coals alone. A blend of the Yallourn brown coal and Shin-Yubari coal showed a synergism: it is considered that hydroaromatics from the Japanese coal promote the hydrogenation of the Yallourn coal. (The tables and captions in this paper are in English).
The authors measured the absorption of CO{sub 2} in alkaline 0.5 M/0.5 M sodium carbonate/bicarbonate buffers containing either saccharose and sodium arsenite or saccharose and formaldehyde. Absorption enhancement increased upon increasing the concentration of either of the catalysts, but the joint action of the two was always less than the sum of their individual effects, the difference being a function of the acidities and concentrations of the catalysts and the pH of the carbonate/bicarbonate buffer solution
Red mud, and red mud activated by dissolution in hydrochloric acid and reprecipitation with ammonia, were tested as catalysts for the hydrogenation of an anthracene oil in a trickle-bed reactor. Conversion data were determined for the different polyaromatic compounds in the anthracene oil. Red mud shows appreciable catalytic activity, which is enhanced by the activation. Although both red mud and activated red mud are less active than a commercial Ni-Mo/[gamma]-alumina hydrotreating catalyst, the difference in activity is smaller when conversion to hydroaromatics instead of total conversion of reactants is considered. 20 refs., 8 figs., 3 tabs.
Hydrogenolysis reactions of a mixture of coal liquid and coal liquefaction residue were carried out using red mud - sulfur or Co-Mo/Al{sub 2}O{sub 3} catalyst. The effect of deashing treatment of coal liquefaction residue were also investigated. Notable synergistic effects such as the increase of n-hexane soluble and the decrease of dichloromethane insoluble were observed only with the hydrogenolysis of the basic fraction of coal liquid and nondeashed coal liquefaction residue using red mud-sulfur catalyst. 4 refs., 2 figs., 2 tabs.
Light microscopy was used to analyze the effects of added catalyst at different conditions (temperature and reaction times) in liquefaction testing of a low pyritic sulfur bituminous coal. Quantitative changes in vitrinite/vitroplast reflectance of coal and liquefaction residues were shown to be useful markers in analyzing and understanding the role of catalyst during the initial stage of coal particle hydrogenation. Lower reflectance values corresponded to increased conversions up to about the 60 min and 375{degrees}C experimental conditions. Microscopical observation of liquefaction residues also revealed the presence of `wall scales` of varying width.
Among the items of the Sunshine Project in fiscal 1981 for development of a solvent extraction and liquefaction plant, this paper describes the achievements in developing secondary hydrogenation. A small continuous hydrogenation device equipped with three reaction columns that can be filled with catalyst of 50 cc, and a dedicated testing room were designed, and orders were placed with manufacturers. The fabrication, assembly, delivery, installation, piping and wiring were all completed. The device passed a completion inspection based on the high-pressure gas safety assurance law in December 1981. After leakage due to gas and material oil was checked, a trial operation was performed, and verified of normal operation. A screening test was carried out on three kinds of commercially available and prototype catalysts before testing the SRC containing material for studying the secondary hydrogenation. The circulating solvent having a boiling point ...
The trend towards more effective use of fossil fuels and reduced environmental pollution represents a major task of improvement within the refinery processes. The highly isomerized and high octane paraffins produced from isobutane and light olefins by alkylation fulfill all the requirements for reformulated gasoline. This doctoral thesis discusses new catalyst systems because of their potential in alkylation. A slurry reactor apparatus for solid-acid catalysed isobutane/butene alkylation was developed and used to investigate the performance of various heterogeneous catalysts. The selected materials were mainly zeolite types with faujasite structures. The samples were characterized by various methods before alkylation. In general, the order of decreasing catalyst activity after 3 h of reaction at 80{sup o}C was found to be: H-EMT >> H-FAU, dealuminated H-FAU >> NS.500, TA-Y, CeY-98 > Nafion-H. The order of ...
In-situ methods are well known as powerful tools in studying catalyst formation processes, their solid state properties under working conditions and the interaction with the feed, intermediates and products to reveal reaction mechanisms. This paper gives a short overview on results of intense studies using in-situ techniques to reveal VPO catalyst generation processes, interaction of educts, intermediates and products with VPO catalyst surfaces and mechanistic insights. Catalytic data of the ammoxidation of toluene on different VPOs complete these findings. The precursor-catalyst transformation processes were preferently investigated by in-situ XRD, in-situ Raman and in-situ ESR spectroscopy. The interaction of aromatic molecules and intermediates, resp., and VPO solid surfaces was followed by in-situ ESR and in-situ FTIR spectroscopy. Mechanistic information was mainly obtained using in-situ FTIR ...
The overall objective of this project was to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrated coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. Heterofunctional solvents were the most effective in swelling coals. Also solvent blends such as isopropanol/water were more effective than pure solvents alone. Impregnating slurry catalysts simultaneously during coal swelling showed that better uptake was achieved with nonswelling solvent and higher impregnation temperature. Some enhancement in initial coal conversion was seen liquefying SO{sub 2}-treated Black Thunder coal with slurry catalysts, and also when hydrogen donor liquefaction ...
An investigation of the mechanism of the oxidation and ammoxidation of propylene was made. The products of the above reactions were acrylonitrile and acrolein for ammoxidation and oxidation, respectively. Also, the ammoxidation and oxidation of allyl alcohol, allyl amine, and their allylic deuterium substituted analogues was studied. It was concluded that oxidation and ammoxidation of propylene have the same rate determining step. Other conclusions about the reaction intermediates were also made.
The electrochemical oxidation as a method to destroy drug residues like Aspirin {sup trademark}, tetracycline or gentamicin in water was investigated with C-Anode (modified by manganese oxides) and Pt Anode. The mechanism of Aspirin {sup trademark} and tetracycline oxidation and the influence of the biocide effect was observed using GC-MS and three different microbiological tests. In general the biological availability increases with progressive oxidation of the antibiotics. (orig.)
The widely accepted oxidative stress theory of aging postulates that aging results from accumulation of oxidative damage. Surprisingly, data from the longest-living rodent known, naked mole-rats [MRs;...Full Text Available
Background. The Free Radical Theory of Aging mechanistically links oxidative stress to aging. Okinawa has among the world's longest-lived populations but oxidative stress in this...Full Text Available
Oxidative stress occurs when the level of prooxidants exceeds the level of antioxidants in cells resulting in oxidation of cellular components and consequent loss of cellular function. Oxidative...Full Text Available
1. Nitric oxide generation is important in the regulation of resistance vessel tone. Until now, however, there has been no evidence of such a role for basal generation of nitric oxide in the skin microcirculation...Full Text Available
Studies were conducted to quantitate the evolution of nitrogen oxides (NO(x)) from soybean [Glycine max (L.) Merr.] leaves during in vivo nitrate reductase...Full Text Available
Potato tuber mitochondria oxidizing malate respond to NAD+ addition with increased oxidation rates, whereas mung bean hypocotyl mitochondria do not. This is traced to a low endogenous content...Full Text Available
The potential for oxidation of ammonia in anoxic marine sediments exists through anaerobic oxidation by Nitrosomonas-like organisms, utilizing nitrogen dioxide, coupling of nitrification,...Full Text Available
Apparatus and method for selective measurement of tritium oxide in an environment which may include other radioactive components and gamma radiation, the measurement including the selective separation of tritium oxide from a sample gas through a membrane into a counting gas, the generation of electrical pulses individually representative by rise times of tritium oxide and other radioactivity in the counting gas, separation of the pulses by rise times, and counting of those pulses representative of tritium oxide. The invention further includes the separate measurement of any tritium in the sample gas by oxidizing the tritium to tritium oxide and carrying out a second separation and analysis procedure as described above.
The theoretical principles underlying the formation of oxide and, in particular, anodic oxide coatings on metals produced by chemical oxidation, anodizing in solutions, and anodizing in cold plasmas are reviewed. The mechanisms and conditions of anodic oxidation are described, and the structure of anodic oxide coatings on aluminum, magnesium, beryllium, zinc, cadmium, iron, cobalt, nickel, titanium, zirconium, tantalum, and chromium alloys is examined. Attention is also given to various applictins of anodized coatings. 54 references.
The growth of an oxide interfacial layer was recently found to increase the open-circuit voltage (OCV) and efficiency by up to 60 per cent in GaAs metal-semiconductor solar cells. Details of oxidation techniques to provide the necessary oxide thickness and chemical structure and using ozone, water-vapor-saturated oxygen, or oxygen gas discharges are described, as well as apparent crystallographic orientation effects. Preliminary results of the oxide chemistry obtained from X-ray, photoelectron spectroscopy are given. Ratios of arsenic oxide to gallium oxide of unity or less seem to be preferable. Samples with the highest OVC predominantly have As(+3) in the arsenic oxide rather than As(+5). A major difficulty at this time is a reduction in OCV by 100-200 mV when the antireflection coating is vacuum deposited.
PurposeCataracts are often considered to be an unavoidable consequence of aging. Oxidative damage is a major cause or consequence of cortical and nuclear cataracts, the most common...Full Text Available
Ethane oxidation was studied in ethane-grown resting cells (mycelia) of an Acremonium sp. and in cell-free preparations of such mycelia. From resting cell experiments evidence was found for a pathway...Full Text Available
Metastable yttrium-oxide films are synthesized using reactive sputter deposition. The yttrium concentration of the as-deposited film is found to vary as a function of the sputter deposition rate. In addition to the synthesis of the cubic equilibrium phase...
Background:To determine nutrient requirements by the carbon oxidation techniques, it is necessary to know the fraction of carbon dioxide produced during the oxidative...Full Text Available
May 31, 2011 ... A Theoretical Solid Oxide Fuel Cell Model for System Controls and Stability Design AUTHOR(S): Kopasakis, George; Brinson, Thomas; Credle, ...
Flowsheets for the dissolution of aluminum-clad spent nuclear fuel have been proposed using 0.002 M mercuric nitrate catalyst in 5 to 6 M nitric acid. Previous calculations for flammable gas control during the dissolution of spent nuclear fuel have been extended to cover a range of dissolver purge rates from 40 to 55 scfm. A range of dissolver solution volumes from 12000 to 15000 liters were considered for the large H-Canyon dissolver (6.4D). Depending on the purge rate, anywhere from four to six bundles of MURR fuel can be initially charged to the dissolver (6.4D). For successive charges where the dissolver solution already contains 0.002 M mercury catalyst and the dissolved aluminum from five bundles of MURR fuel, five to nine bundles of additional fuel can be charged depending on the purge rate and the dissolver solution volume. Similar calculations have been performed for the small H-Canyon dissolver (6.1D) for solution volumes that ranged ...
This report presents the operating results for Run 245 at the Advanced Coal Liquefaction R and D Facility in Wilsonville, Alabama. This run was made in an all-distillate Integrated Two-Stage Liquefaction (ITSL) mode using Illinois 6 coal from the Burning Star mine. The primary run objective was to obtain steady-state ITSL performance by replacing spent HTR reactor catalyst with fresh, sulfided catalyst. Secondary objectives were to maintain an all-distillate (minimum resid production) product slate and to demonstrate the effects of catalyst addition on the net gas production and hydrogen consumption. Run 245 began on 7 November, 1983, and continued through 12 February, 1984. During this period, 179.0 tons of coal was fed in 2045 hours of operation. Eight special product workup material balances were defined, and the results are presented herein. 6 references, 28 figures, 20 tables.
Sulfated zirconia (SO4-ZrO2) catalysts, prepared with three different sulfur loading contents (0.75%, 1.8% and 2.5%) at two calcination temperatures (500degreeC and 700degreeC), were tested for use in the transesterification of purified palm oil (PPO) and the esterification of palm fatty acid (PFA) in near-critical and super-critical methanol. Techniques including BET, XRD, NH3- and CO2-TPD revealed that the sulfur content and calcination temperature strongly affects the catalyst base-acid site, specific surface area, average pore size, phase structure, and thus the catalytic reactivity. The most suitable sulfur loading content was found to be 1.8% and the optimum calcination temperature 500degreeC. The results show that the use of SO4-ZrO2 reduces esterification reaction times, the amount...
Essential to today's modern refineries and the gasoline production process are fluidized catalytic cracking units. By using a computational fluid dynamics (CFD) code developed at Argonne National Laboratory to simulate the riser, parametric and sensitivity studies were performed to determine the effect of catalyst inlet conditions on the riser hydrodynamics and on the product yields. Simulations were created on the basis of a general riser configuration and operating conditions. The results of this work are indications of riser operating conditions that will maximize specific product yields. The CFD code is a three-dimensional, multiphase, turbulent, reacting flow code with phenomenological models for particle-solid interactions, droplet evaporation, and chemical kinetics. The code has been validated against pressure, particle loading, and product yield measurements. After validation of the code, parametric studies were performed on various parameters such ...
Hydrogenation of carbon monoxide at 101.3 kPa has been studied over a series of ion-exchanged Ru catalysts supported on NaX, NaY, KL, Na mordenite, and HY zeolites. The type of zeolite had pronounced effects on the activity and selectivity of the Ru. The specific activity would appear to be related to the dispersion of reduced ruthenium in the zeolite. Methane selectivity, however, seems to be strongly influenced by the type and concentration of alkali cations remaining in the ion-exchanged zeolite. These cations appear to promote chain growth much as traditional alkali promoters would, though perhaps more indirectly. Due to bifunctional properties of the zeolite-supported catalysts, a significant fraction of C/sub 4/ was in the form of isobutane. Formation of isobutane seems to be related to either the Si/Al ratio in the zeolites or the concentration of the remaining alkali cations, but not to the OH concentration. In addition, H/sub 2/ ...
For the coal liquefaction, improvement of liquefaction conditions and increase of liquefied oil yield are expected by suppressing the recombination through rapid stabilization of pyrolytic radicals which are formed at the initial stage of liquefaction. Two-stage liquefaction combining prethermal treatment and liquefaction was performed under various conditions, to investigate the effects of reaction conditions on the yields and properties of products as well as to increase liquefied oil yield. Consequently, it was found that the catalyst contributes greatly to the hydrogen transfer to coal at the prethermal treatment. High yield of n-hexane soluble fraction with products having low condensation degree could be obtained by combining the prethermal treatment in the presence of hydrogen and catalyst with the concentration of slurry after the treatment. This was considered to be caused by the synergetic effect between the improvement of ...
Catalytic reactions of 3-methylpentane and 2,3-dimethylbutane on HY, amorphous silica-alumina, and HZSM-5 have been studied at 500{degree}C. Both kinetic phenomena and product selectivities have been reported. Cracking reactions an HZSM-5 can be attributed to initiation through protonation occurring at Bronsted sites. Bimolecular processes leading to chain reaction via hydride transfer are restricted within the narrow pore pentasil zeolite. On HY and amorphous silica-alumina, initiation of cracking also occurs at Bronsted sited. No direct evidence was found for participation of Lewis acid sites on the catalyst framework itself. Following initiation, reactions on these catalysts are accelerated through a chain process occurring at Lewis sites generated by adsorption of product olefins at Bronsted sites. The resulting change in the dominant cracking mechanism is reflected in the product selectivity, illustrated here by a falling off in formation ...
Ionic liquids can enhance the activity, selectivity, and stability of enzyme catalysts. Enzymes and ionic liquids as catalysts are seen as a more environmentally friendly technology than the use of traditional catalyst materials in biofuels production. This study investigated the lipase catalyzed esterification reaction for biodiesel production in the presence of the ionic liquid BMIM PF{sub 6}. Methyl acetate was used as the acyl acceptor. A titremetric assay was conducted to measure the activity of the lipase with various amounts of ionic liquid. Reaction parameters were investigated in order to determine their effects on biodiesel conversion. An 80 per cent overall methyl oleate biodiesel yield was successfully produced in the presence of the ionic liquid. The ionic liquid improved lipase activity as well as overall biodiesel yield. Results also showed that the addition of the ionic liquid facilitated the separation of ...
ObjectivesThe overall aim of this work is to use an in-situ FTIR probe to investigate selected heterogeneous catalysts in industrially relevant organic reactions. This approach will be broadly applicable to the UK fine chemical manufacturing base.~%~~%~The project has the following specific objectives:~%~~%~- To demonstrate and develop the use of an in-situ FTIR probe in a batch reactor at elevated temperatures (eg greater than 100 deg C) to monitor reactant usage and product formation.~%~~%~- To validat [continued...]DescriptionThis proposal concerns the in-situ study of catalytic processes and reaction kinetics. The catalysts concerned are microporous materials, such as, zeolites, containing pores and cavities of molecular dimensions. These catalysts constitute crystal reactors on a nanometer scale that are selective on a size and shape basis for organic molecules used ...
Taiheiyo coal deashed using acid treatment and loaded with potassium or calcium was hydro-cracked under gaseous phase to discuss effects of these metals on liquefaction reaction. In addition, the loaded coal was added with red mud catalyst to examine effects of the addition. The loaded potassium has a softening power, and particularly the potassium adsorbed into surface and micropores in the coal decomposes selectively HI-BS and BI-PS and generates gas and HS. On the other hand, potassium deposited on coal surface promotes direct gas production from the coal. Irrespective of its loading modes, calcium has a catalytic nature to produce HI-BS selectively. Calcium also acts to impede decomposition of HI-BS into HS. Adding red mud catalyst to potassium loaded coal increases the inversion rate and the liquefaction yield, and most of the increase is accounted for by HI -BS, and BI-PS. When red mud catalyst is added to calcium ...
Hydrogenolysis of quinoline was carried out using red mud catalyst at 390{degree}C and 450{degree}C to study denitrogenation reaction in the first stage liquefaction of coal. Quinoline was decomposed to ammonia via 1-THQ or hydrogenated to 5-THQ. The reaction rate constants obtained at 390{degree}C were k{sub 1} = 1.83 {times} 10{sup {minus}6}, k{sub 2} = 1.16 {times} 10{sup {minus}7}, and k{sub 3} = 3.24 {times} 10{sup {minus}7} mol {center dot} dm{sup {minus}3} {center dot} min{sup {minus}1} {center dot} g {center dot} {sup {minus}1}. The rate constants for hydrogenation of quinoline were in the order of hexadecane > trans-decalin > 1-methylnaphthalene. Ratios of equilibrium adsorption constant between trans-decalin and quinoline and between 1-methylnaphthalene and quinoline were found to be 0.055 and 0.155 respectively. The equilibrium constant of phenol to red mud catalyst adsorption was calculated to be 3 times of that of quinoline, ...
The objectives of this contract are to conduct exploratory coal liquefaction research on modified solvents with slurry phase catalysts and on coal pretreatment. This report describes a review of the existing literature as well as currently on-going research in the areas of: (1) solvent quality effects on coal liquefaction; (2) role of heteroatoms in liquefaction of coal; (3) heteroatoms removal through solvent treatment, extraction and hydrogenation; (4) slurry phase catalysts in hydroprocessing of coal; and (5) effect of coal preparation and pretreatment on liquefaction. The review encompasses both technical papers and presentations as well as the patent literature. This report is comprised of two distinct parts. In Part I all the literature available on the effect of solvent quality, heteroatoms, heteroatoms removal, and slurry phase catalysts on coal liquefaction is incorporated. The existing literature and currently ...
Carbon supported catalysts can lose their activity over a period of time due to the sintering of the nanometer-sized catalyst particles. The sintering of metal clusters on carbon supports can occur due to the weak interaction between the metal and the support and also due to the corrosion of carbon, especially in fuel cell electrocatalysts. The sintering may be reduced by increasing the interaction between the metal and the support and also by increasing the corrosion resistance of carbon supports. In an effort to mitigate the growth of the nanoparticles, carbon-substituted boron defects were introduced in the carbon lattice. The interaction between the Pt nanoparticles on the pure and boron-doped carbon supports was examined using X-ray photoelectron spectroscopy (XPS). The results indicate that the interaction between the Pt nanoparticles and the boron-doped carbon support was slightly stronger than the interaction between the Pt ...
Cyclopropane isomerization to propylene over various Eu[sup 3+] loadings in NaX zeolite have been studied by measurements of steady-state and transient kinetics and by Fourier transform infrared spectroscopy. As Eu[sup 3+] loading increases, the rate of deactivation increases, the conversion increases, apparent activation energies are lowered, and Bronsted acid site strength and amounts increase. Apparent activation energies of 13-15 kcal/mol for propylene formation have been observed for these systems, consistent with literature reports for other metal supported heterogeneous catalyst systems. Deactivation studies have shown that activity can be restored by heating in He at 380[degrees]C between various temperature runs, and that gases desorbed during regeneration are predominantly propylene. Poisoning studies of Bronsted sites with Na vapor lead to deactivation of these catalysts. A reaction mechanism scheme based on [pi] allyl intermediates ...
The objective of our research was to obtain fundamental information regarding the functional dependence of the diffusion coefficient of coal molecules on the ratio of molecule to pore diameter. That is, the objective of our study was to examine the effect of molecule size and configuration on hindered diffusion of coal macromolecules through as porous medium. To best accomplish this task, we circumvented the complexities of an actual porous catalyst by using a well defined porous matrix with uniform capillaric pores, i.e., a track-etched membrane. In this way, useful information was obtained regarding the relationship of molecular size and configuration on the diffusion rate of coal derived macromolecules through a pore structure with known geometry. Similar studies were performed using a pellet formed of porous alumina, to provide a link between the idealized membranes and the actual complex pore structure of real catalyst extrudates. The ...
This quarterly report for the period July through September 1984 summarizes activities in Sandia National Laboratories' continuing program of coal liquefaction research. The primary goals are to: explore novel catalytic concepts and materials for conversion of coal to liquid fuels; determine the effects of process variables on catalyst deactivation; determine the effects of coal structure and solvent properties on low temperature dissolution; study the kinetics and catalysis of hydrogen transfer reactions; develop an understanding of slurry gelling phenomena; and provide a technical assessment of coal liquefaction processes. During this period, work was performed on: the rheology of Illinois No. 6 coal in hydrogenated creosote oil; dissolution chemistry of subbituminous coal; pyrite catalysis; liquefaction of Illinois No. 6 coal in indole; characterization and activity testing of catalyst samples from Wilsonville Run 246; ...
Cobalt supported on Beta zeolite catalysts were prepared by impregnation of metal salts in aqueous solution and were tested for the Fischer Tropsch reaction. The support consisted of a Beta zeolite composed by crystallites of nanometric dimensions and a SiO2/Al2O3 molar ratio of about 50. This support was impregnated with Co(NO3)2 aqueous solution using different metal loads of 7.5, 10, 15 and 20wt% Co. These materials were characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), N2 adsorption (BET), thermal programmed reduction (TPR) and FTIR of adsorbed pyridine (i.e., surface acid sites distribution). All the catalysts showed a significant catalytic activity for the F-T reaction from synthesis gas (CO+2H2), in a continuous fixed bed reactor sys...
Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was ...
The influence of MeV electrons irradiation on the gate oxide layers of hydrogenated polysilicon thin film transistors (TFTs) was investigated by measuring gate leakage currents and threshold voltages. The experimental data revealed a decrease of oxide trap density and increase of positive oxide charge. Improvement in the interface roughness and in the oxide quality near the bottom interface was observed.
The influence of MeV electrons irradiation on the gate oxide layers of hydrogenated polysilicon thin film transistors (TFTs) was investigated by measuring gate leakage currents and threshold voltages. The experimental data revealed a decrease of oxide trap density and increase of positive oxide charge. Improvement in the interface roughness and in the oxide quality near the bottom interface was observed.
We report on the fouling of Focused Ion Beam (FIB)-fabricated silicon oxide nanopores after exposure to tap water for two weeks. Pore clogging was monitored by Scanning Electron Microscopy (SEM) on both bare silicon oxide and chemically functionalized nanopores. While fouling occurred on hydrophilic silicon oxide pore walls, the hydrophobic nature of alkane chains prevented clogging on the chemically functionalized pore walls. These results have implications for nanopore sensing platform design.
By means of ESCA the composition and the thickness of passive films formed on austenitic stainless steels were investigated after the attack of nitric acid at various temperatures and acid concentrations. The outermost layers of the oxide film consist of SiO_2, then a layer rich of Cr-oxid follows, containing also some Mo in the four- and sixvalent state. Ni does not contribute to the oxide film. Cr is also enriched in the metal just below the oxide film. (orig.).
The RKR potential energy curves are constructed for the ground states of diatomic hafnium oxide and thorium oxide. Using Lippincott and Hulburt-Hirschfelder potential function the dissociation energies are estimated by curve fitting method. The H-H potential function was found to give a better fit in both cases. The dissociation energies of hafnium oxide and thorium oxide are estimated as 9.04 #+-# 0.02 eV and 10.34 #+-# 0.01 eV respectively. (author).
The effect of sodium on the partial oxidation of methane over MoO{sub 3}-SiO{sub 2} in the presence of molecular oxygen has been investigated. As in the sodium-free case, the major products are formaldehyde, carbon monoxide, carbon dioxide, and water. Kinetic analysis indicates that methane is directly oxidized to formaldehyde and carbon dioxide. Formaldehyde is oxidized to carbon monoxide, which is itself further oxidized, providing an alternative route to carbon dioxide. The kinetic model shows that sodium poisons the direct oxidation of methane to formaldehyde and carbon dioxide, but promotes the oxidation of formaldehyde and carbon monoxide. Model predictions of rates and selectivities are in good agreement with the experimental data. A mechanism that explains both the poisoning and promotion effects of sodium on MoO{sub 3}-SiO{sub 2} is proposed.
Targets for heterogeneous transmutation of americium are composed of a support material, the inert matrix and of an americium oxide compound: AmO{sub 2-x} or Am{sub 2}O{sub 3}. In parallel to the studies using americium, simulated compounds of americium oxide, chosen amongst lanthanide oxides, are used. The selection of these compounds is based on theoretical, physical and crystallochemical considerations. In order to assess the influence of impurities composed of lanthanide oxides, resulting from the separation process, on the physical and chemical properties of such a target, synthesis of oxide powders containing impurities associated with the simulated americium oxide, characterizations, crystallographic studies and sodium compatibility tests have been performed. (author)
Titanium oxides were grown anodically to selected final potentials on grade II polycrystalline titanium under different anodization rates. XPS and RBS results show that the oxide consists of primarily TiO2 with a non-stoichiometric oxide/metal interface, with the slower growth rate associated with a thicker layer at the interface. Characterization using TEM reveals that the structure of the oxide evolves from a primarily amorphous phase to islands of crystallites in an amorphous matrix, to an entirely crystalline phase by increasing the polarization potential. Slower growth rates tend to remain crystalline at higher potentials. The mechanical strength of oxide films extracted from load-depth data by nanoindentation varies dramatically for oxide films grown by different rates at 9.4 V, and to a lesser extent at lower potentials. The variation of film strength is ...
Desulphurization of gasoline and kerosene was carried out using organic and inorganic oxidants. Among the organic oxidants used were hydrogen peroxide in combination with acetic acid, formic acid, benzoic acid and butyric acid, while inorganic oxidants used included potassium permanganate and sodium perchlorate. The oxidation of each petroleum oil was carried out in two steps; the first step consisted of oxidation of the feed at moderate temperature and atmospheric pressure while in the second step, the oxidized mixture was extracted with azeotropic mixture of acetonitrile-water. A maximum desulphurization has occurred with NaClO4 and hydrogen peroxide and acetic acid, which are 68% and 61%, respectively in case of gasoline and 66% and 63%, respectively in case of kerosene oil. The FTIR st...
Synergism has been observed during inhibiting initiated oxidation of styrene or tetralin by organic phosphites in the presence of complex compounds of some transition metals. The results are given of non-additive intensification of antioxidative activity of triphenylphosphite (TPP) and tri-(4-methyl-6-tert.-- butyl)-phenyl-phosphite (TMBP) in the process of initiated oxidation of styrene or tetralin with addition of acetylacetonates of cobalt and vanadyl. During styrene oxidation, inhibition of the reaction with chelate complex of vanadyl is weakened considerably when phosphite is added into the reaction system. During tetralin oxidation, postcatalytic (or branched) oxidation is observed only for large concentration of vanadyl complex. Addition of TPP to above complex sharply increases the induction period. When the induction period is completed, oxidation of ...
This topical report presents data and results obtained from the hydrogen microautoclave. The autoclave has been used to test for the quality of hydrotreater residue product and hydrotreater catalyst activity. Data obtained from Run 242 and the first part of Run 243 is presented in a convenient format and conclusions based upon this data are summarized. Some of the topics discussed in this report are the following: development and description of procedures for the catalyst and hydrotreater residue, the significance of test results and their meaning, and the relationship of test results to process performance. 7 references, 13 tables, 22 figures.
X-ray photoelectron spectroscopy measurements indicate that the Ce{sup 3+} like fraction in {gamma}-Al{sub 2}O{sub 3} supported CeO{sub 2} can be decreased by the incorporation of La{sup 3+}. If La{sup 3+} is incorporated into the {gamma}-Al{sub 2}O{sub 3} before CeO{sub 2} is added, a higher CeO{sub 2} dispersion and a greater range of reversible reducibility of the CeO{sub 2} may also be obtained. These changes offer potential for improvement in the oxygen storage capacity provided by CeO{sub 2} in three-way catalysts. The actual effect of La{sup 3+} incorporation on the activity and durability of a Pt catalyst is assessed by a combination of temperature programmed reduction and flow reactor measurements.
A novel heteropolyanion-based ionic hybrid was prepared by combining the divalent ionic liquid (IL) cation of 1,1'-(butane-1,4-diyl)-bis(3-methylimidazolium) with the Keggin-structured V-containing heteropolyanion, and characterized by ^1H NMR, FT-IR, ESI-MS, XRD, SEM, TG, BET surface area, melting point, and elemental analysis. Its catalytic activity was evaluated in the hydroxylation of benzene with aqueous H2O2, including the testing of the influence of organic cations, catalytic reusability and optimization of reaction conditions. This hybrid is characterized to be semi-amorphous nanoparticles with a IL-like composition. The hybrid catalyst leads to the liquid-solid biphasic reaction system for hydroxylation of benzene with H2O2, presenting such advantages as high catalytic activity, c...
The author analyzes conference materials, emphasizing the studies and latest developments useful for industrial heterogeneous catalysis in view of the requirements of green chemistry. Industrial catalysts is developing along a nanometer scale, so especial attention is devoted to analyzing the reports in the Nanochemistry section on the creation of nanocatalysts, the production of active phase nanoparticles, and the formation of new synthesized material properties. The catalysts developed earlier by Russian research in cooperation with Belarusian scientists are considered, and it is shown that not only are expensive nanocontacts extremely promising for industry, but the efficient and economic low-percentage new generation of nanocatalysts synthesized by wet chemistry and containing nanopart...
Statistically based experimental designs were applied to screen and optimize the bioleaching of spent hydrocracking catalyst by Penicillium simplicissimum. Eleven factors were examined for their significance on bioleaching using a Plackett-Burman factorial design. Four significant variables (pulp density, sucrose, NaNO"3, and yeast extract concentrations) were selected for the optimization studies. The combined effect of these variables on metal bioleaching was studied using a central composite design (CCD). Second-order polynomials were established to identify the relationship between the recovery percent of the metals and the four significant variables. The optimal values of the variables for maximum metals bioleaching were as follows: pulp density (4.0%, w/v), sucrose (90g/L), NaNO"3 (2...
Catalytic activity of industrial metallic wastes in coal liquefaction was examined in a 100lb/day continuous coal processing development unit. Red mud, a waste material from the aluminium industry, and an electric furnace flue dust containing Ni, Mo, Co and Fe showed a pronounced effect on the conversion of a Kentucky bituminous coal. Coal conversion and oil production increased significantly with the addition of red mud and flue dust. Comparison of the catalytic activity of pyrite, red mud, and flue dust, based on selectivity analysis, showed that red mud was the most desirable disposable catalyst. However, if the primary goal of coal liquefaction is high oil production, irrespective of hydrogen consumption, pyrite is the most active catalyst among those discussed in the paper.
Cyclization of deproteinized natural rubber (DPNR) or purified natural rubber latex was effectively performed in latex phase by using trimethylsilyl-trifluoromethane sulfonate or trimethylsilyl triflate (TMSOTF) as a novel catalyst, which is still not reported in the case of natural rubber latex. Various cyclization conditions affecting the degree of cyclization were studied, such as dry rubber contents, temperature, TMSOTF concentrations, and time. The cyclized products were characterized by FTIR, Raman, 1H-, and 13C-NMR spectroscopies, as well as DSC and TGA. The degree of cyclization was estimated by 1H-NMR spectrum. It was found that the degree of cyclization in NR was a function of cyclization conditions. The thermal stability of cyclized DPNR increased with the degree of cyclization....
Biomass gasification provides the potential to efficiently and economically produce a renewable source of a clean gaseous fuel suitable for power generation or synthesis gas (syngas) applications. An important side benefit of the use of biomass is the effective minimization of the primary greenhouse gas, carbon dioxide (CO{sub 2}), by providing a means to close-loop the CO{sub 2} cycle. However, high molecular weight hydrocarbon constituents (tar) in the product gas from gasification can complicate the downstream uses of the gas. This paper discusses both the development of a low cost, disposable catalyst system that can eliminate these heavy hydrocarbons from the gas and the use of the catalyst in conjunction with the Battelle high-throughput gasification process for power generation and synthesis applications. (author)
The cyclic voltammetry indicated that the oxygen reduction reaction (ORR) proceeded by the four-electron pathway mechanism on larger Ag particles (174 nm), and that the ORR proceeded by the four-electron pathway and the two-electron pathway mechanisms on finer Ag particles (4.1 nm), simultaneously. The kinetics towards ORR was measured at a rotating disk electrode (RDE) with Ag/C electrode. The number of exchanged electrons for the ORR was found to be close to four on larger Ag particles (174 nm) and close to three on finer Ag particles (4.1 nm). The zinc-air battery with Ag/C catalysts (25.9 nm) was fabricated and examined. (author)
Data are presented on the insulating properties and capacitance-voltage (CV) characteristics of metal-oxide-semiconductor (MOS) device-thickness (below approx. 100 nm) native oxides formed by wet thermal oxidation of thin InAlP epilayers lattice matched to GaAs. Low leakage current densities of J=1.4 x 10-9 A/cm2 and J=8.7 x 10-11 A/cm2 are observed at an applied field of 1 MV/cm for MOS capacitors fabricated with 17 nm and 48 nm oxides, respectively. TEM images show that the In-rich interfacial particles which exist in 110 nm oxides are absent in 17 nm oxide films. Quasi-static capacitance-voltage measurements of MOS capacitors fabricated on both n-type and p-type GaAs show that the InAlP oxide-GaAs interface is sufficiently free of traps to support inversion, indicating an unpinned Fermi level. These data suggest that InAlP native ...
The aim of this paper is to investigate the total ionizing dose (TID) radiation effects on MOS capacitor with nitride/oxide stack gate. The stack gate MOS capacitors are fabricated with 20 nm oxide, 40 nm nitride or 110 nm nitride respectively. Through the analysis of CV curve of the irradiation capacitors, it is found that the degradation of the CV curve is due to a significant increase of interface traps and somewhat smaller oxide charge. It is also shown that the thicker of the nitride, more interface traps and oxide charge will be occurred. (authors)
The procedure of charge-coupled devices (CCD) are investigated by using MOS capacitors for enhancing their ionizing radiation tolerance. Authors have found that the gate oxidation temperature, thickness of SiO_2 gate insulator and high temperature processes after gate oxidation are crucial for determining the radiation tolerance of the devices, and proposed to decrease the thickness of gate insulator, perform gate oxidation at 1000 deg C by means of dry oxidation and minimize the number of high temperature procedure steps after gate oxidation. All stated above is a necessary preparation for priducing radiation hardened charge-coupled devices.
SiSiC is one of selected materials for the thermal chemical hydrogen production IS (Iodine-Sulfur) process at JAERI. SiSiC was tested in boiling sulfuric acid for 1000 hours. The obtained results showed the following facts. The transverse strength was not changed by sulfuric corrosion, high temperature oxidation and oxidation. Silica scale formed on SiSiC by sulfate corrosion and high temperature oxidation had corrosion resistance in boiling sulfuric acid. Bilayer structure of silica scale produced by high temperature oxidation was not affected by sulfate corrosion. (S.Y.).
Cathodic arc deposition is an established and industrially applied technique for the formation of nitrides (e.g. TiN); it can also be used for metal oxide thin film formation. A cathodic arc plasma source with the desired cathode material is operated in an oxygen atmosphere of appropriate pressure, and metal oxides of various stoichiometric composition can be formed on different substrates. We report here on a series of experiments on metal oxide formation by cathodic arc deposition for different applications. Black copper oxide has been deposited on accelerator components to increase the radiative heat transfer between the parts. Various metal oxides such as tungsten oxide, niobium oxide, nickel oxide and vanadium oxide have been deposited on ITO glass to form electrochromic films for window ...
With an objective to learn reactivity of coal at its surface, surfaces of oxidized coal samples were investigated. Miike coal was oxidized by using {sup 18}O2 in a closed loop system. As the reaction progresses, proportion of CO2 including isotopes increased rapidly as a result of oxidation of CO sites existing in the coal and the newly generated C{sup 18}O sites. The oxidizing reaction progressed via oxygen adsorbing sites generated near the surface, and oxygen containing groups. An FT-IR analysis estimated the depth of the oxidized layer to be 10{mu}m or less from particle surface. The oxidized coal was pulverized to see its surface condition. Functional groups introduced by the oxidation enter into the vicinity of the surface in a form to desorb as CO. CO2 is trapped in inner pores. The coal surface was observed by using an atomic force ...
Zirconium and particularly Zr-2.5wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step pro...
Only 15mol% of l-proline in ethanol proved to be a very efficient catalyst for the one-pot synthesis of a wide variety of highly substituted pyridines at room temperature. The methodology is mild, efficient, high yielding, and the products can be directly recrystallized from hot ethanol.
This report presents the operating results for Run 244 at the Advanced Coal Liquefaction R and D Facility in Wilsonville, Alabama. This run was made in an all-distillate Integrated Two-Stage Liquefaction (ITSL) mode using Illinois 6 coal from the Burning Star mine. The primary objective was to demonstrate the effects of temperature programming an aged catalyst batch on the ITSL product slate, especially on the net C/sub 1/-C/sub 5/ gas production and hydrogen consumption. Other objectives were to demonstrate the effect of fresh catalyst addition and to age the catalyst batch for an extended run with catalyst addition and withdrawal. Run 244 began on 4 July 1983 and continued through 27 September 1983. During this period, 182.9 tons of coal was fed in 1872 hours of operation. Seven special product workup material balances and two hydrotreater balances were defined, and the results are presented herein. ...
The diffusion of alkali vapours in the anode compartment of a DIR-MCFC produces the deactivation of the internal reforming catalyst. Sets of ceramic porous membranes purposed to limit the diffusion have been manufactured by different techniques and the influence of the preparation technique and of the preparative variables on the morphological characteristics of the membranes structures has been studied.
Details are given of the Sasol operation in South Africa. Flow sheets are provided for Sasol 1 and Sasol 2 and 3. The Sasol 1 plant produces waxes, liquid fuels, pipeline gas and chemicals; the Sasol 2 and 3 plants primarily produce ethylene, gasoline and diesel fuel. The versatility of the process is emphasized. The product selectivities of the fixed bed and Synthol reactors are shown and the properties of the products are compared. The influence of the catalyst on selectivity is examined.
It is demonstrated that highly dispersed molybdenum sulfide catalysts are prepared by using Mo(CO){sub 6} adsorbed on the support. The structure of ultradispersed molybdenum sulfide is suggested by EXAFS techniques to be different from that of MoS{sub 2}. The TOF of the thiophene HDS is almost invariant with the dispersion of molybdenum sulfide at a high molybdenum dispersion, whereas the TOF of the hydrogenation greatly increases with increasing dispersion. On the basis of the HDS activity and optimum Co/Mo ratio of Co-Mo/Al{sub 2}O{sub 3} catalysts having a variety of molybdenum dispersion fabricated by using carbonyl complexes, it is demonstrated that highly active HDS catalysts are prepared by highly dispersing molybdenum sulfide phases. Edge decorations of molybdenum sulfides by cobalt are suggested for the synergy generation between cobalt and molybdenum sulfides. (orig.) [Deutsch] Unter Verwendung von auf dem Traeger ...
Structural units of a hydrogen fuel cell whose characteristics are advisable to investigate by different neutron scattering methods are discussed. The results obtained with the use of Bragg diffraction and small-angle neutron scattering from fuel membranes, nanocarbon-platinum catalysts, and Zn_1_-_xCu_xO hydrogen storage systems are presented.
The investigations of lignite hydroliquefaction were aimed at improving reaction control in order to minimize residue and gas portion and hence increase the oil yield. To reach this goal, the process parameters were optimized and various catalysts tested for use in sump phase hydrogenation. Detailed investigations were also carried out on the problem of calcium carbonate agglomeration and the maceral decomposition behaviour of different lignite samples under hydrogenation conditions.
Single and binary metal molybdates, supported on silica (80 wt% active phase/20 wt% SiO{sub 2}), having the formula AMoO{sub 4}, where A = Ni, Co, Mg, Mn, and/or Zn, and some ternary molybdates having the formula Ni{sub 0.45}Co{sub 0.45}X{sub 0.066}MoO{sub 4}, where X = P, Bi, Fe, Cr, V, and Ce, were investigated for the oxydehydrogenation of propane to propylene. The reaction is catalytic and is first order in propane disappearance, consistent with the abstraction of a methylene hydrogen being the rate limiting step. Propane conversion and yields of propylene produced vary greatly with the choice of the A metal of the molybdate and the surface area of the catalyst. At 560{degrees}C and atmospheric pressure, the highest propane conversion and highest propylene yields are obtained with NiMoO{sub 4}/SiO{sub 2} (16% at 27% conversion), closely followed by Ni{sub 0.5}Co{sub 0.5}MoO{sub 4}/SiO{sub 2}. The molybdenum content of the compositions greatly influences the ...
Preparation and electrocatalytic reactions of nano porous materials in biodegradable fluids were studied. Electrochemical etching was conducted to selectively extract metallic elements from alloys to form porous structures. Electrocatalytic properties of the porous electrodes were characterized. Comparative studies on the electrochemical activities of the nano porous metallic electrodes with bulk metallic wire catalysts were performed. It is found that the current density at the nano porous electrode is three times higher than that of the bulk electrode
This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns an experiment in reducing by methanation to a level below 10 ppm the CO that is contained to around 1% in reformate gas.
A general palladium-catalyzed carbonylative Sonogashira coupling of benzyl chlorides with terminal acetylenes has been established. Depending on the alkyne 1,4-diaryl-3-butyn-2-ones or substituted furanones are obtained in moderate to good yields. Best catalytic performance is achieved applying a mixed Pd(PPh(3))Cl(2)/P(OPh)(3) catalyst system. PMID:21968528
The catalytic dehydration of methanol to dimethyl ether was investigated for application on-board a methanol fuelled vehicle. Several catalysts have been tested in a fixed bed reactor. Our approach is to develop a small and efficient reactor converting liquid MeOH under pressure and at low reaction temperatures. (author) 2 figs., 5 refs.
The catalytic performance of alkaline-treated zeolite H-ZSM-5 in the conversion of methanol to gasoline has been studied. After treatment with 0.20M NaOH, the total conversion capacity increased by a factor of 3.3, and the selectivity towards the gasoline fraction increased by a factor of 1.7. Physical characterization indicated the formation of mesopores and improved crystallinity.
The kinetics of the reaction of carbon dioxide in MDEA solutions were studied both experimentally and theoretically. It is concluded that MDEA acts as a homogeneous catalyst for CO/sub 2/ hydrolysis, and as a result the rate of absorption in aqueous MDEA solutions is significantly larger than one would calculate by simply taking into account the alkalinity of the reaction. A possible zwitterion mechanism is proposed for this reaction. The minor effect of ionic strength were also studied with the presence of other ions. 19 references, 6 figures.
Details of a series of reactions for the production of ethylene glycol using a catalyst of Nafion solid perfluorosulfonic acid resin was detailed. The reactions included the carbonylation of formaldehyde and esterification and then hydrogenation of the product of the carbonylation, glycolic acid. Other preparations included in the work included methyl glycolate, acetylglycolic acid, methyl acetylglycolate, and methyl methoxyacetate.
DescriptionEnzymes are natural catalysts that are used increasingly to replace environmentally harmful chemicals and to achieve better catalytic selectivity during pulp and paper processing. The main objective of this project is to identify novel plant enzymes for deeper understanding of the process of fibre formation and for future improvement of the quality parameters of wood fibres. Specific modification of the fibre characteristics will facilitate their use as raw materials for the current pulp and pap [continued...
This paper reports the effectiveness of solvents on the liquefaction of 11 different Turkish lignites investigated by using tetralin, creosote, and anthracene oils. The highest total conversions were obtained with tetralin. The catalytic effects of CoMo and red mud were compared by using creosote oil as the solvent. It was found that red mud catalyzed mainly the asphaltene formation reaction for the given experimental conditions. The additional of CoMo significantly catalyzed the liquefaction reaction, thus increasing the lignite conversion and oil formation.
Some applications of magnetic resonance in coal liquefaction research described briefly are: (1) investigation of the nature of carbon deposits on used coal-liquefaction catalysts, (2) determination of the fate of hydrogen during coal liquefaction, and (3) observation of transient free radicals during coal pyrolysis. The first two applications make use of cross-polarization /sup 13/C magnetic resonance combined with magic angle spinning, and the third application is an electron spin resonance study. (BLM)
Progress reports are presented for the following two areas: catalytic cracking studies with water-wet silica-alumina catalysts; and Fischer-Tropsch reactor studies where similarities and differences between fixed bed and slurry type reactors are investigated and further experiments conducted to measure mass transfer coefficients and reaction kinetics which are to be used in a model slurry reactor. The following are some of the conclusions. (1) The premise that the presence of liquid water might increase catalytic cracking activity was found to be invalid. It was demonstrated that cracking can occur at previously unobserved low temperatures (though at low conversions) and that an anomaly exists in that one of the catalysts tested shows an entirely different cracking behavior and probably follows a different cracking mechanism. (2) the diameter of a fixed-bed Fischer-Tropsch reactor critically affected the resistance of the reactor to plugging ...
The catalytic activities of various iron ores were investigated in the search for a high-activity catalyst for direct coal liquefaction. Laterite ores were shown to have a high catalytic activity in this process. Comparison of the ore with red mud in hydrocracking of 1-methylnaphthalene showed that the ore had higher activity in the hydrogenation of aromatic rings and in hydrocracking of alkylaromatics.
Most chemical reactions in industry and biology are catalytic and play a role at some stage of the processing of about 80% of the goods manufactured in the U.S., yet catalysis is a neglected subject in chemical education. This book integrates the fragmentary treatment accorded the topic until now. It covers, in a unified way, catalysis in solutions, by enzymes, in synthetic polymers within the molecular scale cages of zeolites and other molecular sieves, and on surfaces of inorganic solids. The central ideas are chemical; and principles are illustrated by emphasizing industrial reactions and catalysts.
... However blaming vitamin supplements on deaths, or mortality is silly, as the studies are not exactly kosher. Vitamin C in 2,000mg is good for allergies, and niacin (b3) in 10,0000mg is good for depression. This is all examples on how vitamin supplements can help. I call it a security blanket, as food these days is not so good due vitamin and mineral damage due to light, or storage. By the time we eat the apple from the supermarket, there is minimal vitamin and ...
A process is provided for conducting organic compound conversion over a catalyst composition comprising a supported crystalline zeolite having a high initial silica-to-alumina mole ratio, said supported zeolite being prepared by compositing said crystalline zeolite with alumina, reacting the composite with a particular hydrogen fluoride solution in a specified way, drying the hydrogen fluoride reacted composite, treating the dried composite by hydrolysis, ammonolysis and/or by contact with an ammonium salt solution, and calcining the resulting material.
The catalytic liquefaction of a Chinese bituminous coal was simulated by artificial neural network. Three liquefaction variables, catalyst loading, reaction temperature and reaction time were used as inputs and tetrohydrofuran (THF) conversion and toluene (T) conversion were used as outputs. The artificial neural network, trained by the experimental data, could represent the liquefaction process, with a mean squared deviation of less than 0.025. 7 refs.,1 fig., 3 tabs.
The construction materials used in coolant systems in nuclear power plants become covered with oxide films as a result of exposure to the aqueous environment. The susceptibility of the materials to different forms of corrosion, as well as the extent of the incorporation of radioactive species on the surfaces of the primary circuit, are greatly influenced by the physical and chemical properties of these oxide films. The composition and characteristics of the oxide films in turn depend on the applied water chemistry. This work was undertaken in order to collect and evaluate the present views on the structure and behaviour of oxide films formed on iron- and nickel-based materials in aqueous environments. This survey should serve to recognise the areas in which more understanding and research effort is needed. The review begins with a discussion on the bulk oxides of iron, nickel and ...
The formation of thin SiO_2 layers on silicon and metal silicides was studied by phase- and thickness measurements with Rutherford back-scattering of 2 MeV alfa particles. Thermal oxidation was done in steam and dry oxygen at temperatures between 750 degrees Celsius and 1 100 degrees Celsius, while SiO_2 formation at room temperature was carried out by anodic oxidation. The study of silicon oxidation was done on Si<100>, Si<111> and amorphous silicon substrates. Thermal oxidation of CoSi_2, CrSi_2, NiSi_2, PtSi and TiSi_2 was investigated. The oxidation rates of the silicides were found to be much higher than for silicon. The oxidation process is also diffusion-limited with a higher oxidation rate for steam as compared to dry oxygen. The silicide layers were found to stay intact during thermal oxidation. A ...
The morphological development of oxide scales formed on a low Al substituted #beta#-sialon (z=0.2) oxidised for time periods up to 1024h at 1350 C is discussed in relation to oxidation kinetics. The oxidation process is observed to be accompanied by changes in both the phase assemblage of the external layers and their morphology. Thus as the time of oxidation increases beyond 64h the cristobalite-#beta#-yttrium disilicate phase assemblage changes to cristobalite plus #beta#- and #gamma#-yttrium disilicate. In addition to the changes observed for the surface layers, differences are observed in the morphologies of the polished cross-sections. These changes are consistent with an order of magnitude decrease in oxidation rate. (orig.).
Regularities of deformation-induced dissolution of a surface layer of iron oxides in matrixes of iron-based alloys with bcc and fcc lattices have been studied by the methods of M?ssbauer spectroscopy, transmission electron microscopy, and X-ray diffraction. A method of producing iron alloys strengthened by dispersed oxide nanoparticles and alloyed with elements possessing a high affinity to oxygen (titanium and yttrium) has been proposed, which implies a dynamic dissolution of a surface layer of iron oxides upon strong cold deformation and a precipitation of secondary yttrium and titanium nanooxides upon a subsequent high-temperature sintering of mechanically alloyed powders. There has been demonstrated a possibility of oxide strengthening of pure iron upon its interaction with air without...
MCrAlY coatings are widely used on hot section components of gas turbines to provide hot corrosion and/or oxidation protection by formation of an oxide layer on the surface. As the protective oxide scale exfoliates during service, aluminum from the coating diffuses outward for reformation of the protective scale. Aluminum may also diffuse inward due to the differences in composition between the coating and the substrate. Thus, the coatings degrade due to oxidation, oxide scale spallation, and inward and outward diffusion of aluminum. Service life of these coatings is controlled by the aluminum content in the coating, operating temperature and start- shutdown cycles. In-service degradation of CoCrAlY and CoNiCrAlY coatings is presented. A procedure to predict the remaining service life of coatings under oxidizing conditions is discussed. (orig.) 12 refs.
This was a university-based research project in support of distributed reforming production technologies for hydrogen. Our objective was to examine the steam reforming of bio-ethanol and other related bio-derived liquids over non-precious metal catalyst systems to enable small-scale distributed hydrogen production technologies from renewable sources. The study targeted development of a catalytic system that does not rely on precious metals and that can be active in the 350-550 C temperature range, with high selectivity and high stability. To this end, we adopted a multi-prong research strategy, that included catalyst formulation and synthesis, detailed catalyst characterization, reaction kinetics and reaction engineering, molecular modeling and economic analysis studies. Our approach was an iterative one, where the knowledge gained in one aspect of the study was utilized to modify and fine-tune catalyst ...
Determination of the specific surface of uranium oxides: UO_2 and U_3O_8 using a simplified equation derived from the Brunauer, Emmett and Teller theory. The method is suitable for samples having a surface between 6 to 50 m"2.
PurposeHeavy metals and other forms of oxidative stress have been implicated as key factors in the formation of age-related cataract in humans. Metallothioneins are...Full Text Available
Reactive oxygen species (ROS), inevitable byproducts of aerobic metabolism, are known to cause oxidative damage to cells and molecules. This, in turn, is widely accepted as a pivotal determinant of...Full Text Available
Altered structure, and hence function, of cellular macromolecules caused by oxidation can contribute to loss of physiological function with age. Here, we tested whether the lifespan of bats, which generally...Full Text Available
The influence of surface oxides of variable composition and nonstoichiometry formed at high temperatures in air on the general corrosion resistance of ferritic chromium steel type 08H17T (Fe-17Cr-1Ti) in weak sulfuric acid has been studied. Anodic passive films formed on steel with different pretreatments have also been examined. The surface oxide of nearly stoichiometric composition formed at 300 C provides for the passive state of steel in sulfuric acid despite its depletion by chromium when compared with that for nonstoichiometric Cr-enriched oxide formed at 600 C. The dissolution and transformation of nonstoichiometric thermal surface oxide in sulfuric acid appear to take place through defect sites, {minus}Fe{sup 2+} ions, and oxygen vacancies of the n-type conductor. The passive film formed on the nonstoichiometric oxide film, which had been produced at 600 C, was found to be ...
BackgroundFree nitric oxide (NO) reacts with sulphydryl residues to form S-nitrosothiols, which act as NO reservoirs. We sought to determine whether thiol-preserving...Full Text Available
The purpose of this study was to synthesize biocompatible polyvinylpyrrolidone (PVP)-coated iron oxide (PVP-IO) nanoparticles and to evaluate their efficacy as a magnetic resonance imaging (MRI)...Full Text Available
4-Hydroxynonenal (HNE), a major electrophilic product of lipid peroxidation, is regarded as both a marker of oxidative stress and a mediator of oxidative damage. At subtoxic concentrations,...Full Text Available
The gelation kinetics of an in situ gelable hydrogel formulated from oxidized dextran (Odex) and N-carboxyethyl chitosan (CEC) were investigated rheologically. Both Schiff base...Full Text Available
It is shown analytically and experimentally that thermally stimulated current (TSC) measurements at negative bias incompletely describe oxide-trap charge in SIMOX and bipolar base oxides irradiated at 0 V. Positive-bias TSC is also required.
Rheological properties of moderately concentrated solutions of cellulose in methylmorpholine N-oxide-dimethylformamide mixtures containing hydrophilic montmorillonite nanoparticles were studied. Film composite materials were prepared, and their physicomechanical properties and structural organization were studied.
It has been discovered that iron(III) chloride complexes supported on activated charcoal oxidize phosphine under normal conditions. The process accelerates as the concentration of the chloride ions and the proton acid increases.
We report the use of cysteine-substituted mutants in conjunction with in situ oxidation to determine the physical proximity of a pair of engineered cysteines in the pore region of the voltage-gated...Full Text Available
A series of in situ gelable hydrogels were prepared from oxidized dextran (Odex) and N-carboxyethyl chitosan (CEC) without any extraneous crosslinking agent. The gelation readily...Full Text Available
A multidisciplinary approach was used to study the effects of pollution from a marine fish farm on nitrification rates and on the community structure of ammonia-oxidizing bacteria in the underlying...Full Text Available
This study was conducted to determine by gas chromatography (GC) and mass spectrometry (MS) the identity and the quantity of volatile N products produced during the helium-purged in vivo...Full Text Available
The OH-initiated photo-oxidation of n-butane was used as a source of 1- and 2-butoxy radicals. Reactions producing ketones and other organic compounds are explained. Rates of photolysis were determined and are discussed.
Because copper catalyzes the conversion of H2O2 to hydroxyl radicals in vitro, it has been proposed that oxidative DNA damage may be an important component of copper toxicity....Full Text Available
Oxidative stress has been implicated in the etiology of age-related muscle loss (sarcopenia). However, the underlying mechanisms by which oxidative stress contributes to sarcopenia have not been thoroughly...Full Text Available
Neurons in the hippocampal CA1 region are particularly sensitive to oxidative stress (OS), whereas those in CA3 are resistant. To uncover mechanisms for selective CA1 vulnerability to OS, we...Full Text Available
The neuronal nitric oxide synthase gene (NOS1) is located at 12q24, a susceptibility region for schizophrenia, and produces nitric oxide (NO). NO has been reported to play important...Full Text Available
Quantitative probing of heterogeneous regions in muscle is feasible with phosphorus-31 magnetic resonance spectroscopy because of the differentiation of metabolic patterns of glycolytic and oxidative...Full Text Available
Thermophilic propionate-oxidizing, proton-reducing bacteria were enriched from the granular methanogenic sludge of a bench-scale upflow anaerobic sludge bed reactor operated at 55°C with a mixture...Full Text Available
Bacterial nitric oxide synthases (bNOS) are present in many Gram-positive species and have been demonstrated to synthesize NO from arginine in vitro and in vivo. However, the physiological role...Full Text Available
BackgroundClara cell protein (CC16), the main secretory product of bronchiolar Clara cells, plays an important protective role in the respiratory tract against oxidative stress and...Full Text Available
The oxidation conditions were investigated for obtaining a higher productivity in the production of high strength carbon fiber from polyacrylonitrile (PAN). The effect of incorporation of 2 % comonomer such as methyl acrylate (MA), acrylate containing carboxylate (SA), acrylamide (AAm), and hydroxyethyl acrylate (HEA) on the oxidation conditions was also investigated. The measurement of DSC and bonded oxygen content revealed that the most effective comonomer for promoting the cyclization of nitril group and the bonding of oxygen was found to be SA, and the second best was AAm. The measurement of tensile strength of carbon fiber showed that the copolymer of SA, HEA, and MA gave a high strength fiber. It took a long time to oxidize the carbon fiber when it was oxidized at a temperature on which double layer structure was not formed. To shorten the production time, a method of combining the upper limit ...
BackgroundTrichloroethylene (TCE) may induce oxidative stress which generates free radicals and alters antioxidants or oxygen-free radical scavenging enzymes.MethodsTwenty...Full Text Available
Systemic administration of lipopolysaccharide (LPS), which causes endotoxemia and systemic inflammation, has been reported to induce expression of the gene for type II inducible nitric oxide synthase...Full Text Available
Three nucleic acid probes, two for autotrophic ammonia-oxidizing bacteria of the beta subdivision of the class Proteobacteria and one for alpha subdivision nitrite-oxidizing bacteria, were developed...Full Text Available
The electrochemical behavior of lanthanide oxides in molten alkaline chloride media is of great concern in pyrochemical processes for advanced nuclear fuel cycle. We have studied the solubilities of various lanthanide oxides in LiCl-KCl eutectic melt. In general, lanthanide oxides appeared to be insoluble/sparingly soluble in LiCl-KCl eutectic at 723 K. However, europium oxide exhibited an abnormal behavior in solubility and redox chemistry. The solubility of europium oxide was measured to be 1-2 order of magnitude higher than those of other lanthanide oxides. This abnormal solubility may be attributable to different electrochemical behavior of europium in the same experimental conditions. Most lanthanides ion exists as trivalent oxidation states. However, we observed divalent europium dissolved in LiCl-KCl molten salt by applying electron ...
1. The effect on rat liver peroxisomal beta-oxidation of feeding diets containing various amounts of dietary oils was investigated. With increasing amounts (5-25%, w/w) of soya-bean oil an apparent,...Full Text Available
This patent describes a method comprising applying a passivation layer of CaF{sub 2} to the surface of a superconductive ceramic oxide by evaporation. The CaF{sub 2} layer is effective to passivate the oxide surface without disrupting the superconductive properties.
Suspensions of denitrifying cells of Pseudomonas perfectomarinus reduced nitrate and nitrate as expected to dinitrogen; but, in the presence of acetylene, nitrous oxide accumulated when nitrate or nitrate...Full Text Available
There is increasing evidence of a biochemical link between lipid oxidation and bone metabolism. Paraoxonase 1 (PON1) prevents the oxidation of low-density lipoprotein (LDL) and metabolizes biologically...Full Text Available
BackgroundArsenic (As) exposure during pregnancy induces oxidative stress and increases the risk of fetal loss and low birth weight.ObjectivesIn...Full Text Available
Anionic peroxidase from tomato (Lycopersicon esculentum) fruit oxidized indoleacetic acid (IAA) slowly in the presence of Mn2+ and dichlorophenol in acetate buffers. The...Full Text Available
The aim of the present study was to evaluate the ameliorative potential of quercetin (QC) against paracetamol (PCM)-induced oxidative stress and biochemical alterations in mice blood. A total of 36...Full Text Available
Evolution of nitrogen oxides (NO(x), primarily as nitric oxide) from soybean (Glycine max [L.] Merr.) leaves during purged in vivo nitrate reductase assays...Full Text Available
Increased oxidative stress with elevated levels of reactive oxygen and nitrogen species (ROS/RNS) plays an important role in the pathophysiology of many disease states. Increased ROS/RNS can...Full Text Available
A detection theory is developed for point-contact metal-oxide-metal (MOM) systems. A system with heterogeneous oxide strongly bonded to the substrate is considered. It is shown that the form of the functional connection between the barrier heights and the ultimate compressive strength of the oxide has no substantial influence on the voltage-current characteristics of the system. Quantitative analysis indicates that a MOM system can behave as a tunnel diode and as a diode with a Schottky barrier. The model permits the determination of the optimum construction of long-life detectors based on MOM point-contacts.-
This paper reports on hydrolysis of 10 metal salt aqueous solutions of 6 metal oxides that was conducted in supercritical water. Continuous and rapid production of metal oxide fine particles was achieved by mixing a metal salt aqueous solution with preheated water fed from another line. The reaction time required was less than 2 min. Particle size, morphology, and crystal structure of the obtained metal (hydrous) oxides were examined. Particle size (20 to 600 nm) was different among the system but the size range was relatively narrow in all the cases.
Green River oil shale was air oxidized at subretorting temperatures. Off gases consisting of nitrogen, oxygen, carbon monoxide, carbon dioxide, and water were monitored and quantitatively determined. A mathematical model of the oxidation reactions based on a shrinking core model has been developed. This model incorporates the chemical reaction of oxygen and the organic material in the oil shale as well as the diffusivity of the oxygen into the shale particle. Diffusivity appears to be rate limiting for the oxidation. Arrhenius type equations, which include a term for oil shale grade, have been derived for both the chemical reaction and the diffusivity.
... Title : Effect of Yttrium on the Microstructure of Titanium Alloys,. ... The yttrium was added in the melting stage as an oxide or in the elemental form. ...
Objective of the project is characterization of electrode reactions in molten salt by using metal oxides and silica-based electrode. The scope of project are characterization of metal oxide properties in molten salt and miniaturization of 3-electrode electrochemical test cell. Electrochemical micro-cell for actinide-LiCl-KCl molten salt was newly designed. Electroless and electrochemical deposition technique was applied to Mo coating on quartz tube. From the design of electrode and 3-electrode electrochemical cell suitable for the tests in molten salt electrolyte, so it is anticipated to get the information on the electrochemical behavior of metallic electrode in molten salt and to secure the information on oxidation/reduction behavior of actinide
Measurements were completed on the solubility of cupric and cuprous oxides in liquid water and steam at controlled pH conditions from 25 to 400 C (77 to 752 F). The results of this study have been combined with those reported from this laboratory in two previous EPRI reports to provide a complete description of the solubility of these oxides and the speciation of copper dissolved in liquid water and steam as a function of oxidation state, temperature, pH, and in the case of steam, pressure. These constitute the first set of reliable data for cuprous oxide solubility over this range of conditions. For the more intensively studied CuO case, agreement was found between our results and those of previous studies of its solubility in steam, whereas only partial agreement was evident for its solubility in liquid water. For both oxides this disagreement often amounted to orders of ...
Thermal wet oxidations of GaP and Al{sub 0.4}Ga{sub 0.6}P at 650 degree sign C for various times have been performed. Comparisons are made on oxidation rates and post oxidation morphology. Transmission electron microscopy shows that when oxidizing GaP, polycrystalline monoclinic GaPO{sub 4}{center_dot}2H{sub 2}O forms without noticeable loss of phosphorus. Oxidation for 6 h or more leads to poor morphology resulting in cracks and detachment. A thickness expansion of about 2.5-3 times is noticed as a result of oxidation. In contrast, oxidized Al{sub 0.4}Ga{sub 0.6}P exhibits much better morphology without cracks or detachment from the substrate. The oxide has an almost amorphous-like microstructure. The oxidation process shows typical diffusion-limited reaction at long anneals. Preliminary work on the ...
This articles deals with an approach that has given some key information about the mechanisms of the liquid phase oxidation of butane to acetic acid. This procedure has been developed over the last 34 years; however, much of what will be discussed represents a synthesis of previous insights. Many of the observations are relatively recent and have not been previously published. In principle, this approach should be applicable to many oxidation processes. (orig.)
The behaviour of an elastomeric seal for vehicle brake Tandem master cylinder is measured and analyzed in temperature and brake fluids changed. Working conditions are simulated for different piston rod velocity and cylinder supply pressure, in temperature rising, brakefluid boundary and Nanoaluminum oxide brakefluid oxide brakefluid lubrication. The result shows that Nanoaluminum oxide brakefluid with its ball shape can highly reduce friction coefficient to avoid seal excessive wear and reduce slick slip in brake applications.
The application of kinetic probes that allow one to determine relative reactivities of biologically relevant substrates with oxidizing intermediates in the Fenton reagent (H2O2 plus Fe2+ in acidic aqueous...Full Text Available
A two-step purification protocol was used in an attempt to separate the constitutive NAD(P)H-nitrate reductase [NAD(P)H-NR, pH 6.5; EC 1.6.6.2] activity from the nitric oxide and nitrogen dioxide (NO(x))...Full Text Available
The authors have determined quantitative characteristics for oxide films forming on (111) surfaces of cadmium telluride single crystals on anodic oxidation in 0.1 M KOH: the constants in the Guenterschulze-Betz equation and the film growth constant, which is 2.4 nm/V, from which the activation energy for cadmium telluride electrooxidation has been calculated.
The following methods of quartz ceramics alloying were considered: alloying of initial quartz glass; introduction of alloying additive into water slip of quartz glass; porous materials impregnation with salt aqueous solutions and subsequent salt thermal decomposition with formation of stable oxides in pores of ceramics. Oxygen free compounds BN, SiB_4, SiC, Si_3N_4, REM oxides and transition metal oxides were used as alloying additives. Main properties of the materials and compositions obtained are presented.
During electrolysis of a "2"4"8Cm(III) solution in 2M K_2CO_3 at pH=13, partial oxidation of curium to a higher oxidation state, probably Cm(IV), was observed. The absorption spectra of Cm(III) and Cm(IV) in K_2CO_3 solution were recorded and the molar extinction coefficients of main absorption bands of curium were evaluated. (author).
AQ4N (1,4-bis([2-(dimethylamino-N-oxide)ethyl]amino)5,8-dihydroxy- anthracene-9,10-dione) is a novel alkylaminoanthraquinone N-oxide which, on reduction, forms a stable DNA affinic cytotoxic compound...Full Text Available
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two sha...
Coordination of CoCl2 solutions to the silica polyamine composite, WP-1, made with the branched polymer polyethylenimine (PEI) shows irreversible binding resulting from surface oxidation of the Co2+-Co3+. This is not the case for the silica polyamine composite BP-1 made with the linear polymer polyallylamine where reversible binding and no oxidation is observed. These observations suggested that oxidation of the cobalt was related to the greater coordination number available with the branched polyamine relative to the linear polyamine. A study of the kinetics of cobalt binding to WP-1 indicated initial loading of Co2+ at relatively low coordination number followed by desorption of Co2+ leading to oxidation and irreversible binding. Exclusion of oxygen from the composite-cobalt solution mix...
The invention is regeneration and recirculation of nitrogen oxides in the exhaust gas of a nitric acid plant without using any material current and heat energy other than that generated in the process of producing nitric acid. Nitrogen oxide is recovered by at least two adsorbers each containing an acid resistant zeolite molecular sieve and operating in an alternate heat cycle; adsorption occurring at 20-40 degrees C and regeneration at 300-350 degrees C. The hot gas exiting from the oxidation U used in the production of nitric acid is used to regenerate the adsorbers and the nitrogen oxides set free during the said regeneration are introduced into the main feed stream of the nitric acid plant. In the final stage of the regeneration the adsorbers are cooled by rinsing them with exhaust gas or air at a temperature of 20-40 degrees C.
#beta#-sialon ceramics of equal overall compositions but containing amorphous, partly crystalline and almost completely crystalline intergranular phase(s) have been oxidized in oxygen at 1350 deg C for 20 hours. The obtained weight gain curves do not follow the parabolic rate law (#DELTA#W/A_0)"2= k_pt + #beta#. To the extent that crystallization occurs in the oxide scale during the oxidation experiment, the amorphous cross section area through which oxygen most easily diffuses will decrease with time. A brief description of this new rate law is given, and the obtained oxidation curves will be discussed within that framework. 4 refs., 2 tabs., 2 figs.
Chemical modification of poly(?-caprolactone) PCL by oxidation with potassium permanganate in solution was investigated. According to the data obtained from Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR, after the oxidation reactions the PCL chains exhibited new functional groups (vinyl and hydroxyl) and possible intermolecular recombination, producing an oxidized-polycaprolactone (PCL-OX). Solution viscometry indicated that degradation also occurred during the oxidation reactions (30% drop in viscosity average molecular weight was detected). Differential scanning calorimetry (DSC) also indicated that PCL was chemically modified and degraded. The successive self-nucleation/annealing (SSA) treatment confirmed that a reduction (or interruption) in line...
One-electron oxidation of several derivatives of pyrazolin-5-one, including the drug antipyrine, were studied by pulse radiolysis of aqueous solutions. All the compounds were found to be oxidized by Br2 rapidly but considerably more slowly by weaker oxidants, such as peroxyl radicals. From redox equilibria using p-methoxyphenol and N,N,N',N'-tetramethyl-p-phenylenediamine as reference compounds, the one-electron oxidation potentials of the methyl-substituted 2-pyrazolin-5-ones were found to be in the range of 0.32-0.39 V versus normal hydrogen electrode. The relevance of these findings to the properties of the drug nafazatrom is discussed. Antipyrine was found to have a much higher oxidation potential, estimated as 1.2-1.5 V, which is rationalized on the basis of the phenyl substitution and lack of resonance stabilization of the radical cation.
The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer ...
The chemical composition and the semiconducting properties of passive films formed on nickel based alloy (Alloy 600) in acidic sulphate solution, pH 2.0 at room temperature were studied using Auger analysis, voltammetric techniques and the Mott-Schottky approach. The results obtained revealed that the presence of both chromium and mixed nickel-iron oxides in the films leads to the development of a p-n heterojunction, which controls their electronic structure, similarly manner to the case of stainless steels and Alloy 600 in borate buffer solution. This behavior has been interpreted as representing of an oxide system, which has a duplex character, with an inner p-type semiconducting region, mainly formed by chromium oxide and an outer n-type semiconducting region, containing iron oxide. It could also be observed that the nickel oxide present in the films acts as a barrier layer ...
Transient experiments in a Temporal Analysis of Products (TAP) Reactor were performed to elucidate the role of surface oyxgen species in the oxidation of benzene to phenol on ZSM-5 type zeolites with nitrous oxide as a selective oxidant. It was shown by puls experiments with nitrous oxide that the mean lifetime of the generated surface oxygen species is between 0.2s at 500 C and about 4.2 s at 400 C. Afterwards the surface oxygen species desorb as molecular oxygen into the gas phase where total oxidation will take place if hydrocarbons are present. Dual puls experiments consisting of a nitrous oxide puls followed by a benzene puls allowed studying the reactivity of the surface oxygen species formed during the first puls. The observation of the phenol formation was impeded due to the strong sorption of phenol. Multipulse experiments were necessary to reach a ...
Slurry aluminizing is one method of protecting titanium alloys and intermetallics at temperatures at which oxidation would otherwise significantly degrade mechanical properties. The technique produces a continuous layer of alumina-forming TiAl_3 on exposed surfaces. The influence of composition, film thickness, and diffusion temperature upon the oxidation resistance of these slurry aluminides was studied in cyclic tests to 816degC (1500deg F). Degradation of slurry aluminized #beta#-titanium alloy and #alpha#-Z titanium aluminide intermetallic occurs by localized oxidation at cracks in the coating layer. These cracks are probably due to mismatch of coefficients of thermal expansion between the coatings and substrates. Addition of silicon to the slurry modifies the oxidation behaviour around a crack by introducing a continuous layer of titanium silicide at the boundary of the aluminide coating and ...
The generation of acidic mine drainage is based on the oxidation dissolution of sulfide minerals due to the contact of ores with the natural water and the air. Namely, the sulfuric acid promotes the dissolution of sulfide minerals and gangue minerals, and Fe{sup 2+} is further oxidized to turn into Fe{sup 3+}, which acts as an oxidizer for other sulfide minerals and promotes the dissolution of the same. This paper roughly describes a mine drainage treatment focusing on an Fe{sup 2+} neutralization method and an iron bacteria oxidation method. The iron bacteria oxidation method is a method of oxidizing Fe{sup 2+} into Fe{sup 3+} by using iron bacteria, and then removing Fe{sup 3+} with calcium carbonate. This method has been used for treating the drainage in the Sakuhara Mine and the former Matsuo Mine, with good results. The paper finally introduces, as ...
Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions - with and without in situ wet oxidation - were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 deg. C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and ...
A duplex surface treatment technique based on calorizing and plasma nitriding was developed to improve the wear and oxidation resistance of H13 steel at high temperatures. The effects of the relative thickness of the calorized layer to the depth of plasma nitriding on the wear and oxidation properties at temperatures up to 900 C were investigated in this work. High-temperature wear tests were performed at 500 C with dry conditions in open air using a ball-on-disk type tribotest machine. Isothermal oxidation tests were performed at 900 C for up to 100 h under controlled atmosphere. The results indicated that the specimens with a calorized layer as an intermediate phase between the surface duplex layer and the base metal showed higher wear and oxidation resistance than the specimens with a nitrided layer alone. During exposure to elevated temperatures, the aluminum in the calorized layer diffused to the ...
Papers are presented on the development of oxidation- and sulfidation-resistant ferritic alloys; the microstructural stability of sulfidation-resistant FeCrAl stainless steels around 500 C; age hardening in Fe-Mn-Al-C austenitic alloys; the oxidation/corrosion behavior of low-Cr Fe-Cr-Ni alloys containing Zr or Nb; the high temperature oxidation/corrosion of iron-based superalloys; and the role of Mo in the Na/sub 2/SO/sub 4/ induced corrosion of superalloys at high temperature. Topics discussed include the effect of variations of Co content on the cyclic oxidation resistance of selected Ni-base superalloys; high temperature oxidation of Fe based alloys; the morphological development of high temperature oxide scales of Fe-Mn-Al base alloys; and the oxidation of an Fe-Mn-Al-C alloy at 1000 C. Consideration is given to the corrosion properties ...
New palladium(II) complexes (2), bearing NHC/TPPTS ligands, (NHC=benzimidazol-2-ylidene; TPPTS=triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt) have been prepared and characterized by elemental analyses and spectroscopic methods. Their ability to catalyze the Suzuki-Miyaura reaction in neat water has been studied at 100^oC. Very high activities have been observed in the coupling of phenylboronic acid with aryl chlorides in the presence of 1% of the catalyst. We have compared the electronic properties of cis-[PdBr2(NHC)(TPPTS)] with the related complexes, [PdX2(NHC)]2 and [trans-PdBr2(NHC)(pdca)] (pdca=pyridine-2,6-dicarboxyic acid) (3) via three different techniques: cyclic voltammetry, thermogravimetric analysis and ^1^3C NMR spectroscopy.
One of the design targets for the ITER Tokamak Exhaust Processing system is not to lose more than 10{sup -5} g h{sup -1} into the Normal Vent Detritiation System of the Tritium Plant. The plasma exhaust gas, therefore, needs to be processed in a way that an overall tritium removal efficiency of about 10{sup 8} is reached. Such a high decontamination factor can only be achieved by multistage processes. The third step of the three step CAPER process developed at the TLK is based on a so-called permeator catalyst (PERMCAT) reactor, a direct combination of a Pd/Ag permeation membrane and a catalyst bed. The PERMCAT principle is based on isotopic swamping in a counter current mode. Previous tritium experiments employing laboratory scale PERMCAT reactors have revealed decontamination factors as high as 10{sup 5} for the third CAPER step. First tritium tests with a technical scale PERMCAT reactor led to similar decontamination factors and clearly ...
One of the design targets for the ITER Tokamak Exhaust Processing system is not to lose more than 10"-"5 g h"-"1 into the Normal Vent Detritiation System of the Tritium Plant. The plasma exhaust gas, therefore, needs to be processed in a way that an overall tritium removal efficiency of about 10"8 is reached. Such a high decontamination factor can only be achieved by multistage processes. The third step of the three step CAPER process developed at the TLK is based on a so-called permeator catalyst (PERMCAT) reactor, a direct combination of a Pd/Ag permeation membrane and a catalyst bed. The PERMCAT principle is based on isotopic swamping in a counter current mode. Previous tritium experiments employing laboratory scale PERMCAT reactors have revealed decontamination factors as high as 10"5 for the third CAPER step. First tritium tests with a technical scale PERMCAT reactor led to similar decontamination factors and clearly demonstrated that the ...
This final report summarizes the results of our research under Contract No. DE-AC22-92PC92112, Novel Catalysts for Methane Activation. In this research we prepared and tested fullerene soots for converting methane into higher hydrocarbons. We conducted the methane conversions using dehydrocoupling conditions, primarily in the temperature regimes of 600{degrees}-1000{degrees}C and atmospheric pressures. The research was divided into three sections. The first section focused on comparing fullerene soots with other forms of carbon such as acetylene black and Norit-A. We found that the fullerene soot was indeed more reactive than the other forms of carbon. However, due to its high reactivity, it was not selective. The second section focused on the effect of metals on the reactivity of the soots, including both transition metals and alkali metals. We found that potassium could enhance the selectivities of fullerene soot to higher hydrocarbons, but the effect was unique ...
This paper reports on the superiority of zeolites over amorphous solids which is well documented for solid acid catalysts of industrial use. Crystalline supports, likewise, open attractive perspectives for catalysis by metals, alloys, and ligated metal clusters. Size and location of clusters can be controlled by careful design of the preparation conditions. Pore dimensions control the access of reactants to active sites and escape paths for products. Cage dimensions determine which transition states can be attained; window apertures are functional in isolating metal clusters from each other, thus preventing ther coalescence and growth. The ship-in-a-bottle method permits deisgn of fairly large active complexes entrapped in zeolite cages. Orientation of non-spherical molecules in a zeolite proe helps to direct their collision with a metal particle to the head on mode; however, isolated Pt atoms hidden in niches of the pore walls can attack passing molecules at their ...
The lipid obtained by the toluene extraction of a dried raw Atlanta sewage sludge by the Soxhlet method, was pyrolyzed over activated alumina at atmospheric pressure. A range of weight hourly space velocities (WHSV) from 0.22-1.60/h and a range of temperatures from 400-480[degree]C were selected. A 70 wt % yield of light liquid hydrocarbons was obtained at a WHSV of 0.46/h and 450[degree]C. The sulfur and nitrogen contents of the pyrolysis products were much lower than products from direct liquefaction of sludge. Infrared spectra and [sup 13]C nuclear magnetic resonance confirmed the absence of carbonyl groups in the products. Gas chromatography showed a uniform hydrocarbon chain length distribution across the C[sub 7] to C[sub 17] mass range. The gas product consisted mainly of carbon dioxide and hydrocarbons. Lauric acid was used as a model to study the decarboxylation. The effects of catalyst loading and catalyst moisture content were ...
Nine coals from Spanish, British, German and American mining basins were hydrogenated using Fe catalyst precursors (red mud and FeSO{sub 4}), without solvent at 300, 350, and 400 {degree}C and 10 MPa of H{sub 2}. Overall conversion and product distribution are related to the textural characteristics of the original coals and are studies throughout the distinct hydrogenation processes. Results reveal that with FeSO{sub 4} as a catalyst precursor, conversions increase with coal surface area. However, when red mud (RM) is used, conversions are independent of coal textural characteristics. Higher conversions are obtained with FeSO{sub 4} than with RM at 300 and 350 {degree}C whereas at 400 {degree}C higher conversions are obtained with RM. This different catalytic activity is also reflected in the changes of the textural characteristics observed in each case. Up to 350 {degree}C, the residues from FeSO{sub 4}-catalyzed processes reveal increased ...
This paper describes the development of a computational multiphase fluid dynamics (CMFD) model of the Fischer Tropsch (FT) process in a Slurry Bubble Column Reactor (SBCR). The CMFD model is fundamentally based which allows it to be applied to different industrial processes and reactor geometries. The NPHASE CMFD solver [1] is used as the robust computational platform. Results from the CMFD model include gas distribution, species concentration profiles, and local temperatures within the SBCR. This type of model can provide valuable information for process design, operations and troubleshooting of FT plants. An ensemble-averaged, turbulent, multi-fluid solution algorithm for the multiphase, reacting flow with heat transfer was employed. Mechanistic models applicable to churn turbulent flow have been developed to provide a fundamentally based closure set for the equations. In this four-field model formulation, two of the fields are used to track the gas phase (i.e., small spherical and ...
In the past three years, we followed the work plan as we suggested in the proposal and made every efforts to fulfill the project objectives. Based on our large amount of creative and productive work, including both of experimental and theoretic aspects, we received important technical breakthrough on naphthenic acid removal process and obtained deep insight on catalytic decarboxylation chemistry. In detail, we established an integrated methodology to serve for all of the experimental and theoretical work. Our experimental investigation results in discovery of four type effective catalysts to the reaction of decarboxylation of model carboxylic acid compounds. The adsorption experiment revealed the effectiveness of several solid materials to naphthenic acid adsorption and acidity reduction of crude oil, which can be either natural minerals or synthesized materials. The test with crude oil also received promising results, which can be potentially developed into a ...
All first-stage experimental tests were completed for Task 4 (and the Contract). The first-stage one-liter autoclave tests that were made were duplicates of Run 41-LA. The conditions used were chosen last quarter to reduce the cost of the first-stage of the process from those used at the conclusion of Task 3. Filtration and second-stage tests were made using the products of the first-stage tests. Post-second-stage filtration, tested as an alternative to interstage (pre-second- stage) filtration, resulted in low filtration rates. Different catalyst loadings and type and residence time for second-stage hydrotreating were explored. Longer residence times did not result in significantly more resid conversion. Higher catalyst loadings were more effective in converting the resid at the same residence time. The material and elemental balances for the first-stage were completed. The material and elemental balances for the second-stage were initiated.
During this reporting period four direct coal liquefaction experiments have been completed and a fifth is underway. These experiments have produced conversion and selectivity data on samples of Utah coal slurried in tetralin and catalyzed using iron-titanium hydride. Hydrogen loading of the alloy, catalyst particle size, coal particle size, operating temperatures for alloy addition and liquefaction without the catalysts present, have all been studied during these four experiments. Conversions of 61% DAF in 30 min have been recorded at 485/sup 0/F and 520 psia. The fifth run using the same coal at a reduced particle size has begun, after which we will move to samples of Kentucky and Alabama coals. Equipment manufacture, delivery, and installation delays, totaling over 6 months, greatly reduced the time available for research, making a 6 month no cost extension necessary. The extended time will permit completion of the proposed research tasks. 4 ...
The necessary conditions to design the methanol-fueled direct injection diesel engine with a reservoir type glow plug were cleared up from the points of view to prevent the air contamination and to use as an alternative oil for automotives, and as a result the good engine performance and emission characteristics could be obtained under the wide operating condition. The following facts were clarified: It is necessary to arrange the glow plug on the line of atomizing axis near the nozzle hole to ensure the ignitability under a wide operating condition. The reservoir type glow plug which reserves the premixed gas around the glow plug can shorten the ignition delay time and improve the combustion stability and the net thermal efficiency in the light load region. The combustion in the light load region was accelerated, NO{sub x} emission rate was suppressed and moreover, the net thermal efficiency and catalyst conversion rate were improved by applying an EGR(exhasut gas ...
For the removal and recycle of CO2, a global warming gas, utilization of photosynthesis by micro algae is investigated. Formed micro algae are decomposed into CO2, H2O and CH4 again, which does not result in the permanent fixation. For the effective utilization of these micro algae, creation of petroleum alternate energy was tried through the co-liquefaction of micro algae with coal. Were investigated influences of the reaction temperature during the co-liquefaction and influences of catalysts, such as Fe(CO)5-S, Ru(CO)12, and Mo(CO)6-S, which are effective for the coal liquefaction. Micro algae, such as chlorella, spirulina, and littorale, and Yallourn brown coal were tested. It was found that co-liquefaction of micro algae with coal can be successfully proceeded under the same conditions as the liquefaction of coal. The oil yield obtained from the co-liquefaction in the presence of Fe(CO)5-S, an effective catalyst for coal liquefaction, ...
According to W. H. Wiser and A. G. Oblad, the program at the University of Utah to develop coal conversion techniques, which has received federal grants of $1.35 million since 1969, recently was awarded $425,000 from the U.S. Office of Coal Research for the development of catalysts for coal conversion and low-sulfur fuel oil production. In tests, 100 lb of coal have been converted into 95 lb of products composed of 30 lb liquid fuel like gasoline, 5 lb of diesel or fuel oil, 30 lb of gaseous fuel, and 30 lb of char.
Results of research programs in coal liquefaction are presented. Areas of research include: desulfurization by bioprocessing; characterization of coal liquefaction processes by XAFS spectroscopy; coprocessing of coal with heavy oil and petroleum residuals; liquefaction research in pyrolysis, catalysis and coal dissolution; novel catalysts; data base development; resource evaluation; depolymerization; solvent extraction and chromatography; correlations of liquefaction yields and coal structure. Individual projects are processed separately for the data bases. (CBS)
Air pollution abatement measures are being intensified at the moment: Power plants and district heating systems are being retrofitted with high-efficiency desulphurisation and NO/sub 2/ reduction systems, the 3rd amendment of the Clean Air Technical Guide sets more rigid emission limits, and unleaded petrol and catalysts will significantly reduce car exhaust emissions. The author presents pollutant balances from 1966 to 1982 to contradict the popular notion that pollutant emitters formerly failed to take preventive measures.