Y-zeolitesupportedcatalysts 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. Zeolitesupportedcatalysts 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, zeolitesupportedcatalysts were inferior to alumina supportedcatalysts. This is due to the high ...
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 supportedzeolite 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.
Hydrogenation of carbon monoxide at 101.3 kPa has been studied over a series of ion-exchanged Ru catalystssupported 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-supportedcatalysts, 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 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 ...
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 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 ...
The present paper is a comparative study of the cerium-containing nickel catalystssupported 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/zeolitecatalysts.
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 ...
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.
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-supportedcatalysts 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 aim of this work is to test the catalytic oxidation of pyridine over zeolite-supportedcatalysts and to compare the difference in their activities for the oxidation of pyridine. The catalytic oxidation of pyridine pollutant on a series of copper-supportedcatalysts, 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-supportedcatalysts 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 for the NO{sub x} ...
Calcined and sulfided Ni-Mo catalystssupported 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-supportedcatalysts, and the mordenite-supportedcatalyst also contained MoO{sub 3} crystals. The {alpha}-NiMoO{sub 4} may be attached to the surface of substrates as individual particles ...
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 supportedcatalyst 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 supportedcatalyst 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).
Cobalt supported on Beta zeolitecatalysts 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...
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, ...
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 investigated. Also the ...
Propylene polymerizations were carried out with {phi}{sub 2}C(Flu)(Cp)ZrCl{sub 2} and SiMe{sub 2}(Ind)2ZrCl{sub 2} catalystssupported 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 ...
Propylene polymerizations were carried out with #phi#_2C(Flu)(Cp)ZrCl_2 and SiMe_2(Ind)2ZrCl_2 catalystssupported 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. ...
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/ ...
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 zeolitecatalysts. 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 zeolitecatalyst 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 zeolitecatalysts decreased in the order given and were greater than for a commercial hydrodesulfurization catalyst; ...
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.
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.
A phosphorus-containing low alkali metal content zeoliticcatalyst 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 zeoliticcatalyst 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 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 zeolitecatalysts. 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 zeolitecatalysts.
Hydrocarbon synthesis during CO hydrogenation over Pd/M-ZSM5 (M=H,Na,La) and Pd/SiO/sub 2/ has been investigated. Overall activity depended on the cation-exchanged form of the support and decreased in the order Pd/La-ZSM5 = Pd/Na-ZSM5 > Pd/H-ZSM5 > Pd/SiO/sub 2/. The zeolite-supportedcatalysts showed high selectivity towards saturated C/sub 2/-C/sub 6/ hydrocarbons, whereas Pd/SiO/sub 2/ favored methanol production. Increasing temperature and H/sub 2//CO feed ratio led to higher reaction rates, lower yields of C/sub 2/-C/sub 6/ products, and increased lighter hydrocarbons. A mechanical mixture of Pd/SiO/sub 2/ and Na-ZSM5 showed similar product distribution as Pd/Na-ZSM5. Infrared spectra of the catalysts under reaction conditions indicate the presence of adsorbed oxygenates on the zeolite. Changes in the IR bands during the initial stages of the reaction suggest that surface ...
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 ...
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 ...
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 ZeoliteSupportedCatalysts 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 documents are ...
A process is provided for conducting organic compound conversion over a catalyst composition comprising a specially treated crystalline zeolite having a high initial silica-to-alumina mole ratio, said zeolite having been synthesized from a reaction mixture comprising a diamine as a cation source. The treatment of the zeolite material comprises the sequential steps of reacting the zeolite with a dilute hydrogen fluoride solution, contacting the hydrogen fluoride solution reacted material with aluminum chloride vapor, and then treating the aluminum chloride contacted material to convert it to hydrogen form.
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 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...
The methods of diffuse-reflection optical spectroscopy and EPR were used to study the state of molybdenum in catalysts prepared by impregnating ultrastable zeolite with molybdenum salt solutions and by mixing in the solid phase with MoCl/sub 5/. It has been shown that molybdenum introduced into zeolites in small amounts is found basically in the form of isolated hexavalent ions of molybdenum. In addition, Mo/sup 5 +/ and Mo/sup 4 +/ ions are also present. Heteropolycompounds also form. The molybdenum ions are most readily reduced in the zeolite prepared by impregnation with a solution of ammonium paramolybdate.
Zeolite Y is the active component of most commercial cracking catalysts. Interaction of H[sub 3]PO[sub 4] with extraframework aluminum of ultra-stable zeolite (USY) leads to the formation of different types of aluminum phosphates, while there is no indication of the formation of SAPO zeotype structures. The total acidity of USY slightly decreases upon the H[sub 3]PO[sub 4] treatment, while the maximum in the distribution of acid strength is shifted to milder acidities. Dealumination of the zeolite and creation of POH sites associated with AIPO[sub 4] are responsible for the modifications observed. 37 refs., 8 figs., 3 tabs.
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 zeolitecatalysts 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 ...
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.
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.
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.
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-supportedcatalyst. Heat and chemical treatments of the red mud greatly improve the catalytic activity. Moreover, a combination of acid and heat treatments produces ...
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 zeolitecatalysts. 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 ...
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.
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 supportedcatalyst ...
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.
Badger (Cambridge, MA) and Mobil (Fairfax, VA) are ready to jointly license a new cumene technology that they say achieves higher yields and product purity than existing processes. The zeolite-based technology is scheduled to be introduced at next month's DeWitt Petrochemical Review in Houston. The Mobil/Badger technology aims to challenge the dominant position of UOP's (Des Plaines, IL) solid phosphoric acid (SPA) catalyst process - which accounts for 80%-90% of the world's cumene production. In addition, Monsanto/Kellogg's aluminum chloride-based technology has gained significant momentum since its introduction in the 1980s. And late last year, ABB Lummus Crest (Bloomfield, NJ) also began marketing a zeolite-based cumene technology. While all the technologies make cumene via the alkylation of benzene with propylene, the Mobil/Badger process uses a zeolite-containing ...
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.
In this study, a two-step process was developed to produce biodiesel from Calophyllum inophyllum oil. Pre-treatment with phosphoric acid modified b-zeolite in acid catalyzed esterification process preceded by transesterification which was done using conventional alkali catalyst potassium hydroxide (KOH). The objective of this study is to investigate the relationship between the reaction temperatures, reaction time and methanol to oil molar ratio in the pre-treatment step. Central Composite Design (CCD) and Response Surface Methodology (RSM) were utilized to determine the best operating condition for the pre-treatment step. Biodiesel produced by this process was tested for its fuel properties.
Selectivity control is a key issue in the zeolite facilitated conversion of methanol to hydrocarbons. This work addresses: (a) How the zeolite topology (MFI versus BEA) determines the type of intermediate participating in the catalytic cycle thereby controlling the ethene/propene product selectivity in the methanol to alkenes reaction, and (b) to what extent light alkene formation occurs via aromatic and alkene reaction intermediates for H-ZSM-5. Three catalyst samples have been studied in experiments relying on isotopic labeling. For H-beta, penta- and hexamethylbenzene are involved in an aromatics based hydrocarbon pool type mechanism leading predominantly to propene and the higher alkenes (a very low yield of ethene is observed), whereas for H-ZSM-5, the lower methylbenzenes are the aro...
The kinetic rate constants for the cracking, isomerization, and disproportionation of n-heptane over a CrHNaY (32% chromium exchanged) zeolitecatalyst at 400, 450, and 470/sup 0/C have been calculated. The interaction of n-heptane with a model Lewis acid such as BF/sub 3/ and progress along the reaction coordinate have been studied by means of molecular orbital calculations. From the kinetic results, i.e., activation energies and frequency factors, and the theoretical calculations, it can be concluded that the controlling step in these reactions is not the formation of the carbonium ion, but the subsequent transformation of this carbonium ion. In addition, the theoretical calculations show that the attack of a Lewis acid is more likely to occur on a carbon atom than on a C-H bond.
The increasing use of quantum-chemical methods in catalysis has underscored the importance of developing and improving semiempirical approximations oriented toward calculations of the total energy and geometry, offering a means for examining intermolecular interactions. In this article a general approach is proposed, using weighting factors for certain regions of distances, i.e., introducing different parametrization into the various regions. A scheme designated MINDO/3-HB is presented as an extension of the MINDO/3 scheme to the region of hydrogen bonds and ..pi..-complexes of olefins with Broensted acid centers (BACs). Examples of cluster calculations are given for the adsorption of ammonia, pyridine, ethylene, and ethanol on the BACs of zeolites. In the example of the process of zeolite synthesis, the possibilities of the cluster approach are discussed for calculations related to the formation of catalysts.
An examination of the kinetics of the alkylation of anisole with 1-hexene and 1-hexanol to produce alkylates over zeolite H-beta is presented. Anisole alkylation is found to occur by a set of parallel reactions when hexene is used as the alkylating agent. When hexyl alcohol is the alkylating agent, the reaction follows a multi-step parallel-series mechanism to form monoalkylates and dihexylether. With 1-hexene, a group of isomeric alkylates, viz., ortho-2-hexyl anisole (2-OHA), ortho-3-hexyl anisole (3-OHA), para-2-hexyl anisole (2-PHA), and para-3-hexyl anisole (3-PHA) was obtained. With hexanol, the olefin (hexene) and dihexyl ether were obtained additionally. The influence of process parameters like temperature, catalyst quantity, and alkylating agent on reaction behavior is reported.
Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. ...
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 > ...
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
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) catalystsupported 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...
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 species can undergo further ...
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 oxide ...
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.
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}.
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.
The exchange of Eu[sup 3+] for Na[sup +] cations into the sodalite cages of X zeolite (Eu[sub 25]Na[sub 11]X) leads selectively to the isomerization reaction of cyclopropane to propylene. The latter reaction is catalyzed by Broensted acid sites with an apparent activation energy of 10.6 kcal/mol. Sorption measurements of cyclopropane and propylene with Eu/NaX and NaX zeolites at 40 C support the view that Na[sup +] cations might be considered as sites for sorption of these molecules. Force fields created by Eu[sub 4]O[sup 10+] present in Eu/NaX zeolite may affect sorption. On the other hand, Broensted acid sites in Eu/NaX enhance sorption of cyclopropane and propylene at 40 C. Chemisorption of propylene on the Broensted acid sites of Eu/NaX is reversible and may occur via a propylene carbenium cation intermediate. Small amounts of hexene are formed during this sorption. The amount of Broensted acid ...
Carbon supportedcatalysts 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 ...
In order to design catalysts suitable for primary liquefaction stage and secondary upgrading stage respectively in the multi-stage liquefaction process, various carbon-supportedcatalysts 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 supportedcatalysts. 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 ...
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 ...
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 ...
Ni catalystssupported 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 ...
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 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 active and selective and showed no formation of oxygenates. In ...
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 supportedcatalysts 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) ...
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-supportedcatalysts 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 ...
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.
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 oxygen is predominantly involved in the selective oxidation of propylene to C/sub ...
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 ...
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 ...
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 catalyst surfaces, ...
Neopentane, because of its unique structural features, was found to be a useful probe for the assay of the acidity of various zeolites. The C-C bond was attacked by catalyst protons yielding CH/sub 4/ and the isobutyl carbenium ion in equal quantities. The latter either decomposed to produce isobutene or underwent secondary reactions. New avenues for reaction were opened with isobutane. The reaction of the Bronsted protons with the tertiary CH bonds produced H/sub 2/ and the same isobutyl carbenium ion. Hydride ion transfer of the same tertiary hydrogen to existing carbenium ions also occurred and the results showed that about half of the reaction was carried by this pathway. As with Neopentane, the C-C bond could also be attacked yielding the sec-propyl carbenium ion. These tools are being further developed.
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.)
The effect of chemical pretreatments using NaOH, H2O2, and Ca(OH)2 on Empty Palm Fruit Bunches (EPFB) to degrade EPFB lignin before pyrolyis was investigated. Spectrophotometer analysis proved consecutive addition of NaOH and H2O2 decomposed almost 100% of EPFB lignin compared to 44% for the Ca(OH)2, H2O2 system while NaOH and Ca(OH)2 used exclusively could not alter lignin much. Next, the pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over Al-MCM-41 and HZSM-5 catalysts were 90wt% and 80wt%, respectively compared to 67wt% yield for the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite yielded 70wt% phenols.
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 ...
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 unusual behavior was observed with the Pd ...
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 ...
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 ...
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 ...
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 ...
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. ...
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 ...
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 oxide catalyst, which was chosen for its high stability, was also ineffective. ...
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 kinetic model assumptions. (orig.)
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.
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...
The oxide colloidal route, developed in the laboratory for mono-metallic catalysts, consists in preparing a metallic oxide hydro-sol which leads to the supportedcatalyst 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 oxide particles. To synthesize oxide ...
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.
The preparation and performance of membranes for application to hydrogen separation from coal-derived gas is described. The membrane material investigated was dense amorphous silica deposited on a suitable support by chemical vapor deposition (CVD). Two types of support materials were pursued. One type consisted of a two-layer composite, zeolite silicalite/{alpha}-Al{sub 2}O{sub 3}, in the form of tubes approximately 0.7 cm in diameter. The other type was porous glass tubes of diameter below 0.2 cm. The first type of support was prepared starting from {alpha}-Al{sub 2}O{sub 3} tubes of 1{micro}m mean pore diameter and growing by hydrothermal reaction a zeolite silicalite layer inside the pores of the alumina at the OD side. After calcination to remove the organic template used in the hydrothermal reaction, CVD was carried out to deposit the final silica layer. CVD was carried out by ...
Our research in the general area of acid catalysis involves the characterization of solid acidity and the corresponding assessment of catalytic performance of acidic materials. Acid characterization studies are required to provide essential information about the type of acid site (i.e., Lewis versus Bronsted), the strength of the sites, and the mobility of molecules adsorbed on the acid sites. An accurate measure of acid strength is given by the heat of adsorption of a basic probe molecule on the acid site. A thermodynamic representation of the mobility of adsorbed species on these sites is given by the entropy of adsorption. Important techniques used in these acid site characterization studies include microcalorimetry, thermogravimetric measurements, temperature programmed desorption, infrared spectroscopy and solid state nuclear magnetic resonance. The combination of these acid site characterization studies with reaction kinetics measurements of selected catalytic processes allows ...
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 effect of treatment with hydrogen, hydrogen sulfide, and steam on the catalytic properties of NaY zeolites has been studied. A mechanism has been proposed for activation of the zeolites, which explains the appearance of Broensted acid centers on modified samples. The influence of modification temperature and the degree of decationization of the zeolites on the promoting capacity of the latter in the cumene cracking reaction has been studied.
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.
The efficiency of the synthesized zeolite NaY from rice husk ash (RHA) in the removal of Cr(III) from aqueous solution was studied. Zeolite NaY was synthesized from RHA via seeding technique and the identification of its structure was done by X-ray Diffraction (XRD) technique and the elemental analysis was carried out by X-ray Fluorescence (XRF). The physicochemical properties which were related to the use of the zeolite NaY as a sorbent was also investigated. The synthesized zeolite NaY has higher cation exchange capacity (CEC) than the commercial zeolite NaY due to the higher amount of sodium content in the synthesized as well as the lower ratio of silica to alumina. The synthesized zeolite NaY together with the commercial one as comparison was used in the sorption of the Cr(III) in aqueous solution by batch sorption experiments. The kinetic study showed that ...
Feasibility of depositing continuous films of nano-porous alumino-silicates, primarily zeolites and MCM-41, on metallic and non-metallic substrates was examined with an aim to develop membranes for separation of gaseous mixtures and also for application as hydrogen storage material. Mesoporous silica was deposited in-side the pores of these nano-porous disks with an aim to develop membranes for selective separations. Our study involves supportedzeolite film growth on substrates using in-situ hydrothermal synthesis. Faujasite, Silicalite and Mesoporous silica have been grown on various metallic and non-metallic supports. Metallic substrates used for film growth included anodized titanium, sodium hydroxide treated Titanium, Anodized aluminum, and sintered copper. A non-metallic substrate used was nano-porous aluminum oxide. Zeolite film growth was characterized using Scanning ...
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. ...
The combined Lewis and Broensted acidities were measured of 13X (sodium) zeolite and of its 84.2% calcium-exchanged, 86.0% lanthanum-exchanged, and 69.2% protonated forms, calcined at 400/sup 0/C. The butylamine titrations were performed to visible color changes of Hammett indicators. The H/sub 0/ acidities were 0 for the sodium X zeolite, and 0.2, 0.98, and 0.75 for the calcium, lanthanum, and hydrogen zeolites, respectively. These acidities compared well with trends reported in literature for zeolites pretreated under different conditions. Titration of Broensted sites with arylmethanol indicators did not give satisfactory visible endpoints.
By isomorphous replacement of silicon by phosphorus the authors have synthesized crystalline aluminosilicophosphates with structures of the zeolites type A and faujasite. They determine the adsorption capacity of specimens treated at 575-1275/sup 0/K. They show that the thermal stability and acid resistance of aluminosilicophosphates depend on the quantity of phosphorus in their structure.
The progress of laboratory studies on the removal of NO/sub x/ and SO/sub 2/ with zeolite molecular sieves is reported. The trademark of these zeolite molecular sieves is Zeolon. (LK)
The surface composition and composition near the surface and properties of high-silica zeolites of the TsVK-1 type were studied by XPES, IRS, and low-temperature adsorption of N/sub 2/. It was found that changing the sequence of operations during preparation of the H form of the zeolites results in a different set of acid centers on their surface, caused by migration of cations into the bulk of the zeolites. Migration of elements is also observed during the catalytic reaction of conversion of ethanol.
This paper obtains the acidity spectra of modernites and SVK-zeolites from the heats of adsorption of NH/sub 3/ at 300 C and compares the catalytic activity of these zeolites with the cracking of n-octane and the isomerization of o-xylene. It is shown that the calculation of the specific catalytic activity of centers of different strengths by the method of regional rates allows one to predict the activity of the zeolites from the acidity spectra. It follows from the calculation that only the centers of Bronsted acidity are active towards cracking but that the centers of Lewis acidity are also active towards isomerization.
The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form ...
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 ...
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 ...
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 surface composition of the mixed metal oxide ...
For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-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 first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms ...
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 pyrochemical partitioning process has been conceptually designed so that the transmutation of spent LWR fuels in PEACER can produce mainly low-level waste (Class C waste) for near-surface burial. Chloride salt technology developed for IFR has been employed as the baseline. Electrorefining, reductive extraction and salt recycling steps are used to construct overall flowsheet in order to support PEACER operation. The decontamination factor for transuranic elements was estimated based on both thermodynamic models and reported experimental data. It is expected that overall decontamination factor can be as high as 10{sup 5} for transuranic elements. Final wastes from pyrochemical processing for PEACER are noble metals, alkaline earth metal, and lanthanides. The final wastes are stabilized by mixing with zeolite and glass-frits such that concentration limit for class C waste can be met. The volume of Class C waste is estimated to be small enough to ...
A pyrochemical partitioning process has been conceptually designed so that the transmutation of spent LWR fuels in PEACER can produce mainly low-level waste (Class C waste) for near-surface burial. Chloride salt technology developed for IFR has been employed as the baseline. Electrorefining, reductive extraction and salt recycling steps are used to construct overall flowsheet in order to support PEACER operation. The decontamination factor for transuranic elements was estimated based on both thermodynamic models and reported experimental data. It is expected that overall decontamination factor can be as high as 10"5 for transuranic elements. Final wastes from pyrochemical processing for PEACER are noble metals, alkaline earth metal, and lanthanides. The final wastes are stabilized by mixing with zeolite and glass-frits such that concentration limit for class C waste can be met. The volume of Class C waste is estimated to be small enough to make ...
This award provided for an automated computer-controlled goniometer/diffractometer/manipulator with hot and cold stages and data acquisition system that was interfaced with the high resolution Scienta ESCA-300 X-ray photoelectron spectrometer at Lehigh University. The automation allows angular dependent X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) data to be accurately and rapidly collected without the very time-consuming and labor-intensive manual method that was previously required. It also provides for automated multi-sample analyses, collecting both wide survey scans and selected binding energy range analyses, with complete computer control and data storage. This allows 24 hour data collection without requiring the continuous presence of operators. The overall result is a greater productivity for the XPS laboratory, approximately doubling the output of the laboratory. While the automated computer-controlled goniometer/manipulator with ...
Two families of CeO{sub 2}/Al{sub 2}O{sub 3} (ACE) catalystsupports, 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 ...
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 ...
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 catalystsupported 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...
This illustrated final report for the Swiss Federal Office of Energy (SFOE) presents the results of a project concerning a new, highly active oxygen reduction electrode for PEM fuel cell and zinc/air battery applications. The goal of this project was, according to the authors, to increase the efficiency of the oxygen reduction reaction by lowering the activation polarisation through the right choice of catalyst and by lowering the concentration polarisation. In this work, carbon nanotubes are used as support material. The use of these nanotubes grown on perovskites is discussed. Theoretical considerations regarding activation polarisation are discussed and alternatives to the use of platinum are examined. The results of experiments carried out are presented in graphical and tabular form. The paper is completed with a comprehensive list of references.
This article reports on the UN Environment Programme's (UNEP's) work in supporting the banking and financing sector by creating clean energy finance markets in developing countries. Details are given of the shifting of cash markets to credit, financing solar home systems in India, solar thermal lending in Tunisia, the financing of hotel based solar water heating in Morocco, and the Green Village Credit initiatives in the Yunnan province of China. The importance of providing banks with information needed to gain awareness and experience of renewable energy systems is stressed. The fundamentals of a bank engagement programme, financial catalysts, structuring market oriented approaches, and linking bank lending to policy making are discussed along with the need to shift to credit enhancements to help banks set up their first loan portfolios.
A novel liquid phase alkylation of aniline with methanol over Zn/Cu salts modified kaolin assisted with a pair of porous carbon electrode in slurry-bed reactor under constant current intensity, room temperature and atmospheric pressure was reported. The Zn/Cu salts modified kaolin catalysts were synthesized and characterized by infrared spectrometer (IR), powder X-ray diffraction (XRD) and scanning electron microscopy (SEM), which showed that the transition metals were completely supported on kaolins structure and formed a pored one. The effect parameters, such as initial pH, electrolysis time, metal ratio with kaolin and salts composition in this electrochemical catalytic system, were studied. The procedure was inspected by ultraviolet-visible spectrum (UV-vis), and the product distributi...
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...
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 a ...
Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na{sub 2}O added as NAOH instead of Na{sub 2}CO{sub 3} to avoid severe foaming due to CO{sub 2} evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries ...
Using low-temperature adsorbed dihydrogen and carbon monoxide as molecular probes, the dehydroxylation of the hydrogen forms of the zeolites Y, and ZSM-5 has been studied. The high stability of the high-silica zeolites to dealumination and their difference from faujasites has been established as being due not only to the strength of their Broensted acid sites but also to the nature of their Lewis acid sites. The chemical properties of the Lewis acid sites and their possible role in catalytic reactions are discussed.
Using the infrared spectroscopy method, we have studied the effect of thermal dehydration (under vacuum and in air) and treatment with water vapor on the acid centers of very high silicon zeolites of the ZSM type. We have shown that dehydration under vacuum and in air completely and irreversibly removes the OH groups at 1120/sup 0/K, while treatment with water vapor removes these groups at 770/sup 0/K. The Lewis acid centers of dehydrated zeolites (represented by two types of centers) are more heat-stable than the Bronsted acid centers, but the vapor treatment at 1020/sup 0/K leads to the disappearance of the Lewis acid centers. In this work, we discuss the reasons for destruction of the acid centers of the zeolites under different treatment conditions.
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.
Single and binary metal molybdates of the formula AMoO{sub 4}, where A=Ni, Co, Mg,Mn and/or Zn, were investigated for the oxydehydrogenation of propane to propylene, as well as some ternary molybdates of the formula NiO{sub 0.45}Co{sub 0.45}X{sub 0.066}MoO{sub 4} where X=P, Bi, Fe, Cr, V and Ce. All catalysts were supported on SiO{sub 2} with an active phase/support ratio of 80/20 (wt%). The reaction is catalytic and not a gas phase initiated reaction. It is first order in propane, consistent with the abstraction of the methylene hydrogen being the rate limiting step. Propane conversions and propylene yields vary greatly depending on the metal of the molybdate and surface area of the catalyst. Highest propylene yields (16% at 26.6% propane conversion) are obtained with NiMoO{sub 4}/SiO{sub 2}. Conversion and yield are significantly influenced by the molybdenum content of the compositions. The effect is ...
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.
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 ...
Clays and zeolites are among the most important of natural dusts by virtue of their occurrence through out the world on the earth`s surface and their important industrial uses. (The 1:1 layer silicates, including the serpentine and kaolin minerals, are not addressed in this chapter.) This chapter provides basic information on a variety of important aspects of each mineral, including crystal structure diagrams of each and references to more detailed discussions. 110 refs., 20 figs.
Hydrothermal method for preparing crystal borophosphate with zeolite structure is suggested. To increase absorption capacity and thermal stability of final product, aluminium hydroxide sol, ethylenediamine and ethyl acetate are added to the mixture of crystal boric and concentrated phosphoric acids. Thermal stability of the specimens prepared constitutes 880-950 deg, water absorption capacity is within the limits of 0.30-0.32 cmT/g. 1 table.
An IR spectroscopic study of the reduction of copper-exchanged Linde Na-Y zeolite with hydrogen or carbon monoxide and oxidation with oxygen or oxygen-18 showed that copper(I) and AlO(+1) are formed during reduction, and that oxidation generates copper(II) ions but does not change the aluminum species. Trigonally coordinated aluminum was not detected.
The work presented in part 1 of this study established that the sorption of anhydrous HX into dehydrated Na{sub 56}Y progresses through a sequence of steps involving HX ionization and charge separation, oxygen framework protonation, formation of {alpha}-cage confined cation-anion contact ion pairs, and proton solvation by HX. A logical extension, which is the subjected of this study, concerns the effect of extraframework alkali metal cation type (M = Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}) on the sorption process. The question of the acidity of proton-loaded zeolites compared to Broensted acid zeolites is addressed by using probe reactions with weak bases like ethane and cyclopropane. Additional insight into these systems is also obtained from a quantitative comparison of the kinetic and thermodynamic activation parameters for the dehydrohalogenation of proton-loaded zeolites exemplified by (HX){sub 8}Na{sub ...
A detailed study of adsorption of automobile exhaust hydrocarbons in Ag{sup +}-exchanged zeolites under cold-start conditions (room temperature and in the presence of water) was carried out with FT-IR spectroscopy, using toluene and propylene as probes. The results show that exchanged Ag{sup +} in zeolites is unique for trapping olefin and aromatic hydrocarbons due to its resistance to water adsorption. In contrast, exchanged Cu{sup 2+} in zeolites, which has good hydrocarbon trapping properties under dry conditions, does not trap hydrocarbons under wet conditions. Here, solvation of Cu{sup 2+} screens the interactions of the cation with adsorbed hydrocarbons. The results also show that, in addition to the nature of the cation, the structure of the zeolite also plays a role in hydrocarbon trapping. Aging at high temperatures, with water vapor (=10%) and SO{sub 2} (=15ppm), leads to a decrease of the ...
The nature of extralattice aluminum and its effect on acidity in zeolites was studied. A series of zeolites (some commercial), dealuminated by various methods, were obtained having Si/Al ratios between 1.5 and 20. These were characterized using volumetric sorption, XRD, AA, NMR, and reaction studies. Samples dealuminated using ammonium hexafluorosilicate were found to contain little or no extralattice aluminum. In contrast, steam-dealuminated zeolites had large amounts of extralattice aluminum. In some cases a significant portion of the extralattice aluminum was unobservable by [sup 27]Al NMR, suggesting the existence of an aluminum species of low symmetry. Proton NMR indicated that all the protons were associated with the lattice aluminum atoms. Depending on the preparation history, different groups of H-Y zeolites exhibited different maxima in catalytic activity as a function of aluminum content. The ...
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 catalyst and commercial 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.
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)
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 composition AA/sup 1/BO/sub ...
A fusion reactor (such as NET/ITER) which breeds its own tritium fuel requires tritium recovery, purification and separation from the other isotopes. Cyclic adsorption processes are strong candidates for several of the processes involved: amongst other advantages, they promise a low tritium inventory. A good adsorbent for such processes must have high adsorption capacity, high selectivity and very low tritium retention after each cycle. Pure zeolite powder is shown to have an excellent combination of these three properties. However, in practice problems can arise from tritium which is not removed by reactivation. In this paper we show that tritium retention in zeolites can be caused either by water retained in the zeolite structure, which can be removed by ore rigorous activation, or by water tapped on binders in commercial pellets. (orig.).
We have obtained convincing evidence for localization of the optical electron on a single-ring fragment of a chelated bipyridine-like'' ligand (ie., pyridylpyrazine or 4-Methyl-bipyridine). In addition we have completed studies of Ru(bipyrazine){sub 3}{sup 2+} in aqueous sulfuric acid (0--98% by weight) and find clear evidence for sequential addition of six-protons to the six peripheral nitrogen atoms. Studies of zeolite-entrapped complexes are continuing and a series of homo- and heteroleptic complexes have been prepared and characterized. Finally, the synthesis of zeolite-entrapped metallophthalocyanines has now been developed and the copper and cobalt analogues synthesized. The characterization of these materials is now in progress.
Copper complexes of the amino acids histidine, arginine and lysine have been introduced into the supercages of zeolite Y and, for the first time, into the large intracrystalline cavities of zeolites EMT and MCM-22. The resulting host/guest compounds are characterized by X-ray powder diffraction, UV/VIS-spectroscopy in the diffuse reflectance mode and by catalytic tests in the liquid-phase oxidation of aromatic alcohols (viz. benzyl alcohol, 2- and 3-methylbenzyl alcohol and 2,5-dimethylbenzyl alcohol) with tertiary-butylhydroperoxide as oxidant. It was observed that intracrystalline copper-amino acid complexes possess remarkable catalytic activity, yielding the corresponding aromatic aldehydes and acids. (orig.)
{sup 1}H, {sup 13}C, {sup 27}Al, and {sup 29}Si magic-angle-spinning (MAS) NMR was used to elucidate the nature of the catalytic activity of zeolite H-ZSM-5. {sup 1}H MAS NMR of sealed samples after mild hydrothermal dealumination shows that the enhanced activity for n-hexane cracking is not due to an enhanced Bronstead acidity. The concentrations of the various OH groups and aluminous species suggest that the reason for the enhanced catalytic activity is the interaction of the n-hexane molecule with a bridging hydroxyl group and with extra-framework aluminium species, which give rise to the enhanced activity, cannot be easily removed from their positions, and are therefore immobilized by the zeolitic framework.
When clinoptilolite is immobilized in cement-based composites, a series of reactions occur, leading to release of Cs. These reactions occur in three overlapping stages: a rapid ion exchange, followed by a somewhat slower reaction between clinoptilolite and principally the Ca(OH)_2 component of cement, and, in the longer term, slower reactions with C-S-H leading either to formation of low-lime C-S-H at temperatures below 100"0C or 11 A (1.1 nm) tobermorite at higher temperatures. Kinetic data are presented to evaluate the rate of physical consumption of the zeolites at 70 and 150"0C. Reactions occurring above 100"0C appear to result in the development of extensive microcracking of cement-zeolite composites containing 50% zeolite.
The effect of treatment of Na-forms of zeolites with HCl solutions and of heat treatment of their NH/sub 4/-forms on the stability of aluminum-oxygen tetrahedra has been studied in this work by high-resolution NMR on /sup 29/Si nuclei, using the synthetic zeolites X, Y, and M (mordenite) as the objects of the study. The exchange capacity with respect to Na/sup +/ ions was determined by analyzing the equilibrium solutions after contact of the samples with 0.5 NH/sub 4/Cl solution on a flame photometer. The high-resolution /sup 29/Si NMR spectra of polycrystalline samples were recorded on an SKhR-200 spectrometer with a superconducting solenoid at a frequency of 39.75 MHz with ultrafast mechanical rotation (3 kHz) of the sample at the magic angle to the external magnetic field. The results obtained are given.
A research was started aiming at evaluating the possible use of natural zeolites as exchange conditioners to improve and make durable the soil resilience against the adverse effects of the use of anomalous waters for irrigation purposes. This paper deals with a preliminary investigation on the comparative resilience of an Entisol with poor exchange properties and of a Neapolitan yellow tuff (NYT) sample against the adverse features of a dirty municipal sewage (DSW). Results showed that NYT treatment largely and significantly improved the poor soil exchange activity. In particular. NYT exchange sites selectively took up ammonium from DSW. As a consequence, ammonium was trapped, then protected against losses in the environment and, concurrently, exchangeable cations, such as K and Ca, were made free as plant nutrients. The results highlight the possible positive role of zeolitized tuff in restoring and sustaining soil resilience.
Abstract Remediation of ground water containing anionic contaminants presents a great challenge. Because of its low cost, surfactant-modified zeolite (SMZ) has been studied for >10 years for potential uses as permeable barrier materials to remove anionic contaminants from water. In this study, zeolite aggregates with particle size of 3.4 to 4.8 mm were modified by hexadecyltrimethylammonium (HDTMA) bromide, a cationic surfactant, to a surfactant loading level of 80 mmol/kg and a concurrent counterion bromide loading level of 34 mmol/kg. While no retardation of chromate transport was observed for unmodified columns, a retardation factor of 60 was found for chromate transport through the SMZ columns. Slow but persistent desorption of HDTMA occurred throughout the chromate transport experimen...
The N{sub 1s} XPS band of pyridine chemisorbed on Al-ZSM-5 zeolite was found to be properly deconvoluted into three component peaks. In a previous contribution these three components were assigned to pyridine chemisorbed on two kinds of Bronsted acid sites and one Lewis acid site. This analysis is extended here to Fe-ZSM-5 and B-ZSM-5. Isomorphous substitution of Fe for Si or Al in the zeolite framework leads to a slight decrease in the binding energy of the N{sub 1s} Lewis component. In the case of B substitution a decrease in the binding energy of all three N{sub 1s} components is observed.
The evaluation of the bactericidal effect of different silver-containing materials where silver is available as Ag^+ (silver nitrate and different silver-exchanged zeolites), as metallic Ag^0 (commercial silver nanoparticles) or as oxide (silver (I) oxide) was carried out in order to elucidate the importance of the bioavailability of silver (i.e., as free ions, metallic particles, combination of them, clusters, complexes, partially soluble or insoluble salts, etc.) on its bactericidal action. For the different materials tested, their bactericidal effect is ordered in the following sequence: AgNO"3>Ag-ZSM-5>Ag"2O>commercial silver-exchanged zeolite (granular)>commercial silver-exchanged zeolite (pellets)>Ag nanoparticles. In general, as the content of bioavailable ionic silver increases, th...
Silica and bridged polysilsesquioxane aerogels are low-density materials that are attractive for applications such as thermal insulation, porous separation media or catalystsupports, adsorbents, and cometary dust capture agents. However, aerogels are notoriously weak and brittle making it difficult to handle and machine monoliths into desired forms. This complication prevents the development of many applications that would otherwise benefit from the use of the low-density materials. Here, we will describe our efforts to chemically modify and mechanically enhance silica-based aerogels using chemical vapor techniques without sacrificing their characteristic low densities. Monolithic silica and organic-bridged polysilsesquioxane aerogels were prepared by sol-gel polymerization of the respective methoxysilane monomers followed by supercritical carbon dioxide drying of the gels. Then the gels were reactively modified with silylating agents to ...
A single plasma process involving three consecutive steps has been developed for producing high gas flow catalytic nanostructures on the electrodes of proton exchange membrane (PEM) fuel cells (FC). Using a high density helicon radio frequency (13.56 MHz) plasma, nickel is sputtered onto a porous carbon support. Changing the background gas from argon to methane/hydrogen allowed 2 ?m long, 37 nm diameter carbon nanofibres (CNFs) to be grown by diffusion through the nickel clusters in a 'tip growth' mechanism at the relatively low temperature of 400 deg. C. The third step involves plasma sputtering of platinum onto the CNFs, resulting in nanoclusters (3-8 nm) being formed on the periphery of the CNFs. Four FC cathodes were synthesized on carbon paper and PTFE/carbon loaded cloth (known as gas diffusion layer, GDL), both with and without CNFs, with the Pt/CNFs nanostructures grown on PTFE/carbon loaded cloth having the best FC performances. Compared with conventional ...
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.
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 correlate well with the physical properties. This study, carried out in the absence of composition and ...
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 ...
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.
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 ...
Introduced herein is microwave irradiation for the adsorption and desorption of environmental pollutants. Microwaves may be used in two ways, other than through elevation of temperature of a system as a whole with the adsorbent such as activated carbon serving as the heating medium. The first is the application by which desorption is caused to take place of specified molecules. For example, zeolite that has adsorbed water is regenerated when it is irradiated with microwaves in a stream of cooling gas. This is because only the moisture is heated since zeolite is a non-carbon adsorbent that absorbs microwaves but a little. Another case is reported in which microwaves are utilized to desorb H2S, H2O, CO, etc., from molecular sieves. In the second application, coexisting materials different in absorptivity are exposed to irradiation. The adsorption of microwave-absorbent materials is inhibited while that of the others is accelerated. For example, ...
This document reports the results of testing of spent ion exchange media pretreatment technologies. Emphasis of the testing activities has been on screening pretreatment technologies, such as drying and emulsification, which are compatible with vitrification, cementation, and incineration. Ion exchange media tested for cementation and incineration pretreatment technologies were typical organic ion exchange resins and inorganic zeolites. The ion exchange medium tested for vitrification pretreatment technologies was inorganic zeolite. The results of testing activities are discussed in detail in this report.
In the prevention of atmospheric pollution by sulfur dioxide emissions from acid absorbers in contact process sulfuric acid plants in which the unconverted SO/sub 2/ is accumulated by adsorption in a zeolite adsorbent bed and desorbed back into the acid production system, it is found that ambient moist air, after partial dehydration in an acid scrubber is suitably used both to cool down and hot purge desorb the zeolite beds. In addition the pure water derived from the ambient air is advantageously used in the acid-making system.
SO/sub 2/ adsorption onto faujasite-type zeolites (Na-X, Na-Y) was investigated by combined UV and IR spectroscopy. Formation of chemisorbed HSO/sub 3//sup -/ species, indicated by a UV band around 215 nm and a low-frequency IR band at 1240 cm/sup -1/, was shown to depend significantly upon the presence of water. Differences in the behavior of Na-X and Na-Y were discussed in terms of different site populations.
A novel multilayer mixed matrix membrane (MMM), consisting of poly(phenylene oxide) (PPO), large-pore mesoporous silica molecular sieve zeolite SBA-15, and a carbon molecular sieve (CMS)/Al{sub 2}O{sub 3} substrate, was successfully fabricated using the procedure outlined in this paper. The membranes were cast by spin coating and exposed to different gases for the purpose of determining and comparing the permeability and selectivity of PPO/SBA-15 membranes to H{sub 2}, CO{sub 2}, N{sub 2}, and CH{sub 4}. PPO/SBA-15/CMS/Al{sub 2}O{sub 3} MMMs with different loading weights of zeolite SBA-15 were also studied. This new class of PPO/SBA-15/CMS/Al{sub 2}O{sub 3} multilayer MMMs showed higher levels of gas permeability compared to PPO/SBA-15 membranes. The permselectivity of H{sub 2}/N{sub 2} and H{sub 2}/CH{sub 4} combinations increased remarkably, with values at 38.9 and 50.9, respectively, at 10 wt% zeolite loading. Field ...
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.
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.
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)
... analyzer section for angle resolved measurements, and a thin film evaporator with a quartz crystal microbalance to measure the mass deposition. ...
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 oxide catalysts. 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 formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in ...
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 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.)
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.
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 ...
The challenge for truck engine product engineering is not only to fulfill increasingly stringent emission requirements, but also to improve the engine's economical viability in its role as the backbone of our global economy. While societal impact and therefore emission limit values are to be reduced in big steps, continuous improvement is not enough but technological quantum leaps are necessary. The introduction and refinement of electronic control of all major engine systems has already been a quantum leap forward. Maximizing the benefits of these technologies to customers and society requires full use of parameter optimization and other enabling technologies. The next big step forward will be widespread use of exhaust aftertreatment on all transportation related diesel engines. While exhaust gas aftertreatment has been successfully established on gasoline (Otto cycle) engines, the introduction of exhaust aftertreatment especially for heavy-duty diesel engines will be much mo ...
The vast majority of fundamental studies of metal oxide selective oxidation catalysts 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 oxide catalysts 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 catalyst is still lacking. In an effort to provide an understanding and a ...
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 ...
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. (author)
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 ...
Synthetic zeolite of 0.5 nm pore size (5A) and blue silica gel were tested to determine their capability to be used as radon collectors. Tests conducted in a radon chamber under controlled conditions of temperature and relative humidity indicate that simple, inexpensive and maintenance-free passive devices containing about 250 g of synthetic zeolite or about 270 g of blue silica gel in open face metal canisters that can measure radon conveniently and adequately, the latter though being suitable only for dry-medium dry atmosphere with quite high radon concentrations. Both materials can be recycled for reuse, in a way similar to the recycle and reuse of active carbon. The amount of radon adsorbed in such collectors is determined by counting the gamma rays from the radon decay products. The lower limit of detection (LLD) is estimated to {approx}45 Bqm{sup -3} for the synthetic zeolite and to {approx}350 Bqm{sup -3} for the ...
We report the existence of a previously unsuspected peak in the [sup 1]H magic angle spinning spectrum of commercially available HZSM-5 samples. At 298 K, this resonance is a broad shoulder on the downfield side of the Bronsted acid signal at 4.3 ppm. Cooling the sample caused the line to narrow, and a clear peak at 6.9 ppm was visible at 123 K. This technique resulted in selective broadening of the 4.3 and 6.9 ppm resonances as a result of conflicting averaging of the [sup 1]H-[sup 27]Al dipolar coupling. We conclude that the 6.9 ppm resonance corresponds to a novel aluminum-containing site in zeolite HZSM-5 and is not an artifact due to exchange with the Bronsted site or an aluminum-rich impurity phase. A possible interpretation of these results is a second Bronsted site for the zeolite. 49 refs., 8 figs.
This report summarizes the findings of a five-month LDRD project funded through Sandia's NTM Investment Area. The project was aimed at providing the foundation for the development of advanced functional materials through the application of ultrathin coatings of microporous or mesoporous materials onto the surface of substrates such as silicon wafers. Prior art teaches that layers of microporous materials such as zeolites may be applied as, e.g., sensor platforms or gas separation membranes. These layers, however, are typically several microns to several hundred microns thick. For many potential applications, vast improvements in the response of a device could be realized if the thickness of the porous layer were reduced to tens of nanometers. However, a basic understanding of how to synthesize or fabricate such ultra-thin layers is lacking. This report describes traditional and novel approaches to the growth of layers of microporous materials on silicon wafers. The ...
Development was explained of non-phosphate detergent with zeolite (Z) and alpha-olefin sulfonate (AOS). 4A type Z was taken notice of as a builder to replace phosphate. In calcium ion trapping power, conventional sodium tripolyphosphate (STP) and Z are 158mgCaO/g and 150mg/g, respectively. However, because Z by the conventional method is large in crystal diameter, coagulates and adheres to matter to be washed, was newly developed fine Z, 0.9 {mu} m in primary grain diameter, which does not give abrasion nor occlusion to the washing machine, nor precipitate in the river. Because linear alkylbenzene sulfonate, combined with Z, is poorer in washing power than that, done with STP, was developed AOS, new non-phoshate use interfacial active detergent, which is excellent in all washing power, biodegradation speed and physical powder property. Improvement was variously made also in powdery detergent production technology. Though the non-phosphate detergent controlled water ...
The Process Waste Treatment Plant (PWTP) at the Oak Ridge National Laboratory is designed to remove radioactive contaminants, principally {sup 90}Sr, from process wastewater. Planned upgrades to the PWTP will use chabazite zeolite columns. Pilot-scale studies have shown that mass transfer zone lengths increase from 10 to about 30 cm as the superficial velocity increases from 5.5 to 22 cm/min. Calculations with a multicomponent equilibrium model showed that the distribution coefficient for strontium remains essentially constant over the process conditions, suggesting that a simple kinetic model (the Rosen long-bed solution) should adequately represent breakthrough behavior. Using a distribution coefficient of 4.87 L/g predicted by the equilibrium model, good agreement was found between experimental breakthrough curves and those calculated with the Rosen solution. This model allows prediction of bed depths and cycle times necessary to achieve the required ...
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 ...
On Day 363, a negative 360-degree roll turn with spacecraft ... Ill. DSN Support Assessment. As an indication of the high level support provided by the ...
Abstract In this study, surfactant-modified zeolite (SMZ) was used to remove Remazol Brillant Blue R and Remazol Yellow reactive dyes from aqueous solutions. The influences of suspension pH, temperature, agitation rate, and the SMZ dosage on reactive dyes removal and adsorption capacity were investigated by conducting a series of batch adsorption experiments. The adsorption kinetics was tested for pseudo-first-order, pseudo-second order, intraparticle diffusion model, Elovich, and Bangham models, and rate constants of the kinetic models were calculated. Equilibrium isotherms for the adsorption of reactive dyes were analyzed by the Freundlich, Langmuir, Dubinin-Radushkevich, and Tempkin isotherm models. The Langmuir monolayer adsorption capacities of Remazol Brillant Blue R and Remazol Yell...
Potassium clusters arrayed in zeolite A are known to show ferromagnetic properties at low temperature. The origin of the spontaneous magnetization has been explained by a model of spin-canting in an antiferromagnetically ordered state. The direct information for the magnetic structure, however, has not been obtained so far. In the present work, we measure the neutron powder diffraction by using pulsed neutron source at KEK-KENS below and above the Curie temperature. No significant temperature-dependence was, however, obtained within the statistical errors, namely, magnetic scattering could not be detected separately. We also estimate the intensity of magnetic scattering by assuming some possible magnetic structures with considering the magnetic form factor of the cluster wave function. The intensity of magnetic scattering is estimated to be extremely weak and higher S/N of {approx}10{sup 4} or more is required to detect the magnetic scattering of this material.
Potassium clusters arrayed in zeolite A are known to show ferromagnetic properties at low temperature. The origin of the spontaneous magnetization has been explained by a model of spin-canting in an antiferromagnetically ordered state. The direct information for the magnetic structure, however, has not been obtained so far. In the present work, we measure the neutron powder diffraction by using pulsed neutron source at KEK-KENS below and above the Curie temperature. No significant temperature-dependence was, however, obtained within the statistical errors, namely, magnetic scattering could not be detected separately. We also estimate the intensity of magnetic scattering by assuming some possible magnetic structures with considering the magnetic form factor of the cluster wave function. The intensity of magnetic scattering is estimated to be extremely weak and higher S/N of ?104 or more is required to detect the magnetic scattering of this material.
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 oxide catalysts 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 less well investigated modern multiphase-multielement oxide (MMO) catalysts. The ...
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 and are carbon dioxide selective in the oxidation of volatile organic compounds. The study showed that red mud can be used as ...
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 ...
Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on ...
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 ...
A Lurgi baseline study was requested by the DOE/GRI Operating Committee of the Joint Coal Gasification Program for the purpose of updating the economics of earlier Lurgi coal gasification plant studies for the production of substitute natural gas (SNG) based on commercially advanced technologies. The current study incorporates the recent experience with large size Lurgi plants in an effort to improve capital and operating costs of earlier plant designs. The present coal gasification study is based on a mine mouth plant producing 250 billion Btu (HHV) per day of SNG using the Lurgi dry bottom coal gasification technology. A Western subbituminous coal was designated as the plant food, obtained from the Rosebud seam at Colstrip, Montana. This study presents the detailed description of an integrated facility which utilizes coal, air, and water to produce 250 billion Btu (HHV) per day of SNG. The plant consists of coal handling and preparation, twenty-six Lurgi dry bottom gasifiers, shift ...
To investigate the coal liquefaction characteristics, coal slurry samples were taken from the outlets of the reactors and slurry preheater of NEDOL process 1 t/d process supporting unit (PSU), and were analyzed. Tanito Harum coal was used for liquefaction, and the slurry was prepared with recycle solvent. Liquefaction was performed using synthetic iron sulfide catalyst at reaction temperatures, 450 and 465{degree}C. Solubility of various solid samples was examined against n-hexane, toluene, and tetrahydrofuran (THF). When considering the decrease of IMO (THF-insoluble and ash) as a characteristic of coal conversion reaction, around 20% at the outlet of the slurry preheater, around 70% within the first reactor, and several percents within the successive second and third reactors were converted against supplied coal. Increase of reaction temperature led to the increase of evaporation of oil fraction, which resulted in the decrease of actual ...
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.)
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.
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).
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 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)
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.
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.
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 ...
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.
Platinum(II) complexes have been investigated in the hydration of alkynes. These catalysts offer improved regioselectivity over Hg(II) counterparts. 1 fig., 2 tabs.
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.
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...
An amorphous mesoporous titania-silica aerogel (20 wt%TiO{sub 2} - 80 wt% SiO{sub 2}) and tert.-butylhydroperoxide (TBHP) have been used for the epoxidation of various allylic alcohols. Allylic alcohols possessing an internal double bond were more reactive than those with a terminal C=C bond. Epoxide selectivities could be improved by addition of (basic) zeolite 4 A and NaHCO{sub 3} to the reaction mixture. (orig.)
Outbred Wistar rats were immunised with a single intraperitoneal injection of a mixture of 30 mg of A1(OH)3 and 100microng of gonococcal zeolite antigen (ZA). Ten days after immunisation, ZA prepared...Full Text Available
H{sub 2}Gen, with the support of the Department of Energy, successfully designed, built and field-tested two steam methane reformers with 578 kg/day capacity, which has now become a standard commercial product serving customers in the specialty metals and PV manufacturing businesses. We demonstrated that this reformer/PSA system, when combined with compression, storage and dispensing (CSD) equipment could produce hydrogen that is already cost-competitive with gasoline per mile driven in a conventional (non-hybrid) vehicle. We further showed that mass producing this 578 kg/day system in quantities of just 100 units would reduce hydrogen cost per mile approximately 13% below the cost of untaxed gasoline per mile used in a hybrid electric vehicle. If mass produced in quantities of 500 units, hydrogen cost per mile in a FCEV would be 20% below the cost of untaxed gasoline in an HEV in the 2015-2020 time period using EIA fuel cost projections for natural gas and untaxed ...
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.
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.
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.
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 ...
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 total pressure of 3.5 MPa, the phenol ...
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 ...
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 oxidation catalyst. The improvement consists of using as the oxidation catalyst 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 at a temperature of about 200/sup 0/ to ...
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 ...
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 ...
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 ...
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 ...
In 2005, the American Medical Informatics Association undertook a set of activities relating to clinical decision support (CDS), with support from the office of the national coordinator and the Agency...Full Text Available
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 ...
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 investigated by linear sweep voltammetry and ...
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.)
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. Oxidized catalysts 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)
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.
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.
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.
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 stand is designed to test supports of development workings. To expand the test range for various types of supports, the cross pieces have fixing devices in the form of winches interacting by cables through blocks fastened to the stand body with the support hinges.
Reaction between [V^I^VO(acac)2] and the ONN donor Schiff base Hpydx-aepy (I) (Hpydx-aepy=Schiff base obtained by the condensation of pyridoxal and 2-aminoethylpyridine) resulted in the formation of a complex [V^I^VO(acac)(pydx-aepy)] (1). Addition of aqueous 30% H2O2 to 1 yields the poor stable oxidoperoxidovanadium(V) complex [V^VO(O2)(pydx-aepy)] (2). Its formation has also been demonstrated in solution by treating 1 with H2O2 in methanol. Reaction of vanadium exchanged zeolite-Y with I in methanol followed by aerial oxidation gave zeolite-Y encapsulated dioxidovanadium(V) complex, abbreviated as [V^VO2(pydx-aepy)]-Y (4). The crystal and molecular structure of 1 has been determined, confirming the ONN binding mode of the ligand. The encapsulated complex [V^VO2(pydx-aepy)]-Y (4) catalyse...
Petrographic research for the Nevada Nuclear Waste Storage Investigations focused on xenolithic variability in the Topopah Spring Member and on variations of clinoptilolite composition at Yucca Mountain. Zeolite and smectite occurrences were considered in terms of their relation to a disturbed zone beneath the potential repository, and mineral stability experiments have produced a new clinoptilolite structure as a result of prolonged heating at low temperature. Limitations were defined on the abundance of erionite and of sulfur. X-ray diffraction studies lead to improved analytical methods. Progress was made in the comparative study of mineralogy in sand ramps and in faults. Geological modeling considered the differences of the diffusion of nonsorbing tracers in vertically and in horizontally fractured rock. Modeling also treated the diffusion of a nonsorbing tracer in devitrified and in zeolitized rock. The results of these experiments in all ...
#beta#-SiAlON was synthesized from a zeolite by NH_3 gas nitridation and its formation mechanism was investigated using X-ray diffraction and "2"9Si and "2"7Al NMR spectroscopy. It was revealed that most of the Si and Al atoms react to form #beta#-SiAlON via amorphous forms of Si-Al-O-N and O-SiAlON. Nitridation using NH_3 gas is an effective means of preventing mullite formation and promoting the introduction of nitrogen into aluminosilicate materials at lower temperatures than temperatures required by the carbothermal reduction nitridation process. Further, the NMR spectra showed that the siliceous part of the system changed into low z-value of Si_6_-_zAl_zO_zN_8_-_z (#beta#-SiAlON) and the incorporation of Al components into the #beta#-SiAlON was promoted in the later stages of the reaction. (author)
Hydrogen cyanide is a key molecule for chemical evolution studies because, when it is exposed to different sources of energy, it forms various compounds of biological importance. To understand the role of minerals in chemical evolution, a series of experiments was performed. First, the adsorption capacity of HCN on different surface minerals was studied; the results show that HCN is readily adsorbed onto the solids proposed (zeolite, serpentine, dolomite, and sodium montmorillonite), in particular zeolite and montmorillonite. Second, the radiolysis of HCN adsorbed on olivine (as an example of a mineral surface) was also followed; it was found that the rate of HCN decomposition by gamma irradiation is enhanced in the presence of the solid. The third series of studies show that organic material was produced in high abundance from HCN at high radiation doses. The radiolytic products included gases (CO_2, NH_4, and CO) and oligomeric materials that ...
The acid site distribution over large ZSM-5 crystals was analyzed using FTIR microscopy. Results of the analysis of the OH-stretching vibrations and of vibrations of pyridine adsorbed on Bronsted and Lewis acid sites were found to be in good agreement. The resolution which can be obtained using this novel technique is about 10-20 [mu]m. This limits the application to large crystals as analyzed in this study. Comparison of the results of IR microscopy with aluminum distributions obtained by electron microprobe analysis revealed that IR microscopy cannot resolve inhomogeneities on a scale smaller than the above-state limits. The results of both methods on a larger scale, however, are in very good agreement. Using a combination of both techniques, it is possible to obtain a clearer picture of the distribution of acid sites in large zeolite crystals, where electron microprobing gives the higher resolution, and IR microscopy allows the determination of the types of ...
A research program has been initiated to screen and select electrolyte materials for use in steam electrolyzers in the 300-600/sup 0/C temperature range. Screening of a significant number of acid anhydrides, hydroxides, oxides, and phospates for their electrolytic conductivity properties is underway. Of the binary materials examined to date, only polymerized phosphoric acid, immobilized on an H/sup +/ substituted zeolite, shows promise. A substantial number of ternary compounds remain to be synthesized and evaluated.
The leached glass is subject to leachant attack and results in surface layer alteration which greatly affects the corrosion progress of glass forms. This work studied the composition change, precipitation, pitting corrosion as well as surface layer break and spallation of the leached glass forms. 6 conclusions can be made: 1. The extent of surface layer alteration is related to many factors such as temperature, pH, leachant chemistry, flow rate and leach duration, etc. 2. The alkali element Na is seriously depleted and the elements like U.Ti,Fe, Ca and Mg are enriched in the surface layer. The influence of media has such order: Fe{sub 2}O{sub 3} > Na-bentonite > Zeolite. 3. The precipitate formed in leach test for 56 days at 90 {infinity}C is mostly amorphous, but after 91 days has crystallized. There is K - Ca - Al - Si crystal,the amount of Al, K and Si is increasing, but the amount of Ca is decreasing along with leaching time. CaCO{sub 3} crystal ...
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
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 energy of oxidation inhibition was calculated to be 53.9 kJ/mol. Pilot tests showed ...
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.
...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)
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)
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 ...
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 ...
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...
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 the catalyst surface, and thus its influence on the reaction ...
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).
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.)
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.
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 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 of MTS (methyl ...
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 ...
The Seismic Proving Test of Heavy Component with Energy Absorbing Supports has been conducted to prove the reliability of advanced seismic technology, supporting heavy component such as PWR steam generator with large capacity energy absorbing supports under the sponsorship of Ministry of Economical Trade and Industry. If energy absorbing supports are adopted for NPP heavy components, support structure of facility will be much simplified due to their seismic energy absorbing effect. The paper describes the results of lead damper element test and seismic test at Tadotsu Laboratory, using 1/2.5 scale PWR Steam Generator model supported by Lead Extraction Damper (LED) and development of characteristics evaluation formula of energy absorbing support. (author)
The proposed device incorporates an axle which has a roller bearing support mounted upon it. This support uses a cylindrical sleeve that comes in contact with the housing, the sensors, and the bearing support component. Metering accuracy is improved by placing roller bearing supports into grooves running through the protruding center sections of the sensor elements. These roller bearing supports interface with the cylindrical sleeve.
Studies on the determinants of pain-related support are needed to enhance couples-based treatments for pain. The purpose of this study was to determine the extent to which pain catastrophizing...Full Text Available
Using a theoretical framework of social support, and content analysis, the content and pattern of support in messages posted in a 4-week period on a commercial health network for individuals concerned...Full Text Available
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 ...
A device is presented with handle containing hinges and work support arm, a flexible pin with supports and extra weights. The flexible pin is equipped with cantilevered sergments and weights. The bracket hinges on the handle are perpendicular to the axis of the flexible pin. To reduce handle vibration during drilling hard rock, the handle and brackets are joined to allow relative movement on the surface perpendicular to the hinges of the work support arm. The handle is joined to the work support arm parallel to the sides and the work support arm has holes to accomodate this. Elastic bushings are located between the lateral sides of the work support arm where it is joined to the handle.
... Headquarters Element, Defense Logistics Agency, Support Detachment 3 ... Joint Task Force, Team 6 ... 19th Special Forces Group, Support Element 1 ...
OBJECTIVEEvaluate the qualitative and quantitative differences between moderated and unmoderated on-line social support groups focused on asthma.DESIGNA...Full Text Available
This paper reports an investigation of older adults' needs and preferences concerning online social support. We focused our analysis on seven different aspects of online support: Self disclosure, Deep support, Light support, Community building, Information/Facts, Off topic, and Technical issues. For each aspect we were interested in how older adults perceive this aspect of support, what they think are the similarities and differences of this aspect of support in online settings vs offline settings, and what they perceive are the advantages and disadvantages of communicating this aspect of support online. We did this by conducting detailed interviews with three groups of older adults (31 people in total) with different levels of expertise in using the internet and online communication (olde...
... s guides and "how-to" videos and other materials, and 7. Receive continuing support from GLOBE's ... and educational materials that result from international proposals in its materials and support ...
Quantitative determination of Broensted acid site concentrations in calcined H-mordenite and H-ZSM-5 by means of conductometric titration and infrared spectroscopy reveals that the concentration of Broensted acid sites present is lower than would be expected on the basis of the aluminum content. This discrepancy is attributed to dealumination and dehydroxylation processes occurring during calcination. A model is proposed according to which the degree of these processes strongly depends on the concentration of vicinal aluminum T sites in the zeolite: Broensted acid sites associated with these T sites are lost, and the remaining Broensted acidity is related to the concentration of the (remaining) isolated aluminum T sites. This model quantitatively correlates the experimentally determined concentration of Broensted acid sites with the concentration of isolated aluminum T sites. 33 refs., 4 figs., 2 tabs.
Within the framework of the cluster approach and the semiempirical SCF MO LCAO method in the CNDO/BW valence approximation, possible pathways have been compared for the dehydroxylation of aluminosilicate systems. It has been shown that dehydroxylation as a result of splitting of a water molecule from an acidic bridge hydroxyl group and a more basic terminal group Al-OH is the most energyfavorable. Apparently, such a dehydroxylation pathway is primarily characteristic for amorphous aluminosilicates. Typical of crystalline aluminosilicates at moderate heat-treating temperature is dehydroxylation through splitting of a water molecule from an acidic bridge hydroxyl group and a neutral Si-OH group; at higher temperatures, there is a possible pathway of dehydroxylation of highsilica zeolites as a result of condensation of two acidic surface hydroxyls.
Experimentally, a feasibility study for adsorption and catalytic pyrolysis of spill oils on Cu/ZSM-5 for recycling of light oils has been conducted in the present work. The adsorption and pyrolysis of model compounds such as heptane, toluene, and diesel (to stimulate the spill oils) on Cu/ZSM-5 have been investigated on a continuous fixed-bed reactor. By component fitted X-ray absorption near edge structural (XANES) spectroscopy, catalytic active species such as metallic copper (Cu) (77-84%) and Cu2O (6-7%) are found in the channels of ZSM-5 during pyrolysis of heptane or toluene. Pyrolysis of diesel effected by Cu/ZSM-5 yields gas (C1-C5) (32%) and light oil (68%) that can be used as auxiliary fuels.
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.
This paper is a review concerning the application of Nuclear Analytical Techniques in the Cuban sugar industry. The most complete elemental composition of final molasses (34 elements) and natural zeolites (38) this last one employed as an auxiliary agent in sugar technological processe4s has been performed by means of instrumental Neutron Activation Analysis (INAA) and X-Ray Fluorescence Analysis (XRFA). The trace elemental sugar cane soill-plant relationship and elemental composition of different types of Cuban sugar (raw, blanco-directo and refine) were also studied. As a result, valuable information referred to the possibilities of using these products in animal and human foodstuff so as in the other applications are given. (author). 34 refs., 6 figs., 1 tab.
Counter-current regeneration of 2-stage sodium zeolite softeners has been employed in reducing hardness leakage level of steamflooding water to less than 1 ppm when raw water contains as much as 5,000 ppm of the total dissolved solids. Hardness leakage is caused by sodium displacement of calcium and magnesium from the bottom of the exchanger bed. This study presents nomographs providing for rapid calculations to be made, for which a convenient operational mode does not already exist. The nomographs relate the hardness leakage as a function of salt quality and influent water quality and present solutions for predicting the leakage level, salt quality requirement or the treatability of raw water required for steamflooding projects.
The CO2 adsorption capacity of the low-cost solid sorbents of waste tire char (TC) and chicken waste char (CW) was compared with commercial active carbon (AC) and 5?? zeolite (ZA) using thermogravimetric analysis (TG), pressurized TG, and differential scanning calorimetry (DSC). The sorbents were degassed in a TG up to 150??C to release all gases on the surface of the sample, then cooled down to the designed temperature for adsorption. TG results indicated that the CO2 adsorption capacity of TC was higher than that of CW, but lower than those of AC and ZA. The maximum adsorption rate of TC at 50??C was 0.61% min?1, lower than that of AC, but higher than that of CW, 0.44% min?1. The maximum adsorption rate of ZA at 50??C was 3.1% min?1. When the pressure was over 4?bar, the adsorption rate ...
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 ...
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 ...
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 conditions of 10 to 100,000 hr/sup -1/ hourly space velocity.
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 of 10 to 100,000 hr/sup -1/ hourly space velocity.
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 multicomponent oxide catalysts, containing lead and magnesium oxides, for oxidative conversion ...
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 ...
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 ...
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; ...
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 ...
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 ...
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.)
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 its oxidation state. (author).
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...
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 reversibly its oxidation state.
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.
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...
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...
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 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....
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.)
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)
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.)
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.
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 mz8310 device support module provides support for the following record types: event, pulseCounter, pulseDelay, and pulseTrain. No driver support is needed. Up to 4 mz8310 modules are supported. Each 8310 module contains 10 channels, which are identified as signals O,...9. Each channel is individually configurable. Each mz83 10 has two Am9513 Timing Controller chips. Each Am9513 has 5 counters.
...six months Organising local tours of the area for up to 1000 affected families in the Izu Penninsula area around Mount Fuji Mobile food stalls that wlll serve up to 10,000 bottles of water and 10,000 servings of food Mobile human waste disposal units Building northern Japan support committees Browser does not support script. Browser does not support script. For further information, please contact: Garry Campbell, PR & ...
In 1977 and 1978, workers at Idaho National Engineering Laboratory (INEL) developed and tested a process for the regeneration and reuse of silver mordenite, AgZ, used to trap iodine from the dissolver off-gas stream of a nuclear fuel reprocessing plant. We were requested by the Airborne Waste Management Program Office of the Department of Energy to perform a confirmatory recycle study using repeated loadings at about 150/sup 0/C with elemental iodine, each followed by a drying step at 300/sup 0/C, then by iodine removal using elemental hydrogen at 500/sup 0/C. The results of our study show that AgZ can be recycled. There was considerable difficulty in stripping the iodine at 500/sup 0/C.; however, this step went reasonably well at 550/sup 0/C or slightly higher, with no apparent loss in the iodine-loading capacity of the AgZ. Large releases of elemental iodine occurred during the drying stage and the early part of the stripping stage. Lead zeolite, which was ...
The diffusion of methane confined in nano-porous carbon aerogel with the average pore size 48 {angstrom} and porosity 60% was investigated as a function of pressure at T = 298 K using quasi-elastic neutron scattering (QENS). The diffusivity of methane shows a clear effect of confinement: it is about two orders of magnitude lower than in bulk at the same thermodynamic conditions and is close to the diffusivity of liquid methane at 100 K (i.e. {approx} 90 K below the liquid-gas critical temperature T{sub C} {approx} 191 K). The diffusion coefficient (D) of methane initially increases with pressure by a factor of {approx}2.5 from 3.47 {+-} 0.41 x 10{sup -10} m{sup 2} s{sup -1} at 0.482 MPa to D = 8.55 {+-} 0.33 x 10{sup -10} m{sup 2} s{sup -1} at 2.75 MPa and starts to decrease at higher pressures. An explanation of the observed non-monotonic behavior of the diffusivity in the confined fluid is based on the results of small-angle neutron scattering experiments of the phase behavior of ...
A procedure for lowering an offshore rig support block into water, one with water displacement elements, including transfering a structure ready for installation from construction supports onto the grillage that has been set up on the slide, and then lowering the structure together with the grillage into the water. With the goal of dereasing the volume of hydrotechnical operations, the slides have been extended only to the waterline, and the water-displacing elements of the support block are mounted or the structure in a manner whereby the following conditions are fulfilled: Msigmaless than or equal toM /SUB wi/ sigma-W/Lless than or equal toq where Msigma, M /SUB w/ - are the mass moments of the support block and bouyancy forces correspond to the threshhold; sigma and W - the weight force and bouyancy; L - the support length of the block on the grillage; q - the allowable linear ...
Fuel assemblies in a reactor pressure vessel are disposed in a reactor core shroud. The own weight of the fuel assembly is supported by a reactor core support plate, and is supported, for the horizontal direction, by an upper lattice plate and the reactor core support plate. A support portion for the upper portion of the fuel assembly is disposed above the fuel assembly, and a support portion for the support portion described above is joined to a shroud head by welding. The support portion for the upper portion of the fuel assembly has a network-like portion which absorbs and disperses rising force which exerted on the fuel assembly when the fuel assembly is risen by seismic forces. The rising force exerted on the fuel assembly absorbed by the network-like portion is effectively transferred to the shroud head by the ...
Evaluates experiments aimed at selecting optimum design and technical specifications of a support system for junctions of gate roads and longwall faces mined by shearer loaders and powered supports. A set of supports used at a junction of a working face and a gate road consisted of 2 supports (each made up of a roof bar and two hydraulic props). Roof bar length ranged from 4.0 to 5.5 m and from 7.0 to 9.0 m respectively. The support roof bars were parallel to the longitudinal axis of a gate road. Stress distribution in strata surrounding a junction of a working face and a gate road was analyzed. The finite element method was used. Convergence of the roof and the floor of a gate road depending on support yield strength and distance from a measuring point to the supports was analyzed. Recommendations are made for optimum yield strength of the ...
A manipulator for checking the inside of a vertical, flange-shaped collector of a horizontal steam generator consists of a rotating mast with bearings at the top and bottom ends with a support that can be moved along the length of the mast for the checking system mountings. The support is propelled by a drive spindle placed parallel to the mast with its drive head bearing in the support and locked into a toothed rack attached to the mast. The checking system mountings are fitted in or on the walls of the support and are very close to the box-shaped support. Their retractable arms are hinged.
One of the most complicated tasks during the assembly of the Wendelstein W7-X is the installation of the superconductive coil system. The entire magnet system is enclosed between the Outer Vessel and the plasma vessel in high vacuum at 4 K. The coils are supported by a support structure, the Central Support Structure (CSS). The CSS carries all 70 coils, and it is designed as a closed ring made of 5 modules (10 half modules). The whole structure is supported by 10 Cryolegs which rest on the machine base. This paper describes the final design and manufacture of these Cryolegs.
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.
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.
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.
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 catalyst itself. The high catalytic activity ...
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.
Processes for the hydrogenation of carbon monoxide have had commercial importance since about 1920, when the commercial production of methanol and higher alcohols on oxide catalysts 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 gasification processes ...
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.
... 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 ...
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.
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 ...
Statement of problem Porcelain fracture associated with an implant-supported, metal ceramic crown or fixed partial denture occurs at a higher rate than in tooth-supported restorations, according to the literature. Implant-specific and patient-specific causes of ceramic failure have not been fully evaluated. Purpose The purpose of this retrospective study was to evaluate the potential statistical predictors for porcelain fracture of implant-supported, metal ceramic restorations. Material and Methods Over a 6-month period, a consecutive series of patients having previously received implant-supported, metal ceramic fixed restorations were examined during periodic recall appointments. The number of supporting implants, number of dental units, type of restoration, date of prosthesis insertion, ...
Objective Over recent years the Internet has become an increasingly popular source of support and information for infertility, with a growing number of online support groups now available to individuals affected by fertility problems. The aims of the present study were therefore to explore the online experiences of individuals accessing infertility support groups via the Internet. Methods Ninety-five participants who were recruited from several online infertility support groups completed an online questionnaire containing a series of open-ended questions. Responses to the open-ended questions were analysed using inductive thematic analysis. Results The thematic analysis revealed five recurrent themes, which were labelled: `unique features of online social support', `improved relationship w...
Patient decision support systems have a promising role in the delivery of health care. However, the best approach for further development of these systems is a matter of speculation. To help chart a...Full Text Available
The original plan for support of research in geothermal reservoir engineering, GREMP, is reviewed and compared with accomplishments to date. A commentary on the comparison and an updated plan are presented. Also included are a justification of the updated plan and a revised management plan. (MHR)
Main results of 15-year SSTC NRS activity in the field of technical support of regulatory authority are presented. The article also described management policy, quality assurance system, personnel training system and international co-operation of SSTC. (author)
BackgroundSupport groups have proved to be effective in reducing the burden on family caregivers of dementia patients. Nevertheless, little is known about the factors that influence...Full Text Available
A knowledge-based expert system has been developed to support human decision makers who assess drug products for inclusion in the Saskatchewan Formulary. Formulary inclusion and deletion decisions...Full Text Available
This paper evaluates the Post-Hospital Support Program for the frail elderly and their caregivers using a quasi-experimental design. The program goals were to reduce stress in the caregivers, improve...Full Text Available
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.
ObjectiveMany hospitals utilize antimicrobial management teams (AMTs) to improve patient care. However, most function with minimal computer support. We evaluated the effectiveness...Full Text Available
PURPOSE We wanted to assess the impact of an electronic health record–based diabetes clinical decision support system on control of hemoglobin A1c (glycated hemoglobin),...Full Text Available
Objective To compile and evaluate the evidence on the effects on health and social outcomes of computer based peer to peer communities and electronic self support groups, used by people...Full Text Available
DOE is supporting the development of several conversion processes that are currently in the pilot plant stage. Each of these processes is described briefly and information given as to contractor, contract, funding, site and current progress. Several support projects are treated similarly. (LTN)
Social support is a critical, yet underutilized resource when undergoing cancer care. Underutilization occurs in two conditions: (a) when patients fail to seek out information, material assistance,...Full Text Available
Incorporation of clinical decision support (CDS) capabilities is required to realize the greatest benefits from computerized provider order entry (CPOE) systems. Discussions at a conference on CDS in...Full Text Available
An alternative to synthetic materials for use in solar pond liners is to select clayey soils as hydraulic barriers. This option reduces the cost of construction and the risk of contamination of subsoil and groundwater by hot brines. This paper deals with the physical, chemical and hydraulic properties of different soils tested mainly as compacted clay liners. The underdeveloped nations have the option to use this type of liner, but before doing so several tests are recommended, including those for soil and water composition, permeability, plasticity and X-ray diffraction analysis. In this investigation the following samples are analyzed: native clayey soils with illite, montmorillonite and halloysite, treated and non-treated bentonites in powder and granulated form, a mixture of zeolite and sodium bentonite, and industrial minerals composed largely of halloysite, kaolinite and attapulgite selected clays. Neutral salt aqueous solutions (NaCl and KCl) at different ...
Porous carbon with high surface area and pore volume was prepared by a reverse replication process and its toluene equilibrium adsorption behavior was investigated. The preparation process of the porous carbon was composed of following sub-processes in series: synthesis and template preparation of silica gel, impregnation and polymerization of DVB monomer in silica template, carbonization of DVB polymer in a silica-polymer composite, and HF-assisted selective etching of silica in carbon-silica composite, The prepared porous carbon was nano porous and had ultrahigh specific surface area (2007 m{sup 2}/g) and large pore volume (3.07cm{sup 3}/g). The nanoporous carbon showed rapid toluene adsorption rate and good toluene adsorption capacity, compared with a commercial Y-type zeolite, In the present study, a reverse replication process to prepare nanoporous carbons will be introduced and its application potential as a gas adsorbent will be discussed. (author). 17 ...
The results of studies of radiation-thermocatalytic water decomposition in the 673-773 K temperature range in the presence of BeO and titanium Y-type zeolite are presented. It is found that radiation-thermocatalytic processes of hydrogen production from water are characterized by a lower activation energy (55.4 kJ/mole) as compared with thermocatalytic processes (88.4 kJ/mole). The radiation-thermocatalytic process rate in the presence of oxide systems is not an additive sum of rates of radiation-catalytic (at 296-300 K) and thermocatalytic processes of water decomposition. On the basis of obtained results the conclusion is made that during radiation-catalytic decomposition of water in a heterogeneous system BeO + H_2O the main contribution into this process is made by excitons, radiation-chemical yields of excitons and non-equilibrium charge-carriers are 4.4-4.5 excitons per 100 eV and 3.0-3.2 pairs per 100 eV, respectively.
This paper demonstrates that a commercial-scale facility for encapsulating krypton-85 in zeolite-5A or glass at a 2000 MTHM per year nuclear fuel reprocessing plant can be designed to contain fragments and the 340 to 850 kCi krypton-85 inventory from an assumed catastrophic failure of the high pressure vessel. The vessel failure was assumed as a worst case and was not based on a detailed design evaluation or operating experience. The process design is based on existing commercial hot isostatic pressing technology operated at up to 40 times the scale required for krypton encapsulation. From the calculated process gas inventory in the pressure vessel and vessel design, the maximum explosive energy of 8.4 kg TNT and resulting vessel plug and fragment velocities were calculated. The facility Containment Cell housing the high pressure vessel was designed to contain the gases, fragments, and the shock wave energy calculated for a hypothetical vessel failure. The Access ...
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 pseudo steady state phenol yield. (orig.)
... due to the evolving nature of the Strategy Maps and the changing priority roles, it was decided not to link the SMSP directly with any Strategic Plans. ...
... with the additional US funds supporting Islamic ... the FATA and NWFP, keeping Pakistan's government and ... Without these madrassas, the TTP is left ...
... DARPA UUV and the UUV support simulator. ... Modular connections for robot arm manipulators ... Intelligent mobile robots will be performing many ...
The title invention aims at a vibrations-free running of the flywheel to realize a high speed (18,000-20,000 revolutions per minute). The flywheel consists of a case which holds a central stator, a rotor and two ball-bearings. The ball-bearings have a first radial stiffness and are placed in between the rotor and an upper, respectively lower support bearer. The support bearers are supported on the stator with a second radial stiffness. The top and the bottom of the stator is connected to the case by means of a support with a third stiffness. 6 figs.
sabot: A device fitted around or in back of a projectile in a gun barrel or launching tube to support or protect the projectile or to prevent the escape of ...
with the support and cooperation of the American Meteorological Society, the Marine Technology Society, the National Aeronautics and Space Administration, the National Institute...
The sunlight-induced photocatalytic oxidation of aqueous benzene on TiO(2)-supported gold nanoparticles was considerably improved when the reaction was conducted under a CO(2) atmosphere. 13% yield and 89% selectivity of phenol was obtained on P25-supported gold nanoparticles under 230 kPa of CO(2). PMID:21952312
ABSTRACT Extending the unified theory of acceptance and use of technology (UTAUT) model, this study postulates a model of online social support. The model is empirically tested using data from undergraduates in Taiwan regarding their usage of instant messaging (IM). The test results indicate that all model paths are significant, except that the path between online social support and facilitating conditions is insignificant. This study offers limitations and implications.
Information technology plays an important role in medicine because of the advanced decision support systems (DSS) it can provide. We provide an overview of the building blocks necessary for a medical decision support system and introduce seven research articles in this special issue that describe the development and evaluation of individual medical DSS building blocks or complete medical DSS.
The Coordinated Research Project is a topical collection of research agreements and contracts. The research contracts are awarded with financial support of about 10-20% of the total contract cost. Among the activities of the project is the organization of consultant group meetings and workshops involving several international experts and representatives of users and developers of border radiation monitoring equipment. The project also supports in coordinating the development of equipment and techniques for up-to-date border monitoring and in establishing of a process for providing nuclear forensics support to member states
A zinc-air battery in a case including a zinc particle bed supported adjacent the current feeder and diaphragm on a porous support plate which holds the particles but passes electrolyte solution. Electrolyte is recycled through a conduit between the support plate and top of the bed by convective forces created by a density of differential caused by a higher concentration of high density discharge products in the interstices of the bed than in the electrolyte recycle conduit.
A zinc-air battery in a case is described including a zinc particle bed supported adjacent the current feeder and diaphragm on a porous support plate which holds the particles but passes electrolyte solution. Electrolyte is recycled through a conduit between the support plate and top of the bed by convective forces created by a density of differential caused by a higher concentration of high density discharge products in the interstices of the bed than in the electrolyte recycle conduit. 7 figures.
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 ...
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 ...
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 Katalysatoren erzielt. ...
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)
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 ...
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, ...
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 oxide catalyst 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 catalyst. (3) The HDN reaction ...
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 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 oxide was ...
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 der Reaktion und der ...
This report contains two sections. In the first section a limited review is presented and the preparation of the red mud based additives is described. The additives are characterized by composition and their catalytic activity in hydrocracking is investigated in a batch autoclave under an initial hydrogen pressure of 12 MPa at 435 C and 30 min residence time. A quantitative characterization of the products is given. Comparisons between the red mud additives and coke respectively a commercial catalyst are made. (orig.)
Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.
Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.
;Table of Contents: Gaseous Pollutants Emissions from Coal Combustors and Their Control Technologies in Japan; Simultaneous Determination of Cooper (II) and Iron (III) Using 8-Quinolinol by Solvent Extraction Flow-injection Method; Fundamental Studies on Red Mud as a Catalyst for Coal Liquefaction: Studies on Active Components in Red Mud and Possibilities for Improvement of Its Catalytic Activities; Elution Behavior of Coal-derived Liquids with Sephadex LG-20; Characteristic of Activated Carbon Produced from Scrap Tires at Different Activation Temperatures; Energy Saving Snow Melting System.
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.
A process for the production of transportation fuels from heavy hydrocarbonaceous feedstock is provided comprising a two-stage, close-coupled process, wherein the first stage comprises a hydrothermal zone into which is introduced a mixture comprising a feedstock and red mud having coke-suppressing and demetalizing activity, and hydrogen; and the second, close-coupled stage comprises a hydrocatalytic zone into which substantially all the effluent from the first stage is directly passed and processed under hydrocracking conditions.
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.
A process is claimed for selectively preparing a mixture of two-carbon atom oxygenated hydrocarbons, namely, acetic acid, ethanol and acetaldehyde, by continuously contacting a gaseous reaction mixture containing hydrogen and carbon monoxide with a solid catalyst comprising rhodium in combination with one or more alkali metals selected from the group consisting of lithium, potassium, cesium and rubidium at reaction conditions correlated so as to favor the formation of a substantial proportion of such two-carbon atom products.
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 water addition concentrations, furan selectivity increased from ...
In order to improve the handling capability of red mud, it is mixed with fine-grain coal material such as brown coal or lignite in dust form, in a ratio by weight of between 0.5-10:1. The liquid present in the red mud is bound by the very fine coal admixed therewith so that the resulting mixture can be stored in a silo and even pneumatically conveyed, and the oily properties of the red mud are removed by the treatment. The mixture is particularly suitable for use in connection with the hydrogenating liquefaction of coal in which the red mud is used as a catalyst.
A process for the production of transportation fuels from heavy hydrocarbonaceous feedstock is provided comprising a two-stage, close-coupled process, wherein the first stage comprises a hydrothermal zone into which is introduced a mixture comprising a feedstock and metals-impregnated red mud having coke-suppressing and demetalizing activity, and hydrogen; and the second, close-coupled stage comprises a hydrocatalytic zone into which substantially all the effluent from the first stage is directly passed and processed under hydrocatalytic conditions. The preferred metals for impregnation include transition metals, in particular, nickel and molybdenum.
Scientists of the Institute of Wood Chemistry of the Latvian Academy of Sciences have developed two highly efficient processes for producing furfural, a feedstock for varnishes, synthetic resins and plastics. It is made of production wastes, including branches and small-dimension timber. By one process, the raw material is chipped, treated first with diluted sulphuric acid and then with steam heated to 250 degrees C. The other uses concentrated sulphuric acid as a catalyst. Besides furfural, this process also yields sugar solutions used in alcohol and nutrient yeast production.
Four high-sulphur low-rank coals have been treated at hydrogenation conditions with three iron-based catalyst precursors: Red Mud (Fe[sub 2]O[sub 3]), iron sulphide and iron pentacarbonyl. The obtained yields show a dependence with the sulphur content of the coals; the organic sulphur content correlates with the conversion and THF-solubles when Red Mud and iron sulphide are added. In spite of the high hydrogen sulphide partial pressure in the reaction, the addition of other sources of sulphur enhances the percentages in conversion products. 15 refs., 2 figs., 3 tabs.
We have investigated the stability and catalytic activity of epitaxial overlayers of rhodium on Au(111) and Pd(111). Both surfaces show a strong affinity for hydrogen. We have calculated the energy of adsorption both for a strongly and a more weakly adsorbed species; the latter is the intermediate in the hydrogen evolution reaction. Both the energy of activation for hydrogen adsorption (Volmer reaction) and hydrogen recombination (Tafel reaction) are very low, suggesting that these overlayers are excellent catalysts. PMID:21847482
The key component for improving the energy efficiency and cycle life of the electrically rechargeable zinc-air battery is the bifunctional air electrode. The air electrodes described in this paper contained different types of carbon black as the substrate for the perovskite catalyst (La{sub 0.6}Ca{sub 0.4}CoO{sub 3}). Morphological and physical properties of the carbon substrates play an important role in enhancing the activity and stability of the bifunctional air electrode. Current-potential curves and cycle-life tests were applied in order to gather information on the activity and stability of these electrodes. (authors)
The Balandin type volcano plots have been considered for the main criterion both in catalysis and electrocatalysis to estimate their fundamental properties and optimal activity: ({alpha}) The ones, when some physical feature or catalytic activity itself is plotted usually along transition series, and ({beta}) The others, when catalytic activity arises as a function of some energetic property, the most usually of the adsorption enthalpy of intermediates bonding upon the substrate in the rate determining step (rds). 29 refs.
In 1980 Sasol completed its very large coal conversion complex, Sasol Two and Three in South Africa. This complex, the largest coal-to-liquids facility in the world, utilizes Sasol's proprietary Fischer-Tropsch technology, the Synthol Process. The two key elements of the Synthol Process are its catalyst and its unique fluidized bed reactor, the Synthol Circulating Fluidized Bed Reactor. Details on the catalytic aspects and reaction mechanism have been given elsewhere. In this paper, the history of the development of the reactor is discussed.
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.
The performance of a solar chemical heat pipe was studied using CO{sub 2}reforming of methane as the endothermic reaction. A directly heated vertical reactor, packed with a rhodium catalyst was used. The solar tests were carried out in the Schaeffer solar furnace of the Weizmann Institute of Science. The power absorbed was up to 6.3 KW, the maximal flow rates of the gases reached 11,000 1/h, and the methane conversions reached 85%. A computer model was developed to simulate the process. Agreement of the calculations with the experimental results was quite satisfactory.
Research programs on coal and coal liquefaction are presented. Topics discussed are: coal science, combustion, kinetics, surface science; advanced technology projects in liquefaction; two stage liquefaction and direct liquefaction; catalysts of liquefaction; Fischer-Tropsch synthesis and thermodynamics; alternative fuels utilization; coal preparation; biodegradation; advanced combustion technology; flue gas cleanup; environmental coordination, and technology transfer. Individual projects are processed separately for the data base. (CBS)
Abstract People with a physical disability are a population who for a number of reasons may be vulnerable to social isolation. Research into Internet based support sites has found that social support and an online sense of community can be developed through computer mediated communication channels. This study aims to gain an understanding of the benefits that membership of disability specific online communities may have for people with a physical disability. An online survey was administered to a sample of users of such sites (N = 160). Results indicated that users did receive moral support and personal advice through participating in such online communities. Further, results indicated that online social support and feeling a sense of community online were positively associated with partic...
Background: The Internet has become a popular source of health information for patients with a variety of medical concerns; however, research examining patient interactions on the Internet has been limited. Purpose: Four questions were examined in a survey study of hysterectomy patients who visited http://www.hystersisters.com: (a) Do hysterectomy patients use the support Web site because they perceive their proximal sources of social support to be inadequate? (b) What kinds of support do patients receive from the Web site? (c) What attributes characterize the "Hystersisters" that are perceived to be most helpful? (d) How do informational sources vary depending on the nature of the patient concern? Methods: Women (N = 137) responded to questions about social support, Web site use, and perc...
This study validates a research model that examines usage of instant messaging (IM) from the aspect of online social support. Drawing on the social capital theory, this study postulates that IM usage is indirectly affected by social support via the mediation of the following six dimensions of social capital: commitment, reciprocity, shared codes and language, shared narratives, centrality, and network ties. The model tests data obtained from business organizations in Taiwan, and the results suggest that the indirect influence of social support on IM usage through shared codes and language is significant, and the indirect influence of social support on IM usage through centrality is also significant. Managerial implications and limitations of the empirical findings are provided.
This report presents the work performed at the Institute of Gas Technology (IGT) during the second program quarter from October 1, 1993 to December 31, 1993, under Department of Energy (DOE) Contract No. DE-AC22-93PC92114. This program has co-ordinated funding for Task 1 from IGT`s Sustaining Membership Program (SMP), while DOE is funding Tasks 2--8. Progress in all tasks are reported. The overall objective of this research project is to develop a catalytic process to convert natural gas to liquid transportation fuels. The process consists of two steps that each utilize catalysts and sulfur containing intermediates: (1) to convert natural gas to CS{sub 2} and (2) to convert CS{sub 2} to gasoline range liquids. Experimental data will be generated to demonstrate the potential of catalysts and the overall process. During this quarter, progress in the following areas has been made. An existing unit at IGT was modified to accommodate the sulfur ...
Energy from biomass is a CO{sub 2} neutral, sustainable form of energy. Anaerobic digestion is an established technology for converting biomass to biogas, which contains around 60% methane, besides CO{sub 2} and various contaminants. Most types of biomass contain material that cannot be digested; in woody biomass, this portion is particularly high. Therefore, conventional anaerobic digestion is not suited for the production of biogas from woody biomass. While wood is already being converted to energy by conventional thermal methods (gasification with subsequent methanation), dung, manure, and sewage sludge represent types of biomass whose energy potential remains largely untapped (present energetic use of manure in Switzerland: 0.4%). Conventional gas phase processes suffer from a low efficiency due to the high water content of the feed (enthalpy of vaporization). An alternative technology is the hydrothermal gasification: the water contained within the biomass serves as reaction ...
A system for partial mechanisation of the support work with roadway driving machines consisting of a crawler undercarriage carrying a selective cutter with a cutting jib on a rotary tower is claimed. The system comprises a support manipulator movable in longitudinal direction over the rotary tower and cutting jib and a preassembly table with a number of brackets to take up and preassemble a support structure consisting of profile segments, preferably an arc-shaped support with a cap made up for several parts. The system is characterized in that the preassembly table is mounted on one side of the selective cutter and has one straight vertical guide bar each for at least two cap brackets which can be continuously adjusted in height, and in that the manipulator mounted on the selective cutter has a horizontally suivelling head which may grip under the cap of the preassembled structure on the preassembly ...
Role-limiting approaches support knowledge acquisition (KA) by centering knowledge base construction on common types of tasks or domain-independent problem-solving strategies. Within a particular problem-solving strategy, domain-dependent knowledge plays specific roles. A KA tool then helps a user to fill these roles. Although role-limiting approaches are useful for guiding KA, they are limited because they only support users in filling knowledge roles that have been built in by the designers of the KA system. EXPECT takes a different approach to KA by representing problem-solving knowledge explicitly, and deriving from the current knowledge base the knowledge gaps that must be resolved by the user during KA. This paper contrasts role-limiting approaches and EXPECT`s approach, using the propose-and-revise strategy as an example. EXPECT not only supports users in filling knowledge roles, but also provides ...
The 'high-tension distribution line design support system' was developed for the 'work design support system'. This support system is composed of the work outline editor for preparing work details and facility data and the inference engine for preparing practical design plans, and can check system conditions such as voltage drop and deviation from technical standards automatically. The work outline editor takes charge of selection of work items, selective input of system information, and setting of some conditions such as pole position and reserved load onto a system diagram. The inference engine provides the design plan automatically based on the information inputted by the editor. For the design of high-tension distribution line, such various factors as local condition and load sharing of distribution systems should be considered. This design support system attains ...