Hydrogenating Activity and Adsorption Capacity of Supported Nickel Catalysts Modified by Heteropoly Compounds

The catalytic activity, adsorption capacity, and pore structure of low-percentage nickel catalysts supported on -Al₂O₃or activated carbon and modified by tungsten heteropoly compounds are studied. The activity, selectivity, and thermal stability of the catalysts in the vapor-phase hydrogenation of olefins and aromatic hydrocarbons are higher than those for conventional nickel catalysts. The concentration of nickel in the catalysts is 10–15 times lower than that in commercial catalysts. However, the modified catalysts have higher specific surface areas of metal, higher dispersion, a uniform distribution of metal particles, and a pore-radius distribution other than in the support. The study of water adsorption and desorption showed that the heteropoly compound modifying the -Al₂O₃support covers the support surface completely, and supported nickel interacts with the active surface of the modifying agent rather than with Al₂O₃. A hydrogenation mechanism is proposed, which involves H₂dissociation on Ni particles and the subsequent diffusion of hydrogen atoms via a spillover mechanism to the adsorbed organic compound with the participation of the OH groups of the modifying agent.     

n-Octane reforming over modified catalysts: effect of regeneration on the catalyst performance

The effect of multiple oxidation-reduction cycles on the catalyst performance was studied. Pt-Sn-Sn, Pt-Sn-Ir, Pt-Sn-Au and Pt-Sn-Pd supported on g-Al₂O₃ were compared with the reference Pt-Sn/-Al₂O₃ catalyst in n-octane test reactions. The carbonaceous deposits were burned off from the catalysts after each reaction. The regeneration procedure consisted only two steps: the burn off in air and the reduction in hydrogen. No significant change, as a consequence of the regeneration, was observed in the conversion, the liquid yield and the product distribution, except at the Pt-Sn-Pd and Pt-Sn-Au catalysts. These catalysts lost part of their activity. With the palladium modified catalyst the rupture reactions became more dominant with the number of regeneration cycles. The aromatic part of the product decreased, the isoparaffin part increased in the case of both modified catalysts. The reference, the tin and iridium modified catalysts had stable catalytic performance: the activity and selectivity of the catalysts remained constant after a few oxidation cycles.     

Which Hydrogen Atom of Toluene Protonates PAH molecules in (+)-Mode APPI MS Analysis?

A previous study (Ahmed, A. et al., Anal. Chem. 84, 1146–1151( 2012) reported that toluene used as a solvent was the proton source for polyaromatic hydrocarbon compounds (PAHs) that were subjected to (+)-mode atmospheric-pressure photoionization. In the current study, the exact position of the hydrogen atom in the toluene molecule (either a methyl hydrogen or an aromatic ring hydrogen) involved in the formation of protonated PAH ions was investigated. Experimental analyses of benzene and anisole demonstrated that although the aromatic hydrogen atom of toluene did not contribute to the formation of protonated anthracene, it did contribute to the formation of protonated acridine. Thermochemical data and quantum mechanical calculations showed that the protonation of anthracene by an aromatic ring hydrogen atom of toluene is endothermic, while protonation by a methyl hydrogen atom is exothermic. However, protonation of acridine by either an aromatic ring hydrogen or a methyl hydrogen atom of toluene is exothermic. The different behavior of acridine and anthracene was attributed to differences in gas-phase basicity. It was concluded that both types of hydrogen in toluene can be used for protonation of PAH compounds, but a methyl hydrogen atom is preferred, especially for non-basic compounds.      

Non-catalytic condensation of aromatic aldehydes with aniline in high temperature water

Abstract

The synthesis of diamino triphenyl methanes from aniline and aromatic aldehydes was conducted in near critical water and supercritical water. The reaction parameters, such as temperature, density, and reaction time, have been studied. Significant acceleration of the condensation reaction of aniline and aromatic aldehydes can be achieved by using high temperature water, especially near the critical point, in the absence of any acid catalysts. It has been demonstrated that high temperature water act effectively in the place of conventional acid catalysts.     

Epoxidation of chalcones

Previously undescribed aromatic -keto oxides have been obtained by the epoxidation of chalcones with alkaline hydrogen peroxide in methanolic solution.     

Chemical effects induced by gamma-irradiated alkali halides in organic emulsions

Dissolution of -irradiated alkali halides in the emulsions of aromatic hydrocarbon and water results in the formation of halogen charge transfer complexes and hydrogen. These have been identified by spectrophotometry. Further, their formation has been verified by studying the absorption of a chemical model involving hydrogen incorporated in halogen complex. These products are correlated to the F and hole centers of the irradiated salts.     

Deuterium and tritium exchange studies with phenylalanines and phenylglycine in the presence of homogeneous potassium tetrachloroplatinate(II) catalyst

K₂PtCl₄ was found to be an efficient and very useful homogenous catalyst for deuterium and tritium exchange of the aromatic hydrogens of phenylalanines and phenylglycine. The exchange reactions of the aromatic ring hydrogens, observed in the 80–130°C temperature interval proceed according to an electrophilic substitution mechanisms. The investigated hydrogen exchange processes involve the reversible formation of -complexes with the aromatic ring, analogous to -complexes postulated in deuterium exchange studies with alkylbenzenes. The probable mechanisms of the platinum(II) catalyzed homogeneous deuterium and tritium exchange of aromatic ring hydrogens and of the methoxy and ethoxy para-substituents are discussed.     

Reactions of halogenometalalkoxides

Investigation of the thermal stability of halogenometalalkoxides obtained by reacting Grignard compounds with esters of oxalic acid and containing an indolyl group, is continued. Despite the aromatic nature of the indolyl radical, the ordinary decomposition of the halogenomagnesiumalkoxides with splitting off of aldehyde (ketone) does not take place at 40–110 C. This is due to hydrogen bonding between hydrogen on the nitrogen and the alkoxy group. The IR spectra of the esters of N-indolyl- and -indolylglyoxylic acids synthesized are investigated. The latter are shown to contain a hydrogen bond between the NH group hydrogen and the carbonyl group.For Part XVIII see [12].     

Nonoxidative conversion of methane and <Emphasis Type="Italic">n</Emphasis>-pentane over a platinum/alumina catalyst

Methane adsorption on the Pt–H/Al₂O₃ and Pt/Al₂O₃ catalysts begins at Т = 475°C and is accompanied by the appearance of hydrogen in the reaction medium. At a higher temperature is raised to 550°C, the amount of adsorbed hydrogen increases to 1.1 and 0.8 mol/(mol Pt), respectively. According to the calculated degree of methane dehydrogenation on platinum sites at Т = 550°C, the Н/C ratio is 1.3 (at/at) for the Pt–H/Al₂O₃ catalyst and 1.5 (at/at) for the Pt/Al₂O₃ catalyst. The introduction of n-pentane into the reaction medium increases the yield of aromatic hydrocarbons (benzene and toluene) by a factor of 8.8 over the arene yield observed in individual n-pentane conversion. A mass spectrometric analysis of the arenes obtained with the Pt/Al₂O₃ catalyst has demonstrated that 37.5% of the adsorbed methane is involved in the methane–n-pentane coaromatization yielding benzene and toluene.     

Physico-Chemical and Catalytic Study of the Co/SiO2 Catalysts

This paper is focused on the physico-chemical and catalytic properties of Co/SiO₂ catalysts. Silica-supported cobalt catalysts were prepared by sol-gel and impregnation methods and characterized by BET measurements, temperature programmed reduction (TPR_H2), X-ray diffraction (XRD), and thermogravimetry-mass spectroscopy (TG-DTA-MS). The sol-gel method of preparation leads to metal/support catalyst precursor with a homogenous distribution of metal ions into bulk silica network or on its surface. After drying the catalysts were calcined at 500, 700, and 900°C. The reducibility of the supported metal oxide phases in hydrogen was determined by TPR measurements. The influence of high temperature—atmosphere treatment on the phase composition of Co/SiO₂ catalysts was investigated by XRD and TG-DTA-MS methods. At least five crystallographic cobalt phases may exist on silica: metallic Co, CoO, Co₃O₄, and two different forms of Co₂SiO₄ cobalt silicate. Those catalysts in which cobalt was chemically bonded with silica show worse reducibility as a result of strongly bonded Co-O-Si species formed during high-temperature oxidation. The TPR measurements show that a gradual increase in the oxidation temperature (500–900°C) leads to a decrease in low-temperature hydrogen reduction effects (<600°C). The decrease of cobalt oxide reduction degree is caused by cobalt silicate formation during the oxidation at high temperature (T 1000°C). The catalysts were tested by the reforming of methane by carbon dioxide and methanation of CO₂ reactions.     

Study of amorphous Ni-La-B/g-Al2O3 catalysts for the production of hydrogen peroxide from carbon monoxide, water and oxygen

Summary Novel amorphous Ni-La-B/-Al₂O₃ catalysts have been developed for the production of hydrogen peroxide from carbon monoxide, water and oxygen. The experimental investigation confirmed that the catalyst dried at 120ºC in air shows the best initial activity. The deactivation of amorphous Ni-La-B/-Al₂O₃ catalysts was also studied.     

Five- and six-membered N-H?S hydrogen bonding in aromatic amides

The capacity of sulfur to form intramolecular five- or six-membered S?H-N hydrogen bonding in aromatic amides is assessed. The five-membered S?H-N hydrogen bonding is observed in crystal structures of five compounds, whereas the six-membered S?H-N hydrogen bonding is revealed in crystal structures of three compounds. The trityl group has been used to promote formation of the weak hydrogen bonding because it efficiently inhibits the competition of the intermolecular CO?H-N hydrogen bonding. (2D) ¹H NMR experiments indicate that both patterns also exist in chloroform.     

Selective Hydrogenation of Diethyl Disulfide to Ethanethiol in the Presence of Sulfide Catalysts

The gas-phase reaction of diethyl disulfide hydrogenation at atmospheric pressure in the presence of supported transition metal sulfides was studied. The reaction of diethyl disulfide with hydrogen at T = 200°C resulted in ethanethiol, and the selectivity to ethanethiol was no lower than 94%. The selectivity decreased at a higher temperature because of diethyl disulfide decomposition to ethylene and hydrogen sulfide. The reaction of diethyl disulfide in the presence of hydrogen occurred at a higher rate and selectivity than that in an atmosphere of helium. The activity of metal sulfides supported on aluminum oxide was higher than on the other studied supports—aluminosilicate, silica gel, and a carbon support. Metal sulfides supported on Al₂O₃ were arranged in the following order according to their activity: Rh > Ru > Mo Pd > Ni > W. Bimetallic catalysts were less active than monometallic catalysts. The activity of catalysts increased with the sulfide sulfur content; the partial reduction of metal sulfides also increased the catalytic activity.     

Pathways to Better Stability of Catalysts for Reforming of Gasoline Fractions

Adsorbents AS-31 and AKD-981 based on zinc oxide and alumina are described. They are used in the purification of hydrogen-containing gas of reforming from hydrogen sulfide at 20–120°C and pressures up to 4 MPa. The second of these adsorbents is capable of forming weak adsorption complexes with hydrogen sulfide and can be recovered 2–3 more times than the first one. To remove sulfur-containing compounds from the gaseous feed of reforming at 350–450°C, the KAS-50 catalyst/adsorbent is proposed, which is prepared by mixing manganese dioxide and aluminum hydroxide. The sulfur capacity of this catalyst is 20%. New platinum–rhenium reforming catalysts KR-200 and KR-201 are proposed, which have higher stability when they work with purified feedstock. The concentration of the active catalyst is the same or lower, and these catalysts show better activity than their predecessors. All catalysts and adsorbents are tested and work in industry.     

The geometry of intermolecular interactions in some crystalline fluorine-containing organic compounds

The propensity of C-F groups to form C-F H-C interactions with C-H groups on other molecules has been analyzed. Crystal structures of molecules containing only carbon, hydrogen, and fluorine, but no oxygen, nitrogen, or other hydrogen-bond-forming elements, were chosen for an initial study in which the intermolecular interactions in crystal-structure determinations of polycyclic aromatic hydrocarbons and their analogous fluoro derivatives were analyzed. It is found that C-F H-C interactions occur, but they are weak, as judged by the intermolecular distances and the angles involved. In a study of crystal structures of molecules containing other elements in addition to carbon, hydrogen, and fluorine, it was found that when an oxygen atom is in a neighboring position on an interacting molecule, a C-O group is more likely than a C-F group to form a linear interaction to the hydrogen atom of a C-H group. Thus, in spite of the high electronegativity of the fluorine atom, a C-F group competes unfavorably with a C-O^–, C-OH, or C=O group to form a hydrogen bond to an O-H, N-H, or C-H group. It is found, however, particularly for polycyclic aromatic hydrocarbons with substituted CF₃ groups that, in the absence of other functional groups that can form stronger interactions, C-F H-C interactions may serve to align molecules and give a different crystal packing from that in the pure hydrocarbon (where fluorine is replaced by hydrogen). Thus, C-F H-X (X = C, N, O) interactions are very weak, much weaker than C=O H-X interactions, but they cannot be ignored in predictions of modes of molecular packing in complexes and in crystals.     

Anion Receptor with Xylene Bridged Two Imidazolium Rings

A m-xylene bridged imidazolium receptor 1 has been designed and synthesized. The receptor 1 utilizes two imidazole (C–H)⁺—anion hydrogen bonds and one aromatic hydrogen—anion hydrogen bond. The major driving force of complexation between the receptor 1 and anions comes from two imidazole (C–H)⁺—anion hydrogen bonding. However, some hydrogen bonding energy between aromatic hydrogen and anion exists, although it is expected to be much smaller than that of imidazole (C–H)⁺—anion hydrogen bonds.

     

Elucidation of hydrodesulfurization mechanism on molybdenum‐based catalysts using 35S radioisotope pulse tracer methods

Elucidation of the hydrodesulfurization (HDS) mechanism on molybdenumbased catalysts using radioisotope tracer methods and reaction kinetics is reviewed. Firstly, to investigate the sulfidation state in Mo/Al₂O₃ and Co–Mo/Al₂O₃ catalysts, presulfiding of these catalysts has been performed using a ³⁵S pulse tracer method. Secondly, HDS of radioactive ³⁵Slabeled dibenzothiophene was carried out over a series of sulfided molybdena–alumina catalysts and cobaltpromoted molybdena–alumina catalysts in a pressurized flow reactor to estimate the behavior of sulfur on the working catalysts. Finally, sulfur exchange of a ³⁵Slabeled catalyst with hydrogen sulfide was performed to estimate the relationship between the amount of labile sulfur and catalytically active sites.     

Steric structure of N-arylsuccinimides and N-arylphthalimides

Conclusions The steric structure of N-arylimides is determined by the steric interactions between the carbonyl oxygen and the hydrogen atoms in the ortho positions, and is independent of the -electron character of the imide ring and the substitution in the aromatic radical.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 661–664, March, 1979.     

Effect of precipitation medium and thermal treatment on structure and textural properties of chromium orthophosphates

The effect of the precipitation agent on the structure and textural properties of CrPO₄ (Cr/P=1) catalysts has been studied. Catalysts obtained in propylene oxide-aqueous ammonia exhibited higher thermal stability and, hence, greater surface areas and pore volumes than catalysts obtained in propylene oxide or aqueous ammonia exclusively. The former also showed a small surface area decrease on increasing calcination temperature up to 1073 K. Nevertheless, calcination at 1273 K develops in all cases crystalline CrPO₄, showing the -structure. Moreover, CrPO₄ catalysts thermally treated below 1273 K only exhibited hydrogen bonded hydroxy groups .