Ultra-stable Ni catalysts for methane reforming by carbon dioxide

Methane reforming by carbon dioxide has been studied over ultra-stable Ni catalysts. The catalyst was characterized by XRD, IR and TEM and temperature programmed hydrogenation. The nickel–magnesia solid solution catalyst containing low nickel has shown excellent stability (>3000 h) and no carbon deposition in the methane reforming by carbon dioxide. It was also found that the small nickel metal particle interaction with support surface is effective for the inhibition of carbon formation.     

Dehydrogenation of propane on aluminoplatinum catalysts modified with Re,Zr, Sc,and Sn

The effect of addition of Re, Zr, Sc, and Sn on an aluminoplatinum catalyst in the reaction of dehydrogenation of propane was investigated. It was shown that addition of 0.2–0.5% Zr, Sc, or Re virtually does not alter the catalytic properties of the aluminoplatinum catalyst (APC); addition of 0.2% Sn increases the activity, selectivity, and stability of Pt/Al₂O₃. The amount of coke deposited on the APC after the first 5 min of work decreases by three times in the presence of Sn. The coke is more enriched with hydrogen than the other systems formed on the surface of Pt-Sn/Al₂O₃.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 765–771, April, 1991.     

Quantum-chemical analysis of the reactivity of methanol dimers in their reaction with isocyanates

The CNDO/2 method has been used to investigate the reactivity of methanol dimers of various structures in nucleophilic addition reactions at the N=C bond of isocyanates. It is shown that effect of dimerization on the reactivity of the alcohol is in the same direction as the effect of an electron donating catalyst on the monomer, depending on the structure of the dimer and, in some instances, also on the conformation of the isocyanate.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 3, pp. 345–348, May–June, 1990.     

Promoting effect of Mg in supported Mo/HBeta–Al2O3 catalyst for cross-metathesis of ethene and butene-2 to propene

Promoting effects of Mg in heterogeneous Mo/HBeta–Al₂O₃ catalyst have been carefully studied for cross-metathesis of ethene and butene-2 to propene. The catalyst shows good stability with Mg content in the range of 1–2 wt%. Such effect may be attributed to the elimination of weak acid sites through introduction of Mg which suppresses the side olefin oligomerization reaction, as evidenced from NH₃-TPD and ¹H MAS NMR results. Addition of more Mg content to 3 wt% may change the state and reducibility of Mo species, as indicated from the UV–vis, UV-Raman and H₂-TPR measurements. The increasing difficulty for the reduction of Mo(VI) species is closely related with the poor performance of 3 wt% Mg–4Mo/HBeta–30% Al₂O₃ catalyst in the metathesis reaction.     

Stability of stationary catalysts in the hydrogenation of rapeseed oils

The stability of a nickel-copper-molybdenum-aluminum catalyst without additives and with the addition of promoting metals (chromium and titanium) in the hydrogenation of rapeseed oils has been investigated. It has been established that the addition of a promotor to the composition of a known catalyst raises the activity and improves the stability of the alloy. The possibility has been revealed of using catalysts that have been poisoned by sulfur compounds, after their regeneration. Al-Biruni Tashkent Polytechnic Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 600–604, September–October, 1990.     

Kinetics of the Hydrogenation of Pinane Hydroperoxide to Pinanol on Pd/C

The liquid-phase hydrogenation of pinane hydroperoxide (PHP) to pinanol on a Pd/C catalyst at 20–80°C and hydrogen pressures of 1–11 atm was studied. It was found that the rate of hydrogenation decreased with PHP concentration. The rate of PHP hydrogenation dramatically increased as the pressure of hydrogen was increased in a range of 2.5–3 atm. A mechanism was proposed for the hydrogenation of PHP. According to this mechanism, the step of hydrogen activation (homolytic or heterolytic addition) depends on the redox properties of the catalyst surface (the ratio between adsorbed PHP species and H₂). It was found that pinanol can be prepared with high selectivity by the hydrogenation of PHP on a Pd/C catalyst under mild conditions.     

Enhanced methane decomposition over transition metal-based tri-metallic catalysts for the production of COx free hydrogen

In this study, COx-free hydrogen production via methane decomposition was studied over Cu–Zn-promoted tri-metallic Ni–Co–Al catalysts. The catalysts have been prepared by the constant pH co-precipitation method, and the nominal Ni metal loading was fixed at 50 wt % along with other metals at 10 wt% each. The catalyst activity for methane decomposition reaction was examined in a reactor between 400 °C and 700 °C and at atmospheric pressure. Different techniques such as N₂-physisorption, X-ray diffraction, H₂-TPR SEM, TEM, ICP-MS, TGA, and Raman spectroscopy were applied to characterize the catalysts. The relation between the catalyst composition and their catalytic activity has been investigated. The controlled synthesis has resulted in a series of catalysts with a high surface area. Ni–Co–Cu–Zn–Al was the most active and productive catalyst. Various characterizations indicate that the promotional effects of Cu–Zn interaction were the critical factor in catalysts' activity and stability. Ni–Co–Cu–Zn catalyst gave the highest methane conversion of 85% at 700 °C. Zn addition improves the stability of the catalyst by retaining the active metal size during the decomposition reaction. The catalyst was active for 80 h of stability study. The rapid deactivation of the Ni–Co catalyst was due to the sintering of the catalyst at 650 °C. Moreover, carbon species accumulated during the methane decomposition reaction depend on the catalysts' composition. Zn promotes the growth of reasonably long and thin carbon nanotubes, whereas the diameter of carbon nanotubes on unpromoted catalysts was large.     

Hydrogenolysis of the protolignin from rice husks. III

The hydrogenolysis of the protolignin of rice husks in the presence of a polymetallic catalyst that is used in the hydrocracking of petroleum has been investigated. The dependence of the yield of low-molecular-mass compounds on the reaction conditions has been found. It has been established on the basis of experiments with model compounds that on hydrogenolysis with the use of the polymetallic catalyst both alkyl-aryl C-O-C and C-C bonds are cleaved.Institute of Chemistry of Plant Substances, Academy of Science of the Uzbek SSR, Tashkent. All-Union Scientific-Research Chemical and Technological Institute of the Medicinal and Microbiological Industry, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 679–683, September–October, 1990.     

Reactivity of isomeric pyridinecarboxaldehydes in catalyic hydrogenation

It has been established by a quantum-chemical method (CNDO/2) that there are two possible mechanisms occurring in the vapor phase hydrogenation of 2-, 3-, and 4-pyridinecarboxaldehydes in the presence of a copper-chromium catalyst at 180-300°C. One of these involves a donor-acceptor interaction of aldehyde with catalyst and the addition of hydrogen to the carbon atom of the carbonyl group at the first stage. The second possible mechanism is the synchronous addition of hydrogen to the carbon and oxygen of the carbonyl group of a weakly bound a aldehyde molecule with an unchanged electronic structure.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1082–1086, August, 1994.     

Catalytic synthesis of C-alkylimidazoles over platinum-alumina catalysts

The synthesis of C-alkylimidazoles from 1,2-diamines and carboxylic acids over bifunctional platinum—alumina catalysts has been studied. It has been shown that this method is effective for the synthesis of 2-alkyl and 2,4-dialkylimidazoles including imidazoles with long-chain alkyls. The effect of the reaction temperature, space velocity of the flow of the raw materials, and dilution by hydrogen on the yield of product has been examined for the example of the synthesis of 2-methylimidazole from ethylenediamine and acetic acid, and the stability of the catalyst in continuous reaction cycles with intermediate oxidative regeneration has been studied. The composition of the accompanying products has been established and a mechanism proposed for their formation.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 932–940, April, 1992.     

Low-Temperature Catalytic Oxidation of Sulfide Ions in Aqueous Solutions on a Ni-Oxide System

Catalytic oxidation of sulfide ions in aqueous solutions by air oxygen has been investigated using a Ni-oxide system as a catalyst. The kinetics and the selectivity of the oxidation process were studied by varying the pH, catalyst amount and reaction temperature. A reduction/oxidation mechanism of the reaction has been supposed comprising interaction between the surface active oxygen of the catalyst and HS^– and reoxidizing of the reduced catalyst by the dissolved oxygen. The results obtained show that the Ni-oxide system is a promising catalyst for practical application.     

Facile route to synthesis of functionalised poly(methylalkoxy)siloxane under mild and aerobic conditions in the presence of platinum catalysts

A facile and high yield method of synthesis of novel and functional poly(methylalkoxy) siloxanes is reported. The Si–H groups of poly(methylhydrogen) siloxanes (PMHS) were treated with various simple (primary, secondary, tertiary) alcohols (1a–10a) in the presence of platinum based catalysts (Speier’s and Karstedt’s catalysts). Also oxyethylene, aldehyde, epoxide, halogen and allyl grafted polysiloxane were smoothly and quantitatively prepared by the alcoholysis between linear siloxanes polymer and functional alcohols (11a–20a) with use of Karstedt’s catalysts. It is found that alcoholysis reaction in the presence of the Karstedt’s catalyst proceed faster than Speier’s catalyst .In addition, the rate of alcoholysis reaction is dependent on amount of the catalyst and reaction temperature. The polymers prepared were characterized by IR, NMR spectroscopy and GPC analysis.     

Hydrogenolysis of rice husk protolignin. II

It has been established that the partial hydrogenolysis of rice husk protolignin (RHP) takes place at a temperature of 180°C and an initial hydrogen pressure of 10 atm in an alkaline medium. Conditions have been selected under which the greatest yield of low-molecular-weight products (91% on the Komarov lignin) is obtained: hydrogenolysis in an alkaline medium in the presence of an anthraquinone (AQ) catalyst. The addition of AQ increases the yield of low-molecular-weight products by a factor of 1.8. Semiempirical formulas have been derived for incompletely hydrolyzed lignin residues. A study of the molecular-weight distribution of these lignins has shown that they are polydisperse. It has been established that in the process of hydrogenolysis AQ promotes the demethoxylation of structural units with syringyl nuclei.Institute of the Chemistry of Plant Substances of the Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 734–738, September–October, 1987.     

Temperature dependence of quantitative characteristics of chaotic regime in Belousov-Zhabotinskii reaction

In a Ferroin-catalyzed oscillatory Belousov-Zhabotinskii reaction, the temperature dependences of the largest Lyapunov exponent (LLE) and the induction period for a chaotic regime to appear are linear in the 285–308 interval when plotted on Arrhenius coordinates. For the LLE, the activation energies calculated for different concentrations of the catalyst are in the 82–126 kJ/mole interval, and for the induction period in the 61–95 kJ/mole interval. On the basis of the experimental data, it has been concluded that this autooscillatory chemical system, within a narrow range of catalyst concentrations, is relatively insensitive to random, small, external perturbations.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 2, pp. 186–190, March–April, 1993.The authors wish to thank K. B. Yatsimirskii, Academician of the Academy of Sciences of Ukraine, for discussing the data obtain in this work.     

Effect of Steam in CO2 Reforming of CH4over a Ni/CeO2–ZrO2–Al2O3 Catalyst

CO₂ reforming of CH₄ was carried out with and without steam over a Ni/CeO₂–ZrO₂–Al₂O₃ catalyst. The catalytic performance, amount of carbon deposit and the EXAFS of the Ni K-edge of samples were measured. The results show that when the catalyst is used for CO₂ reforming of CH₄ without the addition of steam, the catalyst gradually deactivates, however, addition of a small amount of steam to the feed gas can significantly inhibits the deactivation, which is due to the great suppression of coke formation on the catalyst during the reaction. The EXAFS result shows that, maybe due to the penetration of more carbon atoms into the Ni lattice, the coordination number of the nearest Ni–Ni of the sample after the reaction without steam reduces more than that of samples after the reaction with a small amount of steam in the feed gas.     

Effect of metals on the catalytic activity of sulfated zirconia for light naphtha isomerization

We studied on the function of the metal in the sulfated zirconia(SO₄^2–/ZrO₂) catalyst for the isomerization reaction of light paraffins. The addition of Pt to the SO₄^2–/ZrO₂ carrier could keep the high catalytic activity. The improvement in this isomerization activity is because Pt promotes removal of the coke precursor deposited on the catalyst surface. Though this catalytic function was observed in other transition metals, such as Pd, Ru, Ni, Rh and W, Pt exhibited the highest effect among them. It was further found that the Pd/SO₄^2–/ZrO₂–Al₂O₃ catalyst possessed a catalytic function for desulfurization of sulfur-containing light naphtha in addition to the skeletal isomerization. The sulfur tolerance of catalyst depended on the method of adding Pd, and the catalyst prepared by impregnation of the SO₄^2–/ZrO₂–Al₂O₃ with an aqueous solution of Pd exhibited the highest sulfur tolerance.Further, we investigated the improvement in sulfur tolerance of the Pt/SO₄^2–/ZrO₂–Al₂O₃ catalyst by impregnation of Pd. The results of EPMA analysis indicated that this catalyst was a hybrid-type one (Pt/SO₄^2–/ZrO₂–Pd/Al₂O₃) in which Pt/SO₄^2–/ZrO₂ particles and Pd/Al₂O₃ particles adjoined closely. This hybrid catalyst possessed a very high sulfur tolerance to the raw light naphtha that was obtained from the atmospheric distillation apparatus, although this light naphtha contained much sulfur. We assume that such a high sulfur tolerance in the hybrid catalyst is brought about by the isomerization function of Pt/SO₄^2–/ZrO₂ particles and the hydrodesulfurization function of Pd/Al₂O₃ particles. Besides, since the hybrid catalyst also provides high catalytic activity in the isomerization of HDS light naphtha, we suggest that the Pd/Al₂O₃ particles supply atomic hydrogen to the Pt/SO₄^2–/ZrO₂ particles by homolytic dissociation of gaseous hydrogen and also enhance the sulfur tolerance of Pt/SO₄^2–/ZrO₂ particles. Finally, we also propose the most suitable location of Pd and Pt in the metal-supported SO₄^2–/ZrO₂–Al₂O₃ catalyst.     

L-asparaginase bound in a polyacrylamide gel

Summary The enzyme L-asparaginase fromE. coli has been included in polyacrylamide gel, and some of its properties have been investigated: stability, pH dependence, heat stability, K_m. It has been shown that the enzymegel obtained has a better stability then the native enzyme.Institute of Organic Synthesis, Academy of Sciences of the Latvian SSR, Riga. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 382–384, May–June, 1976.     

Spectrophotometric analysis of stability of gold nanoparticles during catalytic reduction of 4-nitrophenol

Spectrophotometric monitoring of 4-nitrophenol (4-NP) reduction by sodium borohydride (NaBH₄) using gold nanoparticles (GNPs) as a catalyst has been extensively studied, but the stability of GNPs in terms of change in the surface plasmon resonance (SPR) at different temperatures has not been explored. In the present investigation, our aim was to evaluate the SPR stability of GNPs as a catalyst during the reduction of 4-NP at different elevated temperatures (i.e. 30–60 °C) and sodium borohydride concentrations. Sensitivity of this degradation process toward concentration of GNPs at a range of temperatures is also evaluated. The spectrophotometric results reveal that up to 45 °C, 12 ± 1.5 nm catalyst has a consistent optical density (OD) during the entire 4-NP reduction process, which is related to the surface integrity of catalyst atoms. As the temperature approached 50 °C, the OD gradually decreased and showed a blue shift as the reaction proceeded, which could be related to a decrease in particle size or surface dissolution of gold atoms. The present study may find application in the design of catalysts for the reduction of organic pollutants in industrial wastewater at a range of temperatures.     

Utility of the ion-pair formation for spectrophotometric determination of terfenadine in pure form and in some pharmaceutical formulations

A spectrophotometric procedure for the determination of terfenadine and a number of its pharmaceutical preparations has been developed that offers advantages of simplicity, rapidity, sensitivity and stability indication over the official USP (1995) method. The proposed method is based on the formation of ion-pairs by the reaction of terfenadine with some chromotropic acid mono- and bis-azo dyes. Different variables affecting the ion-pair formation were studied and optimized. At the maximum absorption of 557, 521, 592 and 543 nm, Beer's law is obeyed in the range 0.2–18.6, 0.2–16.4, 0.2–25.0 and 0.2–22.2 g ml^–1 on using reagents I, II, III and IV, respectively. The stoichiometric ratio and stability of each ion-pair were estimated and the mechanism of the reaction is discussed. The molar absorptivity and Sandell sensitivity of the produced ion-pairs were calculated in addition to Ringbom optimum concentration ranges. Statistical treatment of the experimental results indicates that the procedures are precise and accurate. Excipients used as additives in pharmaceutical formulations did not interfere in the proposed procedures. The reliability of the methods was established by parallel determination against the official USP method. The procedures described were successfully applied to the determination of the bulk drug and its pharmaceutical formulations by applying the standard addition technique.