Hydrogenation of xylenes over supported Pt catalysts. Influence of different variables on their catalytic activity

In this work we studied and compared the catalytic activity of various supported Pt systems on the gas-phase hydrogenation of o-, m- and p-xylene. We analyzed the influence of different catalyst preparation variables (solvent, precursor, salt, support and catalyst reduction temperature used) on the catalytic activity and selectivity towards the corresponding cis-and trans-dimethylcyclohexanes.

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- o-, m- -. (, , ) - -.

     

Conversion of hydrocarbons on supported catalysts prepared via decomposition of surface complexes. Preparation and properties of (Ga+Pt)/SiO2 and (Ga+Pt)/Al2O3 catalysts

The addition of gallium is shown to increase Pt dispersity and its stability to deactivation in n-hexane dehydrocyclization, to decrease the rate of n-hexane hydrogenolysis and to increase the selectivity to benzene, apparently, due to the interaction of Pt clusters with surface Ga ions.

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, -, - . .

     

AlPO4?ZrO2 catalysts, II. Synthesis, textural properties and crystal structure of systems obtained in ethylene oxide

The effects of surface dehydration on textural properties, crystallinity and the structure of AlPO₄–ZrO₂ (weight ratio AlPO₄/ZrO₂=3) systems precipitated with ethylene oxide have been studied by N₂ adsorption and XRD measurements. The increase in calcination temperature in the range 773–1273 K decreases the textural parameters as a consequence of AlPO₄ crystallization to the tridymite form.

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, AlPO₄–ZrO₂ ( AlPO₄/ZrO₂=3), , N₂ - . 773 1273 , AlPO₄ .

     

Alumina as a nickel catalysts support for steam reforming of hydrocarbons

The coking resistance of six alumina supported nickel catalysts in n-butane steam reforming mainly depends on the average size of nickel crystallites. Thus, by using suitable preparative methods, it is possible to produce good, coking resistant nickel catalysts even with Al₂O₃ support.

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Al₂O₃ -, , . . ., , - Al₂O₃.

     

Catalytic incineration of n-hexane on Pt/Al2O3

The catalytic incineration of n-hexane over a Pt/Al₂O₃ catalyst has been studied using a fixed bed reaction. The reaction was carried out in dry air between 250 and 350 °C and at 1 atm pressure. The concentration of n-hexane was between 25 and 300 ppm. The reaction was found to be zero order in n-hexane concentration and the activation energy was found to be 21 kcal/mol. The zero order kinetics can be explained by a surface redox cycle known as Mars-van Krevelen mechanism in which the oxidation of surface Pt is the rate-controlling step.

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- Pt/Al₂O₃ . , 250–350°C 1 . - 25–300 .. - –21 /. , — , , , Pt.

     

Mechanism of NO adsorption and decomposition on ruthenium catalysts

Thermal desorption and IR spectroscopic studies of NO adsorption on disperse Ru-black and Ru/Al₂O₃ catalysts have revealed that NO is adsorbed as a surface nitrosyl, nitrite and nitrate complex, the stability of which depends on the temperature. A mechanism for the interaction of adsorbed NO with Ru catalysts is suggested.

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NO Ru Ru/Al₂O₃ , NO , , . (II) .

     

Silylation of porous glass supported platinum catalysts

Effect of silylation with hexamethyldisilazane on adsorption and catalytic properties of porous glass-supported platinum catalysts has been studied. Catalytic activity decreases markedly with an increase in surface coverage by trimethylsilyl groups for all the following reactions examined: hydrogenation of benzene, dehydrogenation of cyclohexane and dehydrocyclization of n-hexane.

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, . , : , -.

     

Measurement of the dispersity of supported ruthenium catalysts by oxygen chemisorption

A highly dispersed (Ø (Ru)<10 Å, from electron microscopy) Al₂O₃-supported catalyst and not so well dispersed silica supported Pt, Ru, Pt, Ru-alloy catalysts were investigated. Oxygen coverage of Ru is found to be close to 2 at 20 °C over the monometallic Ru catalysts as well as over the Pt, Ru-alloy catalysts.

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(Ø (Ru)<10 Å ) Al₂O₃ Pt Ru Pt Ru . Ru 2 20°C Ru, Pt Ru.

     

Influence of organic reagents on nickel alumina supported catalysts. II. hydrogenolysis of n-butane

The influence of organic reagents on the rate, selectivity and activation energy of n-butane hydrogenolysis has been studied. Increasing of the functional groups and coordination place in used organic reagents the caused higher mean values of reaction rates, activation energy and selectivity towards methane.

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, -. , .

     

X-ray study of palladium catalysts. Influence of thermal treatment in hydrogen on the phase composition

The thermal treatment of Pd catalysts in a reducing atmosphere of hydrogen leads to interaction of supported metal and support to form solid solutions.

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, .

     

The catalytic activity of Ni?V oxide catalysts

The activity and selectivity of Ni–V oxide catalysts in relation to the phase composition were investigated. The catalytic activity was measured in the oxidative dehydrogenation of methanol to formaldehyde and in the oxidation of SO₂ to SO₃.The oxide with the atom ratio gives the highest yield of formaldehyde and the slowest rate of SO₂ oxidation. The above phase, as shown by X-ray and IR measurements, has a specific structure characterized by a weakened V=O double bond.

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Ni–V . SO₂ SO₃. SO₂. , , , V=O

     

Poly(vinylpyridine) complexes of palladium as hydrogenation catalysts. Effect of polymeric ligand structure

The title complexes exhibit high catalytic activity, selectivity and stability in hydrogenation of allyl alcohol. The structure of a polymeric ligand (i.e. the position of the nitrogen atom in the pyridine ring) affects catalyst activity. According to the hydrogenation rates of allyl alcohol, the complexes studied are arranged in the sequence: P4VP-Pd>P2VP-Pd>P2M5VP-Pd.

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, - - . ( ) . : 4->2-Pd>25-.

     

Precipitation of iron catalysts for the Fischer-Tropsch synthesis

The batch Fischer-Tropsch wise precipitation of iron catalysts for the synthesis in the pH range of 4.60 to 7.91 is described in detail. Each step of the precipitation has been controlled by measurements of the relevant parameters to produce definite catalysts. Factors influencing the reproducibility are shortly discussed.

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- pH=4,60–7,91. . , .

     

Ammoxidation of halogen-substituted toluenes on V-P-oxide catalysts

The ammoxidation of various halogen-substituted toluenes on crystalline vanadium phosphate catalysts was investigated. The monophosphates and the NH₄VOP₂O₇ are transformed into new NH₄-containing V-P-oxides. The (VO)₂P₂O₇ used is stable in time on stream. These structures are very active and selective ammoxidation catalysts.

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. NH₄VOP₂O₇ V-P , NH₄. (VO)₂P₂O₇ . .

     

Solid aluminiumalkyl-based isomerization catalysts. Surface acidity and catalytic activity

Isomerization catalysts with high activity and selectivity were prepared by chemical anchoring of aluminiumethyldichloride on the surface of inorganic oxides. Surface acidity was studied by calorimetric and IR spectroscopy methods, and was found to correspond well with catalytic activity for m-xylene isomerization.

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. . , -.

     

Preparation and properties of high dispersity palladium catalysts

Preparation methods for monodisperse sols of palladium with 9, 15, 30 and 75 Å particles are suggested. It has been revealed that with decreasing size of palladium particles (d25 Å), the dissolved hydrogen species disappear. As a result, their behavior in dimethyl ethynyl carbinol hydrogenation is close to the platinum properties.

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9, 15, 30, 75 Å. , (d25 Å) , .

     

Selectivity of toluene disproportionation over zeolite catalysts

Three decationated zeolites (H-Y, H-ZSM-5 and H-ZSM-11) were tested in different conditions. Selectivities (to xylenes, S_x, and to para-isomer, S_p) were evaluated, together with activity, vs. time-on-stream. H-ZSM-5 proved to be the best catalyst, showing S_x1 and S_p-values larger than for the equilibrium gaseous mixture.

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(H-Y, H-ZSM-5 H-ZSM-11) . ( , S_x, , S_p) . H-ZSM-5 , S_x1 S_p, .

     

Influence of the preparation method of precipitated Fe?Mn catalysts on their properties in CO hydrogenation

Studies of the properties of precipitated Fe–Mn catalysts in CO hydrogenation have revealed that samples precipitated from iron and manganese nitrates by sodium carbonate are more selective to olefins than those precipitated by ammonia. Difference in the catalytic properties is due to the different phase compositions of the catalysts.

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CO , . , , , , . .

     

A method for preliminary estimation of solid oxidation kinetics and mechanism

The possibility of preliminary estimation of the oxidation kinetics and mechanism using the quantity t_o from the exponential kinetic rate equation is discussed.

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, t_o .

     

Temperature dependence of CO insertion on S-, Ag-, and Cu-promoted Rh/SiO2 catalysts

The addition of sulfur and silver to Rh/SiO₂ inhibits hydrogenation of C₂H₄, but promotes CO insertion and extends the linearity of Arrhenius curves for CO insertion above 543 K.

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Rh/SiO₂ C₂H₄, CO CO 543 .