Kinetic and mechanistic features of carbon dioxide reforming of methane over Co–Ce/ZrO2 catalysts

Carbon dioxide reforming of methane (CDRM) is an effective route to utilize CO₂ and CH₄, the most abundant, thermodynamically stable and hazardous greenhouse gases. To overcome the economical impediments to favor CDRM's industrial applicability, its mechanistic features need to be revealed both for developing efficient catalysts and optimizing operational conditions. In this context, this work aims to obtain power-law type CDRM kinetic expressions over 5%Co–2%Ce/ZrO₂ and 10%Co–2%Ce/ZrO₂ catalysts and compare and analyze mechanistic routes to elucidate the effect of the Co:Ce ratio on kinetics. The empirical power-law type rate expressions were estimated with the reaction orders of 1.63 and 1.12 for CH₄ and 0.29 and –0.12 for CO₂ for 5%Co–2%Ce/ZrO₂ and 10%Co–2%Ce/ZrO₂ catalysts, respectively. Limited CH₄ activation and, thus, carbon formation due to low Co loading lead to accumulation of surface oxygen on ZrO₂ as redox ability of Ce becomes suppressed. This causes higher CO₂ activation barrier. The presence of H₂ in the feed slows down mechanistic steps involving CH_x. The reactions including CH₄ activation, most probably reversible direct CH₄ dissociation, are found to be rate determining.     

Syngas production by combined carbon dioxide reforming and partial oxidation of methane over Ni/α-Al_2O_3 catalysts

Ni/α-Al2O3 catalysts were found to be active in the temperature range 600 ～ 900℃ for both CO2 reforming and partial oxidation of methane.The effects of Ni loading,reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated.Catalysts of xwt%Ni/α-Al2O3(x=2.5,5,8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate.XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst,as compared with the other prepared catalyst samples.An increase of the Ni loading to more than 5wt% led to a reduction in the Ni dispersion.In addition,by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction,the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.     

Syngas production by combined carbon dioxide reforming and partial oxidation of methane over Ni/α-Al2O3 catalysts

Ni/α-Al2O3 catalysts were found to be active in the temperature range 600~900 ℃ for both CO2 reforming and partial oxidation of methane. The effects of Ni loading, reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated. Catalysts of xwt%Ni/α-Al2O3 (x = 2.5, 5, 8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate. XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst, as compared with the other prepared catalyst samples. An increase of the Ni loading to more than 5 wt% led to a reduction in the Ni dispersion. In addition, by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction, the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.     

Vapor-phase synthesis of isoprene from formaldehyde and isobutylene over CuSO4?MOx/SiO2 catalysts

Vapor-phase synthesis of isoprene from formaldehyde and isobutylene over CuSO₄–MO_x/SiO₂ catalysts has been studied. The results show that CuSO₄–MO_x/SiO₂ catalysts exhibit a good catalytic activity; especially when the metal oxides have appropriate basicity, is isoprene yield greatly enhanced. The results of product analysis indicate that there are side-reactions during isoprene production, which are isoprene hydrogenation, polymerization of isobutylene, copolymerization of isobutylene and isoprene, and reaction of C₅ aldehyde and ketone formed during isoprene production. In addition, catalytic behavior of the catalysts and probable mechanism of side-reactions are discussed.

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CuSO₄–MO_x/SiO₂. ; , . , , , , , , C₅ , . .

     

Kinetic simulation of oxidative dehydrogenation of n-butenes over SnO2?Sb2O4 catalysts

A previously suggested reaction mechanism was utilized to evaluate a kinetic model for the oxidation of n-butenes over ShSb=31 mixed oxide catalyst. With this model, kinetic curves measured at 673 K were simulated, illustrating the changes of amounts of undetectable surface components, too.

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- SnSb=31 . , 673 K, .

     

Estimation of kinetic parameters in oxidative dehydrogenation of n-butenes over SnO2?Sb2O4 catalysts

Kinetic curves measured in the oxidation of n-butenes over a SnSb=31 mixed oxide catalyst were fitted by the kinetic model put forward in a previous paper. The goodness of fitting shows that the kinetic behavior of this complex reaction system can be described by a mechanism involving acidic and redox sites on the catalyst surface.

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- SnSb=31 , . , , - .

     

Gas-phase measurements of the surface basicity of AlPO4?TiO2 and AlPO4?ZrO2 catalysts

The amount and strength of basic sites of AlPO₄–TiO₂ and AlPO₄–ZrO₂ catalysts over a different range of AlPO₄/metal oxide weight ratios were measured by studying the adsorption of acid molecules (acrylic acid and phenol) in the gas phase (473–673 K) by using the gas-chromatographic pulse method. The results obtained show that the basicity of AlPO₄–TiO₂ and AlPO₄–ZrO₂ catalysts is far lower than that of pure AlPO₄, and with an increase in the metal oxide (TiO₂ or ZrO₂) weight ratio, the basicity decreases. Besides, the basicity of AlPO₄–ZrO₂ is fairly low compared with that AlPO₄–TiO₂. In both cases, the total basicity (measured at 473 K vs. acrylic acid) gradually decreases with the calcination temperature while the stronger basic sites (measured at 573 K vs. phenol) remained unchanged up to calcination temperatures of 1073 K. Some weak surface basic sites remained in catalysts pretreated at 1273 K.

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- AlPO₄–TiO₂ AlPO₄–ZrO₂ AlPO₄/ , ( ) (473–673 K). , AlPO₄–TiO₂ AlPO₄–ZrO₂ AlPO₄ TiO₂ ZrO₂. , AlPO₄–ZrO₂ AlPO₄–TiO₂. — 473 K — , , 573 K , 1073 K. , 1273 K, .

     

Reduction of carbon dioxide by hydrogen on metal–carbon catalysts under supercritical conditions

The reduction of carbon dioxide with hydrogen on metal–carbon (Ru, Rh, Ir) catalysts is investigated under supercritical conditions for the first time. High selectivity (close to 100%) toward methanation with good stability of catalytic activity is observed for Ru- and Rh-containing catalyst, while the preferred reduction to CO is observed for Ir/C catalyst.     

Methanation of CO2 over Ru?SiO2 catalyst

Using Ru–SiO₂ catalyst, the kinetics of methanation of carbon dioxide has been studied. In the temperature range of 320–460°C a simple power law model is found to predict experimental results with a good agreement over the range of variables studied.

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Ru/SiO₂. , 320–460°C.

     

Unusual selectivity in photooxygenation of alkanes by air in CH3CN solutions catalyzed by CrCl3?C6H5CH2N(C2H5)3Cl

A new system CrCl₃–C₆H₅CH₂N(C₂H₅)₃Cl–CH₃CN for photooxygenation of alkanes is suggested. Unlike metal chlorides and oxocomplexes, it oxidizes alkanes to produce ketones and small amounts of alcohol. Adding of benzene, methylene chloride or ethanol to the cyclohexane solution rises the oxygenation rate and changes the ketone/alcohol ratio. With small amounts of hydroquinone the formation rate of cyclohexanone (but not of cyclohexanol) sharply decreases. Kinetic isotope effect in the oxidation of C₆H₁₂ and C₆D₁₂ is 1 for cyclohexanol and 2.9 for cyclohexanone. Cyclohexanol formation is assumed to follow a mechanism that does not involve free radicals. Free radicals can participate in the route toward ketone.

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CrCl₃–C₆H₅CH₂N(C₂H₅)₃Cl–CH₃CN . , . , /. ( ) . C₆H₁₂ C₆D₁₂ 1 2,9 . , , . , .

     

Catalytic performance in hydrodesulfurization of thiophene and ir investigation of Co and no adsorption over Co?Mo/Al2O3 and Ru?Co?Mo/Al2O3 catalysts

A new Ru–Co–Mo/Al₂O₃ catalyst has been prepared by impregnation of Ru salt as a secondary promoter onto Co–Mo/Al₂O₃ catalyst, and it was found that the Ru–Co–Mo/Al₂O₃ exhibited higher activity than Co–Mo/Al₂O₃ in hydrodesulfurization of thiophene to hydrocarbons. Ir studies on Ru–Co–Mo/Al₂O₃ revealed that the Co and NO adspecies increased significantly in intesnities and displayed a bathochromic shift in frequencies, as compared with Co–Mo/Al₂O₃.

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Ru–Co–Mo/Al₂O₃ Ru, , Co–Mo/Al₂O₃. Co–Mo/Al₂O₃. CO NO, Co Mo, Co–Mo/Al₂O₃. , Mo , Mo³⁺ Mo³⁺ Co Ru–Co–Mo/Al₂O₃.

     

Dielectric Barrier Discharge Initiated Gas-Phase Decomposition of CO2 to CO and C6–C9 Alkanes to C1–C3 Hydrocarbons on Glass, Molecular Sieve 10X and TiO2/ZnO Surfaces

Atmospheric Pressure Dielectric Barrier Discharge (APDBD) initiated decomposition of CO₂ and C₆–C₉ alkanes (in Ar carrier) with uncoated and TiO₂/ZnO coated glass surfaces, and under molecular sieve 10 X packing are presented in this study. Alkanes employed include 2-methylpentane, cyclohexane, n-hexane, n-heptane, n-octane, n-nonane and their decomposition products studied include C₁–C₃ hydrocarbons viz. CH₄, C₂H₄, C₂H₆ and C₃H₈. Generally the yields of all these C₁–C₃ products increased with discharge energy, however to a major extent the parent alkane structure controlled the relative concentration profiles of the individual products. Typically the slopes of the increase in various products yield varied from 0.025 to 0.25 ppm (v/v) mm V⁻¹. However, in the case of cyclohexane the total yield of methane, ethane and propane were only ∼20% of ethylene yield. Use of TiO₂ as well as TiO₂/ZnO coated central glass electrode in the APDBD apparatus showed ∼11% enhancement in degradation efficiency. However, while overall 2-methylpentane decomposition reduced significantly to ∼30%, in case of n-octane its decomposition to the C₁–C₃ products remained unaffected. On the other hand under molecular sieve 10X packing, yield of CH₄ and C₂H₄ increased significantly in both cases.     

Vapor phase methylation of pyridine with CO?H2 and CO2?H2 over a Ni catalyst

Pyridine was methylated selectively to 2-picoline with CO−H₂ and with CO₂−H₂ over a Ni catalyst. 2,6-lutidine was producedvia the methylation of 2-picoline.     

Oxidation of carbon monoxide over Cu1?xCrxCo2O4 in the presence of sulfur oxides

Carbon monoxide oxidation activity and aging of Cu_1–xCr_xCo₂O₄ (03+ (O_h) and Cu²⁺ (O_h) ions in the ternary spinels.

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Cu_1–xCr_xCo₂O₄ (03+ Co²⁺ .

     

Physicochemical properties and hds activity of CoMo?P?Al2O3 catalysts

Porous structure, acidity and hds activity of the CoMo–P–Al₂O₃ catalysts have been studied. Phosphorus was introduced jointly with molybdenum. This method of phosphorus incorporation gave substantial diminution of surface area, moderate changes of acidity and decrease in hds activity for the catalysts with P₂O₅ content higher than 5 wt.%.

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, CoMo–P–Al₂O₃. . , P₂O₅ 5 .%.

     

Alle 16 ges?ttigten Alkohole von C1 bis C5

Ohne Zusammenfassung     

Theoretical studies on anionic clusters of sulfate anions and carbon dioxide, SO 4?1/?2 (CO2)n, n?=?1?4

Geometry optimizations were performed on monoanionic and dianionic clusters of sulfate anions with carbon dioxide, SO₄^−1/−2(CO₂) _n , for n = 1–4, using the B3PW91 density functional method with the 6-311 + G(3df) basis set. Limited calculations were carried out with the CCSD(T) and MP2 methods. Binding energies, as well as adiabatic and vertical electron detachment energies, were calculated. No covalent bonding is seen for monoanionic clusters, with O₃SO–CO₂ bond distances between 2.8 and 3.0 ?. Dianionic clusters show covalent bonding of type [O₃S–O–CO₂]⁻², [O₃S–O–C(O)O–CO₂]⁻², and [O₂C–O–S(O₂)–O–CO₂]⁻², where one or two oxygens of SO₄⁻² are shared with CO₂. Starting with n = 2, the dianionic clusters become adiabatically more stable than the corresponding monoanionic ones. Comparison with SO₄^−1/−2(SO₂) _n and CO₃^−1/−2(SO₂) _n clusters, the binding energies are smaller for the present SO₄^−1/−2(CO₂) _n systems, while stabilization of the dianion occurs at n = 2 for both SO₄⁻²(CO₂) _n and SO₄⁻²(SO₂) _n , but only at n = 3 for CO₃⁻²(SO₂) _n .     

Ammoxidation of 3- and 4-picolines over V2O5?SnO2/γ?Al2O3 catalyst

The ammoxidation of 3- and 4-picolines has been studied over V₂O₅–SnO₂/–Al₂O₃ catalysts prepared by surface impregnation technique. Best results were obtained for the generation of cyanopyridines in the temperature range 400–450°C and sub-stoichiometric value with respect to O₂. Catalysts that were calcined above 700°C showed no activity.

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3- 4- V₂O₅–SnO₂/–Al₂O₃, . 400–450°C O₂. , 700 K, .

     

Syngas production from methane reforming with O2 and CO2 over Ni–La2O3/SiO2 catalysts using EDTA salt precursors

Ni–La₂O₃/SiO₂ catalysts (NLS) were prepared by the incipient-wetness impregnation method using EDTA salt precursors. XRD measurements revealed that the promoter of La₂O₃ is highly dispersed on the NLS. The TPR profiles indicated a strong interaction between NiO and La₂O₃ to form a La–Ni complex oxide like species over the NLS, which may be the origin of its high catalytic performance.