Hydrocarbons from synthesis gas; effect of Mg addition over Pd impregnated silica-alumina catalysts

The effect of Mg addition to Pd impregnated silica-alumina catalysts and the behavior of these catalysts in synthesis gas to hydrocarbons transformation have been studied. Measurements of H₂ chemisorption and temperature programmed NH₃ desorption allow us to consider that Mg addition to Pd containing catalysts increases the Pd dispersity, the support acidity not being modified. The presence of Mg enhances hydrocarbon production. Meanwhile, the hydrocarbon distribution is not modified. A large amount of light alkanes in the reaction products is obtained.     

Oligomerization of styrene over molybdenum oxide on silica-alumina catalyst

Styrene was found to yield saturated and unsaturated linear oligomers in the presence of a surface-supported catalyst, molybdenum oxide on silica-alumina. The reaction rates, the structure, and the molecular weight distribution of the products were found to be controlled by the choice of the solvent. Higher-molecular-weight fractions were favored in isooctane, whereas low-molecular-weight oligomers were preferred in dioxane. The reaction followed first-order kinetics with respect to the monomer. End-group analysis suggests a probable cationic mechanism. Approximate transfer constants K_trK_p were deduced from product distribution data. The behavior of the surface-supported catalyst was compared with other cationic catalyst systems.     

Investigation of n-hexane dehydrocyclization over supported Pt catalyst modified by adsorbed Pd

A -Al₂O₃ supported Pd–Pt bimetallic catalyst prepared by electrochemical metal adsorption has been tested in n-hexane dehydrocyclization. The Pd–Pt/Al₂O₃ catalyst, after calcination in oxygen followed by hydrogen treatment, showed higher activities and better selectivities for benzene and iso-hexane formation. The Pd–Pt/Al₂O₃ catalyst appeared to be less sensitive to the changes in the temperature of hydrogen treatment than the base Pt/Al₂O₃ catalyst.

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Re–Pt, -Al₂O₃, . -. , Re–Pt/Al₂O₃, , , , . , Pt/Al₂O₃.

     

Propane combustion over supported Pd catalysts

We prepared Pd catalysts supported on various metal oxides, viz. γ-Al₂O₃, α-Al₂O₃, SiO₂–Al₂O₃, SiO₂, CeO₂ and TiO₂ by an incipient wetness method and applied them to propane combustion. Several techniques: N₂ physisorption, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), CO chemisorption, temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPO) were employed to characterize the catalysts. Pd/SiO₂–Al₂O₃ showed the least catalytic activity at high temperatures among Pd catalysts supported on irreducible metal oxides, viz. SiO₂, Al₂O₃ and SiO₂–Al₂O₃. Pd/γ-Al₂O₃ was much superior for this reaction to Pd/α-Al₂O₃. The Pd catalyst supported on reducible metal oxides (CeO₂ and TiO₂) with a less specific surface area showed the higher catalytic activity compared with that supported on reducible metal oxides with a higher specific surface area, even though the former had a less Pd dispersion than the latter. In the case of Pd/SiO₂–Al₂O₃, the initially reduced Pd catalyst was superior to the fully oxidized one. The oxidation of metallic Pd occurred in the presence of O₂ with increasing reaction temperature, which resulted in the change in the catalytic activity.     

Effect of alumina in multicomponent bismuth phosphate catalyst supported on silica-alumina for propylene ammoxidation reaction

The effect of compositions of silica-alumina support on multicomponent bismuth phosphate catalyst (MBP) was investigated for the propylene ammoxidation. It is appears that small amounts of Al₂O₃ cause retardation of the ammoxidation reaction, which would be due to activation of the selective oxidation pathway. It is understood from such results that the catalytic action of the MBP is essentially different with that of the multicomponent bismuth molybdate catalyst (MBM), which is generally used as propylene ammoxidation catalyst. This revised version was published online in June 2006 with corrections to the Cover Date.     

Investigation of isomerization of n-pentane over supported Pt catalyst modified by adsorbed Bi and Pd

-Al₂O₃-supported Bi–Pt and Pd–Pt bimetallic catalysts were prepared by electrochemical metal adsorption. Isomerization of n-pentane was studied over these catalysts in a pulse reactor. It can be concluded from the results that the properties of these catalysts differ substantially from the base Pt/-Al₂O₃ catalyst. On the modified catalysts conversion and the yield of i-pentane was found to be lower although selectivity was better. The ratio of cracking reactions was also lower than over the base catalyst.It is very probable that the adsorbed bismuth was slowly desorbing from the catalyst surface during the experiments.

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Bi–Pt Pd–Pt -Al₂O₃. -, . , Pt/Al₂O₃. , - , . , . , .

     

Reduction of benzylideneaniline over supported Pd catalysts

In this work we have carried out a study on the liquid phase hydrogenation of benzylideneaniline, using dihydrogen over various supported Pd catalysts. Benzyl-ideneaniline reduction can be classified as insensitive to the catalyst structure. On the other hand, no compensating effect has been observed in performing the reaction over different supported Pd catalysts.

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Pd , . . Pd , .

     

Phase transition in niobium pentoxide supported on silica-alumina

Nb₂O₅ supported on SiO₂-Al₂O₃ were prepared with a wide loading range (2, 5, 10, 15, 20 and 25 mass%) and analyzed by simultaneous thermogravimetric (TG) and differential thermal analysis (DTA). The materials presented a phase transition close to 1364°C. This phase transition was studied by XRD, FTIR and Raman spectroscopy. Amixture of orthorhombic (T) andmonoclinic (H andM) crystalline phases was evidenced in the supported samples, which is coverage dependent, in contrast to the formation of only the monoclinic phase (H and M) when pure Nb₂O₅ is heated under the same conditions. These results indicate the stabilization of Nb₂O₅ on silica-alumina surface.     

Effect of catalyst confinement and pore size on Fischer-Tropsch synthesis over cobalt supported on carbon nanotubes

This paper studies the impact of structure of cobalt catalysts supported on carbon nanotubes(CNT) on the activity and product selectivity of Fischer-Tropsch synthesis(FTS) reaction.Three types of CNT with average pore sizes of 5,11,and 17 nm were used as the supports.The catalysts were prepared by selectively impregnating cobalt nanoparticles either inside or outside CNT.The TPR results indicated that the catalyst with Co particles inside CNT was easier to be reduced than those outside CNT,and the reducibility of cobalt oxide particles inside the CNT decreased with the cobalt oxide particle size increasing.The activity of the catalyst with Co inside CNT was higher than that of catalysts with Co particles outside CNT.Smaller CNT pore size also appears to enhance the catalyst reduction and FTS activity due to the little interaction between cobalt oxide with carbon and the enhanced electron shift on the non-planar carbon tube surface.     

无定形硅铝负载镍催化剂上乙烯齐聚反应的活性位点结构鉴定

镍(Ni)基催化剂在低碳烯烃聚合领域具有重要的地位,也是该领域研究的热点.自Johnson等报道(J.Am.Chem.Soc.,1995,117,6414–6415)二亚胺配体络合的Ni(Ⅱ)催化剂可有效降低烯烃聚合度,降低产物中非线性烯烃的选择性,甚至可以生成α-烯烃以来,掀起了Ni基催化剂在烯烃聚合领域的研究热潮.从均相到负载型多相Ni基催化剂,从载体类型到配体性质,从Ni纳米粒子的粒径调控到金属表面价态,关于Ni活性中心的研究工作一直存在争论.本课题组之前研究结果表明,曾明确了无定形硅铝(ASA)载体负载的Ni催化剂,经惰性气氛(N2)预处理得到的一价Ni是烯烃齐聚反应的主要活性中心(J.Chem.Soc.Chem.Commun.,1991,126–127).本文进一步深入研究了不同Al2O3含量的ASA载体上Ni活性位点的结构及其在乙烯齐聚反应中的活性.27Al NMR结果表明,催化剂中的铝存在三种配位方式,分别为AlⅣ、AlⅤ和AlⅥ,其中AlⅣ含量随Al2O3含量的增加而增加.载体中铝配位方式的不同,导致其表面金属负载的金属Ni活性位点所处的结构亦不同.原位FTIR-CO和H2-TPR实验结果表明,催化剂表面存在两种不同结构分布的Ni位点,分别是接枝在弱酸性硅醇上的Ni2+阳离子和Si?(OH)?Al桥式羟基离子交换位置的Ni2+阳离子.多数研究者认为,位于离子交换位置处孤立的Ni阳离子是反应的活性中心.然而,近期有研究者提出负载在酸性硅烷醇表面孤立的Ni2+阳离子为反应的活性中心物质.本文研究发现,随着Al2O3负载量的降低,处于离子交换位置处的Ni2+离子含量逐渐减少,而处于硅醇缺陷位点处的Ni2+离子含量则逐渐增多.原位FTIR-CO分析结果表明,处于硅醇缺陷位点处的Ni2+离子物种在惰性气氛中更易于转化为活性中心Ni+.相应的催化反应结果表明,相比于离子交换位置的Ni2+物种,具有与硅醇缺陷位点相连的Ni2+离子结构更有利于表现出更高的乙烯齐聚化活性.由此可知,处于硅醇缺陷位点的Ni2+物种是乙烯齐聚反应的活性中心的前驱体.本文进一步研究了硅醇缺陷位点处的Ni2+离子物种更易于转化为活性中心Ni+的原因.H2-TPR结果表明,相比于离子交换位置的Ni2+物种,处于硅醇缺陷位点的Ni2+物种与载体之间的相互作用力更弱.C2H4-TPD结果进一步表明,具有这种相对较弱的金属载体间作用力结构的催化剂对反应物C2H4分子的吸附作用力相对更强,吸附量也相对增多,因此其乙烯齐聚的催化性能更优.本研究结果对理解活性中心结构和合理设计催化剂提供参考.     

Toluene total oxidation over Pd and Au nanoparticles supported on hydroxyapatite

The total oxidation of toluene was carried out in a series of catalytic systems composed of either palladium or gold, as active phase, with hydroxyapatite as supports. The influence of different parameters on the catalytic reactivity was investigated: the type of support, the active phase content, the preparation method, and the nature of the active phase. Hydroxyapatite supports, impregnated by the active phase, showed better reactivities than that of the classical alumina one. Moreover, low palladium content (0.25 wt%) is enough to get high toluene conversions at low temperatures. Two preparation methods were used to introduce the active phase on the support: the conventional wet impregnation and the nanoparticle deposition achieved by impregnation of a colloidal suspension of the noble metal using the surfactant HEA16Cl. Introducing palladium by either of these methods leads to similar catalytic efficiencies. In addition to this, palladium is much more active than gold, gold was not probably present under the form of highly dispersed nanoparticles. X-ray Photoelectron Spectroscopy (XPS) evidenced PdO presence on the surface of all our catalysts. Palladium impregnated on apatite by conventional method showed an improvement of catalytic reactivity after 13 h under reacting mixture, probably because of Pd(0) formation besides PdO. As a result and after a literature survey, our catalysts could be classified among the most reactive systems towards total oxidation of toluene.     

Size effects in the CO-oxidation over supported Pd particles

Low pressure CO oxidation was studied over small supported Pd particles by means of static secondary ion mass spectrometry (SSIMS). The SSIMS spectra of adsorbed layers on Pd particles with diameters below ～7nm contained, besides other species, Pd _n X⁺ ions (X=C, O, CO;n=1–3). In experiments with Pd films, Pd _n C⁺ species were much less abundant or even absent from the mass spectra. We conclude that CO decomposed in appreciable amounts only on Pd particles. No significant influence of the support material (mica, MgO,α-Al₂O₃) was seen and posthumous TEM analysis revealed well defined particle morphologies with largely (111) and (100) facets. At total pressures below 10^?4 Pa, the relative carbidic intensities Pd _n C⁺/Pd _n ⁺ , which were taken as proportional to the carbon surface concentrations, first increased with increasing temperatures and then decreased after they passed a maximum at T=400–440 K. The smaller the particle size, the more intense were the maxima. For T ?440 K, carbon was removed from the surface via reaction with oxygen. Strong hysteresis effects in the C_ad and CO_ad concentrations occurred during temperature variation measurements. The Pd _n C⁺/Pd _n ⁺ ratios displayed maxima during heating but not during cooling. While the Pd _n CO⁺/Pd _n ⁺ ratios were always high at 300 K and always low at T>550 K, they were more intense in the medium temperature range when subjecting the samples to heating. These hysteresis effects are discussed in terms of asymmetric adsorption and reaction behaviour of CO/O₂ mixtures, involving inhibition of CO₂ formation by adsorbed carbon and carbon monoxide.     

Kinetics of phenol hydrogenation over supported palladium catalyst

Kinetics of vapor phase hydrogenation of phenol to cyclohexanone over Pd/MgO system has been studied in a flow microreactor under normal atmospheric pressure. The reaction rate is found to be negative order with respect to the partial pressure of phenol and has increased from −0.5 to 0.5 with increasing temperature (473 to 563 K). The apparent activation energy (E_a) of the process is found to be close to 65 kJ per mol. On the basis of kinetic results a surface mechanism is proposed.     

Graphyne-oxide supported Pd catalyst with ten times higher nitrobenzenes reduction activity than Pd/C

Research on Chemical Intermediates - Upon oxidation, a graphyne-like porous carbon-rich network (GYLPC), which is a two-dimensional carbon material consisting of sp- and sp2-hybridized carbon atoms...     

A sulfur-tolerant Pd/CeO2 catalyst for methanol synthesis from syngas

The catalytic activity of cefia-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditions. The bifunctional nature of this catalyst opens a route for the conversion of sulfur-contaminated gas streams such as the integrated gasification combined cycle syngas or biogas into liquid fuels if desulfurization by conventional means is not practical.     

Hydrogenation of chloronitrobenzenes over Pd and Pt catalysts supported on cationic resins

Liquid phase hydrogenation of chloronitrobenzene isomers (x-CNB x = 2, 3, 4) to the corresponding chloroanilines (x-CAN) at mild reaction conditions (0.6 MPa, 25°C, diethyl ether-methanol as solvents) over palladium and platinum catalysts containing 1 mass % of metal on trimethylammonium functionalized poly{styrene-co-divinylbenzene} (Dowex-D) was studied. The average selectivities to x-CAN over Pd/D-Cl and Pd/D-OH catalysts were 72 % and 42 %, respectively, at the x-CNB conversion of about 80 %. The average selectivities of 81 % and 84 % were achieved using Pt/D-Cl and Pt/D-OH, respectively, at the x-CNB conversion of approximately 90 %, whereas the average starting reaction rates were 1.2 × 10^?3 mol g^?1 s^?1 and 2.6 × 10^?3 mol g^?1 s^?1 (hydrogen consumption rate per mass of platinum), respectively. Under similar reaction conditions, using palladium catalysts supported on a resin with anionic groups anchored to polymeric chains at the average reaction rate equal to 3.8 × 10^?3 mol g^?1 s^?1 (hydrogen consumption rate per mass of palladium), the selectivities from 85 % (2-CAN and 3-CAN) to 95 % (4-CAN) were achieved (Kratky et al., 2002).     

Ni supported on activated carbon as catalyst for flue gas desulfurization

A series of Ni supported on activated carbon are prepared by excessive impregnation and the desulfurization activity is investigated. It has been shown that the activated carbon-supported Ni is an efficient solid catalyst for flue gas desulfurization. The activated carbon treated by HNO3 exhibits high desulfurization activity, and different amounts of loaded-Ni on activated carbon significantly influence the desulfurization activity. The catalysts are studied by X-ray diffraction (XRD) and X-ray photoelectr...     

Selective hydrogenation of acrylonitrile over a supported Ni catalyst

Acrylonitrile can be selectively hydrogenated into propionitrile at about 400 K over a ceramic-supported Ni catalyst. At low surface coverages, the observed rates of hydrogenation are proportional to the first powers of the partial pressures of both acrylonitrile and dihydrogen, in agreement with Langmuir-Hinshelwood kinetics.

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400 . , , -.

     

A new catalyst for direct synthesis of dimethyl ether from synthesis gas

A new catalyst has been prepared by coprecipitation sedimentation method developed in our laboratory. It exhibits excellent catalytic activity, selectivity and stability for conversion of synthesis gas to dimethyl ether: conversion of CO 92%, selectivity of dimethyl ether 98%. Catalytic properties of the catalyst show no evident change after being used for 100 h.     

Non-stationary effects during conversion of synthesis gas containing added oxygen over supported palladium catalysts

The promotion of hydrogenation of CO to methanol and dimethyl ether by oxygen over supported palladium catalysts increases with increasing oxygen content in the reaction mixture, but the system, becomes less stable with time. A high level of selectivity with respect to oxygen-containing compounds may be achieved by periodic introduction of oxygen into the synthesis gas.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 4, pp. 364–367, July–August, 1992.