The simultaneous activation of methane and carbon dioxide to C2 hydrocarbons under pulse corona plasma over La2O3/γ-Al2O3 catalyst

The pulse corona plasma has been used as an activation method for reaction of methane and carbon dioxide, the product was C₂ hydrocarbons and by-products were CO and H₂. Methane conversion and the yield of C₂ hydrocarbons were affected by the carbon dioxide concentration in the feed. The conversion of methane increased with increasing carbon dioxide concentration in the feed whereas the yield of C₂ hydrocarbons decreased. The synergism of La₂O₃/γ-Al₂O₃ and plasma gave methane conversion of 24.9% and C₂ hydrocarbons yield of 18.1% were obtained at the power input of plasma was 30 W. The distribution of C₂ hydrocarbons changed by using Pd-La₂O₃/γ-Al₂O₃ catalyst, the major C₂ product was ethylene.     

New polyanhydrides derived from C12,C13,C14,C15 dibasic acid: synthesis and characterization

Poly(dodecanedioic acid-tetradecandioic acid) (P(DDDA-TA)) copolymers and poly(brassylic acid-pentadecandioic acid) (P(BA-PA)) copolymers have been prepared by melt polycondensation of the corresponding mixed anhydride prepolymers derived from dodecanedioic acid, brassylic acid, tetradecandioic acid and pentadecandioic acid. The copolymers were characterized by FT-IR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), wide angle X-ray powder-diffraction, and thermal gravimetric analysis (TGA). In vitro studies showed that all the copolymers are degradable in phosphate buffer at 37 °C. The release profiles of hydrophilic model drug, ciprofloxcin hydrochloride, from the copolymers, follows first order release kinetics. All the preliminary results suggested that the copolymer might be potentially used as drug delivery devices.     

Catalytic reactions of C1 and C3 hydrocarbons in the presence of oxygen and oxygen-containing compounds

The reaction rates and selectivity of lower olefines formation in high temperature reactions, such as catalytic methane dehydrodimerization and catalytic pyrolysis of C₃ hydrocarbons are substantialy enhanced by oxygen and oxygen-containing compounds.     

C2 selectivity enhancement in oxidative coupling of methane over microwave-irradiated catalysts

The oxidative coupling of methane over Li/MgO and BaBiO_{3 - x} catalysts irradiated by microwaves and classically heated is reported. Enhanced selectivities in C₂⁺ products are observed at lower temperatures under microwave conditions, especially with the Li/MgO catalyst.

The complex permittivity measurements of BaBiO_{3 - x} show that the regeneration of the active oxygen species on the surface is lower under microwave irradiation than classical heating. X-ray diffraction analyses of the catalyst before and after catalytic reaction, when it is classically heated and when it is heated by microwave irradiation, corroborate these results. Therefore, the CH₃⁻ carbanions are less oxidated at the catalyst surface under microwave irradiation.

On the other hand, the quenching of the output gas probably decreases the oxidation of CH°₃ radicals in the gas phase when the Li/MgO catalyst is irradiated by microwaves. The quenching of the output gas is a unique consequence of microwave irradiation which heats the catalyst without heating the wall of the reactor.     

Photolytic hydrogenation of the polyynes C6H2, C8H2, C10H2, and C12H2 in n-hexane with 253.6 nm radiation

The polyynes C₆H₂, C₈H₂, C₁₀H₂, and C₁₂H₂ in n-hexane exposed to 253.6 nm radiation “disappear” much faster in air-free solutions than in solutions in equilibrium with air. These observations suggest that the disappearance is due to reaction of the polyyne molecules in the ground state with a photolytically produced chemical species which in solutions in equilibrium with air is overwhelmingly scavenged by dissolved O₂. Although no hydrogenation products were firmly established the most likely chemical is atomic hydrogen.     

CO, H2 or C3H8 assisted catalytic combustion of methane over supported LaMnO3 monoliths

The effect of the addition of a second fuel such as CO, C₃H₈ or H₂ on the catalytic combustion of methane was investigated over ceramic monoliths coated with LaMnO₃/La-γAl₂O₃ catalyst. Results of autothermal ignition of different binary fuel mixtures characterised by the same overall heating value show that the presence of a more reactive compound reduces the minimum pre-heating temperature necessary to burn methane. The effect is more pronounced for the addition of CO and very similar for C₃H₈ and H₂. Order of reactivity of the different fuels established in isothermal activity measurements was: CO>H₂≥C₃H₈>CH₄. Under autothermal conditions, nearly complete methane conversion is obtained with catalyst temperatures around 800 °C mainly through heterogeneous reactions, with about 60–70 ppm of unburned CH₄ when pure methane or CO/CH₄ mixtures are used. For H₂/CH₄ and C₃H₈/CH₄ mixtures, emissions of unburned methane are lower, probably due to the proceeding of CH₄ homogeneous oxidation promoted by H and OH radicals generated by propane and hydrogen pyrolysis at such relatively high temperatures.

Finally, a steady state multiplicity is found by decreasing the pre-heating temperature from the ignited state. This occurrence can be successfully employed to pilot the catalytic ignition of methane at temperatures close to compressor discharge or easily achieved in regenerative burners.     

Mechanism of formation of C2-oxygenated compounds from CO + H2 reaction over SiO2-supported Rh catalysts

The mechanism of acetaldehyde and ethanol formation from the CO + H₂ reaction below atmospheric pressure has been investigated by combining infrared spectroscopic measurement and ¹³CO and C¹⁸O isotopic tracer studies with reaction kinetics. The rates of acetaldehyde and ethanol formation are markedly dependent on the nature of metal precursors employed. The addition of sodium cations depresses the total catalytic activity, while the selectivity for ethanol is increased by the addition of manganese cations. From the behavior of surface species under reaction conditions, it is concluded that acetaldehyde is formed through the following two steps: (i) CO insertion into C₁ species which are reaction intermediates for not only hydrocarbons but also for the methyl group in acetaldehyde, and (ii) subsequent formation of acetate ions whose one oxygen atom is supplied from the support, finally producing acetaldehyde. Differences in ¹⁸O distribution in acetaldehyde and ethanol during the C¹⁸O + H₂ reaction indicate that ethanol is not produced via direct hydrogenation of acetaldehyde.     

Synthesis and structural investigation of new graphite intercalation compounds containing the perfluoroalkylsulfonate anions C10F21SO3, C2F5OC2F4SO3, and C2F5(C6F10)SO3

The preparation of graphite intercalation compounds (GIC’s) of three perfluorinated alkylsulfonate anions, C₁₀F₂₁SO₃⁻, C₂F₅OC₂F₄SO₃⁻ and C₂F₅(C₆F₁₀)SO₃⁻ is described for the first time. Pure stage 2 GIC’s are obtained by chemical oxidation of graphite with K₂MnF₆ in a solution containing hydrofluoric and nitric acids for 72 h. One-dimensional electron density maps derived from powder diffraction data are fit to obtain models for the intercalate interlayer regions (galleries) structures: the structure models provide details on anion concentrations, orientations, and conformations. In all cases, anion bilayers are observed with anion sulfonate headgroups oriented towards graphene sheets. Compared with structures calculated for the isolated anions, the intercalated anion conformations show changes in dihedral angles, involving rotations about C-C or C-O bonds. For the GIC containing C₂F₅(C₆F₁₀)SO₃⁻, the anion conformation change is related to the more efficient packing of anions in the intercalate gallery.     

Ni catalysts from NiAl2O4 spinel for CO2 reforming of methane

A series of mixed oxides close to NiAl₂O₄ was obtained by a sol–gel like method (propionic acid). The characterization of the different structures was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) or transmission electron microscopy (TEM). For the stoichiometric ratio of Ni to Al exactly equal to 0.5, homogeneous crystalline spinel phase was formed for a temperature of calcination equal or higher than 725 °C. A solid solution was obtained for a Ni/Al ratio lower than 0.5. The spinel structure is non-tolerant concerning a change of nickel to aluminum ratio higher than 0.5: an excess of nickel gives large particles of NiO on spinel phase. Comparative reduction and dry reforming of these oxides was made to control the formation of Ni and its sintering for applications in methane dry reforming. Preliminary reactivity results in dry reforming of methane are given.     

Solid solutions of C3A---Na2O in C12A7

This paper reports upon the research into the influence of sodium ions on C₁₂A₇. The actual research work consisted in synthesizing C₁₂A₇, treated with the sodium ions as Na₂CO₃, within the sodium concentration range of up to 25% Na₂O by weight in C₁₂A₇. The resultant combinations have been identified by the X-ray analysis, the infra-red spectroscopy and the quantitative chemical analysis.

The identification procedure together with the analysis of free CaO content in the products of C₁₂A₇ sodium synthesis gave evidence that sodium which is introduced into the researched amount of C₁₂A₇ up to 10% Na₂O by weight, contributes to the formation of the ever increasing phase of the solid solutions of Na₂O in C₃A. The continued increase of the sodium volume ( 15% Na₂O by weight ) makes it resolve gradually into sodium aluminate β -NA and free CaO.     

Free-radical reactions involved in C1-C3 hydrocarbons interaction with oxide catalysts

Experimental proofs of a free radical mechanism in methane oxidative coupling, with homolytic rupture of the C---H bond are given. High concentrations of free radical sites are produced by mechanical milling of SiO₂. A study of C₁---C₃alkanes interaction with these sites allows to simulate the, processes of alkanes oxidation and oxidative dehydrogenation. The reactivity of ethane and propane is higher than that of methane in accordance with the Polanyi-Semenov rule. Oxidative dehydrogenation of ethane is studied on Cd-containing zeolites. CH₄, C₂H₆ and C₃H₈ oxidative dehydrogenation by O₂ or CO₂ is studied on a MNO/SiO₂ catalyst. The initiation of radical reactions of hydrocarbons on Cl-containing catalysts proceeds via chlorine atoms generation.     

Molecular thermodynamics of solutions in the normal and critical regions — II. Activity coefficients for the ArN2, C2H6C2H4 and C3H6CO2 systems

Activity coefficients for the ArN₂, C₂H₆C₂H₄, and C₃H₆CO₂ systems are calculated from published vapour-liquid equilibrium compositions at various pressures and temperatures. The activity coefficients are correlated using a two parameter model based on the principles of molecular thermodynamics. The method is used both in the normal liquid and critical regions. The parameters of the model are shown to be reasonably independent of the temperature for the three systems.     

Evidence for C60 aggregation from solvent effects in [Ps-C60] molecular complex formation

Using a molecular probe positronium (Ps), Ps reaction rate constants (k) with C₆₀, a strong Ps acceptor, are determined for the formation of a donor-acceptor type molecular complex in solvents of varying surface tension (σ) and viscosity (η). Within the framework of Smoluchowski’s theory of diffusion, the calculated Stokes radius for C₆₀ in the different solvents deviated from the monomeric value, implying the existence of aggregated clusters in solution and using transmission electron microscopy, C₆₀ aggregation in carbon disulphide (CS₂) is observed with the formation of spherical fractal clusters of ∼90 nm size with aggregation number 1.7×10⁴ and a fractal dimension of 1.9 at a concentration of 0.5 mM. The fractal dimension of 1.9 revealed the mechanism of aggregation to proceed through a diffusion limited process with the estimated diffusion coefficient and the diffusion length of the aggregated cluster to be 2.27×10⁻⁶ cm²/s and 0.63 nm, respectively.     

La2NiO4 tubular membrane reactor for conversion of methane to syngas

La₂NiO₄ tubular membranes of relative density over 92% were used to separate oxygen from air and facilitate the partial oxidation of methane to H₂ and CO at 900 °C. When methane was fed into a tube of inner surface area 5.11 cm² at a rate of 10.5 ml/min, methane throughput conversion was 89%, CO selectivity 96%, H₂/CO ratio 1.5, and the equivalent oxygen flux was 6.8 ml/min. The surface of the La₂NiO₄ membrane exposed to CH₄ decomposed into La₂O₃ and Ni, while the surface in contact with air remained almost unchanged. It is suggested that the conversion of methane in the membrane reactor involves the reforming of methane by the H₂O and CO₂ catalyzed by nickel.     

Preparation of long-chain polyynes of C24H2 and C26H2 by liquid-phase laser ablation in decalin

The longest-chain polyyne that has ever been synthesized is C₂₄H₂ by Estmond et al. [1] using the complicated acetylene coupling method. On the other hand, in simple liquid-phase laser ablation method, we have recently obtained the longest-chain polyyne of C₂₂H₂. In the present study, we report the synthesis of long-chain polyynes of C₂₄H₂ and C₂₆H₂ from graphite pellets in solvent of decalin by liquid-phase laser ablation. It is believed that the termination reaction on both ends of these polyyne molecules hardly occurs in decalin with relatively less number of hydrogen atoms and these long-chain polyynes could be synthesized.     

Transformation of methane formation sites into methanol formation ones during CO---H2 reaction over Pd/CeO2 in its SMSI state

The phenomena of induction period of methanol formation, observed in CO---H₂ reaction over Pd/CeO₂ catalysts under SMSI state, was investigated in depth. The magnitude of the induction period was dependent on the extent of SMSI, and higher temperature H₂ reduction lengthened it accompanied with the increase of the number of active sites for methane formation. On the contrary, by the pretreatment of SMSI surface with water vapor, this induction period almost disappeared with the drastic decrease of methane formation rate. These results indicate that methane formation sites would be transformed into methanol formation sites by the oxidation of water vapor formed during CO---H₂ reaction. Infrared spectroscopic investigation of adsorbed CO after various pretreatments indicated that during the induction period thin layers of reduced ceria, which preferentially covered Pd(1 1 1) plane under SMSI state, were removed from the Pd(1 1 1) plane by formed water vapor during CO---H₂ reaction. It was concluded that Pd(1 1 1) plane adjacent to ceria would be the efficient active sites for methanol formation.     

C5/C9共聚石油树脂聚合工艺研究

以C₅/C₉馏分为原料,无水三氯化铝为催化剂,采用阳离子聚合法合成C5/C9共聚石油树脂。通过单因素条件实验和正交实验对C₅/C₉共聚石油树脂聚合工艺进行选择和优化,确定最佳的聚合工艺条件。实验得到的最佳聚合工艺为:催化剂用量为0.6%,聚合温度为50℃,溶剂比为0.7,C₅:C₉为2:3,反应时间为3h,此时树脂收率可高达49.14%。     

C_5/C_6烷烃异构化催化剂性能研究

研究分子筛种类、硅铝比、扩孔剂和晶粒大小及孔结构对C_5/C_6异构化催化剂Pd/分子筛性能的影响。结果表明,复合型、硅铝比在(18～22)的小晶粒分子筛能获得较好结果,分子筛载体成型时加入扩孔剂X,可进一步提高催化性能。对催化剂进行300 h稳定性测试,异构化性能始终保持稳定,无明显下降。