Autocatalytic gas-phase dehydrogenation of ethane

Homogeneous gas-phase pyrolysis of ethane by continuous CO₂ laser irradiation was used in our experiments for bulk heating of the reaction mixture. Laser energy was absorbed by ethylene, the main product of ethane dehydrogenation, and transferred to the reaction medium via collisional relaxation. A mechanism of ethane dehydrogenation is suggested to describe the pyrolysis process. The mechanism is autocatalytic in respect of ethylene and includes ethane?Cethylene interaction with the formation of methyl and propyl radicals. Rate constants of elementary reactions, selectivity, and yields of pyrolysis products were determined. The composition of ethane dehydrogenation products determined in the experiments was substantially different from the calculated thermodynamic equilibrium composition.     

负载PtSn金属助剂的镁铝水滑石上的丙烷脱氢反应研究

我们研究了以镁铝水滑石作为载体,利用水滑石层间阴离子的可交换性,负载活性金属铂和锡的丙烷脱氢反应.在镁铝水滑石载体中加入Ga能够影响丙烷脱氢活性,当镓的含量为1%时催化剂丙烷脱氢反应活性最高,反应初始时,丙烷转化率为46.5%,反应2 h后,丙烷转化率仍有37.5%.当以Mg(Ga)(Al)O-1%为载体时,考察了不同H_2/C_3H_8摩尔比对丙烷脱氢活性的影响,结果表明当H_2/C_3H_8摩尔比为0.5∶1时,丙烷脱氢反应具有最佳的反应活性,即当在原料气中加入H_2时,能够使得丙烷脱氢的转化率大幅度提升,且选择性也有所提升.烷烃脱氢是一个吸热反应,同时考察了温度对烷烃脱氢反应性能影响,结果表明温度越高,丙烷脱氢反应具有更高的转化率.对催化剂进行长时间寿命实验考察,发现当反应经过40 h后,丙烷的转化率仍有23.5%,说明Pt Sn-Mg(Ga)(Al)O-1%催化剂具有较好的稳定性.     

The hetero‐homogeneous pyrolysis of propane,in the presence or in the absence of dihydrogen,and the measurement of uptake coefficients of hydrogen atoms

Propane pyrolysis is studied in the presence and the absence of dihydrogen between 743 and 803 K, in the propane pressure range 10–100 Torr, and at 20–254 Torr dihydrogen pressure. In unpacked Pyrex reactors, dihydrogen accelerates propane dehydrogenation and demethanation. The reaction is modeled by a conventional homogeneous free‐radical chain mechanism. Propane pyrolysis is strongly inhibited by the walls of reactors packed with stainless steel, zirconium, or palladium foils. Adding dihydrogen to propane still increases the rates of product formation. The reaction in these packed reactors is modeled by the kinetic scheme proposed for the homogeneous reaction and by the heterogeneous process H. ⇄ ½H₂ (w₂)(−w₂) of chain termination and initiation. In the absence of dihydrogen, step (−w₂) is negligible and precise values of uptake coefficients of hydrogen atoms are obtained at 773 K: 0.31 for stainless steel 0.10 for zirconium 0.05 for palladium In the presence of dihydrogen, steps (w₂) and (−:w₂) are instantaneously at equilibrium. The latter system should be useful to study any reaction of hydrogen atoms in the temperature range. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 340–364, 2000     

Autocatalytic gas-phase ethane dehydrogenation in a wall-less reactor

The thermal gas-phase pyrolysis of ethane was studied under conditions of the bulk heating of the reaction mixture with IR-laser radiation. The concentrations of ethane pyrolysis products as functions of reaction time were calculated in accordance with standard kinetic schemes; they showed that a classical radical chain mechanism corresponded to only highly dilute mixtures of ethane with an inert gas. As found by calculations, the experimental data on the kinetics of consumption of the initial substance and on the kinetics of buildup of pyrolysis products in undiluted mixtures of ethane and its conversion products were adequately described by an autocatalytic (with respect to ethylene) mechanism of ethane dehydrogenation. This mechanism involved the step of ethane interaction with ethylene to form methyl and propyl radicals.     

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection

Copper(II)-containing mordenite (CuMOR) is capable of activation of C−H bonds in C₁-C₃ alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with Cu^I sites, formed upon reduction of Cu^II-oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.     

Kinetic modeling of propane oxidation and pyrolysis

Propane oxidation in jet-stirred reactor was modeled using a comprehensive kinetic reaction mechanism including the most recent findings concerning the kinetics of the reactions involved in the oxidation of C₁? C₄ hydrocarbons. The present detailed mechanism is able to reproduce experimental species concentration profiles obtained in our high-pressure jet-stirred reactor (900 ? T/K ? 1200; 1 ? P/atm ? 10; 0.15 ? ? ? 4) and in a turbulent flow reactor at 1 atm; ignition delay times measured in shock tube (1200 ? T/K ? 1700; 2 ? P/atm ? 15; 0.125 ? ? ? 2); H-atoms concentrations measured in shock tube during the pyrolysis of propane and burning velocities of freely propagating premixed propane-air laminar flames. The computed results are discussed in terms of pressure and equivalence ratio (?) effects on propane oxidation. The same detailed kinetic reaction mechanism can also be used to model the oxidation of methane, ethylene, ethane, and propene in similar conditions. © John Wiley & Sons, Inc.     

Hetero-homogeneous pyrolysis of isobutane and platinum wall-effects in conditioned or unconditioned reactors

The pyrolysis of isobutane has been studied at 500°C in a “Pyrex” static reactor packed with platinum. It is shown that both dehydrogenation and demethanat on rates are strongly depressed by the metal packing. The reaction rates are very sensitive to the amount of cabonaceous coating which is deposited on the walls. As this amount increases, both rates first increase, go through a maximum and decrease. These observations are compared with those previously made on propane pyrolysis in a “Pyrex” reactor packed with stainless steel. The present results are interpreted on the basis of a hetero-homogeneous chain mechanism in which the selectivity of the free-radical reaction is not altered referring to the unpacked reactor. © 1994 John Wiley & Sons, Inc.     

Simultaneous propane dehydrogenation andco2hydrogenation overCrOx/SiO2catalyst

Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO₂(DH-CO₂) reactions in the presence and absence of the CrO_x/SiO₂ catalyst have been studied between 673 and 873 K. It was found that the CrO_x/SiO₂ catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO₂on CrO_x/SiO₂can be facilitated by the RWGS reaction.</o:p>     

Studies on the Mechanism of the Direct Synthesis of Styrene form Benzene and Ethylene

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Propane activation by MC5H5 (M = Ni and Co): An experimental and theoretical work

The reactions of MC₅H⁺₅ (M = Ni and Co) with propane in gaseous phase have been studied with an ion trap mass spectrometer; the MC₅H⁺₅ ions are able to activate the propane molecule which undergoes a dehydrogenation reaction. At variance with the reactions of the bare metal ions no loss of methane is observed; the reaction mechanism has been explored by means of DFT calculations and a possible explanation is offered for the different reactivity of these ligated ions.     

Kinetics of Oxidative Dehydrogenation of Propance over a VMgO Catalyst

The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550oC over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts for the dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at 10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, the only by-products were CO and CO2. The reaction rate of propane was found to be first order in propane and close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbon as the rate determining step. The activation energy of the conversion of propane was found to be 122±6 kJ/mol.     

Pyrolysis of propane in the presence of14C2H4 studied by the kinetic isotope method

The kinetic isotope method was used to explain the role of ethylene in the pyrolysis of propane. The mechanism of the radioactivity appearance in methane and propylene is proposed.     

Oxidative dehydrogenation of propane

At temperatures near 650°C and residence times ofca. 3 s, the homogeneous oxidative dehydrogenation (OXD) of propane to propylene and ethylene approached oxygen limiting conditions, even when the reactor was filled with quartz chips. The addition of catalysts that are known to be effective in the OXD of ethane slightly increased the reaction rate, but the selectivities at a given conversion level were the same as those that were achieved in the homogeneous reaction.     

The Dehydrogenation of Propane on Platinum–Tin Glass-Fiber Woven Catalysts

The reaction of propane dehydrogenation on platinum–tin catalysts supported onto different woven carriers (an aluminoborosilicate and two silica materials) was studied. It was found that the catalyst was rapidly deactivated by carbon deposits formed, and the rate of this reaction increased with the specific surface area of the glass-fiber woven material and the Pt content. It was established that the Pt: Sn ratio in surface platinum particles was about 6, and it increased to 39 after the reaction; this fact is indicative of a Sn loss, which led to an increase in the conversion of feed into carbon deposits that deactivated the catalyst. A mixture of propane and 5–10 vol % H₂ should be used for the stabilization of the catalytic system; in this case, the negative effect of hydrogen on the yield of propylene was minimal. On the catalyst supported onto a silica carrier under optimum conditions (550°C; propane space velocity, 480 h^–1), which correspond to minimum selectivity for the formation of carbon deposits, the yield of propylene was ~18%. The test glass-fiber woven catalyst was inferior to granulated platinum–tin catalysts in terms of catalytic activity; therefore, its use in the reaction of propane dehydrogenation is inexpedient.     

Features of propane conversion in the presence of SmVO<Subscript>3</Subscript> and SmVO<Subscript>4</Subscript>

Features of propane conversion in the presence of samarium vanadite and samarium vanadate, both produced via solid-phase synthesis, are studied. It is shown that SmVO₃ catalyzes mainly the propane cracking process to form methane and ethylene, while SmVO₄ equally accelerates both cracking and the dehydrogenation of propane. Based on the results from catalytic experiments, energies of activation are calculated for the thermal cracking of propane (104 kJ/mol) and the conversion of propane in the presence of SmVO₃ (39 kJ/mol) and SmVO₄ (42 kJ/mol). The thermal stability of SmVO₄ in a hydrogen atmosphere is studied via temperature-programmed reduction, while SmVO₃ stability in an oxidizing environment is studied by DTA. Energies of activation for the reduction of SmVO₄ (75 kJ/mol) and the oxidation of SmVO₃ (244 kJ/mol) are calculated using the Kissinger method.     

BiMo基复合氧化物催化剂丙烷直接氧化至丙烯醛研究

The effects of the available zoon above the catalyst bed on the performance of the catalyst were investigated. It has been suggested that propylene is an intermediate species in the reaction of propane to acrolein， and a two-step reaction scheme is proposed， the first step is oxidative dehydrogenation of propane to propylene in the gas phase then followed by the second step， the selective oxidation of propylene to acrolein on the surface of the catalyst. The performance of the catalyst depends on both the oxidative dehydrogenation of propane to propylene in the gas phase and the selective oxidation of propylene to acrolein on the catalyst surface. The thermal cracking， homogeneous oxidative dehydrogenation and heterogeneous catalytic dehydrogenation of propane as well as the selective catalytic oxidation of propane to acrolein over BiMoO based mixed oxides catalysts were studied. Under the optimum reaction conditions of propane dehydrogenation and selective oxidation of propylene， the selectivity and the yield of acrolein approached to 45mol% and 14mol%， respectively under about 30mol% propane conversion.     

Kinetics of the Oxidative Dehydrogenation of Propane over a VMgO Catalyst

The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550℃over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts forthe dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, theonly by-products were CO and CO2. The reaction rate of propane was found to be first order in propaneand close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with theactivation of the hydrocarbon as the rate determining step. The activation energy of the conversion ofpropane was found to be 122±6 kJ/mol.     

CATALYTIC CRACKING OF LIGHT ALKANES IN THE PRESENCE OF O_2 AND SELECTIVE CONTROL OF OLEFIN PRODUCTS

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Gallium-containing catalysts for oxidative dehydrogenation of organic compounds

A method was developed for introducing gallium into Mg-Al hydrotalcites—precursors of oxide catalysts for oxidative dehydrogenation of alkanes. Samples of oxide catalysts were synthesized that contained gallium oxide and also oxides of magnesium, aluminum, chromium, vanadium, molybdenum, and niobium in various combinations. The catalytic properties of the produced catalysts were studied in the oxidative dehydrogenation of ethane, propane, isobutane, and hexane. It was established that the addition of gallium to catalysts increases the ethylene and propylene yields in the oxidative dehydrogenation of ethane and propane. New hydroxo salts with a layered structure of the hydrotalcite type were synthesized: ternary magnesium gallium aluminum hydroxonitrate of variable composition [Al_{1 ? n} Ga _n Mg _m (OH)_{3 + 2m ? 1}][NO₃ · nH₂O] and quaternary magnesium gallium chromium aluminum hydroxonitrate of the composition [AlGaCrMg_1.8(OH)_11.6][NO₃ · nH₂O]; these salts were found to be isostructural.     

Pathways of liquefied petroleum gas pyrolysis in hydrogen plasma: A density functional theory study

A density functional theory (DFT) study has been conducted in this work to investigate the pyrolysis pathways of propane and n-butane, which are the main components of liquefied petroleum gas (LPG), for better understanding the pyrolysis behavior of LPG in hydrogen thermal plasma. Over 60 possible reactions are considered. The reaction enthalpies and activation energies of these reactions are calculated and analyzed with a Gaussian method of B3LYP and basic set of 6-31G (d,p). A most possible reaction pathway is brought up. According to this reaction pathway, the main products of LPG pyrolysis are acetylene, ethylene, methane, ethane and extra hydrogen. Acetylene mainly comes from the pyrolysis of propylene and ethylene, and hydrogen abstraction reactions are the main source of extra hydrogen gas. Active H· radicals are found to play a very important role in many reactions, and they can remarkably lower the energies needed for reactions.