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.     

Homogeneous gas-phase pyrolyses with a wall-less reactor. III. The oxygen–ethane reaction. A double reversal in oxygen and surface effects

The impact of surface and oxygen on the oxidative pyrolysis of ethane at temperatures above 590°C was studied using a wall-less reactor. At very low conversions under homogeneous conditions, ethene formation begins at the same temperature regardless of whether oxygen is present or absent. Between 0.00 and 0.13% conversion (592–632°C), the rate with oxygen is actually less than the rate in the absence of oxygen. A reversal occurs at about 633°C above which oxygen has a promoting effect. It is concluded that under homogeneous conditions the initiation step in the oxygen-promoted pyrolysis is the same as in the oxygen-free pyrolysis; therefore, initiation by direct attack of oxygen on ethane does not make an important contribution. The decrease in rate observed upon addition of oxygen implies the formation of the relatively unreactive HO₂ · radical. As conversion of the HO₂ · radical to the more reactive HO · radical becomes significant, the reaction is highly accelerated. If a stainless steel surface is added, the reaction is inhibited at higher conversions in the presence of oxygen. Again at low conversions, a second reversal occurs, and the stainless steel surface acts as a promoter below 649°C. The rate of surfacecatalyzed ethene formation at 590°C equals the rate of homogeneous ethene formation at 630°C.     

Autocatalytic dehydrogenation of propane

Homogeneous gas-phase pyrolysis of propane was performed by using continuous CO₂ laser irradiation for bulk heating of the reaction mixture. Laser energy was absorbed by ethylene, the main product of propane dehydrogenation, and transferred to the reaction medium via collisional relaxation. A mechanism of propane dehydrogenation is suggested to describe the pyrolysis process. The mechanism involves autocatalysis by ethylene and includes propane–ethylene interaction with the formation of ethyl and propyl radicals.     

High selectivity of oxidative dehydrogenation of ethane to ethylene in an oxygen permeable membrane reactor

An oxygen permeable membrane based on Ba0.5Sr0.5Co0.8Fe0.2O3-delta is used to supply lattice oxide continuously for oxidative dehydrogenation of ethane to ethylene with selectivity as high as 90% at 650 degrees C.     

Gas-phase pyrolysis of 2,2,3,3-tetramethylbutane using a wall-less reactor

The pyrolysis of 2,2,3,3-tetramethylbutane (TMB) has been studied using the wall-less reactor. Under homogeneous conditions up to 670°C, the activation energy is 43.2 kcal/mol and log A is 10.70. The products are 2-methylpropene, hydrogen, propene, 2-methyl-2-butene, ethane, ethene, methane, neopentane, and 2,3-dimethyl-2-butene in order of abundance. Addition of toluene, cyclopentadiene, or nitrous oxide to the system increases both the activation energy and the A factor; whereas oxygen decreases both the activation energy and the A factor. Incorporation of stainless-steel rods to provide surface has only a modest effect upon the rate. In view of this evidence, it appears that the homogeneous pyrolysis of TMB at higher pressures is a chain reaction under the described conditions.     

Photoinduced charge-transfer dehydrogenation in a gas-phase metal-DNA base complex: Al-cytosine

An Al-cytosine association complex has been generated via laser ablation of a mixture of aluminum and cytosine powders that were pressed into a rod form. The ionization energy of the complex is found to be 5.16 +/- 0.01 eV. The photoionization efficiency spectrum of Al-cytosine has also been collected. DFT calculations indicate that binding of Al to cytosine manifests a significant weakening of the N-H bond, predicted to have a strength of 1.5 eV in the complex, and a significant stabilization of the oxo tautomeric form relative to the hydroxy forms. The predicted ionization energy of 5.2 eV agrees well with the experimental value. The threshold for dehydrogenation/ionization of Al-cytosine, forming (Al-cytosine-H)+, is found to occur at photoexcitation energies between 11.4 and 12.8 eV. This is a two-photon process that is proposed to occur via photoinduced electron transfer from Al to an antibonding (sigma) orbital localized on N-H. In the context of this mechanism, this work constitutes the first time charge transfer between a metal and DNA base has been photoinitiated in the gas phase.     

Room temperature dehydrogenation of ethane to ethylene

The transient titanium alkylidyne, (PNP)Ti≡C(t)Bu (PNP = N[2-P(i)Pr(2)-4-methylphenyl](2)(-)), activates a C-H bond of ethane at room temperature, and a β-hydrogen of the resulting ethyl ligand is subsequently transferred to the adjacent alkylidene ligand to form an ethylene adduct of titanium. Treatment of the ethylene complex with two-electron oxidants such as organic azides results in extrusion of ethene concomitant with formation of a mononuclear titanium imido complex.     

Oxidative dehydrogenation of ethane over movmnw oxide catalysts

Catalysts based on mixed oxide of MoVMn are active at relatively low temperature for oxidative dehydrogenation of ethane. Incorporation of tungsten into MoVMn oxides enhances the catalytic activity. Enhancement of the activity is explained in the light of acid-base interaction accompanied with a redox mechanism of surface reoxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Oxidative dehydrogenation of propane in a dense tubular membrane reactor

Oxidative dehydrogenation of propane (ODP) to propylene was investigated in a dense tubular membrane reactor made of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) at 700^oC and 750^oC. The propylene selectivity in the membrane reactor (44.2%) is much higher than that in the fixed-bed reactor (15%) at the similar propane conversion (23-27%). Higher propylene selectivity in the membrane reactor was attributed to the lattice oxygen (O^2-) supplied through the membrane. This revised version was published online in June 2006 with corrections to the Cover Date.     

Oxidative dehydrogenation of ethane to ethene over a superbase supported LiCl system

<正>LiCl-promoted superbase catalysts were found to be stable and highly selective to ethene for oxidative dehydrogenation of ethane,giving 84%ethane conversion and 74%ethene yield at 923 K.Results indicated that the stronger the basicity of LiC1-based catalysts,the better the catalytic performance.     

Modification of VPO catalysts for oxidative dehydrogenation of ethane

Based on the previously discussed hypothesis concerning the mechanism of conversion of paraffins, we have modified the structure of VPO catalysts by developing the (220) plane of VOHPO₄·0.5H₂O and introducing a bismuth additive. We have shown that this leads to an increase in the P/V ratio on the surface, an increase in the number of Lewis centers and the strength of such centers, and a change in the ratio of Lewis centers to Brönsted centers. The change in the surface characteristics of the samples, in accordance with the hypotheses, improves their properties in oxidative dehydrogenation of ethane, increasing the catalytic activity and the yield of the target product ethylene.     

Energy-efficient dehydrogenation of methanol in a membrane reactor: a mathematical modeling

A two-dimensional non-isothermal stationary mathematical model of the catalytic membrane reactor for the process of methanol dehydrogenation is described. Copper supported on the carbonaceous support was considered as a catalyst. The reaction of methanol dehydrogenation was thermodynamically conjugated with a reaction of hydrogen oxidation taking place in a shell side of the membrane reactor. The effects of various parameters on the methanol conversion and the methyl formate yield have been calculated with the developed model and discussed. Two different types of heating the gas flow were considered and compared. In the case of conjugated dehydrogenation process, the methyl formate yield reaches 77%, when the reactor outer wall was heated up to 150 °C. When the inlet gas flows in the tube and shell sides were heated up to 100 and 83 °C, correspondingly, the yield was 72%.     

The role of water in promoting the oxidative dehydrogenation of ethane

The addition of water vapor has a strong positive effect on the rate of ethane oxidation at 575°C. This effect is attributed to the role of H₂O as a third body in the decomposition of H₂O₂ to OH radicals. Carbon tetrafluoride likewise enhances the rate of ethane conversion, although not to the extent realized with H₂O. A kinetic model, based on known elementary reactions, adequately accounts for the conversions and selectivities observed as a function of H₂O pressure, temperature, contact time, and O₂ pressure. © 1994 John Wiley & Sons, Inc.     

羟基化氮化硼催化乙烷氧化脱氢制乙烯

乙烯是最为重要的化工原料之一,目前其工业来源主要来自于烃类的水蒸汽裂解过程.该过程本质上是一个高温均相裂解过程,温度(>800?℃)高,能耗大,碳排放严重.乙烷氧化脱氢制乙烯属于放热反应,反应温度低,速率快,无积碳等限制,是一条更富有竞争力的工艺路线.然而,常用的金属或金属氧化物催化剂容易导致乙烯深度氧化,从而降低了乙烯选择性.纳米碳材料在烃类氧化脱氢反应中展现出一定的催化活性,但容易被氧化,难以用于反应温度高的乙烷氧化脱氢反应.本文报道了羟基化的氮化硼(BNOH)可高效催化乙烷氧化脱氢制乙烯.氮化硼边沿羟基官能团脱氢生成了动态活性位,从而引发了乙烷的脱氢反应.BNOH对乙烷氧化脱氢制乙烯显示出高选择性.当乙烷转化率在11%,乙烯选择性可高达95%;当乙烷转化率增加到40%,乙烯选择性保持在90%.重要的是,当乙烷转化率超过60%时,BNOH仍然可保持80%的乙烯选择性以及50%的乙烯收率.这些性能指标与现有工业乙烷水蒸气裂解过程运行性能相当.进一步优化反应条件,BNOH催化剂能够实现高达9.1 gC2H4 gcat-1 h-1的时空收率.经过200 h的氧化脱氢反应测试,BNOH催化剂活性和选择性基本恒定,表明其具有非常好的稳定性.X射线粉末衍射结果显示,反应前后BNOH催化剂的物相没有发生变化.透射电子显微镜测试证实,反应后BNOH催化剂的形貌和微观结构也没有明显改变.X射线光电子能谱结果显示,反应200 h后BNOH催化剂表面的氧含量仅从反应前的6.9 atom%微增到8.3 atom%.1H固体核磁共振谱测试显示,反应200 h后,BNOH催化剂上羟基含量无明显改变.结合原位透射红外光谱和同位素示踪实验,初步确定了BNOH催化剂上引发乙烷氧化脱氢反应的活性中心.氮化硼边沿的氧官能团并不能引发乙烷的氧化脱氢反应,而羟基官能团才是氧化脱氢反应发生的活性位.在乙烷氧化脱氢条件下,分子氧脱除羟基官能团上的氢原子动态生成BNO·?和HO2·?活性位.密度泛函理论计算表明,乙烷首先在BNO·?或HO2·?位活化生成乙基自由基,这些中间物进一步与气相氧物种发生反应脱氢生成乙烯.动力学测试结果也验证了上述实验和理论结果.     

Modeling of a radial-flow moving-bed reactor for dehydrogenation of isobutane

A mathematical model for the performance of a radial-flow moving-bed reactor for dehydrogenation of light paraffins was developed. Assuming relevant kinetic expressions for the main reaction and catalyst deactivation, the kinetic parameters were obtained through lab-scale fixed-bed reactor testing using the integral method of analysis. The conversion was found to be a function of a dimensionless decay time, i.e., the ratio of a “catalyst deactivation time constant” to the residence time of the catalyst within the reactor. For a large dimensionless decay time (negligible catalyst decay), the performance equation approached that of a simple packed-bed reactor. The predictions of the model were compared with those of a commercial unit, and fair agreements were observed.     

Oxidative dehydrogenation of ethane and propane on CuTh oxide catalysts

CuThO oxides prepared with different atomic ratios Cu/Th have been tested in the oxidative dehydrogenation of ethane and propane. These catalysts are active and selective in the formation of ethene and propene, but the activity and selectivity change with the nature of the alkane.     

Oxidative dehydrogenation of ethane over sufated zirconia supported oxides catalysts

The oxidative dehydrogenation of ethane into ethylene has been investigated on metal oxide-based sulfated zirconia catalysts at temperatures of 400–600°C. It is found that the activity and selectivity toward ethylene depend on the nature of metal oxide and temperature and that Ni and V oxides supported on sulfated zirconia exhibited higher ethylene yields.     

NbMCM-41 mesoporous molecular sieves in oxidative dehydrogenation of ethane and propane

It has been evidenced that the dissolution of niobium in silica mesoporous matrix significantly increases the catalytic effectiveness in the oxidative dehydrogenation of alkanes as compared with unsupported Nb₂O₅. This revised version was published online in June 2006 with corrections to the Cover Date.     

Theoretical investigation of the gas-phase reaction of NiO+ with ethane

To explore the mechanisms for Ni-based oxide-catalyzed oxidative dehydrogenation (ODH) reactions, we investigate the reactions of C₂H₆ with NiO⁺ using density functional calculations. Two possible reaction pathways are identified, which lead to the formation of ethanol (path 1), ethylene and water (path 2). The proportion of products is discussed by Curtin-Hammett principle, and the result shows that path 2 is the main reaction channel and the water and ethylene are the main products. In order to get a deeper understanding of the titled reaction, numerous means of analysis methods including the atoms in molecules (AIM), electron localization function (ELF), natural bond orbital (NBO), and density of states (DOS) are used to study the properties of the chemical bonding evolution along the reaction pathways.