Catalytic decomposition of light alkanes, alkenes and acetylene over Ni/SiO2

The decomposition of different hydrocarbons (CH₄, C₂H₆, C₂H₄, C₂H₂, C₃H₈, and C₃H₆) over Ni (5 wt.%)/SiO₂ catalysts was carried out. The initial rates of decomposition of the hydrocarbons, the kinetic curves of the decomposition and the kinetic curves of the hydrogenation of deposited carbon into methane depended on the types of hydrocarbons. In addition, the catalytic life of the Ni/SiO₂ catalyst was also dependent on the types of hydrocarbons, i.e. the life was longer according to the order, alkanes>alkenesacetylene.

The carbons deposited on the catalyst were characterized by SEM and Raman spectroscopy. The appearances of the deposited carbons were different among alkanes, alkenes, and acetylene, i.e. a zigzag fiber structure from methane, and a rolled fiber structure from alkenes and acetylene. From Raman spectra of the deposited carbons, it was found that the degree of graphitization of deposited carbon was higher in the order, alkanes>alkenes>acetylene. These results suggest that the mechanism of decomposition of hydrocarbons and the growth mechanism of carbon fibers on the catalyst were different among alkanes, alkenes and acetylene.     

Analysis of products of high-temperature pyrolysis of various hydrocarbons

Ethane, ethylene, acetylene, propane and neopentane have been pyrolyzed at 1173 K, and methane at 1372 K in a flow system, and the volatile pyrolysis products analyzed. Eleven aromatic hydrocarbons, containing 14 or fewer carbon atoms, accounted for 98 + % of the liquid products recovered in each case. Benzene was the main product, followed by naphthalene. No compounds with branched chains or multiple substituents were present, and compounds containing even numbers of carbons comprised 93–99% of each mixture. Acetylene was a major component of the gaseous effluent from each of the initial hydrocarbons. The effect of temperature on the composition of the gaseous effluent during pyrolysis of methane, ethane and ethylene was determined. Carbon film deposition from methane commenced at about 1273 K; from ethane at 1015 K and from ethylene at 1100 K, in each instance coinciding with the appearance of acetylene in the effluent. As the temperature was raised, at first the increase in the rate of carbon deposition closely followed the increase in the concentration of acetylene in the effluent. It is proposed that acetylene may be a common factor in the pyrolysis of aliphatic hydrocarbons, perhaps acting as the precursor of both surface carbon and aromatic hydrocarbons by a process of head-to-tail linkage of two-carbon units at active surface sites to form chains that then undergo dehydrogenation to carbon or cyclization and desorption as aromatic species.     

A direct catalytic conversion of natural gas to C2+ hydrocarbons by microwave plasma

Methane, the major constituent of natural gas, was converted to higher hydrocarbons by a microwave plasma. The yield of C2+ products increased from 29.2 % to 42.2% with increasing plasma power and decreasing flow rate of methane. When catalysts were used in the plasma reactor, the selectivities of ethylene and acetylene increased, while the yield of C2+ remained constant. Among various catalysts used, Fe catalyst showed the highest ethylene selectivity of 30 %. And when the actual natural gas was introduced, more C2+ products were obtained (46%). This is due to the ethane and propane in the natural gas. Applying electric field inductance for evolving the high plasma, we obtained high C2+ products of 63.7 % when Pd-Ni bimetal catalyst was used.     

Synthesis of carbon nanotubes on Ni/carbon-fiber catalysts under mild conditions

Methane, n-hexane, benzene, and cyclopentadiene were decomposed at a relatively mild temperature (773 K) over a Ni catalyst supported on either vapor grown carbon fibers (VGCF) or graphitized carbon fibers (GCF). Transmission electron microscopy showed that the morphology of the fibers changed according to hydrocarbon and particle size. Decomposition of methane and n-hexane produced fishbone-type fibers. The fibers from n-hexane sometimes showed intermittent hollow structures but the diameters of the fibers were widely distributed. Decomposition of benzene and cyclopentadiene mainly produced winding type carbon nanotubes of relatively uniform diameters (10-20 nm). Bidirectional fishbone-type fibers (fibers growing outward from a central catalyst particle) were also observed as a by-product. Small Ni particles (10-20 nm) with stretched tails were present on the tips of tubular fibers, some of which frequently changed growth direction. The varying tubular morphologies can be ascribed to liquid-like Ni particles resulting from the freezing point depression due to a fast dissolution of carbons during decomposition of benzene or cyclopentadiene. The formation of bidirectional fibers was also observed in the decomposition of n-hexane. Relatively large well-faceted Ni particles (diameter 50-110 nm) grew bidirectional fibers.     

Conversion of methane to higher hydrocarbons in pulsed DC barrier discharge at atmospheric pressure

Conversion of methane to C₂/C₃ or higher hydrocarbons in a pulsed DC barrier discharge at atmospheric pressure was studied. Non-equilibrium plasma was generated in the barrier discharge reactor. In this plasma, electrons which had sufficient energy collided with the molecules of methane, which were then activated and coupled to C₂/C₃ or higher hydrocarbons. The effect of the change of applied voltage, pulse frequency and methane flow rate on methane conversion, selectivities and yields of products was studied. Methane conversion to higher hydrocarbons was about 25% as the maximum. Ethane, propane and ethylene were produced as primary products, including a small amount of unidentified C₄ hydrocarbons. The selectivity and yield of ethane as a main product came to about 80% and 17% as the highest, respectively. The selectivities of ethane and ethylene were influenced not by the change of pulse frequency but by the change of applied voltage and methane flow rate. However, in case of propane, the selectivity was independent of those condition changes. The effect of the packing materials such as glass and A1₂O₃ bead on methane conversion was also considered, showing that A1₂O₃ played a role in enhancing the selectivity of ethane remarkably as a catalyst.     

Decomposition of methane over Ni catalysts supported on carbon fibers formed from different hydrocarbons

In order to get pure hydrogen without CO and CO₂, the decomposition of methane into hydrogen and carbon fibers (CF) over Ni/carbon catalysts has been investigated. The reason for the use of carbon materials as supports is to avoid a costly elimination treatment of the catalyst from the formed CF. The Ni/carbon catalysts prepared by the impregnation of various carbon materials with Ni(NO₃)₂ dissolved in acetone, followed by reduction in hydrogen at 573 K, showed better catalytic performance in the decomposition of methane than those prepared by the impregnation with aqueous Ni(NO₃)₂. The Ni(40 wt%)/CF(from 1-C₄H₈) showed the highest catalytic performance giving a C/Ni value (moles of deposited carbon per mole of Ni on the catalyst) of 1920 until complete deactivation of the catalyst. SEM and TEM images of the CF formed from methane indicated their thickness to be ≈10-150 nm with the same size of Ni particles at their tips at the early stage of the decomposition of methane, but the thickness changed to ≈40-100 nm at the final stage of decomposition. An estimate of the average size of Ni crystallites from XRD measurement suggested that the carbons deposited from methane on various Ni/CF would modify the size of Ni crystallites during the reaction. It is suggested that ≈20 nm Ni crystallites are most active for the growth of carbon nanofibers.     

电场增强低温等离子催化合成C_2烃

引　言目前 ,将甲烷直接转化为乙烷、乙烯、乙炔等碳二烃的主要方法有常规催化氧化偶联、膜催化、电化学反应、微波热裂解和等离子体反应[1] .大多数甲烷直接转化主要集中在氧化偶联反应 ,如催化转化甲烷和氧气合成乙烷和水 ,乙烷进一步生成乙烯和少量高碳烃 .生成的烃类 (乙烷、乙烯、乙炔和高碳烃 )常被称为Ｃ2 +.因为乙烯的市场需求大和价格高 ,所以乙烯是主要的目的产物 .除碳二烃外 ,还常易生成ＣＯ和ＣＯ2 .这不仅减少碳二烃的生成 ,而且是强放热反应 ,移出反应热是工业生产中很困难的工程问题 ,不利于反应进行 .甲烷偶联反应的目标是…     

Light alkanes CO2 reforming to synthesis gas over Ni based catalysts

The CO₂ reforming of methane and propane has been compared over two different Ni catalysts: one reference Ni/SiO₂ system and a Ni/Mg(Al)O hydrotalcite-derived catalyst, shown previously to display high catalytic stability for long term reforming. By combining the Tapered Element Oscillating Microbalance (TEOM), Temperature Programmed Hydrogenation (TPH), Transmission Electron Microscopy (TEM) and magnetic measurements, the formation of coke and its role on the catalyst activity has been investigated and compared for both hydrocarbons. It was found that Ni/SiO₂ and Ni/Mg(Al)O are both more active for methane reforming than for propane reforming. Coke formation is much more pronounced for propane than for methane over both catalysts. However, for both hydrocarbons a much faster carbon formation is observed over the Ni/SiO₂ catalyst than over the Ni/Mg(Al)O catalyst. The difference in the rates of coke formation for methane and propane is ascribed in the case of propane to partially dehydrogenated C₃ adspecies, which are good coke precursors. The superior stability of the hydrotalcite-derived catalyst is due to the strong interaction of the nickel phase with the support and the capacity of the support to activate CO₂ and channel oxygen to the nickel phase.     

Hydrogen production by decomposition of ethane-containing methane over carbon black catalysts

Mixtures of methane and small amounts of ethane were decomposed in the presence of carbon black (CB) catalysts at 1,073–1,223 K for hydrogen production. Although most of the added ethane was first decomposed to ethylene and hydrogen predominantly by non-catalytic reaction, subsequent decomposition of ethylene was effectively facilitated by the CB catalysts. Because some methane was produced from ethane, the net methane conversion decreased as the added ethane increased. The rate of hydrogen production from methane was decreased by the added ethane. A reason for this is that adsorption of methane on the active sites is inhibited by more easily adsorbing ethylene. In spite of this, the hydrogen yield increased with an increase of the added ethane because the contribution of ethane and ethylene decomposition to the hydrogen production was dominant over methane decomposition. A higher hydrogen yield was obtained in the presence of a higher-surface-area CB catalyst.     

Conversion of methane through dielectric-barrier discharge plasma

Methane coupling to produce C₂ hydrocarbons through a dielectric-barrier discharge (DBD) plasma reaction was studied in four DBD reactors. The effects of high voltage electrode position, different discharge gap, types of inner electrode, volume ratio of hydrogen to methane and air cooling method on the conversion of methane and distribution of products were investigated. Conversion of methane is obviously lower when a high voltage electrode acts as an outer electrode than when it acts as an inner electrode. The lifting of reaction temperature becomes slow due to cooling of outer electrode and the temperature can be controlled in the expected range of 60°C–150°C for ensuring better methane conversion and safe operation. The parameters of reactors have obvious effects on methane conversion, but it only slightly affects distribution of the products. The main products are ethylene, ethane and propane. The selectivity of C₂ hydrocarbons can reach 74.50% when volume ratio of hydrogen to methane is 1.50.     

Helical carbon nanofibers with a symmetric growth mode

Helical carbon nanofibers with a symmetric growth mode were synthesized by the decomposition of acetylene with a copper catalyst. There were always only two helical fibers symmetrically grown over a single copper nanocrystal. The two helical fibers had opposite helical senses, but had identical cycle number, coil diameter, coil length, coil pitch, cross section, and fiber diameter. The irregular tips and helical reversals of the two helical fibers further revealed the symmetric growth mode. This mirror-symmetric growth mode was induced by the shape changes in copper nanocrystals during catalyzing the decomposition of acetylene. Upon contacting the initial copper nanocrystals with irregular shapes, acetylene began to decompose to form two straight fibers (the irregular tips). At the same time, shape changes in copper nanocrystals began. Once they changed from an irregular to a regular faceted shape, the two straight fibers ceased to grow and two regular helical nanofibers with opposite helical senses began to grow. If the regular faceted nanocrystals continue to change shapes during fiber growth, the two helical fibers possibly changed helical senses at the same time, resulting in helical reversals. The shape changes were caused by the changes in surface energy resulting from the acetylene-adsorption on the copper nanocrystals.     

Catalytic synthesized carbon nanostructures from methane using nanocrystalline Ni

Carbon nanostructures synthesized with nanocrystalline Ni catalyst from decomposition of methane are investigated by means of transmission electron microscopy (TEM). Two kinds of carbon nanostructures, carbon fibers and bamboo-shaped carbon nanotubes, are observed. The preferential growth direction of graphene sheets depends on the reaction conditions. The bamboo-shaped carbon nanotubes can be obtained only if the reaction temperature is higher than 1000 K, and carbon fibers can be obtained at lower temperatures. The role and state of the catalyst particles are also discussed.     

Thermo-catalytic decomposition of waste lubricating oil over carbon catalyst

The thermo-catalytic decomposition of waste lubricating oil over a carbon catalyst was investigated in an I.D. of 14.5mm and length of 640mm quartz tube reactor. The carbon catalysts were activated carbon and rubber grade carbon blacks. The decomposition products of waste lubricating oil were hydrogen, methane, and ethylene in a gas phase, carbon in a solid phase and naphthalene in a liquid phase occurring within the temperature ranges of 700 °C-850 °C. The thermo-catalytic decomposition showed higher hydrogen yield and lower methane yield than that of a non-catalytic decomposition. The carbon black catalyst showed higher hydrogen yield than the activated carbon catalyst and maintained constant catalytic activity for hydrogen production, while activated carbon catalyst showed a deactivation in catalytic activity for hydrogen production. As the operating temperature increased from 700 °C to 800 °C, the hydrogen yield increased and was particularly higher with carbon black catalyst than activated carbon. As a result, carbon black catalyst was found to be an effective catalyst for the decomposition of waste lubricating oil into valuable chemicals such as hydrogen and methane.     

The effect of substituted alkynes on nickel catalyst morphology and carbon fiber growth

The growth of shaped carbon nanomaterials from a range of substituted alkynes over a NiO catalyst was investigated. It was found that the structure of the substituted alkyne affected both catalyst morphology and carbon fiber growth. For linear alkynes (1-pentyne to 1-octyne) the fiber morphology and yield varied with the type of alkyne used. It was also found that hetero-atoms (Cl, Br, OH and NH₂) greatly impacted carbon fiber growth and structure. An analysis of the catalyst particles associated with the carbon fibers grown from various alkynes showed that different alkynes gave differently shaped Ni catalyst particles. It was found that pre-treatment of the catalyst with an alkyne such as trimethylsilyl acetylene or ethynyl aniline (that did not give fiber growth), followed by treatment with acetylene initiated fiber growth morphologies (Y-junction, helical or straight fibers) different from that observed after direct treatment with acetylene. Further, sequential fiber growth from two alkynes that were both capable of producing fibers (e.g. methyl prop-2-ynoate followed by prop-2-yn-1-amine) resulted in ‘co-block’ fiber growth. These results highlight the dynamic relationships that exists between carbon source, catalyst morphology and carbon nanomaterial growth.     

Effect of the catalyst structure on the formation of carbon nanotubes over Ni/MgO catalyst

Ni/MgO solid solution catalyst was prepared by decomposition of nickel and magnesium nitrate using dielectric barrier discharge (DBD) plasma operated at atmospheric pressure and less than 175 °C. Well-defined lattice fringes of the Ni (111) plane are clearly observed in the plasma prepared Ni/MgO catalyst. The plasma prepared catalyst possesses fewer defects, compared to the catalyst prepared by thermal decomposition at elevated temperature. It results in a better balance between the carbon formation and the carbon nanotube (CNT) growth. The crystallinity of the Ni particle from thermal decomposition is more complex. It is difficult to distinguish the Ni planes with the thermal decomposed catalyst. CNTs from CO decomposition over the plasma made catalyst show a narrow diameter distribution with a high aspect ratio. The DBD plasma decomposition is a facile, simple and effective way for the preparation of Ni catalysts to fabricate high quality CNTs.     

KINETIC ANALYSIS OF COMPLEX REACTION SYSTEMS-METHANOL CONVERSION TO LOW MOLECULAR WEIGHT OLEFINS

An analysis of the selectivity data when converting methanol to low molecular weight hydrocarbons suggests that methane, propylene and propane are formed by the primary reaction of methanol decomposition, Ethane, carbon monoxide and dimethyl ether are formed by primary reactions and participate in secondary reactions. Carbon dioxide and ethylene are produced by secondary reactions.     

KINETIC ANALYSIS OF COMPLEX REACTION SYSTEMS-METHANOL CONVERSION TO LOW MOLECULAR WEIGHT OLEFINS

An analysis of the selectivity data when converting methanol to low molecular weight hydrocarbons suggests that methane, propylene and propane are formed by the primary reaction of methanol decomposition, Ethane, carbon monoxide and dimethyl ether are formed by primary reactions and participate in secondary reactions. Carbon dioxide and ethylene are produced by secondary reactions.     

Investigation on the structure and the oxidation activity of the solid carbon produced from catalytic decomposition of methane

The structure and the oxidation activity of the solid carbon produced from catalytic decomposition of methane at different temperatures were investigated using TEM, XRD, Raman and TPO techniques. The results show that the graphitization degree of the solid carbon is increased with decomposition reaction temperature. The addition of ethylene or acetylene to methane can change the growth way of the solid carbon and decrease their graphitization degree. The average oxidation temperature of the solid carbon has a close relationship with the corresponding graphitization degree. The addition of ethylene or acetylene to methane can decrease the average oxidation temperature of the solid carbon.     

等离子体射流裂解甲烷制乙炔的数值模拟

针对漏斗形射流反应器中热等离子体法裂解天然气制乙炔的过程进行研究.采用k-ε双方程模型对体系中的传递过程进行模拟,并通过甲烷裂解系列反应的宏观动力学模型对反应过程进行耦合.运用CFD方法进行数值求解,得到了反应器内的速度场、浓度场、温度场和反应速率分布.研究结果表明, 漏斗形结构有利于反应器中温度和浓度的良好混合,使得甲烷充分反应;甲烷与乙烯的裂解反应主要沿温度混合面进行,炭黑浓度则沿反应器轴向逐渐增多.对应于本反应器,在等离子体发生器功率为100 kW,甲烷体积流量为10 m³·h^-1时,甲烷转化率和乙炔收率同时达到最大.模拟结果与实验数据吻合较好,验证了模型与模拟结果的合理性.     

Catalytic filamentous carbon as supports for nickel catalysts

Ni catalysts supported on catalytic filamentous carbon (CFC) were studied in the model reaction of methane decomposition at 525 °C. The supports (CFC) were synthesized by decomposition of methane over metal catalysts (Ni, Ni-Cu, Co and Fe-Co-alumina) at 500-675 °C. The yield of secondary carbon was shown to reach 224 g/g_Ni on the Ni/CFC (Ni-Cu, 625 °C) catalyst. The stability and activity of the Ni/CFC catalysts for deposition of the secondary carbon at 525 °C depend both on textural properties of the support and on the surface structure of the CFC filaments. It seems that highly porous carbon supports are more suitable for development of Ni/CFC catalyst for methane decomposition. The catalytic properties of the supported Ni/CFC systems may be accounted for by generation of weak dispersive interactions between specifically shaped Ni crystallites 30-70 nm in size and basal planes on the surface of the carbon filament.