On the reaction mechanism of CO2 reforming of methane over a bed of coal char

CO₂ reforming of methane was studied over a bed of coal char in a fixed bed reactor at temperatures between 1073 and 1223 K and atmospheric pressure with a feed composition of CH₄/CO₂/N₂ in the ratio of 1:1:8. Experimental results showed that the char was an effective catalyst for the production of syngas with a maximum H₂/CO ratio of one. It was also found that high H₂/CO ratios were favoured by low pressures and moderate to high temperatures. These results are supported by thermodynamic calculations. A mechanism of seven overall reactions was studied and three catalytic reactions of CH₄ decomposition, char gasification and the Boudouard reaction was identified as being of major importance. The first reaction produces carbon and H₂, the second consumes carbon, and the third (the Boudouard reaction) converts CO₂ to CO while consuming carbon. Equilibrium calculations and experimental results showed that any water present reacts to form H₂ and carbon oxides in the range of temperatures and pressures studied. Carbon deposition over the char bed is the major cause of deactivation. The rate of carbon formation depends on the kinetic balance between the surface reaction of the adsorbed hydrocarbons with oxygen containing species and the further dissociation of the hydrocarbon.     

Syngas production from biogas in a polygeneration process: Simultaneous partial oxidation and dry reforming in a piston engine

This work experimentally investigates the fuel-rich combustion of CH₄/CO₂/O₂ mixtures in a piston engine. The focus of the experiments is to determine suitable operating parameters in terms of stable engine operation, syngas production, CO₂ conversion, and avoiding soot emissions. In particular, the spark timing, CO₂ intake mole fraction, equivalence ratio, and compression ratio were varied. Results show stable spark-ignition operation over a wide range of the investigated parameters at a compression ratio of 10. Acceptable operation could be achieved within the spark timing limits of -38° to 10 °CA after top dead center, 7 to 27% CO₂ in the inlet and equivalence ratios from 2 to 2.5. A maximum H₂ yield of 62% could be achieved at an equivalence ratio of 1.9 and a CO₂ intake mole fraction of 4% at a compression ratio of 4.5. Spark time advancing from -10 to -38 °CA enhanced the dry reforming reaction and increased the hydrogen yield per methane from 38 to 45%. A significant influence of compression ratio on the amount of soot in the product gas was observed, showing that higher compression ratios increase soot formation.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Robust Multi-Objective Optimization for Response Surface Models Applied to Direct Low-Value Natural Gas Conversion Processes

The high proportion of CO₂/CH₄ in low aggregated value natural gas compositions can be used strategically and intelligently to produce more hydrocarbons through oxidative methane coupling (OCM). The main goal of this study was to optimize direct low-value natural gas conversion via CO₂-OCM on metal oxide catalysts using robust multi-objective optimization based on an entropic measure to choose the most preferred Pareto optimal point as the problem’s final solution. The responses of CH₄ conversion, C₂ selectivity, and C₂ yield are modeled using the response surface methodology. In this methodology, decision variables, e.g., the CO₂/CH₄ ratio, reactor temperature, wt.% CaO and wt.% MnO in ceria catalyst, are all employed. The Pareto optimal solution was obtained via the following combination of process parameters: CO₂/CH₄ ratio = 2.50, reactor temperature = 1179.5 K, wt.% CaO in ceria catalyst = 17.2%, wt.% MnO in ceria catalyst = 6.0%. By using the optimal weighting strategy w₁ = 0.2602, w₂ = 0.3203, w₃ = 0.4295, the simultaneous optimal values for the objective functions were: CH₄ conversion = 8.806%, C₂ selectivity = 51.468%, C₂ yield = 3.275%. Finally, an entropic measure used as a decision-making criterion was found to be useful in mapping the regions of minimal variation among the Pareto optimal responses and the results obtained, and this demonstrates that the optimization weights exert influence on the forecast variation of the obtained response.     

Dielectric barrier discharge plasma torch treatment of pyrolysis fuel oil in presence of methane and ethane

For the first time, atmospheric-pressure low-temperature plasma treatment of pyrolysis fuel oil (PFO) was investigated in dielectric barrier discharge (DBD) plasma torch reactor. Main parameters including working gas flow rate and Ar/CH₄ ratio along with the effects of separate Ar/C₂H₆ on the cracking of PFO were studied. By increasing the flow of argon and methane, the production rate of hydrocarbons containing ethane, ethylene, acetylene, propane, propylene, C₄, and C₅ increased from 1.72 to 10.48 ml/min for 4000 ml/min argon plus 400 ml/min methane as the working gas. In this case, the production rate of hydrogen increases from 10.58 to 56.86. The production rate of hydrocarbons increased from 3.53 to 13.5 ml/min by decreasing Ar/CH₄ ratio from 40 to 5.6. By changing the type of working gas from methane to ethane, the production of hydrocarbons considerably increased from 6.47 to 17.75 ml/min.     

XeCl laser ablation of polyetheretherketone

Ablation of polyetheretherketone (PEEK), a high temperature thermoplastic, by XeCl laser radiation occurs at fluences in excess of 0.07±0.01 J cm^–2. The volatile products of ablation are CO and C₂H₂ with smaller quantities of CH₄, C₄H₂, C₆H₆ and other C₃ and C₄ hydrocarbons. At fluences close to the threshold ablation produces involatile material of relatively high molecular weight but at high fluences extensive disruption of the PEEK structure occurs with conversion of all of the oxygen in the polymer to carbon monoxide.     

Performance of a tubular solid oxide fuel cell with model kerosene reformate gas

A performance of an anode-supported tubular Ni–8YSZ/Ni–ScSZ/ScSZ/GDC/LSC cell was investigated at 650–750 °C by feeding model kerosene reformate gas (H₂, H₂O, CO, CO₂, and CH₄) to a Ni–8YSZ/Ni–ScSZ anode. Variations of gas composition were observed not only between inlet and outlet of anode to estimate the degree of internal reforming, but also during current input by online quadrupole mass spectrometry and Fourier-transform infrared spectrometry.The electrochemical performance of the cell was independent of reforming temperature of kerosene, i.e. gas composition (in particular CH₄ concentration) at moderate anode gas flow rates. At open-circuit states, 10% or less methane in the kerosene-reformed gas was readily converted by steam or CO₂ over the Ni–8YSZ/Ni–ScSZ electrode so that gas compositions could almost follow the thermodynamic equilibrium at 650–750 °C. This suggests that the internal reforming should proceed almost completely over the Ni anode. Consumption of H₂ and CO and production of CO₂ were observed during current input. I–V characteristics remained constant at 650 °C as long as anodic W/F was more than 0.2 kg mmol^− 1 s. It was demonstrated that a catalytic activity of an anode electrode for hydrocarbons will be important for SOFCs with liquid fuels such as kerosene in order not to deteriorate cell performance.     

Formation of soot particles in pyrolysis and oxidation of aliphatic and aromatic hydrocarbons: Experiments and detailed kinetic modeling

Experiments on pyrolysis and oxidation of rich mixtures of various aliphatic and simple aromatic hydrocarbons in reflected shock waves have been performed. The mixtures C₂H₂/Ar, C₂H₆/Ar, C₂H₄/Ar, C₂H₄/O₂/Ar, CH₄/Ar, CH₄/O₂/Ar, C₃H₈/Ar, C₃H₆/Ar, toluene/Ar, and benzene/Ar were studied. The yield of soot and the temperature of soot particles were determined experimentally by the double-beam absorption emission method. The kinetic model of soot formation during the pyrolysis and oxidation of rich mixtures of aliphatic and aromatic hydrocarbons complemented with a set of nucleations of soot particles from both polyaromatic fragments and unsaturated aliphatic hydrocarbons was suggested. This kinetic model of soot formation was successfully tested. It describes the experimental literature data on the yield of the products of pyrolysis and oxidation of acetylene and diacetylene in a shock tube. The results of our experiments and kinetic calculations of the time, temperature, and concentration dependences are in good agreement for all hydrocarbons under study. All the kinetic parameters of the model remained strictly constant.     

生物油及生物质炭电催化制氢

报道了以生物质热裂解产物-生物油和生物质炭为原料,利用双固定床反应器和电催化水蒸气重整方法高效制氢过程研究．获得的最大绝对氢产率达到110.9 g H₂/1 kg干生物质,气相产物包括72%H₂、26%CO₂、1.9%CO和痕量的CH₄．研究了添加生物质炭对生物油制氢效果的影响,以及重整反应温度、通入催化床的电流等反应条件对生物油和生物质炭制氢效果的影响．结果表明,生物质炭的添加使绝对氢产率增加了大约20%～45%,提     

Sonochemical conversion of CO2 into hydrocarbons: The Sabatier reaction at ambient conditions

In this study, we investigated an alternative method for the chemical CO₂ reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO₂-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO₂ products were found to be mainly CH₄, C₂H₄ and C₂H₆ including large amount of CO which was subsequently converted into CH₄. We have found that introducing molecular H₂ plays a crucial role in the CO₂ conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO₂ + 98% H₂ led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO₂ present in a synthetic industrial flue gas (86.74% N₂, 13% CO₂, 0.2% O₂ and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -$C{O}_2+4H_2\stackrel{\mathit{Ultrasonication}}{\to }C{H}_4+2H_{2}O$ - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.     

Reactivity of surface OH in CH4 reforming reactions on Ni(1 1 1): A density functional theory calculation

The reactivity of surface OH in CH₄ reforming reactions was investigated by using density functional theory calculation. The key reaction pathway from CH₄ into syngas by surface OH follows CH₄ → CH → CHOH → CHO → CO, which is similar with the pathway induced by surface O in CO₂ reforming of CH₄ (CH₄ → CH → CHO → CO). Surface OH decreases the possibility of CH dehydrogenation into surface carbon. Compared to surface O and OH, surface H can eliminate surface carbon deposition more efficiently.     

Equilibrium conditions for the minimum coke formation during the dehydrogenation of propane

The equilibrium distribution of propane conversion products over temperature and pressure range of 700–1000 K and 0.05–0.25 MPa was determined. Calculations of the quasi-equilibrium composition of the gas phase without taking into account C_s formation demonstrated that, along with CH₄ and H₂, high-boiling C₁₄–C₃₆ aromatic hydrocarbons can be formed. The effect of H₂ on the composition was examined; it was shown that its excess with respect to propane required to ensure the zero yield of C_s increases with the temperature. Water vapor was demonstrated to influence the equilibrium composition of the products; conditions for the most effective reduction of the C_s yield were determined.     

The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

Mössbauer study of the evolution of a laterite iron mineral based catalyst: Effect of the activation treatment

The syngas reaction has been studied using a laterite iron mineral, promoted with K and Mn. In situ activation under syngas, as well as pre-treatment with H₂ followed by CO under mild and more severe conditions were tested. These activation procedures led to different iron phase compositions and to different catalytic selectivities. The C₂-C₄/CH₄ ratio was significantly lower for those catalysts which after reaction showed the presence of hexagonal carbide and magnetite compared to the solid, which showed the highest proportion of Hägg carbide.     

The Decomposition of Methane,Ethane, Ethylene and n-Butane in Electrical Discharges of Moderate Pressures

The decomposition of CH₄, C₂H₆, C₂H₄, and n-C₄H₁₀ has been investigated in radiofrequency plasmas operated at power levels of 1–8 cal cm^?3 sec^?1, 10–40 torr and flow rates of the hydrocarbons between 2 and 20 1 (STP) min^?1. It is shown that values of the rate constants are very close for all the hydrocarbons investigated and several orders of magnitude greater than those observed in their pyrolisis at comparable gas temperatures. Energy yields up to 30% can be observed for all hydrocarbons. It is suggested that the rate determining step for the decomposition process of all hydrocarbons investigated involves the rupture of a C-H bond in vibrotationally excited molecules.     

Comparison of CH4/H2 and C2H6/H2 inductively coupled plasma etching of ZnO

CH₄/H₂-based discharges are attractive for dry etching of single crystal ZnO because of their non-corrosive nature. We show that substitution of C₂H₆ for CH₄ increases the ZnO etch rate by approximately a factor of 2 both with and without any inert gas additive. The C₂H₆/H₂/Ar mixture provides a strong enhancement over pure Ar sputtering, in sharp contrast to the case of CH₄/H₂/Ar. The threshold ion energy for initiating etching is 42.4 eV for C₂H₆/H₂/Ar and 59.8 eV for CH₄/H₂/Ar. The etched surface morphologies were smooth, independent of the chemistry and the Zn/O ratio in the near-surface region was unchanged within experimental error after etching with both chemistries. The plasma etching improved the band-edge photoluminescence intensity and suppressed the deep level emission from the bulk ZnO under our conditions, due possibly to removal of surface contamination layer.     

Theoretical and experimental study of methane steam reforming reactions over nickel catalyst

In this work we perform DFT theoretical calculations of methane and steam interactions on Ni(1 1 1) surface. The calculations allow us to improve our understanding of the competition between these reactants by catalytic sites in methane steam reforming (MSR) process. For this purpose we compare theoretical results with kinetic measurements of MSR on a Ni(II)-Al(III) catalyst prepared from lamellar double hydroxides as precursor. This comparison shows that, for low H₂O/CH₄ ratios methane and water intermediate species adsorb on different catalytic sites. While CHO species adsorbs on top of Ni atom, OH one occupies preferentially a tri-coordinate surface site. On the other hand, for high H₂O/CH₄ ratios a competency between these species by Ni sites would establish, diminishing methane conversion. In addition competition between methane and steam for Ni sites would lead to a decrease in CO production. Nevertheless, intermediate species adsorbed on different active sites would produce CO₂, whatever the steam/methane ratio. Thus, it would be optimum steam concentration in hydrocarbon feed and active sites distribution on catalyst surface, which could maximize H₂ production and minimize CO selectivity. The theoretical findings agree with kinetic measurements, which show that maximum methane conversion depends on steam partial pressure in the feed; whereas always, selectivity to CO₂ increases and to CO diminishes.     

Lean or ultra-lean stretched planar methane/air flames

Lean premixed combustion has potential advantages of reducing pollutants and improving fuel economy. In some lean engine concepts, the fuel is directly injected into the combustion chamber resulting in a distribution of lean fuel/air mixtures. In this case, very lean mixtures can burn when supported by hot products from more strongly burning flames. This study examines the downstream interaction of opposed jets of a lean-limit CH₄/air mixture vs. a lean H₂/air flame. The CH₄ mixtures are near or below the lean flammability limit. The flame composition is measured by laser-induced Raman scattering and is compared to numerical simulations with detailed chemistry and molecular transport including the Soret effect. Several sub-limit lean CH₄/air flames supported by the products from the lean H₂/air flame are studied, and a small amount of CO₂ product (around 1% mole fraction) is formed in a “negative flame speed” flame where the weak CH₄/air mixture diffuses across the stagnation plane into the hot products from the H₂/air flame. Raman scattering measurements of temperature and species concentration are compared to detailed simulations using GRI-3.0, C₁, and C₂ chemical kinetic mechanisms, with good agreement obtained in the lean-limit or sub-limit flames. Stronger self-propagating CH₄/air mixtures result in a much higher concentration of product (around 6% CO₂ mole fraction), and the simulation results are sensitive to the specific chemical mechanism. These model-data comparisons for stronger CH₄/air flames improve when using either the C₂ or the Williams mechanisms.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

Inelastic atom scattering from layers of atoms and molecules on Cu(110)

The vibrational properties of adsorbed layers have been studied using inelastic He atom scattering. The substrate was Cu(110) viewed along the [001] and [11̄0] azimuth. The adsorbates included, Kr, Xe, CH₄, CD₄, C₂H₆, CO, CO₂ and O₂ and covered the region of both physisorption and chemisorption. Despite a range of binding energies and mass ratios the vibrational frequencies showed no dependence on the momentum change, i.e. scattering was dispersionless, although intensity changes occurred in the inelastic peaks. There seemed to be no dependence of the adsorbate spectra on coverage below a monolayer. The peaks of CH₄ and C₂H₆ appeared broader than those of Kr and Xe suggesting molecular motions. Further, CH₄ and C₂H₆ gave very similar spectra. Both energy gain and loss events were observed in the inelastic spectrum. For those adsorbates which gave multilayer adsorption (Xe, C₂H₆) changes in the spectra were observed as the second layer developed. In the latter category also, mixed layers (Xe on C₂H₆, Xe on CO and C₂H₆ on Xe) were studied.