Ignition of methane and propane in high-temperature oxidizers with various oxygen concentrations

In this investigation, ignition processes of methane (CH₄ > 98%) and propane (C₃H₈ > 95%) using a high-temperature oxidizer (T_oxi > T_ai) with a varying oxygen concentration (z_O2=0.05÷0.21), applying two types of experimental installations, viz. a constant-volume bomb (CVB) and a co-flow reactor (CFR) were investigated. The influence of the initial temperature of the oxidizer (for methane T_oxi = 960 ÷ 1234 K and for propane T_oxi = 803 ÷ 1055 K), the equivalence ratio and oxygen concentration in the oxidizer on ignition of gaseous fuels is analyzed and discussed. It is shown that in order to achieve an effective reaction of ignition (taking into account the minimum value of ignition delay time τ_ig and maximal value of the increment of temperature ΔT) the oxidizer temperature need not be maximized. There are optimal values of temperature of the oxidizer (for methane T_oxi ≈ 1100 K and for propane T_oxi ≈ 950 K) in which the parameters mentioned above reach their extreme values.     

Ethene/ethane mixture diffusion in the MOF sieve ZIF-8 studied by MAS PFG NMR diffusometry

The adsorption and diffusion of ethene/ethane mixtures is explored by ¹H and ¹³C MAS NMR spectroscopy and by the combination of PFG NMR with magic-angle spinning (MAS PFG NMR). Some indication for a preferential adsorption of the molecules close to the methyl-groups of the imidazole-rings was found, however no evidence for structural changes upon adsorption of an ethene/ethane mixture.MAS PFG NMR allows an individual but simultaneous observation of both molecules in adsorbed state and as well as in the gas phase. The intracrystalline MAS PFG NMR diffusivities are in consistent agreement with our previous data obtained by IR microscopy. Our consideration includes the loading dependence and the correlation of self-diffusion with transport diffusion by accounting for the influence of the thermodynamic factor.The diffusion selectivity is determined to D_ethene:D_ethane = 5.5 at a loading of four molecules per cavity. The higher mobility of ethene can be rationalized by its smaller size compared to ethane. This conclusion is validated by the measured activation energies for diffusion which are considerably higher for ethane. On the other hand, differences in the guest-host interaction between the saturated and non-saturated molecules can be excluded as possible reason for the different diffusivities.     

An investigation of the causes of the difference in coal particle ignition temperature between combustion in air and in O2/CO2

The ignition temperatures of a Loy Yang brown coal and a Datong bituminous coal were investigated in a wire-mesh reactor where the secondary reactions of the evolved volatiles were minimised. An increase in the average particle ignition temperature of 21 °C was observed for the brown coal when air (21% O₂ + 79% N₂) was replaced with a mixture of 21% O₂ + 79% CO₂. Combustion was also carried out in the mixtures of 21% O₂ + 79% argon and 21%O₂ + 79% helium in order to determine the effects of heat transfer on the observed particle ignition temperature. It is concluded that the thermal conductivity of gas atmosphere surrounding the particles greatly influences the observed particle ignition temperature while the effects of the heat capacity of the gas atmosphere was very minor under our experimental conditions. The structure of char and the reactions involving the char (char-O₂ and char-CO₂) can greatly affect the observed particle ignition temperature. In particular, the char-CO₂ reactions were largely responsible for the observed difference in particle ignition temperature in air and in 21% O₂ + 79% CO₂. Alkali and alkaline earth metallic (AAEM) species in the brown coal also significantly affect the observed particle ignition temperature.     

Kinetic modeling of oxidative coupling of methane over Mn/Na2WO4/SiO2 catalyst

A comprehensive kinetic model for oxidative coupling of methane (OCM) on Mn/Na₂WO₄/SiO₂ catalyst was developed based on a microcatalytic reactor data. The methane conversion and ethylene, ethane, carbon monoxide and carbon dioxide selectivities were obtained in a wide range of operating conditions including 750 < T < 875 °C, 4 < CH₄/O₂ < 7.5 and space time between 30 and 160 kg · s/m³ at P = 657 mmHg. The reaction networks of five kinetic models with appropriate rate equation type were compared together. The kinetics rates parameters of each reaction network were estimated using genetic algorithm optimization method. After comparing the reaction networks, the reaction network presented by Stansch et al. was found to best represent the OCM reaction network and was further used in this work. This kinetic network considers both catalytic and gas-phase as well as primary and consecutive reaction steps to predict the performance of the OCM. Comparing the experimental and predicted data showed that presented model has a reasonable fit between the experimental data and the predicted values with average absolute relative deviation of ± 9.1%.     

Computer simulation for storage of methane and capture of carbon dioxide in carbon nanoscrolls by expansion of interlayer spacing

We perform a molecular simulation study on methane and carbon dioxide storage in carbon nanoscrolls. The effects of temperature and pressure, interlayer spacing, VDW gap and innermost radius on the gas storage have been examined extensively. It is found that the adsorption of gases on pristine carbon nanoscrolls is relatively low. However, once the interlayer spacing is expanded, both adsorption capacities of methane and carbon dioxide exhibit a significant improvement. In particular, the excess uptake of methane reaches 13 mmol/g at p = 6.0 MPa and T = 298.15 K and VDW gap Δ = 1.1 nm, which is about 3.5 times of uptake of the pristine carbon nanoscrolls; while the uptake of carbon dioxide could also be raised by 294.9% at T = 298.15 K and p = 3.0 MPa and Δ = 1.5 nm, reaching 30.21 mmol/g at 6.0 MPa. This work demonstrates that carbon nanoscrolls with an expansion of interlayer spacing may be a suitable material for methane storage and carbon dioxide capture.     

Hydrothermal gasification of olive mill wastewater as a biomass source in supercritical water

In this study, the hydrothermal gasification of biomass in supercritical water is investigated. The work is of peculiar value since a real biomass, olive mill wastewater (OMW), is used instead of model biomass compounds. OMW is a by-product obtained during olive oil production, which has a complex nature characterized by a high content of organic compounds and polyphenols. The high content of organics makes OMW a desirable biomass candidate as an energy source. The hydrothermal gasification experiments for OMW were conducted with five different reaction temperatures (400, 450, 500, 550 and 600 °C) and five different reaction times (30, 60, 90, 120 and 150 s), under a pressure of 25 MPa. The gaseous products are mainly composed of hydrogen, carbon dioxide, carbon monoxide and C₁-C₄ hydrocarbons, such as methane, ethane, propane and propylene. Maximum amount of the gas product obtained is 7.71 mL per mL OMW at a reaction temperature of 550 °C, with a reaction time of 30 s. The gas product composition is 9.23% for hydrogen, 34.84% for methane, 4.04% for ethane, 0.84% for propane, 0.83% for propylene, 49.34% for carbon dioxide, and 0.88% for minor components such as n-butane, i-butane, 1-butene, i-butene, t-2-butene, 1,3-butadiene and nitrogen at this reaction conditions.     

Production of bio-oil from fixed bed pyrolysis of bagasse

The objective of this work was to produce renewable liquid fuel (bio-oil) from locally produced bagasse by pyrolysis in a batch feeding and fixed bed reactor. The experiments were performed at different temperatures ranging from 300 to 600 °C. The bio-oil was collected from two condensers of different temperatures and defined as oil-1 and oil-2. The maximum total yield of bio-oil was found to be 66.0 wt% based on bagasse. The carbon based non-condensable gases were CO, CO₂, methane, ethane, ethene, propane and propene. The density and viscosity of oil-1 were found to be 1130 kg/m³ and 19.32 centipoise and that were 1050 kg/m³ and 4.25 centipoise for oil-2, respectively. The higher heating values (HHV) of them were 17.25 and 19.91 MJ/kg, respectively. The pH of the bio-oils was found to be around 3.5 and 4.5 for oil-1 and oil-2, respectively. The water, solid and ash contents of oil-1 and oil-2 were determined and found to be around 15, 0.02 and 0.03 wt% and 11, 0.01 and 0.02 wt%, respectively based on bagasse.     

Effect of La-doping on the properties of CaCu3Ti4O12 dielectric ceramics

Nano-size Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ (χ = 0.00, 0.05, 0.10, 0.15 and 0.20) precursor powders were prepared via the sol–gel method and the citrate auto-ignition route and then processed into micro-crystal Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics under heat treatment. Characterization of the as-obtained ceramics with XRD and SEM showed an average grain sizes of ∼1–2 μm, indicating La³⁺ amount to have little impact on grain size. The room-temperature dielectric constant of the Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics sintered at 1000 °C was of the order of 10³–10⁴ despite the variation of χ values. Compared with CaCu₃Ti₄O₁₂, La³⁺-doped CaCu₃Ti₄O₁₂ showed a flatter dielectric constant curve related to frequency. It was found that the loss tangent of the Ca_1−χLa_2χ/3Cu₃Ti₄O₁₂ ceramics was less than 0.20 in ∼600–10⁵ Hz region, which rapidly decreased to a minimum value of 0.03 by La³⁺doping with χ = 0.05. Our measurement of the ceramics conductivities (σ) also indicated that the appropriate introduction of La³⁺ into CaCu₃Ti₄O₁₂ would distinctly result in its dielectric properties.     

Non-oxidative methane coupling using Cu/ZnO/Al2O3 catalyst in DBD

Non-oxidative methane coupling into higher hydrocarbons was investigated in dielectric-barrier discharge (DBD) conditions using a stationary catalytic bed (Cu/ZnO/Al₂O₃). The experiments were carried out at the frequency of about 6 kHz, at 240 °C, at the pressure of ∼1220 hPa and with the overall gas flow rate 2 NL/h (0 °C, 1013 hPa). The effects of gas composition on the conversion, the effect of packing on the obtained products and activity of the catalyst under plasma conditions during long-term experiments were studied. Hydrocarbons from 2 to 5 atoms of carbon were identified in the outlet gas. It was found that in the presence of catalyst in plasma zone, overall methane conversion decreased, however the conversion towards ethane was higher, as compared to the process without packing.     

Catalytic test of supported Ni catalysts with core/shell structure for dry reforming of methane

Supported nickel catalysts with core/shell structures of Ni/Al₂O₃ and Ni/MgO-Al₂O₃ were synthesized under multi-bubble sonoluminescence (MBSL) conditions and tested for dry reforming of methane (DRM) to produce hydrogen and carbon monoxide. A supported Ni catalyst made of 10% Ni loading on Al₂O₃ and MgO-Al₂O₃, which performed best in the steam reforming of methane (97% methane conversion at 750 °C) and in the partial oxidation of methane (96% methane conversion at 800 °C), showed also good performance in DRM and excellent thermal stability for the first 150 h. The supported Ni catalysts Ni/Al₂O₃ and Ni/MgO-Al₂O₃ yielded methane conversions of 92% and 92.5%, respectively and CO₂ conversions of 95.0% and 91.8%, respectively, at a reaction temperature of 800 °C with a molar ratio of CH₄/CO₂ = 1. Those were near thermodynamic equilibrium values.     

An experimental study of biomass ignition

An experimental study has been conducted to determine the ignition temperature of biomass at 21% O₂, both under pulse ignition conditions and under thermogravimetric conditions. In the pulse ignition experiments, samples of about 2 g wheat straw were placed in an isothermal reactor. The ignition temperature was determined from the transient CO and CO₂ profiles to approximately 255 °C at a superficial gas velocity of 14 cm/s (STP). The ignition temperature increased for decreasing superficial gas velocity.Thermogravimetric experiments at 20% O₂ and heating rates of 5 °C/min with finely milled biomass indicated ignition temperatures of approximately 220 °C for wheat straw, 235 °C for poplar wood, and 285 °C for eucalyptus wood. These values are significantly lower than values obtained for coal under similar conditions and confirm the relationship between volatile matter content and ignition temperature previously reported for coal.A mechanistic model for ignition of biomass is proposed. We believe that the ignition process is initiated by oxidation reactions on the straw surface. These reactions raise the surface temperature above that of the surrounding gas and promote ignition of the volatiles. Once ignited, the volatiles may form a homogeneous diffusion flame away from the particle surface. The superficial gas velocity affects the particle heating rate as well as the transport of oxygen to the surface. For this reason the ignition process is not entirely controlled by kinetics at low temperatures.     

The Fischer-Tropsch reaction on a cobalt (0001) single crystal

The Fischer-Tropsch reaction is studied on a cobalt (0001) single crystal. Under the reaction conditions (1 bar synthesis gas; H₂CO = 21;T=250 °C) methane is the major product, with lesser amounts of heavier hydrocarbons. It is shown that the readsorption and subsequent hydrogenation of initially formed ethene is an important pathway to ethane. The activation energies for methane, ethane and propane formation are equal, which suggests that the rate-determining steps are similar.     

Modeling effect of the biodiesel mixing ratio on combustion and emission characteristics using a reduced mechanism of methyl butanoate

This paper describes a modeling study on the effects of the mixing ratio of biodiesel derived from rice on combustion and emission characteristics. In order to model ignition and combustion processes, a combined mechanism of methyl butanoate and n-heptane was used after modifying some reaction constants. The oxygen content of rice oil was maintained at the measured value (11 vol.%) by assuming that one mole of rice oil was composed of one mole of methyl butanoate and two moles of n-heptane. The fuel property library of the KIVA code was expanded to include physical properties such as density and surface tension of rice oil (i.e., biodiesel). In addition, a discrete multi-component fuel evaporation model was employed to model the fuel injection, atomization, and evaporation.Calculated pressure histories and carbon monoxide (CO) and hydrocarbon (HC) emissions of the present study agreed reasonably with experiments at a 100 MPa injection pressure and a 10° BTDC injection timing for D100, BD20, and BD40. However some discrepancies were observed in predicting nitrogen oxide (NO_x) emissions. The effect of the start of injection timing on fuel consumption and CO emissions were also studied.     

Influence of the presence of chlorine on the selectivity to ethane and ethene during methane coupling over samarium-based catalysts

The oxidative coupling of methane to ethane and ethene has been investigated on chlorine-containing catalysts. The sensitivity of the product distribution to temperature, gas composition, flow-rate, catalyst mass, and reactor dimensions has been demonstrated. It has been found that a long contact time is an important factor in raising the C₂H₄/C₂H₆ ratio, and that reactions within the catalyst bed are important for the conversion of ethane to ethene. Back-mixing of the reagents into the gas space above the catalyst bed tended to lead to combustion, but appeared to have little influence on enhancing the C₂H₄/C₂H₆ ratio. Experiments have been performed with Sm₂O₃, SmOCl and SmCl₃ and with various pairs of these catalysts when separated by a gas space. These experiments have demonstrated the importance, under certain circumstances, of gas phase chlorine species, especially radicals, in the conversion of ethane to ethene. However, the results also show that these chlorine-induced gas phase reactions occur within the voids between the particles in the catalyst bed and not in the free gas space outside the catalyst bed.     

Oxidative desulfurization of Gas oil by polyoxometalates catalysts

Several polyoxometalates: Na₂HPM₁₂O₄₀, H₃PM₁₂O₄₀, Na₂HPM₁₂O₄₀, (VO)H[PM₁₂O₄₀] and (n-Bu₄N)₃[PM₁₂O₄₀] (M = Mo and W) as well as (n-Bu₄N)_3 + x[PW_12−xV_xO₄₀] (x = 0–3) were synthesized and characterized. Benzothiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene were used as model sulfur compounds in gas oil. The oxidation reaction was performed using different polyoxometalates as catalyst and H₂O₂/acetic acid. The experimental results show that the W-based polyoxometalate catalysts are more active than the Mo catalysts. The oxidation reactivity of the catalysts depends on the type of countercation: Na⁺ > H⁺ > (VO)⁺ > (n-Bu₄N)⁺. In a series of (n-Bu₄N)_3 + x [PW_12−xV_xO₄₀] (x = 0–3) the order of catalytic activity is V₃ > V₂ > V₁ > V₀. The reactivity order of the sulfur compounds is: dibenzothiophene > 4,6-dimethyldibenzo-thiophene > benzothiophene. The catalytic system in this work was used for the oxidation of gas oil combined with solvent extraction to remove sulfur content in gas oil. Under mild reaction condition, high sulfur removal up to 98% can be achieved with high oil recovery (90%).     

Direct conversion of methane to acetylene or syngas at room temperature using non-equilibrium pulsed discharge

Non-catalytic direct conversion of methane to valuable products was studied using non-equilibrium pulsed discharge under the conditions of ambient temperature and atmospheric pressure. Acetylene was produced with 95% selectivity and 52% methane conversion. An addition of oxygen, carbon dioxide and steam contributed significantly to suppress the carbon deposition and produced carbon monoxide as well as acetylene. Methane conversion increased with an increase in the pulse frequency while the product selectivity remained almost constant. The selectivity depended on the composition of the feed gas. The effect of the partial pressure of oxygen was examined, and it was found that the pulsed discharge would be able to produce synthesis gas by partial oxidation of methane. Carbon monoxide selectivity of 79% with methane conversion of 76% was obtained under the conditions of CH₄/O₂=25/25 cm³ min⁻¹, gap distance of 10 mm and the frequency of 45 Hz.     

Experimental study of the structure of a rich premixed 1,3-butadiene/CH4/O2/Ar flame

The structure of a laminar rich premixed 1,3-butadiene/CH₄/O₂/Ar flame has been investigated, 1,3-butadiene, methane, oxygen, and argon mole fractions being 0.033, 0.2073, 0.3315, and 0.4280, respectively, for an equivalence ratio of 1.80. The flame has been stabilized on a burner at a pressure of 6.7 kPa. The concentration profiles of stable species have been measured by gas chromatography after sampling with a quartz probe. The quantified species include carbon monoxide and dioxide, methane, oxygen, hydrogen, ethane, ethylene, acetylene, propyne, allene, propene, cyclopropane, 1,3-butadiene, butenes, 1-butyne, vinylacetylene, diacetylene, C₅ compounds, benzene, and toluene. The temperature distribution in the flame has also been measured. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 6, pp. 89–95, November–December, 2006.     

Influence of vent air valve opening on combustion characteristics of a down-fired pulverized-coal 300 MWe utility boiler

Industrial experiments have been performed on a down-fired pulverized-coal 300 MWe utility boiler with vent air valve opening of 100% and 40%. The gas temperature distribution along the primary air and coal mixture flow, gas temperature distribution in the furnace, and gas components such as O₂, CO, CO₂ and NO_x in the near-wall region were measured for the first time. The influence of vent air valve opening on coal combustion in the furnace was determined. The results indicate that ignition of the primary air and pulverized-coal mixture is delayed. The position of the gas temperature peak is above the arches. Emission of NO_x is up to 2101 mg/m³ (at 6% O₂ dry) with vent valve opening of 40%.     

Factors affecting coal particle ignition under oxyfuel combustion atmospheres

A set of 13 coals of different rank has been tested for ignition propensity in a 20-L explosion chamber simulating oxyfuel combustion gas conditions. Their char residues were also analysed thermogravimetrically. The effects of coal type, coal concentration (from 100 to 600 g/m³), O₂ in CO₂ atmospheres (up to 40% v/v) and particle size were investigated.The higher rank coals were significantly more difficult to ignite and mostly required higher energy chemical igniters (1000 or 2500 J) whereas the lower rank coals could be ignited with a 500 J igniter even at low coal dust concentrations.The minimum explosibility limit/ignition concentration in air varied slightly around a value of 200 g/m³, a little higher for low volatile coals and a little lower for high volatile coals.The ignition limit changed significantly, however, with O₂ concentration in CO₂, where coals required more oxygen to ignite. Most coals failed to ignite at all in 21% v/v O₂ in CO₂, but an increase to 30 or 35% v/v O₂ gave ignition patterns similar to those in air. In addition, the minimum ignition concentration decreased with increase in O₂. However, a further increase to 40% v/v O₂ did not generally affect the minimum ignition concentration.Particle size had a non-linear effect on coal ignition. The fine particles (<53 μm) behaved almost identical to the whole coal. However, the larger size fraction (>53 μm) was generally more difficult to ignite and exhibited a much lower weight loss.     

Study of morphology and phase diagram of the H-shaped (AC)B(CA) ternary block copolymers using self-consistent field theory

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymer systems, the micro-phase morphologies of the H-shaped (AC)B(CA) ternary block copolymer system are studied in three-dimensional (3D) space. By systematically varying the volume fractions of the components A, B, and C, six triangle phase diagrams of this H-shaped (AC)B(CA) ternary block copolymer system with equal interaction energies among the three components are constructed from the weaker segregation regime to the strong segregation regime. In this study, thirteen 3D micro-phase morphologies for this H-shaped ternary block copolymer system are identified to be stable and seven 3D micro-phase morphologies are found to be metastable. It is found that in the weaker segregation regime (χ_ABN = χ_ACN = χ_BCN = 45), the minority component can be mixed with other two majority components to form the mixed phase regions, while in the intermediate segregation regime (χ_ABN = χ_ACN = χ_BCN = 60 and 75), the mixed phase regions phase-separate into three distinct phase regions. In the strong segregation regime (χ_ABN = χ_ACN = χ_BCN = 90, 100, and 125), the distinct blocks tend to separate with each other and the phase behavior of this H-shaped (AC)B(CA) ternary block copolymer is similar to that of the three-arm star-like ABC ternary block copolymer. Moreover, the order-disorder transitions and the order-order transitions by varying the interaction parameters are discussed. These results may help in the design of the microstructures of complex block copolymers.