Quality of gas produced from wheat straw in a dual-distributor type fluidized bed gasifier

A 400 kW, dual distributor type fluidized bed gasifier was used to investigate the production rate and composition of the gas produced from wheat straw at various equivalence ratios (0.17, 0.20, 0.25, 0.35) and fluidization velocities (0.28, 0.33 and 0.37 m s⁻). The results showed that the equivalence ratio was the major parameter affecting the gas composition. The equivalence ratio of 0.25 appeared to be the optimum with respect to the quality of the gas. The mole fractions of the combustible components reached their maximum values at this equivalence ratio. A typical gas composition at the equivalence ratio of 0.25 was 7% H₂, 7% hydrocarbons (CH₄, C₂H₂, C₂/H₄ and C₂H₆), 14% C0₂, 22% CO and 50% N₂. The higher heating value of the produced gas (6.3–7.3 MJ Nm⁻³) obtained at this equivalence ratio appeared to be higher than most values reported in the literature for several types of biomass fuels.     

Mechanism of soot initiation in methane systems

Thermochemical and kinetic evaluations of the very rapid elementary radical reactions consuming the C₂H₂ produced in a chlorine catalyzed polymerization of CH₄ are presented. An earlier examination of the data and mechanism leading to C₂H₂ supports a methyl and chloromethyl recombination path to C₂ hydrocarbons. The relative yield of CH₃ and CH₂Cl depends on the excess of methane.

In the CH₄, system consumption of C₂ species to ultimately form benzene is shown to proceed by a stepwise addition of CH₃ radicals to C_nH_m species. When n is even the dominant species is an unsaturated polyolefin molecule. When n is odd the dominant species is a conjugated, unsaturated radical such as allyl, pentadienyl, benzyl, etc. Mono-olefins or saturated molecules are rapidly stripped to these species by radical catalyzed dehydrogenations. In the current system chloromethyl radicals are equivalent kinetically to methyl and play a dominant role. Their addition to unsaturated species produces chlorinated radicals that dechlorinate rapidly or recombine with chloromethyl to produce dichlorohydrocarbons that dehydrochlorinate very rapidly.

A very important reaction in the sequence is the isomerization of propenyl and chloropropenyl radicals to allyl and chlorallyl by a 1–3 H (or Cl) atom shift. Its high pressure Arrhenius parameters at 1300 K are estimated to be log [k(sec⁻¹)] = 13.7 − 37/θ = 13.7 - 37/0 where 0 = 2.303 RT in kcal/mol. It appears likely that benzene conversion to soot also proceeds via a CH₃/CH₂Cl radical, sequential addition mechanism.

Stoichiometry considerations applied to the product yield distribution support the role of methyl and chloromethyl predicted by the proposed mechanism. Ionic pathways are shown to be insignificant in the formation of aromatics.     

Nitrous oxide formation and destruction in lean, premixed combustion

Concentraion profiles of N₂O, NO, and N₂ from atmospheric pressure, flat-flame burner experiments are presented. Axial profiles of species and temperature are described for CH₄-air and H₂---O₂---Ar flames doped with either NH₃, NO, or N₂O.

Species concentrations were determined by microprobe sampling and direct analysis by gas chromatography or chemiluminescence analysis, for flames ranging in temperature from 1300 to 2000 K. Burner surface temperatures were also estimated for these flames, using heat transfer analysis and an optical method. Nitrogen-atom balances were achieved in each of the H₂---O₂---Ar flames to within experimental error and better than 6%.

Axial profiles of N₂O were similar for all flames. At sampling locations nearest to the burner (0.5–1.0 mm), N₂O concentrations were highest. Concentrations decreased monotonically in the downstream direction, with N₂O destruction essentially complete in the postflame region (height greater than 3 mm) for all flames except the one at the lowest temperature (1300 K). With NH₃ as dopant, early-flame and postflame N₂O concentration varied inversely with temperature. The lowest early-flame N₂O concentration was observed with NO as dopant, and the highest was observed with direct N₂O addition. Increased initial concentrations of NH₃ led to higher early-flame N₂O concentrations. With N₂O as dopant, product branching to NO and N₂ in the postflame region is approximately 8% and 92%, respectively. An NO removal process involving NH_i is active in lean, NO-doped flames.     

Decomposition of nitrous oxide at medium temperatures

Flow reactor experiments were done to study the decomposition of N₂O at atmospheric pressure and in a temperature range of 600–1000°C. Dilute mixtures of N₂O with H₂, CH₄, CO with and without oxygen with N₂ as carrier gas were studied. To see directly the relative importance of the thermal decomposition versus the destruction by free radicals (i.e.: H, O, OH) iodine was added to the reactant mixture suppressing the radicals’ concentrations towards their equilibrium concentrations. The experimental results were discussed using a detailed chemistry model. This work shows that there are still some uncertainties regarding the kinetics of the thermal decomposition and the reaction between N₂O and the O radical. Using the recommendations applied in this work for the reaction N₂O + M ↔ N₂ + O + M and for N₂O + O ↔ products, a good agreement with the experimental data can be obtained over a wide range of experimental conditions. The reaction between N₂O and OH is of minor importance under present conditions as stated in latest literature. The results show that N₂O + H ↔ N₂ + OH is the most important reaction in the destruction of N₂O. In the presence of oxygen it competes with H + O₂ + M ↔ HO₂ + M and H + O₂ ↔ O + OH, respectively. The importance of the thermal decomposition (N₂O + M ↔ N₂ + O + M) increases with residence time. Reducing conditions and a long residence time lead to a high potential in N₂O reduction. Especially mixtures of H₂/N₂O and CO/H₂O/N₂O in nitrogen lead to a chain reaction mechanism causing a strong N₂O reduction.     

Comparisons of computed and measured premixed charge engine combustion

Comparisons are presented of computed and measured cylinder pressure in a reciprocating engine with a pancake combustion chamber and premixed propane/air charges. Engine operating conditions range over volumetric efficiency of 30–60%; equivalence ratio of 0.87–1.1; and rpm of 1000–1500. The computations start from the actual spark times and simulate the growth of the flame kernel into a fully developed turbulent flame by taking into account the increasing influence of turbulent eddies on the growing flame kernel. A k-ε submodel is used for turbulence. The species conversion submodel assumes that the species (C₃H₈, O₂, H₂O, CO₂, CO, H₂, and N₂) concentrations approach their local thermodynamic equilibrium values with a characteristic conversion time that is a combination of a turbulent mixing time and a chemical conversion time in laminar propane---air flames. In all cases computed and measured cylinder pressure agree well in trends and magnitudes during the entire duration of combustion. The difference in magnitudes generally is much less than 8%. The main conclusion is that laminar flame processes must be explicitly accounted for in order to reproduce certain elements of premixed charge engine combustion.     

纤维素温和条件下一步水热法制备甲烷的研究

生物质发酵法制备甲烷存在甲烷收率低、CO₂含量高等问题。本研究以纤维素为原料,在温和条件下采用水热催化转化的方法制备甲烷。对一系列催化剂进行了考察,发现Ru/C对该反应的催化活性最高。采用Ru/C催化剂进一步考察了一系列反应条件,结果表明,升高反应温度、延长反应时间、增加催化剂用量以及提高氢气初始压力对甲烷的生成具有促进作用。在1 MPa H₂、220℃、12 h反应条件下,甲烷碳摩尔收率最高,达88%,反应过程中无CO₂产生。采用TEM、BET、XRD和FT-IR等对催化剂进行了表征,结果表明,Ru/C催化剂的高催化活性可能与催化剂本身比表面积大、钌粒子颗粒小且分散均匀的特性有关。本研究采用的催化转化方法具有甲烷收率高、CO₂排放量小（<5%）、反应条件更为温和等特点。     

Emission factors of wood and charcoal-fired cookstoves

In the developing countries, energy required for cooking often has the biggest share in the total national energy demand and is normally met mostly by biomass. This paper presents the results of experimental studies on emission conducted on a number of traditional and improved cookstoves collected from different Asian countries using wood and charcoal as fuel. The emission factors from this study are comparable to those reported in the literature. In the case of wood combustion, CO₂ emission factor is in the range of 1560–1620 g kg⁻¹. The emission factors for pollutants CO, CH₄, TNMOC and NO_x were in the ranges 19–136, 6–10, 6–9 and 0.05–0.2 g kg⁻¹, respectively. In the case of charcoal combustion, CO₂ emission factor is in the range of 2155–2567 g kg⁻¹. The emission factors for pollutants CO, CH₄, TNMOC were in the ranges 35–198, 6.7–7.8, 6–10 g kg⁻¹, respectively.

Comparison between wood and charcoal fired stoves shows that, CO₂ and CO emission factor values for wood are lower as compared to charcoal. CH₄ and TNMOC emission factors for wood are with the same range as compared to charcoal. Emission factors for NO_x using wood is slightly lower than charcoal. The emission of all the pollutants per unit of useful heat was found to decrease with increasing stove efficiency for both wood and charcoal fired stoves.     

Potential GHG mitigation options for agriculture in China

China's agriculture accounts for about 5–15% of total national emissions of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). Land-use changes related to agriculture are not major contributors of greenhouse gas emissions in China.

Mitigation options are available that could result in significant decrease in CH₄ and N₂O emissions from agricultural systems, and are likely to increase crop and animal productivity. Implementation has the potential to decrease CH₄ emissions from rice paddies, ruminants, and animal waste by 4–40%. Improving the efficiency of plant utilization of fertilizer N could decrease N₂O emissions from agriculture by almost 20%. Analyses of several of the proposed options show positive economic as well as environmental benefits.     

Production of hydrogen gas from novel chemical hydrides

Six ligand-stabilized complexes have been synthesized and tested for use as hydrogen storage media for portable fuel cell applications. The new hydrides are: [HC(3,5-Me₂pz)₃]LiBH₄ (1), {[H₂C(3,5-Me₂pz)₂]Li(BH₄)}₂ (2) (pz = pyrazolyl), [(TMEDA)Li(BH₄)]₂ (3) (TMEDA = (CH₃)₂NCH₂CH₂N(CH₃)₂), [HC(pz)₃]LiBH₄ (4), {[H₂C(pz)₂]Li(BH₄)}₂ (5) and Mg(BH₄)^.₂ 3THF (6) (THF = tetrahydrofuran). Hydrolysis reactions of the compounds liberate hydrogen in quantities which range from 56 to 104 (± 5%) percent of the theoretical yield. Gas chromatographic analysis of the product gases from these reactions indicate that hydrogen is the only gas produced. Thermally initiated reactions of the novel compounds with NH₄Cl were unsuccessful. Although the amount of hydrogen energy which can be theoretically obtained per unit weight is lower than that of the classical hydrides such as LiBH₄ and NaBH₄, the reactions are less violent and hydrolysis of compounds 1, 2, 4, 5 and 6 releases less heat per mole of hydrogen generated.     

Kinetic study on fermentation from CO2 and H2 using the acclimated-methanogen in batch culture

Methane was produced from H₂ and CO₂ using the acclimated-mixed methanogens in a 3.71 fermentor in batch culture at pH 7.2 and 37°C. The Fermentation kinetics parameter for the growth of methanogens, overall mass transfer coefficient of the reactor, and the conversion rate of H₂ and CO₂ to CH₄ by the acclimated-mixed culture were determined using the technique of Vega et al. The maximum specific growth rate (μ_max) and H₂ specific consumption rate (q_max) were found to be 0.064(h⁻¹) and 104.8 (mmol h⁻¹ g⁻¹) respectively. Monod saturation constants for growth (Kp) and for inhibition (K′p) were found to be 3.54 (kPa) and 0.57 (kPa), respectively. These findings indicate that without very low dissolved H₂ levels, the fermentations are carried out under μ_max, and the specific uptake rate (q) was almost not affected at any dissolved H₂ level in the range studied. The yield of CH₄ (Yp/s) was calculated to be 0.245 (mol CH₄ mol⁻¹ H₂), which is near the stoichiometric value of 0.25. DH₂ was also measured using the Teflon tubing method and was in good agreement with those estimated by kinetic calculations.     

Comparison of species profiles between O2 and NO2 oxidizers in premixed methane flames

The profiles of the species H, OH, CH, NH, CN, NCO, NO₂, and CH₃O are compared in a series of five premixed stoichiometric 15-torr CH₄/O₂/NO₂/N₂ flames with NO₂ comprising between 0% and 40% of the oxidizer. Relative species concentrations were measured by laser-induced fluorescence (LIF) and these results are compared with calculations using measured temperature profiles. The reaction mechanism of Miller and Bowman incorrectly predicts the standoff from the burner in flames containing more than 20% NO₂; addition of several reactions involving NO₂ and HONO produces excellent agreement with experiment for most species. The reaction CH₃ + NO₂ → CH₃O + NO is found to be particularly important in the reaction mechanism. LIF profiles of CH₃O show this species to be present in far larger quantities in the NO₂ supported flames than in the CH₄/O₂ system. The nitrogen-containing intermediates CN, NCO, and NH are all overpredicted by a factor of two in the 40% NO₂ flame relative to the 10% NO₂ flame. This indicates an inaccuracy in either the reburn reactions or the fuel nitrogen chemistry when large amounts of NO are present. The kinetic modeling shows that in the 40% NO₂ flame, the dominant pathway to N₂ formation is through N₂O, which is produced primarily by the reaction of NCO with NO. Comparison of emission profiles of NO₂* for the various flames indicates that the appearance of an orange-yellow luminous zone at the base of NO₂ supported flames is caused by thermal excitation of NO₂, not by a chemiluminescence mechanism.     

Anthropogenic emissions of CO2 and CH4 in an urban environment

Regular observations of atmospheric mixing-ratios of carbon dioxide and methane in the urban atmosphere, combined with analyses of their carbon-isotope composition (δ¹³C, δ¹⁴C), provide a powerful tool for assessing both the source strength and source partitioning of those gases, as well as their changes with respect to time. Intense surface fluxes of CO₂ and CH₄, associated with anthropogenic activities result in elevated levels of these gases in the local atmosphere as well as in modifications of their carbon-isotope compositions. Regular measurements of concentration and carbon-isotope composition of atmospheric CO₂, carried out in Krakow over the past two decades, were extended to the period 1995–2000 and also to atmospheric mixing-ratios of CH₄ and its carbon-isotope composition. Radiocarbon concentrations (δ¹⁴C) in atmospheric CO₂ recorded at Krakow are systematically lower than the regional background levels. This effect stems from the addition of ¹⁴C-free CO₂ into the local atmosphere, originating from the burning of fossil fuels. The fossil-fuel component in the local budget of atmospheric carbon calculated using a three-component mixing model decreased from ca. 27.5 ppm in 1989 to ca. 10 ppm in 1994. The seasonal fluctuations of this component (winter–summer) are of similar magnitude. A gradually decreasing difference between the ¹⁴CO₂ content in the local atmosphere and the regional background observed after 1991 is attributed to the reduced consumption of ¹⁴C-free fuels, mostly coal, in southern Poland and the Krakow municipal area. The linear regression of δ¹³C values of methane plotted versus reciprocal concentration, performed for the data available for Krakow sampling site, yields the average δ¹³C signature of the local source of methane as being equal to −54.2‰. This value agrees very well with the measured isotope signature of natural gas being used in Krakow (−54.4±0.6‰) and points to leakages in the distribution network of this gas as the main anthropogenic source of CH₄ in the local atmosphere.     

水蒸气气氛下生物质与聚丙烯共气化产气特性数值分析

搭建生物质与废塑料共气化动力学模型,并用实验数据对其进行验证。选用6种生物质和聚丙烯作为共气化反应物,以水蒸气为气化剂,计算气化温度在300～1000℃之间、气化压强在0.1～0.8 MPa之间、聚丙烯和松木锯末质量比例在0.5～2.5之间,以及不同生物质类型等对生物质和聚丙烯共气化产气特性的影响。结果表明：松木锯末气化中添加聚丙烯后,最高产气量和最大产气速率增加,最高产气总流量提高21.46%,最高产气速率提高4.64%,H₂和CO最高产量分别提高54.27%和79.51%;压强增加不利于提高共气化产气的H₂和CO含量,有利于提高CH₄含量;6种常见生物质和聚丙烯共气化产氢量大小顺序为：果皮>棉花秆≈玉米秸秆>杨树木屑>稻秆>条浒苔;聚丙烯掺混比率增加有利于提高H₂、CO和CH₄等组分产量。     

Reduction of NiAl2O4 containing catalysts for steam methane reforming reaction

Reducibility of a NiAl₂O₄ containing catalyst was studied. On a measurement of NiAl₂O₄ concentration in a catalyst, a peak area ratio of NiAl₂O₄ in XRD analysis was verified to express the NiAl₂O₄ concentration. The reducibility of NiAl₂O₄ was confirmed to be dependent on the calcining temperature to form NiAl₂O₄, not dependent on the calcining time. The catalyst containing NiAl₂O₄ was ascertained to be reduced under convenient conditions to actual plant operations; H₂/N₂ = 30/70 at 1023K for 1 h + steam/CH₄ = 6 at 1023K for 17 h.     

Electrochemical and structural characteristics of metal oxide-coated lithium manganese oxide (spinel type): Part I. In the range of 2.5–4.2 V

The electrochemical and structural characteristics of the metal oxide-coated spinel were investigated in the range of 2.5–4.2 V. Metal oxide coating on commercial spinel powder (LiMn_2−xM_xO₄, M=Zr, Nikki, Japan) was carried out using the sol–gel method. Al₂O₃/(PtO_x or CuO_x)-coated spinel exhibited improved cyclability compared to bare spinel. Impedance analysis results indicated that electrochemical resistance value was not consistent with cycle performance. The improved cycle performance of metal oxide-coated spinel may be due to formation of a new Li₂Mn₄O₉, Li₂MnO₃ phase, which is expected to have stability to phase transition (Jahn–Teller distortion).     

Homogeneous formation of NO and N2O from the oxidation of HCN and NH3 at 600–1000°C

The oxidation of HCN and NH₃ with CO, CH₄, or H₂ addition has been studied in the temperature range between 600 to 1000°C. In most of the tests 10% oxygen was used. The experiments were carried out under well-defined conditions in a flow tube reactor made of quartz glass. The effects of NO addition and oxygen level have been tested. To study the importance of O/H radicals in the reaction mechanism and to confirm previous studies, iodine was added in some tests. A detailed chemical kinetic model was used to analyze the experimental data. In general, the model and experimental results are in good agreement. The results show that under the conditions tested CO significantly promotes NO and N₂O formation during HCN oxidation. During NH₃ oxidation carbon-containing gaseous species such as CO and CH₄ are important to promote homogeneous NO formation. In the system with CH₄ addition, the conversion of HCN to N₂O is lower compared to the other systems. In the HCN/NO/CO/O₂ system NO reduction starts at 700°C and the maximum reduction of approx. 40% is obtained at 800°C. For the NH₃/NO/CO/O₂ system the reduction starts at 750°C and the maximum reduction is 50% at 800°C. Iodine addition shifts the oxidation of HCN, NO, and N₂O formation as well as NO reduction to higher temperatures. Under the conditions tested, it was found that iodine mainly enhances the recombination of the O-radicals. No effect on NO formation was found in the HCN/CH₄/O₂ system when oxygen was increased from 6% to 10%, but when oxygen was increased from 2% to 6% NO formation decreased. The role of hydrocarbon radicals in the destruction of NO is likely to become important at low oxygen concentrations (2%) and at high temperatures (1000°C).     

Preparation and properties of transparent conducting zinc oxide and aluminium-doped zinc oxide films prepared by evaporating method

Undoped and aluminium-doped zinc oxide films have been prepared by thermal evaporation of zinc acetate [Zn(CH₃COO)₂ 2H₂O] and aluminium chloride [AlCl₃] onto a heated glass substrate. The structural and optoelectrical properties of the films have been studied. The effects of heat treatment for the as-deposited films in air and vaccum are investigated. Highly transparent films with conductivity as low as 2×10⁻³ Ω cm can be produced by controlling the deposition parameters. The electron carrier densities are in the range 0.2–7×10¹⁹ cm⁻³ with mobilities of 22–58 cm² V⁻¹ s⁻¹.     

Ni-Co双金属催化剂上沼气重整制氢宏观动力学

用传统湿式浸渍法制备La2O3掺杂的商业γ-Al2O3负载的沼气重整催化剂Ni-Co/La2O3-γ-Al2O3,通过对NiCo双金属催化剂上沼气重整制氢在常压下的宏观动力学分析,得出该催化剂上CH4与CO2消耗、H2与CO生成时的表观反应速率方程.通过改变进料中CH4与CO2的分压,求出各物质的反应分级数,确定总反应...     

Structural and electrochemical properties of Li1+xNi0.5Mn0.5O2+δ (0 ≤ x ≤ 0.7) cathode materials for lithium-ion batteries

A comparative analysis of the properties of LiNi_0.5Mn_0.5O₂ and Li_1+xNi_0.5Mn_0.5O₂ (0.2 ≤ x ≤ 0.7) powders, obtained by the freeze drying method, was performed. Lattice parameters of Li_1+xNi_0.5Mn_0.5O₂ decreased considerably with growing amounts of Li until x = 0.3; at x > 0.5 trace amounts of Li₂MnO₃ are observed by X-ray diffraction (XRD) patterns. X-ray photoelectron spectroscopy (XPS) analysis displayed an increase of Ni³⁺/Ni²⁺ ratio at 0.3 < x < 0.5, while Mn 2p spectra were almost identical in all samples. Rechargeable capacity values (V = 2.5–4.6 V) increased systematically with x reaching its maximum (185–190 mAh g⁻¹) at x = 0.5. Samples with superstoichiometric lithium content also demonstrated good C rate characteristics.     

NiO–ScSZ and Ni0.9Mg0.1O–ScSZ-based anodes under internal dry reforming of simulated biogas mixtures

Solid oxide fuel cells (SOFCs) with NiO–ScSZ and Ni_0.9Mg_0.1O–ScSZ-based anodes were operated by directly feeding a fuel mixture of CH₄, CO₂ and N₂ (CH₄ to CO₂ ratio of 3:2). Stable operation under constant current load (200 mA cm⁻²) was achieved with a NiO–ScSZ type anode during 200 h operating hours at 900 °C. Less stable operation occurred with a Ni_0.9Mg_0.1O–ScSZ type anode. In the case of SOFC with Ni_0.9Mg_0.1O–ScSZ as the anode, the methane reforming activity was higher than that with NiO–ScSZ. This was explained by change in the microstructure promoting reforming reactions. However, the addition of MgO resulted in degradation of electrochemical performance due to increase in ohmic resistance of the anode material during operation.