O_2/CO_2条件下生物质焦和煤焦燃烧动力学特性

为得到富氧条件下生物质焦和煤焦的燃烧动力学特性规律,利用热重研究了麦秆焦,木屑焦以及烟煤焦在富氧气条件下的燃烧特性。实验结果表明:无论是生物质焦还是煤焦,相同的O2浓度下,O2/CO2气氛下焦样的着火相对于O2/N2气氛均发生了延迟,燃烧特性指数也均低于O2/N2气氛下对应值;在O2/CO2气氛和O2/N2气氛下,随着O2浓度的增加,焦样的着火温度均降低,燃烧特性指数增大,且提高O2浓度对煤焦着火的改善程度显著优于木屑焦。     

生物质与煤混合富氧燃烧过程中NO和N_2O的排放特性研究

为了研究燃烧气氛、进口氧气浓度、生物质掺混比、燃烧温度以及过量氧气系数对循环流化床(CFB)富氧燃烧过程中NO,N_2O排放特性以及燃料中N的转化特性的影响,以棉秆和大同烟煤为燃料,在50 k W循环流化床燃烧试验台上进行了空气气氛和O_2/CO_2气氛下的生物质与煤混合燃烧试验。试验结果表明:与空气气氛相比,O2/CO2气氛下,NO,N_2O的排放量和燃料中N的转化率均降低;随着进口氧气浓度和燃烧温度的升高,NO的排放量均升高,N_2O的排放量和燃料中N的转化率均降低;随着生物质掺混比的增大,NO的排放量和燃料中N的转化率降低,N_2O的排放量升高;NO,N_2O的排放量以及燃料中N的转化率均随过量氧气系数增大而升高。     

O2/CO2气氛下煤燃烧NOx排放特性的实验研究

利用管式电阻炉在O₂/CO₂气氛和O₂/N₂气氛下对煤粉燃烧过程中NO_x排放特性进行实验,研究在不同停留时间、炉内燃料/氧化学当量比、温度、氧浓度等因素对燃煤过程中NO_x放特性的影响,并对这两种燃烧方式下NO_x的排放特性进行对比。结果表明:在O₂/CO₂气氛下NO_x的生成量要远远低于O₂/N₂气氛下NO_x的生成量。随着停留时间的延长,NO_x沿程释放特性是先增大后减少。随着燃料/氧化学当量比的增加,NO_x排放浓度也呈现出先增加后降低的趋势。随着炉内温度的增加,2种气氛下NO_x的排放浓度均增加。随着氧浓度的提高,NO_x排放浓度增大。     

流化床O2/CO2燃烧（Ⅱ）-高氧浓度的中试研究

为给大型循环流化床O2/CO2燃烧系统在高氧气浓度下的燃烧提供参考,在燃烧室直径140 mm、高度6 000 mm的0.15 MW循环流化床燃烧试验系统上,在O2/N2气氛中,进行了煤在高氧浓度下的燃烧试验。实验结果表明,在一次风氧气浓度49.0%～53.3%、二次风氧气浓度50.8%～56.0%时仍可以安全、稳定燃烧。煤在燃烧过程中SO2收率为92.2%～94.0%,配风对SO2收率影响不大。不同风量配比下,NOx收率为6.71%～7.64%,N2O收率为5.13%～7.23%。降低一次风氧量,有助于降低NOx收率和N2O收率。推迟二次风加入时间,有助于降低N2O收率,但会使NOx收率升高。     

O_2_CO_2气氛下煤燃烧产物的热力学分析

利用ASEPN PLUS软件平台对O2/CO2气氛下煤的燃烧产物进行了热力学模拟计算,计算中对煤在O2/CO2气氛下和空气中的燃烧产物进行了对比,研究在O2/CO2气氛下燃烧温度、过量氧系数φ对煤燃烧产物的影响。结果表明,煤在O2/CO2气氛下燃烧,形成的NOx量远低于空气气氛中的生成量;随温度和φ增大,NOx量增大;温度对SO2和SO3量的生成影响很小;当φ<1时,随φ增大SO2的量增大,当φ>1时,φ变化对SO2量影响不大;随φ增大,SO3有微量增长。计算表明应用ASPEN PLUS模拟煤的富氧燃烧是可行的。     

富氧气氛下循环流化床煤燃烧试验研究

在O2／CO2气氛和O2／N2气氛下,对氧浓度为21％～35％的循环流化床进行了煤燃烧的试验研究,比较了不同气氛下的煤燃烧特性和炉内温度分布以及NOx、NO2的排放规律和脱硫效率．试验显示富氧气氛下煤能够稳定燃烧,循环回路通畅;给煤量一定,随着试验气氛中氧含量的增加,燃烧效率逐渐增高．O2／CO2气氛下的燃烧效率略低于相同氧含量的O2／N2气氛下的燃烧效率;随着试验气氛中氧含量的增加,NOx排放量增加,SO2排放量略有减小,石灰石脱硫效率略有提高．     

O2/CO2气氛下循环流化床煤燃烧污染物排放的试验研究

富氧燃烧技术不仅能使分离收集CO2和处理SO2容易进行,还能减少NOX排放,是一种能够综合控制燃煤污染物排放的新型洁净燃烧技术。进行了O2/CO2气氛和O2/N2气氛下的循环流化床煤燃烧试验,重点分析了煤燃烧生成的污染物NOX、SO2的排放规律及石灰石脱硫效率,进行了循环流化床富氧燃烧系统的平衡分析并得到了相关试验的证实,为循环流化床富氧燃烧技术的工业应用做了基础和重要的准备。图9表2参9     

O2/CO2气氛下煤粉燃烧反应动力学的试验研究

在热重分析仪上进行了模拟空气气氛及不同O2浓度(21%、30%、40%、80%)的O2/CO2气氛下3种不同品质煤粉(龙岩无烟煤、贵州烟煤、元宝山褐煤)的燃烧特性试验,确定了3种煤粉的燃烧特征参数并进行了动力学分析.结果表明,O2/CO2气氛下煤粉的燃烧分布曲线与O2/N2气氛下有明显不同,在相同O2浓度的条件下,O2/CO2气氛下煤粉燃烧速率低,燃尽时间长;随着O2浓度的增加,燃烧DTG曲线向低温区偏移,着火温度及燃尽温度降低,燃尽时间缩短,可燃性指数及燃尽指数明显提高;O2/CO2气氛下煤粉燃烧基本属于一级反应,动力学参数随燃烧气氛与煤质变化的不同有较大差异.     

O2/CO2/H2O气氛下CO燃烧机理的分子动力学模拟研究

采用反应分子动力学(ReaxFF MD)模拟方法研究了O₂/CO₂/H₂O气氛下CO的燃烧。结果表明：根据化学平衡原理,高浓度CO₂抑制CO的氧化,同时CO₂在高温下参与反应CO₂+H—→CO+OH,进一步抑制CO氧化。在较低温度条件下,较高浓度H₂O的三体效应显著,抑制了CO氧化。另一方面,在较高温度条件下,H₂O参与的H₂O+H—→H₂+OH和H₂O+O—→OH+OH反应占据其化学作用的主导地位,进而促进CO氧化。随着O₂浓度的增加,CO的氧化速度加快。     

O2/CO2气氛下炉内煤粉切圆燃烧数值研究

对某电厂600 MW切圆燃烧锅炉进行了O2/CO2气氛下炉内流动、传热和燃烧过程的数值研究。结果表明:在O2/CO2气氛下,随着氧气摩尔浓度的增加,炉内温度升高,高温区变大,对煤粉的着火燃烧有利;但考虑到燃烧器安全和水冷壁结渣,氧气摩尔浓度不能太高,对燃用文中煤质的锅炉其极限摩尔浓度在40%至45%之间。O2/CO2气氛对现有切圆燃烧锅炉的上层燃烧器煤粉的燃烧影响较小,对下层燃烧器煤粉的燃烧影响较大。与空气气氛煤粉燃烧相比,炉内火焰中心上移,且在氧气摩尔浓度不太高时,炉内温度分布特性有利于防止水冷壁的结渣。     

Explosion behavior of CH4/O2/N2/CO2 and H2/O2/N2/CO2 mixtures

In this work, the explosion behavior of stoichiometric CH₄/O₂/N₂/CO₂ and H₂/O₂/N₂/CO₂ mixtures has been studied both experimentally and theoretically at different CO₂ contents and oxygen air enrichment factors. Peak pressure, maximum rate of pressure rise and laminar burning velocity were measured from pressure time records of explosions occurring in a closed cylindrical vessel. The laminar burning velocity was also computed through CHEMKIN–PREMIX simulations.     

Hydrogen permeation through a Pd-based membrane and RWGS conversion in H2/CO2, H2/N2/CO2 and H2/H2O/CO2 mixtures

This study investigated the effect of gases such as CO₂, N₂, H₂O on hydrogen permeation through a Pd-based membrane −0.012 m² – in a bench-scale reactor. Different mixtures were chosen of H₂/CO₂, H₂/N₂/CO₂ and H₂/H₂O/CO₂ at temperatures of 593–723 K and a hydrogen partial pressure of 150 kPa. Operating conditions were determined to minimize H₂ loss due to the reverse water gas shift (RWGS) reaction. It was found that the feed flow rate had an important effect on hydrogen recovery (HR). Furthermore, an identification of the inhibition factors to permeability was determined. Additionally, under the selected conditions, the maximum hydrogen permeation was determined in pure H₂ and the H₂/CO₂ mixtures. The best operating conditions to separate hydrogen from the mixtures were identified.     

Laminar burning velocities and transition to unstable flames in H2/O2/N2 and C3H8/O2/N2 mixtures

Effects of positive flame stretch on laminar burning velocities, and conditions for transition to unstable flames, were studied experimentally for freely propagating spherical flames at both stable and unstable preferential-diffusion conditions. The data base involved new measurements for H₂/O₂/N₂ mixtures at values of flame stretch up to 7600 s⁻¹, and existing measurements for C₃H₈/O₂/N₂ mixtures at values of flame stretch up to 900 s⁻¹. Laminar burning velocities varied linearly with increasing Karlovitz numbers—either decreasing or increasing at stable or unstable preferential-diffusion conditions—yielding Markstein numbers that primarily varied with the fuel-equivalence ratio. Neutral preferential-diffusion conditions, however, were shifted toward the unstable side of the maximum laminar burning velocity condition that the simplest preferential-diffusion theories associate with neutral stability. All flames exhibited transition to unstable flames: unstable preferential-diffusion coditions yielded early transition to irregular flame surfaces, and stable preferential-diffusion conditions yielded delayed transition to cellular flames by hydrodynamic instability. Conditions for hydrodynamic instability transitions for H₂/O₂/N₂ mixtures were consistent with an earlier correlation due to Groff for propane/air flames, based on the predictions of Istratov and Librovich.     

Burning velocities and kinetics of H2/NF3/N2, CH4/NF3/N2, and C3H8/NF3/N2 flames

The combustion characteristics and reaction mechanism of mixtures containing nitrogen trifluoride (NF₃) were investigated. Burning velocities for H₂/NF₃/N₂, CH₄/NF₃/N₂, and C₃H₈/NF₃/N₂ flames were determined for the first time at various equivalence ratios and N₂ mole fractions. The burning velocities of the latter two flames were similar and showed peaks at equivalence ratios of ∼1.0, while those of the H₂/NF₃/N₂ flames had the pronounced peak at low equivalence ratios where the formation of the wrinkled flames was observed. A detailed kinetic model was constructed to simulate the laminar burning velocities of H₂/NF₃/N₂ and CH₄/NF₃/N₂ flames. The model accurately reproduced the experimental results. Analyses of the reaction mechanism revealed the major reaction pathways that involve the decomposition of NF₃, the oxidation and chain-fluoridation of H₂ and CH₄, and the formation of N₂.     

High performance composite hollow fiber membranes for CO2/H2 and CO2/N2 separation

The search for a clean energy source as well as the reduction of CO₂ emissions to the atmosphere are important strategies to resolve the current energy shortage and global warming issues. We have demonstrated, for the first time, a Pebax/poly(dimethylsiloxane)/polyacrylonitrile (Pebax/PDMS/PAN) composite hollow fiber membrane not only can be used for flue gas treatment but also for hydrogen purification. The composite membranes display attractive gas separation performance with a CO₂ permeance of 481.5 GPU, CO₂/H₂ and CO₂/N₂ selectivity of 8.1 and 42.0, respectively. Minimizing the solution intrusion using the PDMS gutter layer is the key to achieving the high gas permeance while the interaction between poly(ethylene oxide) (PEO) and CO₂ accounts for the high selectivity. Effects of coating solution concentration and coating time on gas separation performance have been investigated and the results have been optimized. To the best of our knowledge, this is the first polymeric composite hollow fiber membrane for hydrogen purification. The attractive gas separation performance of the newly developed membranes may indicate good potential for industrial applications.     

Role of CO2 in the CH4 oxidation and H2 formation during fuel-rich combustion in O2/CO2 environments

The effect of CO₂ reactivity on CH₄ oxidation and H₂ formation in fuel-rich O₂/CO₂ combustion where the concentrations of reactants were high was studied by a CH₄ flat flame experiment, detailed chemical analysis, and a pulverized coal combustion experiment. In the CH₄ flat flame experiment, the residual CH₄ and formed H₂ in fuel-rich O₂/CO₂ combustion were significantly lower than those formed in air combustion, whereas the amount of CO formed in fuel-rich O₂/CO₂ combustion was noticeably higher than that in air. In addition to this experiment, calculations were performed using CHEMKIN-PRO. They generally agreed with the experimental results and showed that CO₂ reactivity, mainly expressed by the reaction CO₂ + H → CO + OH (R1), caused the differences between air and O₂/CO₂ combustion under fuel-rich condition. R1 was able to advance without oxygen. And, OH radicals were more active than H radicals in the hydrocarbon oxidation in the specific temperature range. It was shown that the role of CO₂ was to advance CH₄ oxidation during fuel-rich O₂/CO₂ combustion. Under fuel-rich combustion, H₂ was mainly produced when the hydrocarbon reacted with H radicals. However, the hydrocarbon also reacted with the OH radicals, leading to H₂O production. In fact, these hydrocarbon reactions were competitive. With increasing H/OH ratio, H₂ formed more easily; however, CO₂ reactivity reduced the H/OH ratio by converting H to OH. Moreover, the OH radicals reacted with H₂, whereas the H radicals did not reduce H₂. It was shown that OH radicals formed by CO₂ reactivity were not suitable for H₂ formation. As for pulverized coal combustion, the tendencies of CH₄, CO, and H₂ formation in pulverized coal combustion were almost the same as those in the CH₄ flat flame.     

Experimental and numerical investigation of low-pressure laminar premixed synthetic natural gas/O2/N2 and natural gas/H2/O2/N2 flames

The oxidation of laminar premixed natural gas flames has been studied experimentally and computationally with variable mole fractions of hydrogen (0, 20, and 60%) present in the fuel mixture. All flames were operated at low pressure (0.079 atm) and at variable overall equivalence ratios (0.74<?<1.0) with constant cold gas velocity. At the same global equivalence ratio, there is no significant effect of the replacement of natural gas by 20% of H₂. The small differences recorded for the intermediate species and combustion products are directly due to the decrease of the amount of initial carbon. However, in 60% H₂ flame, the reduction of hydrocarbon species is due both to kinetic effects and to the decrease of initial carbon mole fraction. The investigation of natural gas and natural gas/hydrogen flames at similar C/O enabled identification of the real effects of hydrogen. It was shown that the presence of hydrogen under lean conditions activated the H-abstraction reactions with H atoms rather than OH and O, as is customary in rich flames of neat hydrocarbons. It was also demonstrated that the presence of H₂ favors CO formation.     

Direct NaBH4/H2O2 fuel cells

A fuel cell (FC) using liquid fuel and oxidizer is under investigation. H₂O₂ is used in this FC directly at the cathode. Either of two types of reactant, namely a gas-phase hydrogen or an aqueous NaBH₄ solution, are utilized as fuel at the anode. Experiments demonstrate that the direct utilization of H₂O₂ and NaBH₄ at the electrodes results in >30% higher voltage output compared to the ordinary H₂/O₂ FC. Further, the use of this combination of all liquid fuels, provides numerous advantages (ease of storage, reduced pumping requirements, simplified heat removal, etc.) from an operational point of view. This design is inherently compact compared to other cells that use gas phase reactants. Further, regeneration is possible using an electrical input, e.g. from power lines or a solar panel. While the peroxide-based FC is ideally suited for applications such as space power where air is not available and a high energy density fuel is essential, other distributed and mobile power uses are of interest.     

Novel inorganic precursors [Co4.32Zn1.68(HCO2)18(C2H8N)6]/SiO2 and Co4.32Zn1.68(HCO2)18(C2H8N)6]/Al2O3 for Fischer–Tropsch synthesis

The silica- and alumina-supported Co–Zn catalysts were synthesized by thermal decomposition of new inorganic precursors [Co_4.32Zn_1.68(HCO₂)₁₈(C₂H₈N)₆]/SiO₂ or Al₂O₃. A novel coordination polymer formulated as [Co_4.32Zn_1.68(HCO₂)₁₈(C₂H₈N)₆] (1) was prepared using the solvothermal technique and characterized by elemental analysis, FT-infrared spectroscopy. Thermal stability of the complex 1 was investigated by thermogravimetric analysis and differential scanning calorimetry, and its structure was determined by single-crystal X-ray diffraction. Characterization of catalysts was carried out using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET specific surface area. The catalysts were evaluated for Fischer–Tropsch synthesis (FTS) in the temperature range 200–300 °C. The results revealed that the synthesized catalysts have higher selectivity to the desired products at 260 °C. The performance of the catalysts was compared to those of catalysts constructed via impregnation method and the fabricated catalysts show higher activity and selectivity than the reference catalysts.     

Mg2FeH6–LiBH4 and Mg2FeH6–LiNH2 composite materials for hydrogen storage

Two composite hydrogen storage materials based on Mg₂FeH₆ were investigated for the first time. The Mg₂FeH₆–LiBH₄ composite of molar ratio 1:5 showed a hydrogen desorption capacity of 5.6 wt.% at 370 °C, and could be rehydrogenated to 3.6 wt.% with the formation of MgH₂, as the material was heated to 445 °C and held at this temperature. The Mg₂FeH₆–LiNH₂ composite of 3:10 molar ratio exhibited a hydrogen desorption capacity of 4.3 wt.% and released hydrogen at 100 °C lower then the Mg₂FeH₆–LiBH₄ composite, but this mixture could not be rehydrogenated. Compared to neat Mg₂FeH₆, both composites show enhanced hydrogen storage properties in terms of desorption kinetics and capacity at these low temperatures. In particular, Mg₂FeH₆–LiNH₂ exhibits a much lower desorption temperature than neat Mg₂FeH₆, but only Mg₂FeH₆–LiBH₄ re-absorbs hydrogen.