煤粉燃烧中焦炭燃烧模型的比较与分析

对已有的焦炭燃烧模型进行归纳总结,对常用的简化处理如单膜/双膜模型、忽略斯蒂芬流、忽略气化反应等带来的计算偏差进行了细致的分析比较.结果表明,与双膜模型相比,单膜模型的计算精度高;忽略斯蒂芬流会造成表面温度、燃烧速率的计算偏差,但可以通过对传质系数KD的简单修正进行改进;焦炭与CO2和H2O的气化反应不能忽略,否则会使得表面温度的计算明显偏高,而燃烧速率偏低,且偏差在富氧燃烧条件下更为明显.     

木屑炭水蒸气催化气化制取合成气研究

以木屑炭为原料,K2CO3作为催化剂,以固定床气化炉为实验设备,进行水蒸气催化气化木屑炭的探究。考察木屑炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H2/CO比值随K2CO3催化剂质量分数(0~8%)、水蒸气流量(0.15~0.35 g/(min·g))、气化温度(800~950℃)变化的规律。实验结果表明:K2CO3催化剂可显著提升碳转化率及产氢率,K2CO3质量分数为8%时,碳转化率和产氢率分别达到86.3%和125.6 g/kg,同时合成气中CO体积分数显著增加,H2/CO比值降至2.43。增加水蒸气流量,合成气中H2含量显著增大,H2/CO比值随之增大。温度可有效促进炭气化过程,950℃时碳转化率和产氢率分别达到84.3%和127.1 g/kg,但合成气中CO体积分数增大,H2/CO比值降至2.48。实验得到H2/CO比值在2.43~5.16范围的合成气。气化反应温度在900℃、水蒸气0.2 g/(min·g)、K2CO3质量分数3%时,碳转化率可达80.4%,产氢率109.6 g/kg,合成气中(H2+CO)体积分数82.4%,同时H2/CO比值高达3.05。     

O2/CO2气氛下考虑斯蒂芬流的碳粒燃烧模型

针对富氧燃烧中的O2/CO2气氛,考虑表面氧化反应、表面还原反应和斯蒂芬流,建立了新的碳粒燃烧理论模型.实验表明,与未考虑斯蒂芬流的模型相比,该模型的预报结果与实验值符合得更好.对斯蒂芬流影响的分析计算显示,无论斯蒂芬流存在与否,燃烧速率均随氧体积分数(20%和30%)、粒径(100～240,μm)、表面温度(1,750～1,900,K)、环境气体温度(1,200～1,400,K)的增大而增大,但由于斯蒂芬流阻碍了反应气体向颗粒表面的扩散,减缓了反应进程,因此在本文计算条件下,新模型计算得到的燃烧速率比未考虑斯蒂芬流的情况低1/4～1/3.     

反应温度对木屑炭水蒸气气化产物的影响

以木屑炭为原料,在固定床反应器中进行了水蒸气气化试验。试验在水蒸气流量为0.854 g/min,温度为800～1 000℃条件下,反应15 min。主要考查气化反应温度对碳转化率、合成气产率、燃气热值及燃气组成的影响。研究结果表明,在高温条件下木屑炭与水蒸气具有很高的反应活性,燃气产率为0.9～3 L/g;在气化温度为1 000℃时,碳转化率最高达到80%;燃气热值为8.9～9.4 MJ/m3,合成气(H2+CO)比例为68%～79%,H2/CO为4.02～6.32。     

分解炉内贫氧高CO2燃烧条件下挥发分NO生成机理

基于GRI3.0详细动力学反应机理数据库,采用生成速率分析方法,从化学反应动力学角度分析水泥分解炉内煤粉挥发分贫氧燃烧时低温、高浓度CO2条件下挥发分NO生成机理及挥发分中HCN转化生成NO的主要转化路径.分析结果表明,煤粉在过量空气系数为0.8的贫氧燃烧条件下,分解炉内高浓度CO2气氛会促进NO生成,增大NO的排放浓度;850～950℃温度范围内,CO2体积分数为0%～35%条件下挥发分NO生成的主要机理反应式为N+O2(→)NO+O、HNO+H(→)H2+NO和N+CO2(→)NO+CO;高体积分数CO2通过推进反应FINO+H(→)H2+NO和N+CO2(→)NO+CO促进NO生成;其中HNO是NO生成过程中最重要的活性含氮中间产物,对NO生成起主要的贡献作用;HCN氧化生成NO的主要反应路径为HCN先转化生成NHi,再进一步转化生成HNO活性含氮中间体,最终生成NO.     

考虑颗粒边界层气相反应的炭粒气化过程模型预报

建立了描述炭粒气化过程的移动火焰锋面模型(MFF-G 模型),模型考虑了颗粒边界层气相反应(CO 燃烧和水煤气置换反应)的影响,以及 CO 和 H2 对气化的抑制作用、颗粒孔隙变化的影响等.新模型被用于气流床气化炉的一维数值计算中,预报结果显示在燃烧/气化的连续过程中炭粒与环境之间有着明显的温度差异,考虑颗粒边界层气相...     

高温加压气流床内生物质气化特性的实验研究

在15～20 kg/h规模的沉降式加压气化实验装置上,实验研究了高温条件下,不同O/C摩尔比对生物质气化特性的影响,并根据实验气化炉的边界条件,建立了相应的气化模型.模型计算结果与实验结果吻合较好,模型能够很好的预测气化参数对生物质气流床气化特性的影响.研究结果袁明:在气化还原反应区,高温有利于气化反应向吸热方向进行;O/C比在1.0～2.0范围内,随O/C比的增加,CO、H2均呈现先增加后减小的趋势,可燃气体成分(CH4 H2 CO)占总合成气的50%左右;部分燃烧反应区温度在1600 K以上时,碳转化率大于90%,冷煤气效率达到50%左右.     

等离子体辅助甲烷燃烧的主要反应路径/通道

通过实验和模拟的方法,对等离子体辅助甲烷燃烧主要基元反应进行了研究.实验测量了等离子体辅助甲烷燃烧火焰不同位置的发射光谱图,得到了参与该过程的重要组分;模拟过程中,基于密度泛函理论,研究了甲烷燃烧反应中O_2+H→OH+O、CH_4+OH/O/H→CH_3+H_2O/OH/H_2、CH_3+O→CH_2O+H、CH_2O+OH/O/H→CO+H_2O/(H+H_2O)/(H+H_2)等几个重要基元反应,在B3LYP/6-311++G**水平找到了各反应可能的反应路径/通道,并进行分析.在此基础上,对比分析了放电等离子体作用下各反应路径/通道的变化,结果表明,在研究等离子体辅助甲烷燃烧机理时,应基于甲烷燃烧机理进行完善,通过加入*2HO(v)、O(1D)、CH_4(v)等激发态组分,并对一些基元反应进行拆分或合并,重新计算各反应活化能;生成的激发态组分会提升反应势能面,降低活化能,加速反应进程;在CH_2O与O/OH/H的反应中,放电等离子体可将生成的HCO直接分解,降低了HCO对H原子的消耗,同时还会释放一个H原子,有利于燃烧反应的进行.     

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。     

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.     

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.     

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.     

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.     

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.     

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.     

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.