煤粉富氧燃烧CO2富集特性与NOx生成量模拟预测研究

分析了富氧下的煤粉燃烧特性、CO₂富集特性和NO_x生成特性,并模拟了CO₂富集和NO_x生成量的协同控制趋势。结果表明：与空气燃烧相比,富氧燃烧条件下CO₂富集分布与NO_x体积分数分布是负协同效应;不同O₂/CO₂体积分数比的富氧下,随着O₂体积分数的增加,炉膛出口的CO₂体积分数和NO_x体积分数都先上升到最大值后稍微下降,呈正协同效应,但出现拐点的O₂体积分数不同;CO₂富集到一定程度时,能有效抑制NO_x的生成量;在富氧条件下,可实现炉膛出口的高CO₂富集与低NO_x生成量的协同控制技术。     

O2/N2和O2/CO2气氛下煤半焦-生物质的混燃特性及影响因素

为掌握煤半焦与生物质在O₂/N₂和O₂/CO₂条件下的混燃特性及其影响因素,采用全自动物理化学吸附仪获得了煤半焦-生物质混合燃料的孔隙结构,采用热重实验分析了两种燃料的混燃特性和反应动力学,通过多元线性回归法研究了燃料比、比表面积与混燃特性参数之间的关系。结果表明,O₂/N₂气氛下,掺混生物质可改善煤半焦的着火、燃尽及综合燃烧特性;O₂/CO₂气氛下,掺混生物质能改善煤半焦的着火特性,但会延迟其燃尽。混燃的活化能在低温区和高温区有显著差异,生物质掺混比增大,两个温区的活化能都降低;两种气氛下,低温区的活化能相近,但O₂/CO₂气氛下高温区的活化能显著高于O₂/N₂气氛下的。O₂/N₂气氛下孔隙结构对燃烧特性的影响更显著,而O₂/CO₂气氛下...     

柴油在O_2/CO_2氛围下燃烧特性模拟和试验

为研究柴油在O_2/CO_2氛围下的着火特性,提出了柴油表征燃料(正庚烷)在65%O_2/35%CO_2氛围下的着火延迟时间模型.该模型考虑到了O_2和CO_2对燃烧反应速率的影响,得到了温度和着火延迟时间的关系,推导出了着火延迟时间的计算公式,运用稳定状态法对正庚烷的基元反应进行缩减,计算了正庚烷在空气和65%O_2/35%CO_2氛围下的着火延迟时间;搭建了定容燃烧弹可视化试验系统,对柴油在空气和65%O_2/35%CO_2氛围下的着火过程进行了可视化研究;对试验所得的着火延迟时间、火焰浮起长度和燃烧压力变化进行了比较分析.结果表明:该着火延迟时间模型可以很好地模拟柴油在65%O_2/35%CO_2氛围下的着火过程,柴油在此氛围下的着火延迟时间变化非常明显,比在空气氛围下缩短了50%;柴油在此氛围下的火焰浮起长度短于在空气氛围中的;喷油压力的改变会对柴油的着火延迟时间及定容燃烧弹内的最大燃烧压力产生影响.     

O2/CO2和O2/N2氛围下煤粉富氧燃烧数值模拟

在目前煤炭依然作为能源主体的背景下，控制燃煤污染物排放有着重要意义。基于CFD数值模拟，建立伴流燃烧器模型，控制燃料、氧化剂入口流量恒定，设计了O₂/CO₂、O₂/N₂氧化剂氛围中O₂浓度在21%～40%内的多种工况，对煤粉燃烧特性及燃烧产生的污染物进行了研究。分析了不同工况下煤粉燃烧的温度分布、燃烧速率、碳烟、NO_x的生成情况。结果显示，在O₂/CO₂、O₂/N₂两种氧化剂氛围中，随着O₂浓度的上升，煤粉燃烧温度升高、燃烧速率增大，碳烟生成量均增加，同等O2浓度条件下，O₂/CO₂氛围的煤粉燃烧温度和燃烧速率均高于O₂/N₂氛围，碳烟生成量小于O₂/N₂氛围，且O₂/CO₂...     

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。     

NH3/DME混合物着火特性试验与数值模拟研究

为了探究NH₃/DME混合物的着火特性，利用激波管测量了初始温度T=1 250～1 800 K、当量比Φ=0.5～2.0、DME掺混比X_DME=0～1.0、压力p=1 MPa条件下NH₃/DME混合物的着火延迟时间。基于测量的试验数据，更新了Issayev等人构建的NH₃/DME燃烧反应动力学模型的部分基元反应，更新后的模型表现出对NH₃/DME着火延迟时间的良好预测。在此基础上，进一步开展了NH₃/DME着火特性值模拟研究。结果表明：NH₃/DME高温着火延迟时间随二甲醚(DME)掺混比的增加呈指数降低；NH₃/DME的着火延迟时间随当量比的增加先降低后升高，且不同温度下达到最低着火延迟时间的当量比不同；中低温下NH₃/DME的着火延迟时间随初始温度的变化规律与高温下不同，呈现出明显的负温度系数(NTC)现象。     

二甲醚/聚甲氧基二甲醚-3简化机理的构建及验证

采用基于误差的直接关系图法(DRGEP)、敏感性分析法以及同分异构聚合法对二甲醚/聚甲氧基二甲醚-3(DME/DMM₃)的联合详细化学反应机理进行简化，最终构建了一个包括65个组分和308个反应方程式的DME/DMM₃简化化学动力学机理．为了验证其可靠性，分别用二甲醚(DME)和聚甲氧基二甲醚-3(DMM₃)详细机理及试验数据与DME/DMM₃简化机理计算得到的着火延迟、层流火焰燃烧速度和组分摩尔分数等进行了比较，并分析了DME/DMM₃反应路径．最后验证了柴油机转速为1 600 r/min，当量比为0.18和0.34，燃料DME与DMM₃体积配比为1∶9时的仿真与试验的缸内压力和放热率以及CO、CO₂、NO_x和HC排放物．结果表明：该DME/DMM₃简化机理的着火延迟时间、层流火焰燃烧速度及射流搅拌反应器(JSR)中组分摩尔分数、缸内压力、放热率以及CO、CO₂、NO...     

水合物法分离CO2工艺研究进展

随着温室效应加剧,CO₂减排行动已迫在眉睫。水合物法分离CO₂工艺作为一种发展前景广阔的新型CO₂分离技术,为CO₂减排提供了一种解决思路。水合物法分离CO₂工艺相比于化学吸收、物理吸附、深冷分离和膜分离等技术具有分离效率高、过程简单无副产物、条件温和的优势,为减缓CO₂排放增加对环境造成的影响提供了一个中短期解决方案,以此为前提将允许人类继续使用化石燃料直至可再生能源技术广泛应用。本文综合分析了国内外的相关文献,介绍了水合物法分离CO₂工艺的基本原理,并比较了水合物法分离CO₂不同工艺的优劣之处,为进一步优化水合物法分离CO₂工艺提供指导。     

Combustion Characteristics and NO Emissions during Co-Combustion of Coal Gangue and Coal Slime in O2/CO2 Atmospheres

Coal slime has low ash content, and adding coal slime during coal gangue combustion may have influence on combustion character; and at this process, NO will emit, and lead to environmental pollution. O₂/CO₂ atmosphere is conducive to NO emission reduction. Thus combustion characteristics and NO emissions during co-combustion of coal gangue and coal slime in O₂/CO₂ atmospheres were studied. The results showed the addition of coal slime increased the com...     

HDMR correlations for the laminar burning velocity of premixed CH4/H2/O2/N2 mixtures

Correlations for the laminar burning velocity of premixed CH₄/H₂/O₂/N₂ mixtures were developed using the method of High Dimensional Model Representation (HDMR). Based on experiment data over a wide range of conditions reported in the literature, two types of HDMR correlation (i.e. global and piecewise HDMR correlations) were obtained. The performance of these correlations was assessed through comparison with experimental results and the correlation reported in the literature. The laminar burning velocity predicted by the piecewise HDMR correlations was shown to agree very well with those from experiments. Therefore, the piecewise HDMR correlations can be used as an effective replacement for the full chemical mechanism when the prediction of the laminar burning velocity is needed in certain combustion modeling.     

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.     

Synthesis and dehydrogenation of LiCa(NH2)3(BH3)2

We report the synthesis of a new hydrogen storage material with a composition of LiCa(NH₂)₃(BH₃)₂. The theoretical hydrogen capacity of LiCa(NH₂)₃(BH₃)₂ is 9.85 wt.%. It can be prepared by ball milling the mixture of calcium amidoborane (Ca(NH₂BH₃)₂) and lithium amide (LiNH₂) in a molar ratio of 1:1. The experimental results show that this material starts to release hydrogen at a temperature as low as ca. 50 °C, which is ca. 70 °C lower than that of pure Ca(NH₂BH₃)₂ possibly resulting from the active interaction of NH₂⁻ in LiNH₂ with BH₃ in Ca(NH₂BH₃)₂. ca. 4.1 equiv. or 6.8 wt.% hydrogen can be released at 300 °C. The dehydrogenation is a mildly exothermic process forming stable nitride products.     

The structural characterization of (NH4)2B10H10 and thermal decomposition studies of (NH4)2B10H10 and (NH4)2B12H12

The structure of (NH₄)₂B₁₀H₁₀ (1) was determined through powder XRD analysis. The thermal decomposition of 1 and (NH₄)₂B₁₂H₁₂ (2) was examined between 20 and 1000 °C using STMBMS methods. Between 200 and 400 °C a mixture of NH₃ and H₂ evolves from both compounds; above 400 °C only H₂ evolves. The dihydrogen bonding interaction in 1 is much stronger than that in 2. The stronger dihydrogen bond in 1 resulted in a significant reduction by up to 60 °C, but with a corresponding 25% decrease in the yield of H₂ in the lower temperature region and a doubling of the yield of NH₃. The decomposition of 1 follows a lower temperature exothermic reaction pathway that yields substantially more NH₃ than the higher temperature endothermic pathway of 2. Heating of 1 at 250 °C resulted in partial conversion of B₁₀H₁₀²⁻ to B₁₂H₁₂²⁻. Both 1 and 2 form an insoluble polymeric material after decomposition. The elements of the reaction network that control the release of H₂ from the B₁₀H₁₀²⁻ can be altered by conducting the experiment under conditions in which pressures of NH₃ and H₂ are either near, or away from, their equilibrium values.     

Catalytic conversion of CH4 and CO2 to synthesis gas on Ni/SiO2 catalysts containing Gd2O3 promoter

A series of Ni/SiO₂ catalysts containing different amounts of Gd₂O₃ promoter was prepared, characterized by H₂-adsorption and XRD, and used for carbon dioxide reforming of methane (CRM) and methane autothermal reforming with CO₂ + O₂ (MATR) in a fluidized-bed reactor. The results of pulse surface reactions showed that Ni/SiO₂ catalysts containing Gd₂O₃ promoter could increase the activity for CH₄ decomposition, and Raman analysis confirmed that reactive carbon species mainly formed on the Ni/SiO₂ catalysts containing Gd₂O₃ promoter. In this work, it was found that methane activation and reforming reactions proceeded according to different mechanisms after Gd₂O₃ addition due to the formation of carbonate species. In addition, Ni/SiO₂ catalysts containing Gd₂O₃ promoter demonstrated higher activity and stability in both CRM and MATR reactions in a fluidized bed reactor than Ni/SiO₂ catalysts without Gd₂O₃ even at a higher space velocity.     

Visible-light-driven ZnIn2S4/CdIn2S4 composite photocatalyst with enhanced performance for photocatalytic H2 evolution

ZnIn₂S₄/CdIn₂S₄ composite photocatalysts (x = 0–1) were successfully synthesized via a hydrothermal route. Compositions of ZnIn₂S₄/CdIn₂S₄ composite photocatalysts were optimized according to the photocatalytic H₂ evolution rate. XRD patterns indicate the as-prepared samples are mixtures of hexagonal and cubic structures. FESEM and TEM images show that the as-prepared samples are composed of flower-like microspheres with wide distribution of diameter. There is obviously distinguishing distribution of Zn, Cd elements among the composite architectures. UV–vis absorption spectra of different compositions exhibit that absorption edges of ZnIn₂S₄/CdIn₂S₄ composites slightly move towards longer wavelengths with the increment of CdIn₂S₄ component. A typical time course of photocatalytic H₂ evolution from an aqueous Na₂SO₃ and Na₂S solution over unloaded and PdS-loaded ZnIn₂S₄/CdIn₂S₄ composite photocatalyst is carried out. The initial activity for H₂ evolution over 0.75 wt% PdS-loaded sample is up to 780 μmol h⁻¹. And the activity of unloaded sample also reaches 490 μmol h⁻¹ with consistent stability.     

Catalytic effect of Gd2O3 and Nd2O3 on hydrogen desorption behavior of NaAlH4

This study investigated the effect of Nd₂O₃ and Gd₂O₃ as catalyst on hydrogen desorption behavior of NaAlH₄. Pressure-content-temperature (PCT) equipment measurement proved that both two oxides enhanced the dehydrogenation kinetics distinctly and increasing Nd₂O₃ and Gd₂O₃ from 0.5 mol% to 5 mol% caused a similar effect trend that the dehydrogenation amount and average dehydrogenation rate increased firstly and then decreased under the same conditions. 1 mol% Gd₂O₃–NaAlH₄ presented the largest hydrogen desorption amount of 5.94 wt% while 1 mol% Nd₂O₃–NaAlH₄ exerted the fastest dehydrogenation rate. Scanning Electron microscopy (SEM) analysis revealed that Gd₂O₃–NaAlH₄ samples displayed uniform surface morphology that was bulky, uneven and flocculent. The difference of Nd₂O₃–NaAlH₄ was that with the increasing of Nd₂O₃ content, the particles turned more and more big. Compared to dehydrogenation behavior, this phenomenon demonstrated that small particles structure were beneficial to hydrogen desorption. Besides, the further study found that different catalysts and addition amounts had different effects on the microstructure of NaAlH_4.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.     

Influence of metal oxide on LiBH4/2LiNH2/MgH2 system for hydrogen storage properties

In this study, various nanoscale metal oxide catalysts, such as CeO₂, TiO₂, Fe₂O₃, Co₃O₄, and SiO₂, were added to the LiBH₄/2LiNH₂/MgH₂ system by using high-energy ball milling. Temperature programmed desorption and MS results showed that the Li–Mg–B–N–H/oxide mixtures were able to dehydrogenate at much lower temperatures. The order of the catalytic effect of the studied oxides was Fe₂O₃ > Co₃O₄ > CeO₂ > TiO₂ > SiO₂. The onset dehydrogenation temperature was below 70 °C for the samples doped with Fe₂O₃ and Co₃O₄ with 10 wt.%. More than 5.4 wt.% hydrogen was released at 140 °C. X-ray diffraction indicated that the addition of metal oxides inhibited the formation of Mg(NH₂)₂ during ball milling processes. It is thought that the changing of the ball milling products results from the interaction of oxide ions in metal oxide catalysts with hydrogen atoms in MgH₂. The catalytic effect depends on the activation capability of oxygen species in metal oxides on hydrogen atoms in hydrides.     

Synergistic effect of Cu2O/TiO2 heterostructure nanoparticle and its high H2 evolution activity

Cu₂O/TiO₂ nanoparticles were prepared by solvothermal method, which formed the heterostructure of Cu₂O/TiO₂. Due to the heterostructure, the H₂ evolution rate under simulated solar irradiation was increasingly promoted. Meanwhile a certain amount of Cu particles which were confirmed by Transmission Electro Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS), formed on the surface of Cu₂O/TiO₂, and the photoactivity was accordingly further enhanced. The stabilized activity was maintained after many times irradiation. It is interesting that after a few hours irradiation the amount of Cu particles on the surface kept unchanged in the presence of Cu₂O and TiO₂. The Cu particles that formed during hydrogen generation reaction play a key role in the further enhancement of the hydrogen production activity. In this study, it is the first time to study the details on the formation of the stable ternary structure under simulated solar irradiation and their synergistic effect on the photoactivity of the water splitting.