稀释剂对H2/CH4预混火焰熄灭特性影响

掺氢天然气在稀释气体作用下的熄灭特性研究对实际燃烧设备的设计和优化具有重要的指导意义。本文利用对冲火焰法测量了掺氢天然气层流火焰在N₂和CO₂作用下的熄灭拉伸率,并采用数值模拟耦合详细化学反应机理对N₂,CO₂和He的稀释剂效应展开研究。结果表明,Li、GRI Mech 3.0和FFCM-1机理均能定性反映燃料熄灭拉伸率随当量比的变化规律,且FFCM-1机理综合预测精度最高。实验和模拟发现,不同稀释剂气体对掺氢天然气熄灭拉伸率降低幅度满足:He22。进一步研究发现,CO₂由于热容大,在反应体系中会降低火焰温度,同时增强了链终止反应强度,通过热效应和化学效应两方面对火焰熄灭特性起作用。He则能显著改变燃料混合物的平均摩尔质量,从而改变体系中重要反应物和自由基的扩散特性,从扩散效应方面影响火焰的熄灭特性。     

滑动弧裂解CO2机理

建立了一维滑动弧裂解CO₂的反应机理模型. 利用对流冷却的特征频率计算横向气流对流引起的等离子体组分损失. 将等离子体密度和温度的数值模拟结果与文献中滑动电弧等离子体反应器的实验数据进行了对比,吻合较好. 模拟结果表明,滑动弧裂解CO₂会产生大量O和O₂等活性助燃粒子以及可燃的CO. 随着对流冷却特征频率的增加,放电过程中最大电子数密度和电子温度减小,CO₂转化率下降. 在整个CO₂裂解机制中e+CO₂→e+CO+O的贡献最大,准稳态中贡献率为90.63%,瞬态中贡献率为98.43%. 反应CO+O+M→CO₂+M对CO₂生成的贡献率最大. 在实际应用中,为提高CO₂转化率,可以通过增大放电电流,增大e+CO₂→e+CO+O的反应速率,同时选择合适的气体流量,避免过大的速度引起CO₂转化率下降.      

CS2燃烧火焰光谱辐射模型的构建与特征污染产物浓度反演研究

CS₂在当今化工等领域占据了重要地位,而CS₂火灾污染事故危害性极大。通过研究CS₂燃烧火焰光谱辐射以探究其火灾污染特性极为必要。搭建了CS₂燃烧火焰光谱测试平台,采用黑体辐射源对VSR仪器进行了标定,通过多用途傅里叶变换(VSR)红外光谱辐射仪测试了5,10和20 cm三种燃烧尺度下CS₂燃烧的火焰光谱,并通过热电偶测试了整个燃烧时间段内不同燃烧时刻下的火焰温度,以及在火焰上方安装了烟气分析仪对火焰中的燃烧产物浓度进行监测。测量了CS₂整个燃烧时间段内火焰温度,以及不同燃烧时间、不同燃烧尺度下的火焰光谱、燃烧产物组分信息。测试结果表明,CS₂火焰中主要含有高温SO₂,CO₂,CO气体和空气中卷入的H₂O分子,并获取了特征污染产物SO₂的浓度。由于现有光谱仪测量分辨率有限,室内实验测量的火焰尺度有限,为了能实现火灾在线监测需要建立一个火焰光谱辐射模型来反演CS₂火灾时的污染物浓度相关信息。基于HITRAN数据库可知在2.7 μm附近为高温水蒸气的发射峰,4.2 μm附近特征峰为高温CO₂气体的发射峰,4.7 μm附近有CO微弱的发射峰,在7.4 μm附近特征峰为高温SO₂气体的发射峰,并获得了CS₂燃烧时产生的SO₂,CO₂,CO和H₂O气体在火焰燃烧相同温度下的吸收系数,通过计算得到了CS₂燃烧时产生的SO₂,CO₂,CO和H₂O混合气体的透过率与发射率,并结合气体辐射传输方程、气体吸收系数等方程,创建了CS₂燃烧的火焰光谱辐射模型。利用该光谱辐射模型反演了不同燃烧时间下特征污染产物SO₂的浓度,并与实验测得的数据进行了对比分析。结果表明,该模型精度高,可用于燃烧产物浓度的定量化反演,SO₂分子含量在燃烧时间20,40,60和80 s时的反演精度分别是89.5%,82.5%,85.6%和86.5%。为遥感反演CS₂型大尺度火灾中燃烧产物的浓度奠定基础。     

脉冲CO2激光器的多频动力学模型

建立了适用于各种气压下(20×133—20×10⁵ Pa)的脉冲CO₂激光器的六温度多频动力学模型，该模型考虑了增益谱线重叠效应，序列带、热带的影响，以及非洛伦兹线型效应.对模型进行数值求解可以预言和解释不同气压下的脉冲CO₂激光器的输出特性，有助于评价不同的抽运设计和研究可调谐特性，为设计脉冲CO₂激光系统提供理论支持. 关键词： 2激光器')" href="#">CO₂激光器 激光动力学 六温度模型 增益谱线重叠     

CO2及其碳同位素比值高精度检测研究

改进了一种基于傅里叶变换红外光谱法测量CO₂气体的装置, 改进后的装置能够提高CO₂检测精度, 并能同时测量CO₂碳同位素比值. 研究了温度和压力对CO₂浓度值和CO₂碳同位素比值测量的影响规律. 利用该装置连续测量了标准CO₂气体和环境大气, 对标准CO₂气体测量得到的CO₂浓度值及其碳同位素比值进行温度和压力影响修正, 获得了较好的精度和准确度. 关键词： 光谱学 同位素比值 傅里叶变换红外光谱 二氧化碳     

超临界CO2萃取黑色素条件的优化和筛选

以整穗黑糯玉米为原料,CO₂流量、萃取温度、萃取压力和萃取时间作为考察因素,采用正交试验优化黑糯玉米中黑色素的超临界CO₂萃取工艺。最终确定最佳工艺条件为:CO₂流量为120L/h,萃取压力为30MPa,萃取温度为50℃,萃取时间为90min。经过重复性实验验证,该工艺稳定可行,可作为黑糯玉米中黑色素的提取方法。     

H2/Air/CO2点火过程中的热辐射和化学反应效应

本文采用基于详细化学反应机理的化学反应流自适应数值模拟技术,研究了添加二氧化碳对氢气/空气预混气体点火的影响,获得了不同当量比下最小点火能随稀释率的变化情况。本文引入最小点火能的热辐射敏感度与化学反应敏感度,重点分析了CO₂的热辐射效应和化学反应效应对最小点火能的影响。研究结果表明二氧化碳的热辐射效应和化学反应效应只有在接近极限稀释率时才会导致最小点火能有显著升高。     

一维湍流模型对He平面羽流和CH4/H2/N2射流火焰的数值模拟

本文采用一维湍流模型（ODT）对氦气平面羽流和CH₄/H₂/N₂射流火焰进行数值模拟,和前人的实验结果进行定量地对比。结果表明,ODT模型能够准确地预测平面羽流基本特征,湍流涡团的分布同流场拉伸率之间具有密切的关系,涡团强度的分布能够直观地表明当地的湍流强度。ODT模型埘CH₄/H₂/N₂瞬态火焰的模拟定性反应了火焰特性及其与湍流作用的规律,对温度-混合分数的预测值和实测值进行比较,发现甲烷火焰燃烧在富燃料侧并未达到平衡状态,因而基元反应对火焰特性的预测具有重要作用。     

超临界CO2-丙烷混合物管内传热特性数值研究

采用SST k-w湍流模型对超临界CO₂/丙烷混合工质水平管内的传热特性进行数值模拟研究。管径d=4 mm,加热段L₂=800 mm;混合工质浓度配比为100/0、95/5、90/10、85/15、80/20、75/25;质量流速为150～250 kg·m^?2·s^?1;热流密度为30～40 kW·m^?2,入口温度293 K,入口压力7.5～30 MPa。随着丙烷浓度的增加,CO₂/丙烷二元混合工质的临界压力降低,临界温度升高,丙烷浓度从5%增加到25%,换热系数峰值降低6.19%～31.45%,但增加丙烷浓度可提高拟临界温度后的换热效果。P=7.5～8.5 MPa,换热系数有明显峰值;P=20～30 MPa,换热系数变化规律无明显峰值,并随压力的升高而减小。混合工质的换热系数随质量流速的增大而增大。同一流体温度所对应的换热系数,随着热流密度的增加而减小。     

超临界CO2-丙烷混合物管内传热特性数值研究

采用SST k-w湍流模型对超临界CO₂/丙烷混合工质水平管内的传热特性进行数值模拟研究。管径d=4 mm,加热段L₂=800 mm;混合工质浓度配比为100/0、95/5、90/10、85/15、80/20、75/25;质量流速为150～250 kg·m^?2·s^?1;热流密度为30～40 kW·m^?2,入口温度293 K,入口压力7.5～30 MPa。随着丙烷浓度的增加,CO₂/丙烷二元混合工质的临界压力降低,临界温度升高,丙烷浓度从5%增加到25%,换热系数峰值降低6.19%～31.45%,但增加丙烷浓度可提高拟临界温度后的换热效果。P=7.5～8.5 MPa,换热系数有明显峰值;P=20～30 MPa,换热系数变化规律无明显峰值,并随压力的升高而减小。混合工质的换热系数随质量流速的增大而增大。同一流体温度所对应的换热系数,随着热流密度的增加而减小。     

Electrical conductivity and defect structure of Mg-doped Cr2O3

The electrical conductivity of Cr₂O₃ nominally doped with 2 mol% MgO has been studied by the four point a.c. technique as a function of the oxygen activity (O₂ + Ar, CO + CO₂ and H₂ + H₂O) in the temperature range 400–1200 °C. It is concluded that Cr₂O₃ doped with MgO is an extrinsic conductor and that the dissolved Mg-dopant is compensated by the formation of electron holes at near atmospheric oxygen pressures and by oxygen vacancies (or possibly interstitial chromium ions) at highly reduced oxygen activities (in CO + CO₂ and H₂ + H₂O gas mixtures). In H₂ + H₂O mixtures Mg-doped chromia also dissolves hydrogen as protons and significantly affects the defect structure and electrical conductivity. The defect structure of the oxide under various conditions is discussed.     

H2/n-C4H10/Air预混气在Swiss-Roll燃烧器中的催化燃烧特性

在微尺度催化燃烧中,由于燃料和氧气对于催化剂表面活性位的竞争,导致了可燃下限为富燃的情况。为了提高燃料利用率,拓宽可燃范围,本文在正丁烷/空气的混合气中加入一定量的氢气,在Swiss-roll燃烧器内研究了氢气/正丁烷/空气预混气的燃烧特性。结果表明,氢气能够有效拓宽正丁烷的可燃范围,可燃下限能够低于1,以贫燃的条件实现高燃料利用率。对于稳定燃烧温度的实验结果表明,燃烧器最高温度出现在富燃料一侧。     

Surface interaction between H2 and CO2 over silicalite-supported platinum

Infrared spectroscopic evidence is presented for the formation of linearly bonded CO species, as a result of surface interaction between H₂ and CO₂ at room temperature over silicalite-supported Pt. Comparison with direct CO adsorption results suggests that the active sites for this CO₂ reaction are the corner or step sites on platinum particles. The CO formed on these active sites then migrates to other sites on the surface of Pt particles. Co-adsorbed hydrogen and water make the linearly bonded CO species more strongly adsorbed on Pt particles. However, exposure to oxygen or air at room temperature effectively removes these CO species.     

Evidence for bicarbonate formation on vacuum annealed TiO2(110) resulting from a precursor-mediated interaction between CO2 and H2O

The reaction of CO₂ and H₂O to form bicarbonate (HCO⁻₃) was examined on the nearly perfect and vacuum annealed surfaces of TiO₂(110) with temperature programmed desorption (TPD), static secondary ion mass spectrometry (SSIMS) and high resolution electron energy loss spectrometry (HREELS). The vacuum annealed TiO₂(110) surface possesses oxygen vacancy sites that are manifested in electronic EELS by a loss feature at 0.75 V. These oxygen vacancy sites bind CO₂ only slightly more strongly (TPD peak at 166 K) than do the five-coordinated Ti⁴⁺ sites (TPD peak at 137 K) typical of the nearly perfect TiO₂(110) surface. Vibrational HREELS indicates that CO₂ is linearly bound at the latter sites with a ν_a(OCO) frequency similar to the gas phase value. In contrast, oxygen vacancies dissociate H₂O to bridging OH groups which recombine to liberate H₂O in TPD at 490 K. No evidence for a reaction between CO₂ and H₂O is detected on the nearly perfect surface. In sequentially dosed experiments on the vacuum annealed surface at 110 K, CO₂ adsorption is blocked by the presence of preadsorbed H₂O, adsorbed CO₂ is displaced by postdosed H₂O, and there is little or no evidence for bicarbonate formation in either case. However, when CO₂ and H₂O are simultaneously dosed, a new CO₂ TPD state is observed at 213 K, and the 166 K state associated with CO₂ at the vacancies is absent. SSIMS was used to tentatively assign the 213 K CO₂ TPD state to a bicarbonate species. The 213 K CO₂ TPD state is not formed if the vacancy sites are filled with OH groups prior to simultaneous CO₂+H₂O exposure. Sticking coefficient measurements suggest that CO₂ adsorption at 110 K is precursor-mediated, as is known to be the case for H₂O adsorption on TiO₂(110). A model explaining the circumstances under which the proposed bicarbonate species is formed involves the surface catalyzed conversion of a precursor-bound H₂O–CO₂ van der Waals complex to carbonic acid, which then reacts at unoccupied oxygen vacancies to generate bicarbonate, but falls apart to CO₂ and H₂O in the absence of these sites. This model is consistent with the conditions under which bicarbonate is formed on powdered TiO₂, and is similar to the mechanism by which water catalyzes carbonic acid formation in aqueous solution.     

The effect of hydrogen addition on flammability limit and NOx emission in ultra-lean counterflow CH4/air premixed flames

The effect of hydrogen addition to ultra lean counterflow CH₄/air premixed flames on the extinction limits and the characteristics of NO_x emission was investigated by numerical simulation. Detailed chemistry and complex thermal and transport properties were employed. The results show that the addition of hydrogen can significantly enlarge the flammable region and extend the flammability limit to lower equivalence ratios. If the equivalence ratio is kept constant, the addition of hydrogen increases the emission of NO in a flame due to the enhancement in the rate of the NNH or N₂O intermediate NO formation routes. The addition of hydrogen causes a monotonic decrease in the formation of NO₂ and N₂O, except flames near the extinction limits, where the emission of NO₂ and N₂O first increases, and then decreases with the increase in the fraction of hydrogen. Overall, hydrogen enrichment technology allows stable combustion under ultra lean conditions, resulting in significant CO₂ and NO emission reduction.     

A numerical study on the effect of CO addition on extinction limits and NO x formation in lean counterflow CH4/air premixed flames

The effect of CO addition on extinction and NO _x formation in lean premixed counterflow CH₄/air flames was investigated by numerical simulation. Detailed chemistry and complex thermal and transport properties were employed. A method that gradually switched off the initial reactions of NO formation from different routes was used to analyse the variation of NO formation mechanism. The results indicate that the addition of certain amount of CO increases the strain extinction limits and reduces the radiation extinction limits. As a result, the lean flammability limit of CH₄/air premixed flame is extended to leaner side by the addition of CO. The formation of NO in a flame is increased with the addition of CO at a constant equivalence ratio. For an ultra-lean flame, the increase in the formation of NO is mainly because of the increase in the contribution from the NNH intermediate route, while for a near stoichiometric flame, this increase is mainly attributable to the rise in the contribution from the thermal route. With the fraction of added CO being gradually increased, the formation of NO₂ in a flame first decreases and then increases at a given equivalence ratio. The addition of CO reduces the formation N₂O in an ultra-lean flame, while affects little on the formation of N₂O in a near stoichiometric flame.     

NH4H2PO4和ND4D2PO4晶体微结构的拉曼光谱研究

本文利用偏振拉曼光谱和第一性原理, 对磷酸二氢铵(NH₄H₂PO₄, ADP)和不同氘含量磷酸二氢铵DADP晶体的晶格振动模式进行了研究. 实验测得了不同几何配置、200–4000 cm^-1范围的偏振拉曼光谱, 分析在不同氘含量条件下921 cm^-1和3000 cm^-1附近拉曼峰的变化. 在ADP晶体中, 基于基本结构单元NH₄⁺ 和H₂PO₄^-基团的振动模, 用第一性原理进行了数值模拟, 进一步明确拉曼峰与晶体中原子振动的对应关系; 通过洛伦兹拟合不同氘含量DADP晶体的拉曼光谱中2000–2600 cm^-1处各峰的变化讨论了DADP 晶体的氘化过程, 结果表明氘化顺序是先NH₄⁺ 基团后H₂PO₄^-基团, 研究结果为今后此类材料的生长和性能优化奠定了基础.     

Synthesis and characterization of NiMn2O4 nanoparticles using gelatin as organic precursor

Nanoparticles of NiMn₂O₄ were successfully obtained by mixing gelatin and inorganic salts NiCl₂·6H₂O and MnCl₂·4H₂O in aqueous solution. The mixture has been synthesized at different temperatures and resulted in NiMn₂O₄ nanoparticles with crystallites size in the range of 14–44 nm, as inferred from X-ray powder diffraction (XRPD) data. We have also observed that both the average crystallite size and the unit cell parameters increase with increasing synthesis temperature. Magnetic measurements confirmed the presence of a magnetic transition near 110 K.     

Enhancement of Kr2 excimer generation in a pulsedrare-gas jet discharge with H2 gas contact cooling

A novel excitation scheme for Kr₂ rare-gas excimer formation is developed. A pulse discharge excited Kr jet is dynamically mixed with a H₂ neutral gas flow located downstream in a vacuum chamber. Rapid contact cooling of the high temperature Kr plasma jet by H₂ gas collisions increases the Kr₂ excimer emission at 148 nm by a factor of more than three compared with that observed without the cooling downstream. Significant decreases of both electron temperature and density in the Kr plasma when mixed with H₂ gases downstream are measured with time-resolved spectroscopic methods